(Semiconductors and Semimetals 9) R.K. Willardson and Albert C. Beer (Eds.) - Modulation Techniques-Academic Press (1972)

SEMICONDUCTORS
AND SEMIMETALS
Edited by R. K . WILLARDSON
BELL AND HOWELL ELECTRONIC MATERIALS DIVISION
PASADENA, CALIFORNIA
ALBERT C. BEER
BATTELLE MEMORIAL INSTITUTE
COLUMBUS LABORATORIES
COLUMBUS. OHIO
VOLUME 9
Modulation Techniques
1972
ACADEMIC PRESS New York and London
COPYRIGHT 1972, BY ACADEMIC

PRESS, mC.
ALL RIGHTS RESERVED
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BY PHOTOSTAT, MICROFILM, RETRIEVAL SYSTEM, OR ANY
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List of Contributors
Numbers in parentheses indicate the pages on which the authors contributions begin.
R. L. AGGARWAL,
National Magnet Laboratory, Massachusetts institute of
Technology, Cambridge, Massachusetts (1 5 1)
D . E . ASPNES,
Bell Telephone Laboratories, Znc., Murray Hill, New Jersey
(457)
IVAR BALSLEV,
Physics institute, Odense University, Odense, Denmark (403)
BRUNOBATZ, Semiconductor Laboratories, Free University of Brussels,
Brussels, Belgium (315 )
DANIEL
F . BLOSSEY,
Xerox Research Laboratories, Rochester, New York (257)
N. BOTTKA,Michelson Laboratory, China Lake, California (457)
PAULHANDLER,
University of Illinois, Urbana, Illinois (257)
B. 0. SERAPHIN,
Optical Sciences Center, University of Arizona, Tucson,
Arizona (1)
vii
Preface
The extensive research that has been devoted to the physics of semiconductors and semimetals has been very effective in increasing our understanding
of the physics of solids in general. This progress was made possible by
significant advances in material preparation techniques. The availability of
a large number of semiconductors with a wide variety of different and often
unique properties enabled the investigators not only to discover new phenomena but to select optimum materials for definitive experimental and
theoretical work.
In a field growing at such a rapid rate, a sequence of books which provide
an integral treatment of the experimental techniques and theoretical
developments is a necessity. The books must contain not only the essence of
the published literature, but also a considerable amount of new material.
The highly specialized nature of each topic makes it imperative that each
chapter be written by an authority. For this reason the editors have obtained
contributions from a number of such specialists to provide each volume with
the required detail and completeness. Much of the information presented
relates to basic contributions in the solid state field which will be ofpermanent
value. While this sequence of volumes is primarily a reference work covering
related major topics, certain chapters will also be useful in graduate study.
In addition, a number of the articles concerned with applications of specific
phenomena will be of value to workers in various specialized areas of device
development.
Because of the important contributions which have resulted from studies
of the 111-V compounds, the first few volumes of this series have been devoted
to the physics of these materials : Volume 1 reviews key features of the 111-V
compounds, with special emphasis on band structure, magnetic field
phenomena, and plasma effects. Volume 2 emphasizes physical properties,
thermal phenomena, magnetic resonances, and photoelectric effects, as
well as radiative recombination and stimulated emission. Volume 3 is
concerned with optical properties, including lattice effects, intrinsic absorption, free carrier phenomena, and photoelectronic effects. Volume 4 includes
thermodynamic properties, phase diagrams, diffusion, hardness, and
phenomena in solid solutions as well as the effects of strong electric fields,
ix
PREFACE
hydrostatic pressure, nuclear irradiation, and nonuniformity of impurity

distributions on the electrical and other properties of 111-V compounds.
Volume 5, which is devoted to infrared detectors, is the first of a number of
volumes to deal specifically with applications of semiconductor properties.
Volume 6 is concerned with injection phenomena in solids, including
current injection and filament formation, double injection, internal photoemission, and photoconductor-metal contacts. The next volume is again
devoted to devices (issued in two parts, 7A and 7B) and includes applications
of bulk negative resistance phenomena as well as effects due to barriers and
junctions. Volume 8, concerned with transport and optical properties,
consists of two chapters on photoluminescence, as well as articles on Faraday
rotation, thermal emf, and galvanomagnetic effects in 111-V compounds
with indirect gaps. The present volume is devoted to modulation techniques
such as electroreflectance, interband magnetooptical effects, electroabsorption, derivative spectroscopy by thermal and wavelength modulation,
piezooptical effects, and electric field effects on the dielectric function.
Subsequent volumes of Semiconductors and Semimetals will include
further work on infrared detectors and a variety of fundamental phenomena
such as lattice dynamics, transport properties, tunneling, and nonlinear
optical phenomena.
The editors are indebted to the many contributors and their employers
who made this series possible. They wish to express their appreciation to
the Bell and Howell Company and the Battelle Memorial Institute for
providing the facilities and the environment necessary for such an endeavor.
Thanks are also due to the U.S. Air Force Offices of Scientific Research
and Aerospace Research and the U.S. Navy Office of Naval Research and
the Corona Laboratories, whose support has enabled the editors to study
many features of compound semiconductors. The assistance of Crystal
Phillips, Martha Karl, and Inez Wheldon in handling the numerous details
concerning the manuscripts and proofs is gratefully acknowledged. Finally,
the editors wish to thank their wives for their patience and understanding.
R. K. WILLARDSON
ALBERT
C. BEER
Semiconductors and Semimetals

Volume 1 Physics of 111-V Compounds
C . Hilsum, Some Key Features of 111-V Compounds
Franco Bassani, Methods of Band Calculations Applicable to 111-V Compounds
E. 0. Kane, The k - p Method
V . L. Bonch-Brueuich, Effect of Heavy Doping on the Semiconductor Band Structure
Donald Long, Energy Band Structures of Mixed Crystals of 111-V Compounds
Laura M . Roth and Petros N . Argyres, Magnetic Quantum Effects
S . M. Puri and T. H . Geballe, Thermomagnetic Effects in the Quantum Region
W. M. Becker, Band Characteristics near Principal Minima from Magnetoresistance
E. H. Putley, Freeze-Out Effects, Hot Electron Effects, and Submillimeter Photoconductivity
in InSb
H. Weiss, Magnetoresistance
Betsy Ancker-Johnson, Plasmas in Semiconductors and Semimetals
Volume 2 Physics of 111-V Compounds

M . G.Holland, Thermal Conductivity
S . I. Novikova, Thermal Expansion
U. Piesbergen, Heat Capacity and Debye Temperatures
G.Giesecke, Lattice Constants
J . R. Drabble, Elastic Properties
A . U . Mac Rae and G. W . Gobeli, Low Energy Electron Diffraction Studies
Robert Lee Mieher, Nuclear Magnetic Resonance
Bernard Goldstein, Electron Paramagnetic Resonance
T. S. Moss, Photoconduction in 111-V Compounds
E. Antodik and J . Tauc, Quantum Efficiency of the Internal Photolectric Etrect in InSb
G. W . Gobeli and F. G.Allen, Photoelectric Threshold and Work Function
P. S.Pershan, Nonlinear Optics in 111-V Compounds
M . Gershenzon, Radiative Recombination in the 111-V Compounds
Frank Stern, Stimulated Emission in Semiconductors
Volume 3 Optical Properties of 111-V Compounds

Marvin Hass, Lattice Reflection
William G.Spitzer, Multiphonon Lattice Absorption
D. L. Stierwalt and R. F. Potter, Emittance Studies
H . R. Philipp and H . Ehrenreich, Ultraviolet Optical Properties
Manuel Cardona, Optical Absorption above the Fundamental Edge
Earnesf J. Johnson, Absorption near the Fundamental Edge
John 0. Dimmock, Introduction to the Theory of Exciton States in Semiconductors
B. Lux and J . G . Mavroides, Interband Magnetooptical Effects
xi
xii
CONTENTS OF PREVIOUS VOLUMES
H. Y. Fan, Effects of Free Carriers on the Optical Properties

Edward D. Palik and George B. Wright, Free-Carrier Magnetooptical Effects
Richard H. Bube, Photoelectronic Analysis
B. 0. Seraphin and H . E. Bennett, Optical Constants
Volume 4 Physics of IIEV Compounds

N. A . Goryunova, A . S. Borscheuskii, and D. N. Tretiakov, Hardness
N . N. Sirota, Heats of Formation and Temperatures and Heats of Fusion of Compounds A"'BV
Don L. Kendall, Diffusion
A. G. Chynoweth, Charge Multiplication Phenomena
Robert W. Keyes, The Effects of Hydrostatic Pressure on the Properties of 111-V Semiconductors
L. W. Aukerman, Radiation Effects
N . A. Goryunova, F. P.Kesamanly, and D. N. Nasledov, Phenomena in Solid Solutions
R . T . Bate, Electrical Properties of Nonuniform Crystals
Volume 5 Infrared Detectors

Henry Levinstein. Characterization of Infrared Detectors
Paul W. Kruse, Indium Antimonide Photoconductive and Photoelectromagnetic Detectors
M. B. Prince, Narrowband Self-Filtering Detectors
Ivars Melngailis and T. C. Harman, Single-Crystal Lead-Tin Chalcogenides
Donald Long and Joseph L. Schmit, Mercury-Cadmium Telluride and Closely Related Alloys
E. H. Putley, The Pyroelectric Detector
Norman B. Stevens, Radiation Thermopiles
R. J . Kcyes and T. M. Quisr, Low Level Coherent and Incoherent Detection in the Infrared
M . C. Teich, Coherent Detection in the Infrared
F. R. Arams, E. W. Sard, B. J. Peyton, and F. P. Pace, Infrared Heterodyne Detection with
Gigahertz I F Response
H. S. Sommers, Jr., Microwave-Biased Photoconductive Detector
Robert Sehr and Ruiner Zuleeg, Imaging and Display
Volume 6 Injection Phenomena

Murray A. Lampert and Ronald B. Schilling, Current Injection in Solids: The Regional Approximation Method
Richard Williams, Injection by Internal Photoemission
Allen M . Burnett, Current Filament Formation
R. Baron and J. W. Mayer, Double Injection in Semiconductors
W . Ruppel, The Photoconductor-Metal Contact
Volume 7 Applications and Devices: Part A

John A. Copeland and Stephen Knight, Applications Utilizing Bulk Negative Resistance
F. A . Padovani, The Voltage-Current Characteristic of Metal-Semiconductor Contacts
P. L. Hower, W. W . Hooper, B. R. Cairns, R. D. Fairman, and D. A. Tremere, The GaAs FieldEffect Transistor
Marvin H. While, MOS Transistors
G. R. Antell, Gallium Arsenide Transistors
T. L. Tansley, Heterojunction Properties
CONTENTS OF PREVIOUS VOLUMES
xiii
Volume 7 Applications and Devices: Part B

T. Misawa, IMPATT Diodes
H. C . Ukean. Tunnel Diodes
Robert B. Campbell and Hung-Chi Chang. Silicon Carbide Junction Devices
R. E. Ensrrom, H . Kressel, and L. Krassner, High-Temperature Power Rectifiers of GaAs, -,P,
Volume 8 Transport and Optical Phenomena

Richard J . Stirn, Band Structure and Galvanomagnetic Effects in IIILV Compounds with
Indirect Band Gaps
Roland W . Ure, Jr., Thermoelectric Effects in Ill-V Compounds
Herbert Piller. Faraday Rotation
H . Barry Bebb ond E. W . Williams, Photoluminescence I : Theory
E . W . Williams and H . Barry Bebb, Photoluminescence I1 : Gallium Arsenide
CHAPTER 1
Electroreflectance
B . 0. Seraphin
I . INTRODUCT~ON .
. . . . . . . . . . . .
11. ELECTROREFLECTANCE
I N PHENOMENOLOGICAL
DESCRIPTION
1. General Features . . . . . . . . . . . . .
. .
2 . Homogeneous Modulation ofthe Rejecting Medium
.
3. Inhomogeneous Modulation of the Reflecting Medium
111. THEORETICAL
CONCEPTS IN ELECTROREFLECTANCE
. . .
4 . Electric Field Effects in One-Electron Approximation .
5 . Electron-Lattice Interactions and the Dielectric Function
6 . Electric Fieid Eflects on Coulomb Interactions . . .
Iv . EXPERIMENTAL
METHODSIN ELECTROREFLECTANCE
. .
7 . General Features . . . . . . . . . .
8 . Surface Barrier Electrorejectance . . . . . .
9 . Transverse Electroreflectance . . . . . . .
10. Combination Techniques . . . . . . . .
V . EXPERIMENTAL
RESULTS . . . . . . . . .
1 I . Electrorejectance of Semiconductors
. . . .
12. ElectrorefIectance of Metals . . . . . . .
13 . Electrorejectance of Ferroelecirics . . . . .
VI. ANALYSIS
OF ELECTROREFLECTANCE
SPECTRA
. . . .
14. Scope, Intention, and Problems of the Analysis . .
. . . .
15 . Fundamentals of a Symmetry Analysis
16 . Signatures of Electrorejecronce Spectra . . . .
VI1 . ADDENDUM . . . . . . . . . . . . .
. . . .
17. Analysis of Electroreflectance Spectra
18 . Experimental Results . . . . . . . . .
19 . Experimental Methods . . . . . . . . .
20 . Photoreflectance
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I Introduction
The first chapters of this volume review the various modulated reflectance
techniques developed during the last five years. All techniques modulate
the reflectance of a sample through a periodic change of an external parameter such as an electric field. pressure. or temperature. Modulation of the
reflected beam is detected synchronously and phase.sensitively separated
from the unmodulated background. and amplified.
B. 0.SERAPHIN
Various modulation parameters define a whole family of modulated

reflectance techniques such as electroreflectance, piezoreflectance, and
thermoreflectance. The sample can be prestressed by one parameter and
modulated by a second, establishing combinations of the three basic techniques. Modulation by rotation is possible, and a magnetic field can be added
to all techniques.
Under similar conditions, modulated reflectance techniques better define
the spectral contrast of structure than do static reflectance techniques. A
rather featureless reflectance curve is replaced by a modulated trace rich in
structure compressed into narrow regions of photon energy.
A response so sharply localized in energy suggests a correlation to discontinuities in parameters of the band structure. Consequently, band structure analysis in particular has taken an interest in the results of modulated
reflectance techniques. Most of what follows will therefore be reviewed from
this point of view. Other promising aspects, such as the apparent potential
of electroreflectance in surface physics, for example, take second place.
In a considerable effort during the last decade, energy band calculations
have been used to establish the key features of the electronic structure of
solids, to provide a basis for the qualitative interpretation of numerous
experimental results, and to guide further investigations.
As a matter of economy rather than principle, the most successful of these
calculations rely on some input from properly interpreted experimental
results. Although we can solve the Schrodinger equation for such complicated systems as crystals, the definition of a physically realistic crystal potential is complicated by exchange, correlation, and relativistic effects. Recent
improvements in the computational tools permit us to treat these effects
more rigorously, but the return is hardly worth the increase in effort. We can
improve accuracy more efficiently by adding reliably interpreted experimental features to the procedure. A rough classification of the available
methods can actually be obtained by considering the first principle effort
that enters the initial stage of computation before some parameter of the
computational scheme is adjusted to experiment.
The accuracy of such empirically adjusted calculations depends (to a
varying degree) on the proper interpretation of experimental results. The
collation of existing band models and new experimental evidence, which has
been amazingly successful in the past, must be continued. The better the
general features of a band structure are known, the more successful further
analysis becomes.
Information from a number of experimental methods is available for the
identification of the lowest band extrema. Away from these fundamental
edges, however, the interpretation of reflectance measurements was the main
source of experimental information. A bridge to band structure parameters
1.
ELECTROREFLECTANCE
is built by assigning structure in the reflectance spectrum to critical pointsanalytical singularities in the interband density-of-states function which
determines the imaginary part E~ of the dielectric function.
As the field moves into a phase of further refinement, at least two limitations
of the assignment procedure evolve. The first relates to the sole responsibility
of critical points for structure in the static reflectance curve. After all, the E~
curve derived from such a reflectance measurement represents the sum of all
electronic transitions at a given photon energy, originating in large and
widely separated areas of the Brillouin zone. Coarse structure in E~ reflects
the spectral profile of this sum rather than contributions from a localized
area near critical points. Their contributions probably appear as fine
structure only, which may or may not be near the broad peaks with which
they must not be exclusively associated.
This aspect strongly influences the interpretation of optical spectra. No
longer can E~ be expected to assume the line shape predicted at critical points;
the number of critical points is irrelevant to the number of coarse structural
features in the experiment. The predominance of peaks in E~ rather than
the predicted thresholds no longer calls for the unlikely arrangement of two
critical points back-to-back at nearly the same energy. Instead, c2 reflects
the energy contour of a summation over extended rather than localized
regions in the Brillouin zone. Instead of adjusting high-symmetry transitions
to the coarse structure in the experimental spectrum, a calculated band
structure must reproduce E~ by adding up all transitions possible at a given
photon energy, irrespective of their origin in momentum space.
The importance of the critical-point concept as a bridge between experiment and theory is untouched by this development. True, we can no longer
associate structure in c2 with critical points-but the need to know their
transition energy, their class, and their location in the Brillouin zone still
exists. Band structure calculations depend on the input from experiment, and
critical points serve as the basis for the adjustment procedure. The type of
experiment from which this input is to be gained, however, must change,
and we must look for a mechanism that separates the massive background of
noncritical transitions from the much smaller contribution of a critical
point.
The second limitation of the assignment procedure results from the fact
that the experimentalist leaves the theorist considerably short of information
required for the full identification of a critical point. No direct procedure
is available for the assignment of photon energies, at which structure is
observed in static reflectance, to key transitions to which the parameters of
the calculation are adjusted. Circumstantial evidence guides the theorist
in unfolding the one-dimensional sequence of transition energies into the
three dimensions of k space. The more he knows about a band structure, the
B. 0.SERAPHIN
less ambiguous the assignment becomes. However, this interplay introduces

the danger of a cyclic progression of errors. Agreement between theory and
experiment may confirm the original assignment rather than reflect accuracy
in the calculation of the band structure.
In view of this situation, the development of modulated reflectance
techniques was timely. We are acutely aware of the necessity to clearly
identify, using criteria directly derived from experiment, the transitions to
which semiempirical calculations are being fitted. We further realize that
structure in c 2 cannot be directly associated with critical points and that
we must turn to a mechanism, such as the modulation of the reflectance, that
apparently lifts a critical-point contribution from the noncritical background.
The separation ofcritical points from noncritical background in modulated
reflectance, versus the observation of both in the static version, is first suggested by entirely different line shapes. On a qualitative basis, the modulated
response can be approximated by the differential of the predicted c2 line
shapes at critical points, whereas this approximation calls for considerable
imagination in the case of static reflectance. The spectral width of the
modulated response is typically 20-50 times smaller than the width of
reflectance structure. And-last but by far not least-no response is obtained
over large regions of the spectrum, suggesting that only limited areas of the
Brillouin zone are affected by the modulation.
The separation ofcritical points and background is probably accomplished
by utilizing the analytic singularities of the joint density-of-states function
at critical points. A periodic change in the band structure generated by the
modulation parameter is most effectively seen at these singularities. Tuning
the detection to the phase and frequency of the modulation amplifies the
synchronously modulated contribution from the slope discontinuity of the
joint density-of-states function, rejecting the unmodulated background from
areas where this function is smooth.
The high spectral resolution resulting from this separation must not be
overemphasized, however. It is of rather minor significance that structure
can now be located on the spectral scale to 0.001 eV rather than to 0.1 eV.
A far greater promise rests with the increase in diagnostic potential inherently
provided by the isolation of the critical-point contribution. The higher
sensitivity t o external perturbation, provided by the modulation, will probably lead to the identification of critical points without assistance from existing band structure calculations. Static reflectance, originating in extended
and widely separated areas of the Brillouin zone, responds more reluctantly
to diagnostic perturbation and only to the extent that the response characteristics of widely scattered contributions do not average out in destructive
interference. A vectorial modulation parameter will automatically perturb
the optical isotropy of a cubic crystal. Anisotropies are observed as functions
of the angle between this modulation vector and the axes of the crystal or the
polarization of the incident light, which can be explained without further
assumption by one, and only one, location of the correlated critical point.
A variety of external parameters can be used for the modulation of the
band structure. The way of forming the derivative on the joint densityof-states function differs from technique to technique. No attempt has so
far been made to delineate the similarities and differences of these techniques,
nor do we have more than a qualitative understanding of their basic mcchanisms.
The potential of the various techniques with respect to an analysis of the
band structure varies according to the character of the modulation parameter, vectorial or scalar, and its impact on the band structure or the optical
transition probability.
The vectorial character of &he modulation in electroreflectance and
piezoreflectance lowers the symmetry of the sample crystal. In a cubic
crystal, for example, the dielectric tensor and, consequently, all optical
properties are isotropic. Under the action of the electric field (or the uniaxial
strain), the cubic symmetry is destroyed, a preferred direction is established,
and the tensorial character of the dielectric function becomes important.
Orientation and polarization effects are observed that can be interpreted in
terms of the k-space symmetry of the critical point. The symmetry information to be obtained through matrix element effects is particularly important
for critical points off the center of the Brillouin zone. The necessary tensor
anaIysis is famiIiar from piezooptical studies.
In both techniques the symmetry-breaking effect of the uniaxial modulation introduces tensorial anisotropies of the response that enter through the
matrix element of the optical transition probability. In electroreflectancethe
electric field adds anisotropies of nontensorial character that enter through
the interband part of the transition probability. A strong sensitivity of this
interband part to the direction of the electric field results, which increases
the diagnostic value of electroreflectance.The basic mechanism centers the
action of the electric field at the critical points, leaving noncritical parts of
the band structure unaffected. This results in extremely sharp spectra.
The basic mechanism of piezoreflectance is quite different, however, and
could account for broad structure cut out from a large background, as usually
observed. The wavelength of the strain field is long compared to the wavelength of the light or the atomic dimensions of the crystal. This results in
a shift of the band structure as a whole, by a different amount or direction
for different subbands, so that degeneracies are lifted. In a sense, the piezooptical effect can therefore be described as taking the derivative of E ~
properly superimposing the various derivatives at degenerate points. This
effect operates throughout the Brillouin zone, and critical points are lifted
B. 0. SERAPHIN
from the background mainly because they occur at slope discontinuities of the
density-of-states function. This establishes a remarkable contrast to electroreflectance. In piezoreflectance, critical points dominate in regions of large
density of state, i.e., large interband reduced mass. Electroreflectance,
breaking the translational symmetry of the crystal along the field direction,
centers changes in the density of states at the critical points proper, in a
manner that makes critical points with small reduced interband mass emerge
more clearly.
The effect of a temperature modulation on the band structure as a whole
places thermoreflectance and piezoreflectance in the same class. The scalar
character of the modulation parameter, however, gives thermoreflectance a
special position with respect to the vectorial techniques that can expect
guidance in the identification of a critical point through anisotropies of the
response.
Thermoreflectancelacks this potential. A simplicity of the basic mechanism
seems to compensate for this handicap, however. In principle, the number
of possible effects of temperature modulation on the band structure is large,
particularly in semiconductors. A few examples of successful analysis
demonstrate, however, that one or the other of these effects seems to dominate. Good agreement between experiment and theory is obtained by assuming that the temperature change simply shifts the spectral position of an
interband edge. In other cases, an assumed change in the electron-phonon
interaction reproduces the observed line shapes. This in turn makes therrnoreflectance applicable to a study of electron-phonon interactions such as
indirect, phonon-assisted transitions.
Magnetooptics has made considerable contributions to our knowledge
of the parameters of the lowest extrema of valence and conduction band. In
principle, magnetoreflectanceshould be applicable at photon energies above
the fundamental edge where absorption measurements fail. Scattering is
strong for these photon energies, however, and the resulting lifetime broadening wipes out the quantum effects produced by the magnetic field. Magnetoreflectance studies in the past have been restricted to materials with small,
zero, or inverted energy gaps such as InSb, Bi, graphite, and HgTe.
Modulation of the Landau-level structure improves sensitivity and resolution sufficiently to observe an oscillatory pattern in magnetoreflectance that
extends far beyond the fundamental absorption edge. If, in addition to the
static magnetic field, the sample is subjected to moddation by an electric
field, stress, or temperature, the reflectance responds in a spectrum that is
characteristic for transitions between the Landau ladders of valence and
the conduction band.
Modulated reflectance has considerably expanded the range of magnetooptical experiments beyond the photon energies of the fundamental edge
and has produced results in a number of new materials. We can expect

modulated magnetoreflectance to extend the established potential of
magnetooptical studies to a wider spectrum of energies and phenomena.
We have tried to sketch in this introduction the position of modulated
reflectance with respect to band structure analysis. The following chapters
show in detail how modulated reflectance upgrades the information available
to band structure analysis from optical studies in precisely the two aspects on
which the reexamination of the assignment procedure centers. There seems
to be agreement that the observed structure in modulated spectra indeed
relates to the critical points proper, without considerable admixture from
noncritical areas.
Our present understanding of what causes this modulation is qualitative
at best, however. Consequently, an identification of critical points ab initio
is a promise that is only gradually being fulfilled. A variety of mechanisms
seems responsible in most cases. Synthesis of an observed line shape from
any such mechanism has rarely been successful, probably due to present
limitations in the definition of the experimental parameters. Identification
on the basis of quantitative line shape discussion seems therefore limited
at the present.
More progress can be expected from an evaluation of the symmetrybreaking effect of the modulation parameter. Although presently in an early
stage only, directional experiments will eventually give to the analysis of
higher interband edges a degree of certainty that presently, mainly through
cyclotron resonance and magnetooptics, can be achieved for the lowest band
extrema only.
XI. Electroreflectance in Phenomenological Description
1. GENERAL
FEATURES
The relative modulation A R / R impressed onto the reflected beam of intensity R is the basic quantity measured in electroreflectance.In the experimental
section we will describe various ways to measure this ratio ARIR as a function
of photon energy. In this first section we will be concerned with the phenomenological aspects of an analysis of the ARIR spectrum.
Spectral resolution and contrast of modulated reflectance spectra is considerably greater than in previously available static reflectance measurements. Consequently, a primitive analysis based on the existence of
structure at certain photon energies is often considered sufficient. Transition
energies of critical points are simply equated with the approximate photon
energy of structure. Such analysis can satisfy on a very low level of approximation only. Structure can be located far below, at, or above the correlated
B. 0.SERAPHIN
edge, depending upon the spectral range in which it occurs. It can furthermore be very complex and, although sharply defined in its parts, can consist
of a series of oscillations that are difficult to correlate to any one photon
energy.
A primitive analysis serves well, however, if only differences in photon
energy are of interest. Spin-orbit splittings and their ratio are often the key
to identification of structure. The components of spin-orbit split structure
are usually replicas of each other. In such cases their differences in energy
can be read out, because of the sharpness of the structure, to within 5 meV
or less.. A similar advantage holds for the precise determination of temperature coefficients from shift of s t r ~ c t u r e . ~
Restriction of the analysis to the spectral position of structure underrates
the potential of modulated reflectance. If such structure is actually indicative
of contributions from critical points, we should try to evaluate the spectral
line shape as well. Information as to modulation mechanism, class, and location of a critical point may be gained from such an evaluation.
Before we enter such an analysis even on the phenomenological level, we
must make an assumption about the manner in which the modulation
parameter affects the sample. In the most simple case, we can assume that
the modulation induces a homogeneous change in the optical constants
and e 2 . The reflecting surface is then a discontinuous interface between
two media that are homogeneous throughout at a given time. Piezoreflectance and thermoreflectance can probably be treated in this manner. In
electroreflectance, the situation can be more complicated. The ratio of
field penetration to light penetration governs the use of either of two different approaches. If the light penetrates little compared to the electric
field, we can consider the medium homogeneously affected. If, however, the
light penetrates much further than the electric field, it encounters a medium
of variable optical properties on its way in and out of the surface. A different
and much more complicated analysis must then be used.
2. HOMOGENEOUS
MODULATION
OF THE REFLECTING
MEDIUM
a. Diflerential of Fresnels Equation
We assume in this section that the dielectric function E = s1 is, of the

reflecting material is uniformly changed by the modulation by amounts
A E and
~ AE.
The reflecting surface then establishes a discontinuous interface between
two different, but homogeneous, media for which Fresnels reflection equation
K. L. Shaklee, M. Cardona, and F. H. Pollak, Phys. Rev. Lett. 16.48 (1966)
B. 0. Seraphin, J . Appl. Phys. 37, 721 (1966).
B. 0.Seraphin, R. B. Hess, and N. Bottka, J . Appl. Phys. 36,2242 (1965).
I
-0.03-
4 eV
FIG.1. The fractional coefficients a and B in Eq. (2) for Ge.
applies. For normal incidence of light, it has the form

R=
(Ell
(El2
+
+
+ 2(&,1 +
+ [2&1 + 2(&12+
- [2E1
&,2)12
E22)12
E22)1/2]12
E22)1/2]12
+1
+ 1.
(1)
Its total differential with respect to and E~ provides a phenomenological

description of the reflectance modulation475
ARIR = ~
+P(E~,
A E ~
( E I~ , 2 )
EZ)
A E .~
(2)
We will express the coefficients a and j in a mixed notation. Although

e2 and their differentials A & , ,
are the quantities to be interpreted, the
values of the coefficient must be calculated from tables which usually list n
and k.
a = 2y/(y2
S2),
(3)
p = 26/(y2 S 2 ) ,
+
+
y = (n/no)(n2 - 3k2
- no),
6 = (k/no)(3n2- k2 - no),
(4)
where no is the refractive index of the nonabsorbing medium of incidence.

Through and z2, the fractional coefficients a and B are functions of photon
energy. Their sign and relative magnitude determine the result of an analysis
of the modulated-reflectance spectrum in the different spectral regions. The
B. 0.Seraphin and N. Bottka, Phys. Reu. 145, 628 (1966).
Y. Hamakawa, F. A. Germano, and P. Handler, Phys. Rev. 167,709 (1968).
10
B. 0.SERAPHIN
0.04
0.02
-0.02
4 eV
FIG. 2. The fractional coefficients a and fi in Eq. (2) for Si
values of both coefficients,calculated from experimental values for
e2, are plotted in Figs. 1,2, and 3 for Ge, Si, and GaAs, respectively.6*
and
In the analysis of a modulated-reflectance spectrum, the discussion of the

coefficients a and fi is a prerequisite for three reasons. First, their sign and
relative magnitude establish the phase relation between modulation and reflectance response. It is of physical significancewhether an increase in electric
field, pressure, or temperature results in an increase or a decrease of the
reflectance. Conclusions about the underlying mechanism can be drawn
from the sign of this phase relation.
Second, the line shape of a reflectance response can be discussed only after
its composition from AE, and AcZ is dissected. In a A&,-dominated region,
for which /l > a, an absorptive line shape is preserved in the reflectance
response. If the Kramers-Kronig relation must be applied to such a line
shape in a A&,-dominatedregion (a > fi), however, the reflectance response
consists of an up-down sequence of two peaks of opposite sign. Fractional
admixture will result in reflectance responses with line shapes anywhere in
between these two extrema.
It follows, finally, that the spectral position of the reflectance response
with respect to the correlated critical point is strongly influenced by the size
and relative magnitude of the two coefficients.
At normal incidence the coefficientsa and /l in Eq. (2) are simply functions
of the optical constants and e2. At nonnormal incidence they are functions
H. R. Philipp and E. A. Taft, Phys. Rev. 120, 37 (1960).
B. 0. Seraphin and H. E. Bennett, in Semiconductors and Semimetals (R. K. Willardson

and A. C. Beer, eds.), vol. 3, p. 499. Academic Press, New York, 1967.
1.
ELECTROREFLECTANCE
4 eV
FIG. 3. The fractional coefficients a and
B in Eq. (2) for GaAs.
of the angle of incidence $o as well. For light polarized parallel to the plane
of incidence, this angular dependence is peculiar.* It can be used in the
recognition of Ael and A& if the angle of incidence replaces the spectral
coordinate as the variable parameter of the experiment : Scanning through
various angles of incidence near the Brewster angle-at fixed photon energy
and modulation4isplays an angular line shape of (ARIR), that portrays
the characteristic features of A& and A&. Starting from the general form of
Fresnels equation, Eq. (1) (the standard approximations prove inadequate
in the derivative near the Brewster angle), differentiation with respect to
and E gives the coefficients
a,,=
2us
(u
= -
ap = a,,
+ u)
(u [(u - s)
(32-
2us
(u2
+ u)
3Ll
[(u - S l 2
+ (u 2ut
+ u)
- s)
+ u][(u + s) + u]
Y2
- s2)
+ u 2 ] [ ( u + s)2 +
(u2
[(u - t)
3u - t)
u21
+ v 2 ] [ ( u+ t) + u]
* J. E. Fischer and B. 0.Seraphin, Solid State Commun.5, 973 (1967).
(5)
(6)
(7)
B. 0.SERAPHIN
12
a"
-.---p\\v
1
60
70
80
90
Angle of incldence (DEGI
Angle of incldence (DEG)

(a)
(b)
FIG.4. The fractional coefficients a and p for nonnormal incidence of light as functions of
the angle of incidence &. The two parts of the diagram show the coefficients for (a)light polarized normal (a", /?,) and parallel (ap,p,) to the plane of incidence. The calculation is based on the
optical constants of Ge at three photon energies of a spectral region in which a strong electroreflectance response is observed.
where we use the following definitions

s = no
cos 4 0 ,
t = no sin (b0 tan 40,

u2 - v 2 = c1 - no2 sin2 +o,
uv = -&2/2.
The incident medium, refracting but not absorbing, is described by no,

the material under study by
and e 2 . In solving explicitly for u and v,
the signs of square roots are determined by requiring e2 2 0 and R , , R , < I.
Thus, in Eqs. (5)-(8), u 2 0 and v < 0.
Figure 4 plots the coefficients [Eqs. (5)-(8)] versus angle of incidence for
the 2.1-eV region in Ge. The normal components an and f?, decrease monotonically with increasing c$o, indicating that (ARIR), also decreases. The
parallel components, on the other hand, exhibit extrema in a small angular
13
region about the Brewster angle & (74.4' in our example). These extrema
reflect singularitiesin Eqs. (7) and (8) at u = t that are damped by absorption.
The smaller the absorption (small values of u), the sharper are the extrema.
The near-singularities in the parallel coefficients amplify the reflectance
modulation considerably over the normal incidence values. In the case of
Fig. 4 this amplification factor is more than one order of magnitude. It
varies through the different spectral regions according to the admixture of
apand /?,in Eq. (2).In As,-dominated spectral regions, u is large, the singularity in Eqs. (7) and (8) is damped, and the angular line shape is broadened.
In A&,-dominatedregions the angular line shape is very sharp, and amplification of the parallel reflectance modulation over normal incidence may reach
100 or more. Thus, observation at oblique incidence near the Brewster angle
may be applicable to the study of weak modulation signals.
Of greater significance than this amplification, however, is the manner in
are "staggered" on the angular
which the angular line shapes of ap and /?,
scale. As we increase & through $B, the differential response changes from
A&,-dominatedto A&,-dominated.At 75", (ARIR), will essentially duplicate
the spectral dependence of Ac2 (/?, >> ap), whereas for &o 2 78", the line
Consequently, we can extract the sign and
shape of As1 emerges (ap >> /?J
approximate magnitude of both As, and As2 from a single sweep through
the angle of incidence 4owithout recourse to the Kramers-Kronig dispersion relation. Furthermore, the differences of the response functions As1
and
for critical points of different type are preserved in the oblique
incidence spectra, aiding in the interpretation of experimentally observed
structure.
Preliminary experiments (see data in Fig. 5 ) on the (2.1/2.3)-eV electroreflectance structure in Ge confirm the features predicted by Eqs. (5H8).9
The parallel component ARp/Rpis amplified by one order of magnitude over
its value at normal incidence, and positive and negative peaks appear in the
proper order and shift into the proper direction as the angle of incidence
increases through the Brewster angle. The normal component ARn/Rnnot shown in Fig. 5 4 r o p s monotonically as the angle of incidence
approaches 90".
b. Diflerential Kramers-Kronig Relations

Separate interpretation of A E and
~ Ae, in Eq. (2) requires not only knowledge of the optical constants and s2 of the unperturbed material, but also
of two differential quantities. The reflectance modulation AR/R is obtained
from experiment. A second quantity can be determined through the dispersion relation that connects real and imaginary parts of the complex
F. Lukes and B. 0.Seraphin, cited in Fischer and Seraphin.'
B. 0.SERAPHIN
14
ARP
-
2.5
Photon energy (eV)

2.4 2.3
2.2
2.1
2.0
Wavelength (rnp)
FIG. 5. Electroreflectance response A R d R , at the (2.1/2.3)-eV doublet in Ge, at 300"K,

measured for various angles of incidence straddling the Brewster angle. Notice the increase
over the response at normal incidence, shown as a solid line. (After Lukes and S e r a ~ h i n . ~ )
reflection coefficientga
i = R1/ZeiB
(9)
Differentiation of Eq. (9) gives, using Eq. (1) for R and Eq. (4) for the coefficients y and 6,
1 AR
A E=
~ -7 - - 6 AO,
2 R
1 AR
i yA0.
AE, = - 6 2 R
If AR/R is known from experiment for a sufficiently large range of photon

energies E, the Kramers-Kronig dispersion relation" gives for the differential A0
"See, for example, p. 98 of Philipp and Ehrenreich.I4

F. Stern, Solid State Phys. 15, 327 (1963)
lo
15
Eg
FIG.6. Line shape of A E (broken

~
line) and A E (solid
~
line) at the four types of critical points
in response to a modulation of their spectral position E , .
In electroreflectance, it is assumed that the electric field acts on c 2 . The

correlated modulation of c 1 can then be derived from a different form of the
Kramers-Kronig relation
Equation (13) establishes peculiar transformation relations between A&, and

AE, at the four different types M iof critical points. Considering the familiar
square-root dependence of the interband density-of-state function at M o
through M3,12 we obtain the line shapes of Fig. 6 for a modulation that
shifts the spectral position E , of the edge.j Although oversimplified, these
relations between Acl and Ac2 are often helpful in a cursory discussion of
structure.
The integrands of Eqs. (12) and (13) must, in principle, be known over an
infinite range. The experiment necessarily falls short of this requirement,
and extrapolations outside the range of measurement are familiar from static
dispersion relations. This extrapolation procedure is less critical in
differential dispersion relations of the type in Eqs. (12) and (13). Contributions
to the integral are restricted to spectral regions in which the modulation
affects the variable. Some of the neglected structure outside the range of
measurement will consist of positive and negative contributions that tend to
cancel each other. Furthermore, the denominators in Eqs. (12) and (13)
increase so rapidly that even the neighboring structure of a spin-orbit
split transition can be ignored, as was shown for the fundamental edge of
Ge.
B. 0. Seraphin and N. Bottka, Phys. Reo. 139, A560 (1965).
D. Brust, Phys. Rev. 134, A1337 (1964).
l 3 B. Batz, Sold State Commun. 5,985 (1967).
l4 H. R. Philipp and H. Ehrenreich, in Semiconductors and Semimetals (R. K. Willardson
and A. C. Beer, eds.), Vol. 3, p. 93. Academic Press, New York, 1967.
I
16
B. 0. SERAPHIN
3. INHOMOGENEOUS
MODULATION
OF THE
REFLECTING MEDIUM
Fresnel's reflection equation, Eq. (l),and the dispersion relations, Eqs. (12)
and (13), as well as all the conclusions drawn from them in the last section,
apply for a perturbation of the reflecting medium that is homogeneous over
the penetration depth of the light. While this is a legitimate assumption for
stress modulation and thermal modulation, it may fail for electroreflectance
where the spatial variation of the electric field over the penetration depth of
the light can be considerable. Aspnes and FrovalSa pointed out that a
perturbation inhomogeneous over the penetration depth of the light requires
a description different from the uniform perturbation assumed in deriving
the coefficients of Eqs. (3) and (4).'5b*c
We assume a semi-infinite dielectric - 03 < z < z, in which the dielectric
function E = el is, is perturbed by a z-dependent change AE(z) = Ael(z) +
i Ae,(z) that is small and disappears at large distances into the medium so
that IA&(z)l<< IEJ and limz+-a IAe(z)l = 0. The effect of AE(z) upon wave
propagation of an electric field of magnitude E in the dielectric can be
approximated by a trial solution
E(z) = EOe"- K z +&)I
(14)
of the wave equation, where q(z) is a complex z-dependent phase and K

is the unperturbed propagation constant.
Neglecting terms of second order in A~(z)/e,the relative change in reflectance can be written (rp' is the derivative of q)as
where
(AE)
(Aq)
+ i (AE,)
= -2iKeziKZs
AE(z')
(16)
and a and p are the fractional coefficients defined in Eq. (3). Equation (1 6)
shows that the effect of the inhomogeneous perturbation can be described
in terms of effective changes (At1), (Ae2) in the real and imaginary parts
of E. It involves a mixing of a, 8, A&,,and Ae, in Eq. (1 5) such that the coefficient a will not influenceAcl only and B Ae, only, since K is generally complex.
In particular, if K is real and the field decays over a distance (z, - zd),
"'D.
E. Aspnes and A. Frova, Solid State Commun. 7, 155 (1969).

ISbEarliersuggestions by Cardona et a/.'5cand Z00k~*preceded Aspnes and Frova's calculation.
'"M. Cardona, K. L. Shaklee, and F. H. Pollak. Phys. Rev. 154.696 (1967).
1.
-20
17
ELECTROREFLECTANCE
20
-20
20
hw-Eg ImeW
(a)
(b)
FIG.7. Changes in the (a) real and (b) imaginary part of the dielectric function at the fundamental edge of intrinsic Ge, as induced by a homogeneous electric field (top row) and spacecharge fields of a surface value F,. (After Aspnes and Frova."")
short compared to the penetration of the light, Eq. (16) becomes approximately
dz' AE(z')= - 2iK(z, - zd)&,
(17)
and the real and imaginary parts of A&completely interchange. This shows
the errors that can arise if the uniform perturbation approximation is used
18
B. 0. SERAPHIN
indiscriminately. The uniform field approximation results for
in which case ( A E ) + A&.

The results are valid for any mechanism producing AE(z) within the
approximation made. Aspnes and Frova illustrate them by calculating the
reflectivity change induced by the electric field of the space charge region in
intrinsic Ge, whose spatial dependence is well known. It is assumed that the
field-induced changes in the dielectric function are of the Franz-Keldysh
type. Using plausible constants for the region of the fundamental edge,
the changes in real and imaginary parts of the dielectric function are plotted
in Fig. 7 for a successive contraction of the space-charge layer, as indicated
by increasing values of the surface field. Starting on top with a homogeneous
perturbation, the space-charge layer shrinks as the surface field increases
toward the bottom. The oscillations of the homogeneous case disappear
and the weight of the response shifts systematically among the negative
center spike and its positive satellites on either side.
If it is applied to the fundamental edge of Ge, the calculation agrees well
with experiment. Since A R / R in this spectral region is proportional to Ael
only, we can compare the left-hand side of Fig. 7 with experimental spectra
recorded as a function of the surface field. It is interesting to note that, in
contrast to the uniform-perturbation approach, a calculation based on
inhomogeneous perturbation correctly reproduces the systematic pattern
in which the weight of the response shifts inside a group of structure as the
surface field is varied. It had been known for some time that the variations
of the line shape at the fundamental edge of Ge follow such a pattern with
variations in the surface condition^.^ It complicated the interpretation, since
conflicting conclusions could be drawn from observations at different surface
conditions. There was a wide margin for the assignment of the edge inside
the region of structure.
The systematicvariations of the threefold structure-red and blue satellites
on either side of a negative center peak-with the surface field F, is plotted
in Fig. 8. The diagram was calculated by applying lifetime broadening*
of various strength r to Aspnes and Frovas numerical calculation. For small
fields, the blue peak dominates, grows through a maximum, and shrinks
again toward larger fields. The negative center peak and the red satellite
grow monotonously with field. The sizes of the red and blue peaks cross over
at larger fields as the lifetime broadening parameter r increases.
This pattern is in good agreement with spectra recorded as a function of
the surface field adjusted in two different ways, relating to the (a) and (b)
19
AR/R
- Fs
FIG.8. Size of three major peaks (red, center, and blue) in the electroreflectance response
A R / R Acl for different values of the lifetime broadening parameter r, as a function of the
surface field F, calculated for the fundamental edge of intrinsic Ge at room temperature. (After
Aspnes and Frova."')
parts of Fig. 9.lSdUsing 30 ohm-cm n-type Ge in the wet-sandwich configuration, a constant ac modulation operates at 208K around various
values of the quiescent surface potential as adjusted by "dc bias." At 300K
the width of the "ac swing" around a floating quiescent surface potential
is varied. In both runs, the surface potential us at the extremum of the ac
modulation is determined from a measurement of the surface conductance.
From the surface potential us of a material with the potential ub in the bulk,
the field F, at the interface can be determined by a function F(x, y) derived
lSdB.
0. Seraphin and N. Bottka, Solid State
Commun. 7,497 (1969).
20
B. 0.SERAPHIN
1.4/10
1.8/18
0120
- 2.0739
1.4 147
-2.1/70
3.3/68
0.810 0 8 2 3 0.842
eV
-2.2195
- 2.3 / I I 2
Photon energy
0.78
(0)
0.80
eV
(b)
FIG.9. Line shapes of the electroreflectance response at the fundamental absorption edge of
30ohm-cm n-type Ge as a function of the surface field Fs as determined from simultaneous
measurement of the surface conductance. (a)dc bias, 208K; (b) ac bias, 300K. (After Seraphin
and B ~ t t k a . ' ~ ~ )
through a solution of Poisson's equation according to' 5 e * 1 5 f
where L , is the Debye length of 0 . 7 5 ~assumed in Aspnes and Frova's

numerical example at room temperature. The proper corrections must be
made for 208" K
As the maximum field increases, the line shape in both runs changes
through the following three phases. For weak fields, the negative center
spike is flanked by a small red and a large blue satellite, both positive.
Through a second phase of intermediate fields, the red satellite grows and
the blue one shrinks. Finally, strong fields generate an u p d o w n sequence of
equal components.
15eR.H. Kingston and S. F. Neustadter, J . Appl. Phys. 26,718 (1955).
IsrC. G. B. Garrett and W. H. Brattain, Phys. Rev. 99. 376 (1955).
21
Agreement with the pattern of Fig. 8 is satisfactory. The crossover occurs

at fields smaller than calculated. This can be corrected b y assuming a reduced
surface mobility'5g rather than the bulk mobility in evaluating the fieldeffect measurement. Note that the pattern is compressed to smaller field
values in the 208K trace since the lifetime broadening is smaller at the
lower temperature.
Size and spectral sequence of the structure are correctly reproduced in
Fig. 8. The size varies sublinearly with surface field, because the modulating
space-charge layer contracts as the surface field increases. The ratio of the
field-affected to field-free fraction of the light penetration depth varies
accordingly, with the consequences predicted by the inhomogeneous
perturbation model.
It is interesting t o note that the wave equation must be solved for the
inhomogeneous medium in order to produce the correct pattern of line
shape modification. Evangelisti and Frova' compare carefully surfacecontrolled spectra with an analysis that considers the field nonuniformity
by averaging the uniform-field effect over the field profile. Their experimental results are also in excellent agreement with Fig. 9. The analysis,
however, deviates definitely from the experimental behavior by not generating the strong increase in the red satellite.
We draw the following conclusions from the agreement between experiment and calculation.
(1) An analysis based on inhomogeneous perturbation of the reflecting
medium adequately describes the modification of the line shape at the
fundamental edge of Ge as induced by changes in the surface field.
( 2 ) Monitoring the systematic pattern in which the weight is shifted
among the various parts of structure as the field increases permits us to
discriminate between satellites and main structure. If a spectrum is measured
over an extended range of surface conditions, we reduce the risk of overinterpretation such as assigning transitions or their spin-orbit split companions
to satellite structure. The weak but richly structured response in the 2.83.7-eV region of Ge has probably suffered from such overinterpretation,
which is of little value to band structure analysis.15'
( 3 ) The spectral position of an edge relative to the components of structure can be determined with higher accuracy. This is particularfy important
for u p d o w n structure of equal size as frequently observed at larger photon
energies. In the case of GaAs, the uncertainty of where to place the edge has
led to controversial interpretations.**'5 c If, on the other hand, spectra such
"*J. R.Schrieffer, Phys. Reo. 97,641 (1955).
IshF.Evangelisti and A. Frova, Solid Stare Commun. 6, 621 (1968).
i 5 i For a review, see McElroy."'
22
B . 0.SERAPHIN
as shown in Fig. 9 are evaluated on the basis of the systematic line shape
pattern for satellite structure predicted by the inhomogeneous approximation, a more accurate value for the transition energy can be obtained. Identifying the edge with the crossover point of the strong field case, we obtain a
value of Egap= 0.825 4 0.005 eV for the direct gap of Ge at 208K, in agreement with that obtained from other method^.'^'
(4) No conclusion can be drawn for an exclusive responsibility of either
interband or excitonic mechanisms. Although the Franz-Keldysh theory is
used for calculating the line shapes, Aspnes and Frovas treatment of the
inhomogeneous perturbation is not connected to any model in particular.
When quantitative theories for other modulation mechanisms are available,
we can investigate to what degree inhomogeneous perturbation generally
explains the systematic line shape variations in electroreflectance spectra,
so long an impediment to their unambiguous interpretation.
Aspnes and Frova present similar calculations for the A transition at
2.1 eV. The absorption index here is not negligible, which appreciably
reduces the depth of the region contributing to the reflectance, but the
spatial nonuniformity of the field affects the spectra in a way very similar
to the case treated before. Since c( and p coefficients are nearly equal here,
A R / R should be given approximately by an equal admixture of the real and
imaginary parts of E . At high field, the structure should reduce to a very deep
negative spike at the singularity point with small positive peaks on both
sides. This behavior has been observed experimentally by Hamakawa
et a1.
111. Theoretical Concepts in Electroreflectance
The mechanisms involved in a modulation of the optical properties by an

electric field are probably very complex. The complexity has essentially two
facets. The first is common to all modulation techniques; the second is a
peculiarity of electroreflectance.
In analyzing reflectance modulation, we must first realize that the modulation parameter not only produces interband effects (Franz-Keldysh effect
in the case of electroreflectance), but also influences the electron-lattice and
electron-hole interaction. Their fractional contribution varies not only
between materials but, for the same material, through the spectral range.
Consequently, the interpretation of line shapes in modulated reflectance
must consider several mechanisms.
L. Rubin, and B. Lax, Phys. Rev. Lett. 17,8 (1966).Their room-temperature
value of 798 m V is adjusted to 208K using the temperature coefficient of 3.7 x 10-4 eV/K
determined by Seraphin et u I . ~
15jR. L. Agganval,
1. ELECTRQREFLECTANCE
23
A second complex aspect results from the different effect of the electric
field on the two components of the imaginary part c2 of the dielectric function
2
-d3k
leMi,12 6(AE - E )
- leMif12J ( A E ) ,
(19)
which determines the optical properties at photon energy E and polarization

vector e through the band structure parameters incorporated in the matrix
element \eMiflzbetween initial and final states of the energy separation AE
and the joint density-of-states function J(AE). The modulation results from
an effect of the electric field on both constituents. The integration in (19) is
throughout the k space of the Brillouin zone.
The symmetry-breaking effect on the matrix element is common to all
vectorial modulation techniques. In a cubic crystal, for instance, the optical
isotropy is destroyed under the action of the electric field or the uniaxial
stress, a preferred direction is established, and the tensorial character of
the dielectric function becomes important.
To the tensorial effects on the matrix element electroreflectance adds
peculiar anisotropies of nontensorial character, resulting from the effect of
the electric field on the joint density-of-states function. Compared to other
modulation parameters, this effect complicates the analysis, but increases
the diagnostic value of electroreflectance.
These nontensorial anisotropies are most pronounced at higher interband
edges of the saddle-point type. Their inclusion into the theory of field effects
on the dielectric function was stimulated by electroreflectance, which eliminated the previous restriction of the experiment to transmission effectsa t the
fundamental edge. A detailed treatment of this recent generalization and
expansion of theory is the subject of a separate chapter in this volume.16
We wiIi discuss the basic concepts, however, as far as they are relevant to an
analysis of electroreflectance spectra with respect to band structure and to
limitations encountered in the determination of experimental parameters
such as the effective modulating field. Much of the diagnostic potential of
electroreflectance in an identification of critical points rests on the strong
anisotropies predicted by the generalized Franz-Keldysh theory. We must
pay attention t o the way in which this theory interfaces the experiment.
4. ELECTRIC
FIELD
EFFECTS
IN
ONE-ELECTRON APPROXIMATION
Inserting the potential energy term - Fx into the one-electron Harniltonian

of the unperturbed crystal breaks up the invariance to lattice translation
in the direction x of the electric field F. As a consequence, the component
''
D. E. Aspnes and N.Bottka, Chapter 6 , this volume.
24
B. 0.SERAPHIN
k , of a wave vector is no longer a good quantum number. We can build the

field-perturbed wave functions from linear combinations of the unperturbed
Bloch functions with wave vectors parallel to the field direction.
Using these functions in the derivation of Eq. (19), we obtain an expression
for the dielectric function cZ(E,F) in the presence of an electric field. Aspnes
et al. show that for electric fields typically present in electroreflectance
experiments, the field-perturbed dielectric function can be obtained by
convoluting the zero-field function, Eq. (19), with an Airy function according
to
with
Equation (20) describes qualitative features of the effect of an electric field

on the dielectric function that are basic for the interpretation of electroreflectance spectra. We will therefore discuss it in detail. Comparing Eq. (20)
with the zero-field expression Eq. (19) we notice that the energy conserving
delta function 6(AE - E ) is replaced by the term in curly brackets. The
asymptotic properties of the Airy function Ai(x) for large values of the
argument x F-213guarantee that this term shrinks back into the delta
function as the electric field F vanishes. For finite values of the field, however,
this term accomplishes the mixing of Bloch functions required for the
description of the field-perturbed wave function. For zero field, only pairs
of states Ei and Ef separated by the photon energy E contribute to absorption.
With increasing field this contributing surface AE = E engulfs neighbor
shells of the interband energy surface, stretching further as the field grows.
The dielectric function is now determined by the way in which the electric
field forms a weighted average over a finite range of the density-of-states
function.
The effect is small if the electric field mixes states in smooth regions of the
density-of-states function. The change is drastic, however, if the convolution
extends over a slope discontinuity in the density-of-states function. It is
therefore immediately apparent how the formation of the weighted average
centers the action of the electric field at the critical points, although the
convolution operates throughout the Brillouin zone.
The character of the convolution and therefore the field-effect on E~ is
determined by the parameter hR. Its variable constituents are the electric
D. E. Aspnes, P.Handler, and D. F. Blossey, Phys. Rev. 166,921 (1968)
25
FIG.10. Two-dimensional model of the interband energy surface at a saddle point of principal
direction P. Shown are the sections in which the interband effective mass p assumes a negative
or positive sign, respectively, determining the choice of the electrooptical function for an electric
field in this section.
field F and the reduced interband mass pLlrin the direction of the electric
field, coupled into the dimension of an energy. It is defined as the characteristic energy of the electrooptical effect. For mass values near the freeelectron mass and field strengths of the order lo5 V/cm typically present in
the experiment, the characteristic energy is of the order 10 meV.
The Airy function is highly uneven, decaying exponentially for positive
arguments and extending in damped oscillations far into the region of negative argument. Consequently, it is of great significance that the reduced
interband mass pI, in the field direction can assume negative and positive
values and, since it enters with one-third power, can give the characteristic
energy, and therefore the argument of the Airy function, either the positive or
the negative sign. Accordingly, this function assumes its exponential or
oscillatory pattern, and the influence of the electric field on the dielectric
function is drastically different in the two cases.
It is through the reduced mass that the field direction enters the dielectric
function. The effect is slight a t a parabolic threshold. The curvature of the
interband energy surface, and therefore the sign of the reduced mass, is
the same in all directions. Any anisotropy is one of size, but not of sign.
At a saddle point of the interband energy surface, however, the reduced
mass can assume both signs in sectors separated by a line in which the
curvature and, therefore, reduced mass and field-effect disappear. A twodimensional model of the interband energy surface is shown in Fig. 10.
As the electric field swings from the negative-mass sector into the positivemass sector, the characteristic energy changes sign and the Airy function
enters a different branch.
26
B. 0.SERAPHIN
The resulting anisotropy of the optical field effect with respect to the field
direction at a saddle point is significant in the identification of critical points.
This is most easily demonstrated not in the dielectric function itself, but in
its field-induced change LIE,at the four different types of critical points.
Expressing the reduced-mass ellipsoid near critical points as
Aspnes18 solved the integral, Eq. (20), in closed form and described the
effect of an electric field on the dielectric function at the four types of critical
points in terms of two electrooptical functions F ( q ) and G ( q )
where A = BR/E and B = (2e2/m2h4)~eMif12(8~(,pL,~L,)1~2.

The quantity
As can be obtained through the Kramers-Kronig relation Eq. (13). Figure 1 1
summarizes the results for both A E , and As, at the four different critical
points, the saddle points M and M, having two entries for the two sectors
more parallel or more perpendicular to the direction of the odd-sign mass.
Note that no superposition principle applies to the field components. There
are two branches of the electrooptical functions at saddle points that converge in the zero-field limit. Their functional dependence on (AE - E)/hQ
is quite different, and the angle between the electric field and the mass axis
of odd sign determines which branch lo use. The two branches do not mix :
Either one or the other, but not both, occur for any given field direction.
Although the six different line shapes of Eq. (23) are combinations of the
two functions F and G, these combinations are unique for each case. Sign
and shape of the Aeis and the position of the oscillatory pattern with respect
to the edge are not alike for any two cases. If these line shapes can be
recognized in a spectrum as the electric field swings through various directions, identification of a critical point seems within reach-giving not only
the location in k space, but also the type and, in the case of a saddle point,
the direction of its principal axis as well.
A principal feature of saddle points moderates this expectation, however.
Symmetry excludes them from the center of the Brillouin zone, and their
contribution always consists of a sum from the off-center branches in the
equivalent directions. The k vectors of the multivalley star form various
angles with the field direction. Some valleys contribute with a parallel and
others with a transverse component, the dividing line being fixed by the ratio
D. E.Aspnes, Phys. Rev. 153,972 (1967).
1.
ELECTROREFLECTANCE
27
1
~
M,
I
i
FIG.1 1 . A summary of the field-induced change in the dielectric function at the various types
of critical points. Line shapes for the two columns of A E , ( E F
, ) and A&#, F ) calculated at the
condition: E, = 0.8 eV and B = 1. Here 7 = ( E - E,)/hB, A = BO''2/w2. (After Hamakawa
et d 5 )
of longitudinal to transverse reduced mass. The angular algebra of this

superposition from the equivalent branches greatly reduces the anisotropies,
as Bottka and R o e ~ s l e r 'have
~
shown. Using reduced-mass values derived
from pseudopotential calculations of the band structure of G a s , * ' they
synthesized a field swing through the principal crystalline directions,
assuming a position of the saddle-point edge in either the X - or the Adirection. Figure 12 shows the loss in line shape contrast resulting from the
summation over equivalent branches.
l9
N. Bottka and U. Roessler, Solid State Commun. 5, 939 (1967).

M. L. Cohen and T. K. Bergstresser, Phys. Rev. 141, 789 (1966).
B . 0.SERAPHIN
FIG.12. Reflectance modulation at a hypothetical saddle-point edge located at the X or the

L point of the Brillouin zone, with the electric field oriented along the three principal directions
of the cubic crystal. (After Bottka and Roessler.)
Some of the angular contrast is restored if the effect of selection rules

on the matrix element is included in the calcuiation. Phillips2 pointed out
that the polarization vector samples the equivalent branches in a different
manner once the cubic symmetry is broken by the modulation, cutting out
some branches and emphasizing others in accordance with the selection rule.
In a numerical example based again on GaAs, Aymerich and Bassani
demonstrated the value of this additional probe of k-space symmetry.
21
22
J. C. Phillips, Proc. Int. Sch. Phys. Enrico Fermi, Course X X X I V (J. Taw, ed.), p. 316.
Academic Press, New York, 1966.

F. Aymerich and F. Bassani, Nuouo Cimento 56B,295 (1968).
1.
ELECTROREFLECTANCE
5 . ELECTRON-LATTICE
INTERACTIONSAND
THE
29
DIELECTRIC
FUNCTION
Scattering probabilities grow rapidly as the photoelectron is lifted higher

in the band structure for increasing values of the photon energy E . The
shortening of its lifetime in the excited state leads to an uncertainty in the
energy described by a relaxation energy r. The optical transition now
operates between states that are broadened through the limited lifetime, and
E~ is described by the convolution4
Lifetime-broadening effects can be treated in the one-electron approximation of the preceding section. Then A Ecan
~ still be described by two electrooptical functions F( fq ) and G( fq). The real argument q = (AE - E)/hQ is
now replaced by a complex argument, however, into which the ratio of the
characteristic electrooptical energy hQ to the relaxation energy
enters
For the special case r = thQ, the six possible line shapes to be expected
at the four different types of critical points are shown in Fig. 13. The lifetime-broadening has rounded off the sharp spike at the edge and dampened the oscillations following it. Both features move the theoretical line
shape closer to the reality of the experimental observation.
In the preceding section, we emphasized the strong effect of size and
sign of the characteristic energy hQ on the line shape. Lifetime broadening
now requires that this important parameter hQ be compared to the relaxation energy r. This has drastic implications, as one would expect from the
dominant position of hR :
(1) Scattering possibilities, and therefore the relaxation energy r, increase
with photon energy. This should tend to broaden and flatten electroreflectance structure toward higher energies-a conclusion in agreement with
experiment.
(2) Size and contrast of structure at critical points is determined by the
ratio r/hQ.For a small characteristic energy hR, the structure will be all
but dampened out by lifetime broadening.
Either a small electric field or a large reduced mass can make the characteristic energy too small. We can increase the field within limits, but we
have to live with a given reduced mass, which must be sufficiently small,
at least in one direction, in order to resolve structure. In a certain sense,
this is contradictory to the convolution mechanism of Eq. (20),which suggests
that the field effect is roughly proportional to the unperturbed density of
30
B. 0.SERAPHIN
FIG. 13. The various line shapes of Fig. 1 1 lifetime broadened with
and Cardona.)
(-hR (After Aspnes
states. A high-density edge, however, makes for a strong damping of lifetime

broadening, since the reduced mass is large and the characteristic energy
small.
This establishes a significant difference between electroreflectance and
piezoreflectance. In piezoreflectance, high-density edges with large reduced
masses are dominant in the spectrum. In electroreflectance, these edges will
tend to be strongly dampened and difficult to resolve against the lifetime
broadening.
(3) The functional dependence of the complex argument in Eq. (25) upon
the electric field is such that the original one-third power dependence can
only be expected in the case of small relaxation energy. Switching on lifetime broadening, the one-third power dependence of AQ >> r gradually
approaches a quadratic dependence as r >> hQ.
23
D. E. Aspnes and M. Cardona, Phys. Reo. 173,714 (1968).
1.
ELECTROREFLECTANCE
31
This implies that the interpretation of spectra observed with the electric
field as the variable parameter must be based on the variable ratio r/hC!,
which influences the functional relationship. It further implies that modulation in the beam reflected from a surface barrier is representative of a wide
range of characteristic energies given by the inhomogeneity of the field
distribution in the surface region. We will discuss the consequences of this
in the analysis section.
6. ELECTRIC
FIELD
EFFECTS
ON COULOMB
INTERACTIONS
We discussed field effects so far in the one-electron approximation, which

does not include the Coulomb interaction between electron and hole.
This is a serious omission for two reasons. The potential drop of typical
electrooptical fields across the orbit of an exciton is of the order of its binding energy. The electric field can therefore be expected to break up the
Coulomb interaction. Furthermore, electrooptical effects center at critical
points for which, by definition, electron and hole have the same group
velocity. Traveling together, they are in a particularly favorable position to
interact with each other.
It can therefore be expected that electroreflectance will further outline
the limitations of the one-electron approximation with respect to Coulomb
interactions. Since a large range of the band structure is covered, information
can be obtained on this interaction at all types of critical points.
We can treat the subject in two stages. We will first discuss the effect of
Coulomb interactions on the dielectric properties of the unperturbed
crystal and then consider how the electric field acts on a dielectric function
that includes the Coulomb interaction. The first aspect has recently received
considerable attention from theorists, and certain concepts emerge. Very
little information, of a qualitative nature only, is available on field effects.
Elliottz4 treated electron-hole interaction in the effective-mass approximation at a parabolic edge oftype M , and established the existence ofthe exciton
as a stable bound state. At higher edges of the saddle-point type, the existence
of metastable states has been advocated and rejected.26 Since a quasistationary state below a saddle-point edge always overlaps a continuum
ofstates into which it can decay, the stability of such quasi-localized modes
depends upon the reduced mass in the scattering direction.
Toyozawa et aL2 have recently investigated the problem of such a
coexistence of local and band aspects in the fundamental optical spectra.
24
25
26
R. J. Elliott, Phys. Rev. 108, 1387 (1957).

J. C. Phillips, Phys. Rev. 146, 584 (1966).
C. B. Duke and B. Segall, Phys. Rev. Lett. 17, 19 (1966).
Y . Toyozawa, M. Inoue, T. Inui, M . Okazaki, and E. Hanamura, J . Phys. SOC.Japan 22,
1337 (1967).
32
B. 0. SERAPHIN
They arrived at line shape expressions in which both aspects, the metastable
exciton and the critical-point singularities, can coexist. As the Coulomb
interaction between nearest neighbors is gradually turned on in a cubic
lattice, the density-of-states function at critical points undergoes a metamorphosis. The square-root singularities expected at these points are distorted
by shifting the weight to critical points of type M o and M iand reducing it
near M , and M 3 . Since the total density is constant, a preference of M o
and M edges results from the Coulomb interaction and should be seen in
electrooptical spectra as well. A similar result has been obtained by Velicky
and Sak. The calculations receive tentative support from measurements.
Whereas a qualitative understanding is gradually approached in this
respect, we still know very little about the influence of an electric field on
the Coulomb-distorted dielectric function. Duke3 and Duke and Alferieff3
investigate the field decay of excitons at M o edges and predict broadening
and spectral shift of the absorption spike in an electric field. Ralph3 presents
a numerical solution of the effective-mass equation in the presence of an
electric field and arrives at markedly different results. Measurements on
PbI, and CdI,33 favor Ralphs interpretation, especially with respect to the
field shift of the exciton absorption.
Excitonic features determine the optical spectra of most solids in regions
of intermediate photon energy before lifetime broadening becomes the
shape-determining factor. Their influence on electroreflectance spectra in
this energy region can be expected to be of equal importance. As a criticalpoint phenomenon with emphasis on regions of strong interaction, electroreflectance will help to outline the limitations of the one-electron approximation and further the understanding of Coulomb interaction. At present,
theory provides only qualitative criteria for the effect of electric fields on
line shapes. At some later stage, we will be able to discuss line shapes on the
same firm basis as we can now discuss interband effects, providing an
estimate of their fractional contribution to modulated spectra.
IV. Experimental Methods in Electroreflectance
7. GENERAL
FEATURES
All modulated reflectance techniques share the basic experimental

features with ordinary reflectance measurements. Two variations establish
** B. Velicky and J. Sak, Phys. Stutus Solidi 16, 147 (1966).
K. L. Shaklee, G. A. Rowe, and M. Cardona, Phys. Rev. 174,828 (1968).

C. B. Duke, Phys. Rev. Lett. 15, 625 (1965).
3 1 C. B. Duke and M . E. Alferieff, Phys. Rev. 145,583 (1966).
32
H. I. Ralph, J. Phys. C,Proc. Phys. Soc. (London) 1,378 (1968).
3 3 Ch. Gahwiller and G. Harbeke, Bull. Amer. Phys. Soc. 13, 387 (1968).
29
33
the characteristic differences of the modulated version. First, the sample

holder carries some provision to modulate a specific parameter in the reflecting surface. And second, the modulation thereby impressed onto the reflected
beam is detected synchronously and phase-sensitively.
Many stability problems encountered in an absolute reflectance measurement can be disregarded in modulated reflectance. This advantage is more
than balanced, however, by the problem of lifting a modulation depth A R / R
of typically 10- or less from the noise background. Lock-in amplifiers are
well suited for this. Their input stages are sometimes saturated by other
signals, such as the 120-Hz fluctuation of lamps, and the signal is distorted.
Narrow-band preamplifiers usually solve the problem. In electroreflectance,
a fraction of the modulation voltage serves as reference voltage for the
phase-sensitive and synchronous detection of the reflectance modulation.
Strong lamps of ripple-free output help to lower the limit ofdetection to a
modulation depth of
or less. Gas discharge lamps give sufficient output,
but introduce noise through arc fluctations, even if they are dc operated.
Although much weaker, a battery-operated filament in a quartz envelope
often gives better results. The requirement for low ripple and fluctuations
in the lamp output makes electroreflectance measurements in the vacuum
ultraviolet presently difficult, since most lamps in this spectral region are
of the gas discharge type and are ac operated. The optical requirements are
modest. Except in low-temperature excitonic spectra, the line width ofelectroreflectance spectra, although sharper than in any other version, is still
not limited by the resolution of a prism monochromator. In early studies,
lifetime broadening was assumed to explain an observed widening of
structure toward the ultraviolet. This reveals an experimental rather than a
physical limitation, however. Refined measurements on thin-film structures
show that the line width of, for instance, the 5.5-eV peak in Ge is actually
smaller than that of structure in the visible and that lifetime effects apparently
enter at a much higher photon energy only.34 If the lamp difficulties can be
overcome, the prospects of vacuum ultraviolet electroreflectance up to 10 or
12eV are good, especially since transmission and reflectance of the semitransparent metal electrodes improve in this spectral range.
The relative modulation depth ARIR is formed in various ways, depending
upon the detector being used. Photomultipliers o r photovoltaic cells generate
an intensity-proportional dc voltage, which can be divided into the modulation-proportional dc output of the lock-in amplifier by means of ratiometers,
computers, or retransmitting slide-wires. Servomechanisms can be used to
operate photomultiplier tubes or light sources at constant output in the R
channel, eliminating the division of two dc voltages. In a third approach. a
J.
E. Fischer, N. Bottka,and B. 0. Seraphin, E d [ . Amcr. h ~ s SOC.

. 14,415 (1969).
34
B. 0. SERAPHIN
fraction of the reflected light is chopped at a different frequency, detected by a

second lock-in amplifier, and divided into the A R channel. Cross talk
between the two channels is difficult to avoid at very small modulation depths,
but the method can be applied to photoconductive detectors such as the
PbS cell. Even photoconductive detectors can be operated in intensityproportional control, however, by compensating the dark current or setting
the zero of a retransmitting slide-wire accordingly.
8. SURFACE
BARRIER
ELECTROREFLECTANCE
Space-charge layers in the surface of a sample material conveniently
solve the problem of modulating an electric field in the reflecting plane. Even
the thin space-charge region by which a rnetal adjusts to the presence of an
interface is apparently sufficient for modulation, although the light penetrates
a thousand times further. Semiconductors are particularly suitable candidates. In their surface region, a space-charge layer is ordinarily present that
typically extends as far as the light penetrates into the reflecting surface.
Reflectance modulation from variations in the space-charge field is
observed in metals and semiconductors alike. However, the analysis with
respect to changes in
and E~ varies drastically from the case of a thin
field-affected sheet of a thickness small compared to the penetration depth,
to the case in which the reflected light on most of its way in and out of the
surface sees a material under the electric field of a thick space-charge
layer. The relative penetration of light and electric field into the surface
determines whether the data must be reduced through the differential of
Fresnels equation, Eq. (2), using the coefficients Eqs. (3) and (4), o r whether
the analysis of Section 3 applies. In the two cases, quite different conclusions
are drawn from a n experimental A R / R trace with respect to the field-induced
changes A E and
~ A E ~which
,
then enter an interpretation in terms of the
band structure.
The role of the space-charge layer in generating the electroreflectance
response of metals is still disputed. The situation is more straightforward
in the potential barrier of semiconductors, which is adjustable in direction
and strength by a dc bias at an opposite electrode. Accordingly, a superimposed ac modulating field can operate around different values of the
surface potential cps, swinging the energy bands, and therefore the internal
electric field, around different center positions. The reflectance modulation
responds to the variation of surface conditions in a systematic manner,
manifested in a variety of line shapes. This strong sensitivity of the line
shape to the point of operation is a typical feature of surface-barrier
electroreflectance. Consequently, quantitative interpretation of this line
shape requires control of the surface potential around which the ac field
modulates.
1.
ELECTROREFLECTANCE
35
Although the periodic change of a voltage across the terminals of the

system causes the modulation of the surface potential, the exact fraction of
the potential drop across the space-charge layer will generally be a complicated function of various parameters. We must know this functional relationship between the external voltage and the modulation of the surface
potential if we wish to interpret electroreflectance spectra. Assumptions on
the fraction of the modulation voltage that appears across the space-charge
layer are not sufficient. A measurement of either the surface conductance or
capacity establishes this relationship directly.
O n its way in and out of the surface the reflected light samples a highly
inhomogeneous distribution of the electric field, given by Poissons law for
the space-charge density. The modulation of the reflected light therefore
represents a complicated superposition from a wide spectrum of values of the
electric fight strength. This presents a further problem for line shape discussions. Considering the complexity of the process, the definition of an
effective field cannot be more than an artifact. Field-dependent features
such as the separation of crossover points in the oscillatory response reflect
the integral superposition of a large scale of field values rather than being
representative for one effective field. We will discuss the situation in more
detail in the analysis section of this chapter.
The electric field of the potential barrier is always directed normal to the
reflecting surface. Therefore, at normal incidence the polarization vector
e is always perpendicular to the modulating field F. This reduces the amount
of information to be gained in configurations that permit alignment of the
polarization under various angles to the electric field, as in oblique-incidence
or transverse electroreflectance.
We have so far described features characteristic of the space-charge
layer inside the surface. They are common to all surface-barrier techniques.
Their differences are established by the manner in which the space-charge
layer is controlled and modulated from outside the interface.
u.
Field-EfSect Electrorejlectcmce
This technique takes its name from the similarity of the sample configuration, shown in Fig. 14(a and c), with the classical field-effect of the surface
conductance. The potential distribution shown in Fig. 14(c and d) is adjusted
and modulated by means of a semitransparent field electrode opposite the
polished and etched surface. Early work used Mylar or Saran spacers,
matching interfaces optically with suitable l i q ~ i d s . ~ - Care
~ must be taken
35
36
37
B. 0. Seraphin, in Physics of Semiconductors (Proc. 7th Int. Conf.), p. 165. Dunod. Paris
and Academic Press, New York, 1964.
9.0.Seraphin and R. B. Hess, Phys. Rev. Lett. 14, 138 (1965).
B. 0.Seraphin, J . Phys. 28, C3-73 (1967).
36
B. 0.SERAPHIN
Dielectric
Semiconductor
electrode
Electrolyte
Field
electrode
(a)
Semiconductor
electrode
Pt
electrode
(b)
(Cl
FIG.14. Experimental configuration (a, b) and potential distribution (c, d) in field effect (a, c)
and electrolytic (b, d) version of the electroreflectance method.
in these wet sandwiches to eliminate parasitic signals from the vibrations of

this interferometer. More recent work uses thin-film technique^.^^-^'
The dielectric of these dry sandwiches consists of evaporated quartz or
38
39
40
R. Ludeke and W. Paul, in II-VI Semiconducting Compounds (Proc. 1967 Int. Conf..
Providence) (D. G . Thomas, ed.), p. 123. Benjamin, New York and Amsterdam, 1967.
S. H. Groves, C. R. Pidgeon, and J. Feinleib, Phys. Rev. Lerr. 17, 643 (1966).
C. R. Pidgeon, S. H. Groves, and J. Feinleib, Solid State Commun. 5, 677 (1967).
37
photo resist coated with SnO, or thin metal films as field electrodes. They
have been used successfully at liquid helium t e m p e r a t ~ r e . ~ '
Wet sandwiches require hundreds of volts for modulation, since the capacity of the dielectric is small compared to that of the space-charge layer. In
thin-film sandwiches the capacities are comparable, and sufficient modulation requires only a few volts. The upper limit of the modulation frequency is
set by the inverse lifetime of the minority carriers, and the lower limit is set
by the relaxation into slow surface states, giving a range from approximately
l&104 Hz for standard semiconductors.
The spectral range extends from approximately 0.2-5 eV. Dielectrics made
of A1,0, or LiF with metal field electrodes expand this range even further
into the ultraviolet. Dry sandwiches consisting of an Al,03 spacer of a thickness small enough to avoid interference fringes have proved to be superior
to other systems. Strong response on Ge is observed out to 6eV, and the
structure of the 5.5-eV peak shows no sign of lifetime b r ~ a d e n i n g ,as~ ~
assumed in the interpretation of earlier results on inferior sample configurations.
Reliable control of the surface conditions is the main advantage of the
field-effect technique over other versions. Only at sufficiently low temperatures is it possible to adjust the point of operation over a wide range of the
surface potential, scanning the resulting variety of line shapes. The surface
conductance can be measured simultaneously, and the relationship between
electrical modulation and optical response can be established. Figure 9 shows
the results of such a simultaneous measurement on Ge.3 The drastic dependence of sign and line shape of the optical response upon the surface potential
is apparent.
Reliably adjusting and controlling the surface field as the prime agent
of the effect is of major importance. An identification of critical points
through line shape interpretation will materialize only by rigorous control
of the relationship between electric field and optical response-a requirement at the present most conveniently met by the field-effect technique. The
gain seems to outweigh the larger experimental effort in sample preparation.
6. Electrolytic Electrorefectance
Variations of the potential barrier inside the reflecting surface generate
the modulation of the electric field in the field-effect as well as in the electrolytic version of electroreflectance. A variable potential across a spacer of
constant dielectric properties affects the surface potential barrier in the
field-effect technique. Variations in the dipole layer adjacent t o the sample41
C. R. Pidgeon and s. H. Groves, in "IILVI Semiconducting Compounds" (Proc. 1967 Int.

Conf., Providence)(D. G . Thomas, ed.),p. 1080. Benjamin, New Yorkand Amsterdam, 1967.
38
B. 0.SERAPHIN
electrolyte interface that result from variations in the electrode potential

accomplish the modulation in the electrolytic version.
Space-charge layers at semiconductor-electrolyte interfaces were first
used in electrooptical work by Williams.42 As a n alternate to the fieldeffect technique, Cardona and co-workers adapted Williams' configuration
to electr~reflectance.~~
Sample configuration and potential distribution in
the electrolytic cell is shown in Fig. 14(b and d). The potential drop outside
the interface is distributed between two regions, the dipole-type Helmholtz
layer next to the interface and the diffusion-type Gouy layer extending
further into the electrolyte. In strong electrolytes, the potential drop across
the Gouy layer can be disregarded; in weak electrolytes, however, slow
adjustment processes in this layer can lead to a drift of the point of operat i ~ n . ~ ~
The Helmholtz layer is typically lo-' cm thick and therefore simulates a
field electrode of extreme proximity and nearly unlimited breakthrough
strength. Since the capacities of all space-charge layers on either side of the
interface are of the same order of magnitude, external potential differences
of only a few volts cause drastic changes of the surface potential. Large field
strength and large reflectance changes caused by small modulation voltages
are therefore a characteristic advantage of the electrolytic technique. The
field is so strong that optical changes in the electrolyte cannot be disregarded,
and in some cases may even be responsible for the generation of a response,
as in the electroreflectance of metals.44
The bias at the platinum electrode, placed at an arbitrary position in
the cell, adjusts the potential distribution at the sample4ectrolyte interface. The potential of the sample electrode ought to be measured against a
saturated calomel reference, although in most electroreflectance papers
only the potential between sample and platinum electrode is given.
In the past, most electrolytic electroreflectance work modulated around
a bias value that sets the point of operation in the range of minimum current
flow. This flat portion of the current-voltage characteristic between anodic
or cathodic current flow is approximately 1 V wide, unless the material is
covered by an insulating oxide layer as in Si. Among the early electrolytic
work, only Hamakawa et al. operated in the region of anodic polarization. 5 -45-4 7
R. Williams, Phys. Rev. 117, 1487 (1960).
K. L. Shaklee, F. H. Pollak, and M. Cardona, Phys. Rev. Lett. 15,883 (1965).
44 J. Feinleib, Phys. Rev. Lett. 16. 1200 (1966).
4 5 Y. Hamakawa, F. A. Germano, and P. Handler, Proc. I n t . Conf: Phys. Semicond.. Kyoto.
1966 ( J . Phys. SOC.Japan 21, Suppl.), p. 111.
46 Y. Hamakawa, P. Handler, and F. Germano, Phys. Lett. 25A,617 (1967).
47 Y. Hamakawa, F. A. Germano, and P. Handler, Phys. Rev. 167, 703 (1968).
42
43
1.
ELECTROREFLECTANCE
39
Recent results by Gobrecht rt ~ 1 . ~ question

'
that electroreflectance
spectra obtained in the blocking range can be reliably interpreted, however.
Gobrecht's work has bridged the gap to the electrochemistry of the semiconductor electrode which had previously established that the external potential
across the cell is shared between surface potential and Helmholtz layer in
a complicated
A slow sweep from cathodic to anodic polarization changes the state of oxidation of the surface. The hydride-like surface
of the cathode is gradually replaced by a hydroxide-like surface as the sweep
approaches anodic polarization, a mixed coverage being present in the
intermediate range. The gradual exchange influences the dipole moment at
the interface and therefore the potential distribution between inside and
outside. The point of operation with respect to the surface potential, which
so drastically influences sign and line shape of the electroreflectance response,
consequently depends upon the parameters of this redox reaction-prepolarization history, rate of change of the polarization, supply of reaction
products, etc., to name just a few.
The complicated hysteresis of the point of operation resulting from the
chemical reactions at the interface can be determined by measuring the
interfacial capacity. A parabola of the capacity versus polarization with a
minimum at approximately the flat-band position is observed in a range in
which the external modulation is passed on to the semiconductor spacecharge layer without noticeable change of the potential across the Helmholtz layer. This is then the bias range to operate in if a reliable correlation
between electrical and optical modulation is required for the interpretation
of the results.
Gobrecht and co-workers have demonstrated in a simultaneous measurement of electroreflectance, surface capacity, and current-voltage characteristic that the blocking range predominantly used in previous work is not
the proper range of operation. In the blocking range of the cell as determined
by the current versus electrode potential curve of Fig. 15(c), the surface
capacitance C (b) and the electroreflectance response (a) of an n-type Ge
electrode show a distinct hysteresis with respect to the polarization direction.
The hysteresis disappears and a unique line shape of the optical response
is obtained for anodic electrode potentials outside the blocking range.
A parabola of the interfacial capacitance indicates that in this region the
external potential modulation is passed on to the space-charge region,
48
49
50
52
H. Gobrecht, M . Schaldach, F. Hein, and R. Thull, E m . Bunsenges. Phys. Chem. 73.68 (1969).
W. H. Brattain and P. J. Boddy, J . Electrochem. SOC. 109, 574 (1962).
P. J. Boddy and W. H. Brattain, J . Electrochem. SOC. 110, 570 (1963).
H. Gerischer, M. Hoffmann-Perez, and W. Mindt, Ber. Bunsenges. Phys. Chem. 69,130 (1965).
H . Gobrecht, M. Schaldach, F. Hein, R. Blaser, and H. G. Wagemann, Ber. Eunsenges.
Phys. Chem. 70, 646 (1966).
40
B. 0.SERAPHIN
30
20
u)
LL
10
-1 0
400
-;200
0
E l e c t r o d e potentlal (rnV)
(C)
FIG. IS. Electroreflectance response at 0.81 eV (a) and surface capacitance (b) at an n-type
G e electrode in 0.1 N H,SO, during one cycle of the electrode potential, proceeding into the
cathodic direction and back at a rate of 5 mV/sec. The dotted line in (b) represents the theoretical
values. Note the strong hysteresis in the blocking direction of the current-voltage characteristic
(c).(After Gobrecht et
establishing the correlation between electrical and optical modulation

required for quantitative line shape discussion.
The complex response of the chemical reactions to the modulation of the
electrode potential is demonstrated by the sensitivity of the line shape and
even the sign of electrolytic electroreflectance to changes in the modulation
amplitude. In the blocking range shown at negative potentials in Fig. 16,
the line shape and sign respond in a rather erratic manner to an increase of
the modulation swing from 100 to 800mV. Again, a more systematic
behavior is observed as the electrode potential approaches positive values.
Modulation swings larger than 500 mV apparently shift the point of operation irreproducibly, since the symmetric modulation is superimposed on a
nonlinear rectifier characteristic. Analogous shifts are familiar from studies
of the field effect of the surface conductance, in which the modulation
operates along the nonlinear master curve. The parameters that determine
1 . ELECTROREFLECTANCE
-600
-400
-200
41
Electrode potenllal (mV)
FIG.16. Electroreflectance response at 0.81 eV for the Ge electrolyte system of Fig. 15 at the rate
of 5 mV/sec as a function of the ac modulation swing. Note the complicated dependence for
electrode potentials in the blocking range. (After Gobrecht et
equilibrium at the interface are numerous and are difficult to control and
reproduce. Simultaneous measurement of the interfacial capacitance seems
mandatory in reliable measurements of the electrolytic electroreflectance.
If the system is then operated on either side of the interfacial capacitance
minimum, the electroreflectance response at the fundamental edge of Ge
inverts sign and is in agreement with the results of the field-effect technique
(Fig. 17).
These results indicate the extreme sensitivity of the line shape to a variety
of parameters in electrolytic work, which seems characteristic of the technique. This sensitivity is advantageous if a broad range of surface conditions
is to be covered. However, if line shapes of electrolytic spectra are to be
interpreted quantitatively, the electrochemistry of the semiconductorelectrolyte interface must be taken ihto proper consideration. The complexity
of the processes at the Ge-electrolyte interface-the only system for which
the necessary electrochemistry is sufficiently known-indicates caution
in an extrapolation to all the other materials for which electrolytic
42
B. 0.SERAPHIN
electroreflectance spectra are available and have even been discussed with
respect to their line shapes.
The use of the electrolytic method at low temperatures is limited. Aqueous
electrolytes freeze near 273K ; nonaqueous electrolytes permit operation
to approximately 150K. Their inherently low concentration makes the
assumption questionable, however, that the potential drop across the Gouy
layer can be ignored.
The spectral range of the electrolyte technique extends to 6 eV, farther
than the field-effect technique. Very thin layers of electrolyte must be used,
however, to reach only 0.6 eV in the infrared.s3,s4
The modulation frequency is restricted to a few hundred hertz by the low
mobility in the ionic space-charge layer. Magnitude and type of the conduction of the sample electrode are of importance.
The electrolytic method is popular because it is convenient. Irregular
surfaces can be used with a minimum of sample preparation, and small
voltages produce large signals. The results are satisfactory if a qualitative
picture of the electroreflectance spectrum of a material is to be obtained,
with emphasis on the approximate spectral position of structure only. However, for quantitative analysis, and in particular for an interpretation of line
shapes, rigorous control of the surface conditions will be required in order
to fully develop the potential of the method.
c. Photoreflectance
In this technique the optical properties of the reflecting surface are modulated by strong intermittent illumination under normal incidence. The
monochromatic sampling light is incident under a large angle and is filtered
by two monochromators in order to avoid crosstalk with the strong modulating light source.
Spectrally localized response in the order of
has been observed in
Ge, GaAs, and CdS at photon energies where structure is observed with other
modulated techniques. In CdS, size and line shape change with the ambient
atmosphere; Ge and GaAs are much less sensitive to such
A variety of mechanisms could be responsible for the reflectance modulation. Thermal effects can be ruled out, because little frequency dependence
and no steady-state rise of the sample temperature is observed. Flattening
53
54
55
57
58
F. Lukes and E. Schmidt, Phys. Lett. 23,413 (1966).

M. Cardona, K. L. Shaklee, and F. H. Pollak, Phys. Lett. 23, 37 (1966).
E. Y. Wang, W. A. Albers, Jr., and C. E. Bleil, in 11-VI SemiconductingCompounds(Proc.
1967 Int. Conf., Providence)(D. G. Thomas,ed.), p. 136. Benjamin, New York and Amsterdam,
1967.
J. G. Gay and L. T. Klauder, Phys. Rev. 172,811 (1968).
E. Y. Wang and W. A. Albers, Phys. Lett. 27A, 341 (1968).
R. E. Nahory and J. L. Shay, Phys. Rev. Lett. 21, 1569 (1968).
1.
07
43
ELECTROREFLECTANCE
08
09
10
Photon energy (eV)
FIG.17. Spectral dependence of the electroreflectance response of the Geeelectrolyte system

of Fig. 1 5 for values of the electrode potential at the left and the right of the parabola in the
interfacial capacity characteristic (Fig. 15b). In this range of electrode potential, the external
modulation is reproducibly passed on to the surface potential, resulting in the expected sign
inversion of the electroreflectance signal on either side of the flat-band position. (After Gobrecht
et ~ 1 . ~ ~ )
of the bands by the injection of photogenerated electron-hole pairs is

consistent with the dependence of the line shape upon the ambient atmosphere in CdS, since the modulation of the surface field by the pair production
depends upon the initial bending of the bands.
An alternate mechanism is given by the strong pumping of electrons from
filled to unfilled bands, which changes the effective density of states for
interband transitions. The reflectance modulation expected from this blocking mechanism agrees with the experimental results.s6 It has recently been
discredited, however, since a response can be obtained even if the exciting
44
B. 0. SERAPHIN
light spectrum is cut off below the photon energy of the sampling light.58
This strongly suggests modulation by carrier injection into the potential
barrier.
A fourth mechanism could act on the binding energy of excitons via the
large increase in carrier density. This mechanism would be active even if
the excitation is restricted to energies below the spectral range under
investigation.
More experimental work is required to decide among the various mechanisms. However, the theoretical controversy does not impair the usefulness
of the method, which is flexible with respect to sample mounting and preparation, can be used over a wide temperature range, and is spectrally not limited
by a front electrode.
9. TRANSVERSE
ELECTROREFLECTANCE
In techniques that modulate through variations of the surface spacecharge layer, the electric field is necessarily oriented normal to the reflecting
surface. At normal incidence the polarization vector of the sampling light
is always perpendicular to the electric field. This restricts the diagnostic
potential of surface-barrier electroreflectance. Transverse electroreflectance
overcomes this restriction by placing the electric field into the plane of this
surface. This offers the following advantages :
(1) The polarization vector of the incident light can be oriented parallel
or perpendicular to the modulating field. Differences between the two cases
can be interpreted in terms of optical matrix elements and selection rules.
(2) The orientation of the modulating field in the reflecting plane can be
varied, for a (1 10)-plane through all three principal directions of a cubic
crystal, for instance. As we will see in the analysis section, this samples
the nontensorial anisotropies of electroreflectance and provides information
on symmetry character and location of the correlated critical point.
( 3 ) The technique does not require a front electrode of limited spectral
range.
It is sometimes emphasized that a further advantage can be seen in the

homogeneity of the modulating field. It is tempting to assume spatial and
temporal homogeneity of the electric field in the transverse configuration,
eliminating the field inhomogeneities of surface-barrier techniques. Such
an assumption will be justified when the existence of a space-charge field
normal to the surface and to the modulating field can be ruled out. Criteria
that a truly transverse field satisfies are uniform response from local illumination of the interelectrode space, invariance of the phase to polarity,
and disappearance of the first harmonic of the signal. Present results still
violate one or several of these conditions, suggesting that the effective field
45
consists of a superposition of the coplanar modulation with a surface field

normal to the reflecting plane. Piezoeffects should also be considered in
materials that lack a center of symmetry.
In view of its promise, it is unfortunate that the technique seems limited
to insulators. It can be shown that the depolarizing field as well as sample
heating limits application to materials of a specific resistivity greater than
10 ~ h m - c m . ~
Transverse electroreflectance was first used by Gahwiller in a study of
BaTiO, in which the light was incident on the thin edge of a parallel-plate
condenser.60.6 Rehn and KyseP2 independently developed a version in
which two Ds back-to-back surround the sample disk and the light is
incident on the 1-mm gap between the backs. On semi-insulating GaAs
the authors observe differences in line shape for EliF and E IF that can be
interpreted in terms of the interband effective mass of the (A3 - A,)-transition.22,63Aligning E and F separately along the three principal directions
produces nine distinctly different line shapes that are capable of guiding
the assignment if fitted to the proper theoretical line shape. l 9
A third version of transverse electroreflectance was developed by Forman
and C a r d ~ n and
a ~ ~applied to CdS, ZnS, and ZnSe. The same techniqueevaporating Au electrodes onto the reflecting surface-is used by Weiser and
S t ~ k on
e ~single
~
crystals of trigonal Se. Field F and polarization
are
aligned parallel and perpendicular to the optical axis, respectively, and
strong differences are observed in two peak groups at 2.0 and 3.1 eV.
10. COMBINATION
TECHNIQUES
a. Piezoelectrorejlectance
The response of the reflectance to uniaxial stress has long been recognized
as a diagnostic tool in the determination of the band structure of
The action of the stress is twofold. It first produces a strain that reduces the
V. Rehn, Bull. Amer. Phys. Soc. 13,470 (1968).
Ch. Gahwiller, Helv. Phys. Acta 39, 595 (1966).
6 1 Ch. Gahwiller, Solid Stare Commun. 5.65 (1967).
V. Rehn and D. Kyser, Phys. Rev. Left. 18, 848 (1967).
b 3 N. Bottka and B. 0. Seraphin, Bull. Amer. Phvs. Sac. 13,428 (1968).
R. A. Forman and M. Cardona, in 11-VI Semiconducting Compounds (Proc. 1967 Int.
Conf., Providence) (D. G. Thomas, ed.),p. 100. Benjamin, New York and Amsterdam, 1967.
6 5 G. Weiser and J. Stuke, Proc. IX In!. Conf. Phys. Semicond., Moscow, 1968, Vol. 1 , p. 228,
Publishing House Nauka, Leningrad, 1968; Phys. Status Solidi 35. 747 (1969).
6b H . R. Philipp, W. C. Dash, and H. Ehrenreich, Phys. Rev. 127, 762 (1962).
U. Gerhardt, Phys. Lett. 9, 117 (1964).
U . Gerhardt, Phys. Rev. Lett. 15,401 (1965).
69
W. Paul, Proc. Int. Sch. Phys. Enrico Frrmi, Course X X X I V ( J . Taw. ed.),p.257. Academic
Press, New York, 1966.
59
6o
46
B. 0.SERAPHIN
(lo9 dyn-cm-')
FIG.18. Energies of the peaks correlated to the fundamental edge of Ge at [ I 101 face as a
E,,(l); 0 :E0(2);A:E , + Ao. (After Pollak and
function of uniaxial stress along x 11 (001). 0 :
Cardona.' '1
symmetry of the material. In cubic crystals, for instance, the strain establishes a preferred direction that breaks up the optical isotropy. Secondly,
the strain changes the band structure by shifting energy levels in a specific
manner so that removal of degeneracies can result.
The diagnostic value of piezooptics derives from symmetry relations
between the strain components and the polarization direction of the incident
light that can be evaluated in terms of the location of the critical point.
For strain-split levels, the selection rules can be sampled by aligning the
polarization either parallel or perpendicular to the stress direction. In
addition, the deformation potentials of bands involved in a transition can
be determined by following the spectral shift of reflectance structure quantitatively as a function of stress magnitude.
In practice, this information could be gained from static piezoreflectance
measurements only after considerable experimental difficulties were overcome. Stress-induced changes of the static reflectance are small, and few
materials withstand the strain required to observe them. Since static reflectance peaks are usually broad, the splitting of degenerate levels under strain
could actually never be observed in static piezoreflectance.
Piezoelectroreflectance considerably improved this situation. This method,
first developed by Pollak and c o - w ~ r k e r s , ~exploits
~ . ~ ' the diagnostic value
F. H. Pollak, M. Cardona, and K. L. Shaklee, Phys. Rev. Lett. 16,942 (1966).
F. H. Pollak and M. Cardona, Phys. Reo. 172,816 (1968).
47
of a uniaxial stress by sampling the strain-shifted band structure with the

high spectral resolution and sensitivity of electroreflectance. In their work
on Ge, Si, and GaAs, the strain-induced splittings of energy levels are now
clearly observed. Polarization and orientation effects permit us to deduce
the symmetry character of initial and final states and to determine values for
the deformation potential coefficients.
Monitoring the strain-shifted band structure by electroreflectance rather
than by static reflectance is superior for reasons other than a mere experimental improvement.
recognized that static piezooptics samples the
stress dependence of large areas of k space, so that destructive interference
from regions of opposite deformation potential can result. In contrast, the
modulation technique monitors localized regions of the Brillouin zone that
respond more sensitively to the strain.
Through its analysis, piezoelectroreflectance is more a part of piezo- than
ofelectrooptics and will be treated in detail in a later chapter ofthis v01ume.~
We will only sketch the results by Pollak et
on Ge, Si, and GaAs.
In these crystals of the diamond and zinc blende type, the applied stress
lifts degeneracies of two different kinds :
~
(1) The top of the valence band near k = 0 is, according to its p-character,
sixfold degenerate. Part of this degeneracy is lifted by spin-orbit interaction,
but the fourfold degeneracy of the upper J = 3 band remains. Uniaxial
1
stress splits this multiplet into the doubly degenerate groups mJ = -+r
and m, =
so that now three separate energy levels are available as
initial states for the transition that represents the fundamental edge. Only
the uppermost level mJ = &* is allowed for both directions of the polarization, parallel and perpendicular to the stress. The middle level mJ = k;
responds to perpendicular polarization only, and therefore generates a new
peak in the structure (Fig. 18).
(2) A different kind of degeneracy is removed at off-center critical points.
The various branches of a multivalley critical point, equivalent in the unstressed crystal, have different projections of their k vectors in the direction
of a uniaxial stress, so that an interband splitting results. An existing spinorbit splitting is also slightly affected, but only to second order.
+;,
The assignment of the structure at 3.0 eV in GaAs to a critical point in the

(1 11)-direction is clearly confirmed by Pollaks piezoelectroreflectance
results. Stress in the (100)-directionaffects all equivalent branches equally,
so that the degeneracy of the (111)-star is not removed. However, (111)stress separates the aligned branch from the star of the remaining three.
Transitions from this aligned branch are allowed for the perpendicular
I. Balslev, Chapter 5, this volume.
48
0. 0.SERAPHIN
"7
'
-n
x=o.o
LL
2 90
3 10
3 30
Photon energy (eV)
FIG.19. Electroreflectance spectrum of GaAs at the (A,-A,)-edge for zero stress (top) and
stress along ( 1 1 1 ) with the polarization vector of the incident light oriented parallel (-) and
perpendicular (---) to the direction of stress. (After Pollak and Cardona.")
polarization only, so that the two sets can be separated. Two peaks appear
for the perpendicular polarization allowed for both sets and one for the
parallel polarization having an allowed component for the nonaligned
branches only. Figure 19 clearly shows this splitting for polarization perpendicular to (1 11)-stress.
The directional effects in piezoelectroreflectancewill contribute considerably to a recognition of the symmetry of a critical point. In addition, information on hydrostatic and shear deformation potentials can be obtained by
following peak positions as a function of stress. Values obtained by Pollak
on Ge and GaAs agree well with previous results obtained by static optical
methods.Discrepancies probably result from the localized character of contributions in the modulated technique.69Nonlinearities in the stress dependence
of peak positions are explained as stress coupling of energy levels.71
In the electrolytic method no front electrode is in mechanical contact
with the stressed sample. The potential of the technique is apparent in
cases where peaks actually split under stress. Caution is in order, however,
when conclusions must be drawn from line shape interpretations, particularly for satellite structure. The point of operation and therefore sign and
line shape of the response change rapidly in response to a variety of parameters, most of them unknown. In particular, it has been shown that the point
of operation changes with the state of stress.73 Other versions without a
73
G . Abowitz, E. Arnold, and J. Ledell, Phys. Reo. Lerr. 18, 543 (1967).
49
front electrode, such as transverse electroreflectance, permit the monitoring

of surface conditions and will develop piezoelectroreflectance to its full
inherent potential.
b. Rotoelectrorejectance
Anisotropies of the reflectance generated by a uniaxial stress can be

detected by rotation of the sample around a suitable axis. If the isotropybreaking parameter consists of an electric field normal to a reflecting (1 10)plane, rotation of the sample around the field direction produces periodic
variations of the reflectance of polarized light.
~
the differences between E 11(110) and E I\(11 1)
Cardona et ~ 1 . measured
or E (((100)in a rotoelectroreflectance experiment on Si. The results simply
reflect anisotropies of the dielectric tensor of a cubic crystal perturbed by the
electric field.
More information is obtained in a rotational experiment by Feldman75
on Si and SrTiO, .Although this is part of piezoreflectance, we will deal with
it in the context of modulation by sample rotation. A uniaxially stressed
sample is rotated perpendicular to the stress axis while linearly polarized
light is reflected along the axis of rotation. The stress-produced anisotropy
in the reflection coefficient causes modulation, aligning the plane of polarization periodically into directions parallel or perpendicular to the direction
of stress. In principle, the spectral line shape of ( RII - RL)could give information on the position of the correlated critical point in the Brillouin zone.
In this respect Feldmans experiment is similar to transverse electroreflectance, and the experiment could be performed with a static electric field
instead of the uniaxial stress in the rotating sample.
Rotational modulation has the advantage that the detection frequency
is at least twice the rotation frequency, so that parasitary signals from misalignment of the sample, for instance, are eliminated. Furthermore, spurious
signals are expected to be independent of polarization of the incident light.
Rotating the plane of polarization by 90 changes the phase of the meaningful
response, but leaves the spurious background unchanged. Cerdeira et a17
rotate a linear polarizer in an unpolarized monochromatic beam incident
on the sample at oblique incidence. The reflected light produces a dc and an
ac component, the ratio of which is independent of light intensity and
detector sensitivity. The optical constants of Ge are measured at two angles
of incidence without the use of dispersion relations.
4
75
76
M. Cardona, F. H. Pollak. and K. L. Shaklee, Proc. Int. Cor~f:

Pkys. Sernicond.. Kpoto. 1966
1J. Phys. SOC.Japan 21, Suppl.), p. 89. Phys. SOC. Japan, Tokyo, 1966.
A. Feldman. Pkys. Lett. 23, 627 (1966).
F. Cerdeira. R. Lettenberger, and M. Cardona, Bull. Amer. Phys. SOC.12, 1049 (1967).
B . 0. SERAPHIN
c. Magnetoelectrorejlectance
Electroreflectance measurements in the presence of a magnetic field have

been performed in both the field-effect and the electrolytic version of the
technique. Several interesting features result from the simultaneous presence
of an electric and a magnetic field.77
The situation is similar to piezoelectroreflectance. The strain-induced
changes in the band structure are difficult to detect using the piezoreflectance technique. The modulating electric field simply serves as a probe of
greater resolution and sensitivity.
Similarly, the changes in the band structure induced by a magnetic field
are difficult to detect in static reflectance. Above the fundamental edge,
scattering is so strong that the quantum effects produced in the band structure by the magnetic field are all but leveled out through lifetime broadening.
Again, a modulating electric field increases resolution and sensitivity sufficiently to observe an oscillatory pattern of the modulated reflectance that is
characteristic for transitions between the Landau ladders of the valence and
the conduction band.
There is one characteristic difference, however. We can consider electroreflectance as an improved probe on the band structure only as long as the
electric and magnetic fields act independently and their effects can simply
be superimposed. This is the case for parallel fields. In the crossed-field
case-not yet tried in modulated magnetoreflectance-this independence is
no longer guaranteed.
The effect of either an electric or a magnetic field on the optical properties
of solids has been studied for over ten years. It is only recently, however, that
the effects of their simultaneous presence received attention, mainly by the
group working with
Their results indicate that the relative orientation of the two fields determines the character of a magnetoelectrooptical
spectrum, which is distinctively different for either parallel or crossed electric
and magnetic fields.
Parallel fields act independently on the electron to produce two simultaneous motions : quantized magnetic-type motion transverse to both fields
and nonquantized electric-type motion along the fields. The effects of the
S. H. Groves, C. R. Pidgeon, and J. Feinleib, Phys. Reo. Lett. 17, 643 (1966).
B. Lax, in Physics of Semiconductors (Proc. 7th Int. Conf.), p. 253. Dunod, Paris and

Q. H. F. Vrehen and B. Lax, Phys. Rev. Lett. 12,471 (1964).
H. C. Praddaude, Phys. Rev. 140, A1292 (1965).
W. Zawadski and B. Lax, Phys. Reo. Lett. 16, 1001 (1966).
M. Reine, Q. H. F. Vrehen, and B. Lax, Phys. Rev. Lett. 17, 582 (1966).
8 3 M. Reine, Q. H. F. Vrehen, and B. Lax, Phys. Reo. 163, 726(1967).
8 4 M. H. Weiler, W. Zawadski, and B. Lax, Phys. Rev. 163,733 (1967).
79
I.
51
ELECTROREFLECTANCE
two fields are simply superimposed on each other. The Franz-Keldysh

effect of the electric field perturbs the transitions between equivalent levels
of Landau ladders independently produced by the magnetic field.
If the magnetic field is oriented perpendicular to the electric field, a more
complex situation results, in that the magnetic and electric motions are
no longer independent. Lax first indicated that the character of this crossedfield case distinctively depends upon the ratio FIH of the two fields. As H
increases from small values, the absorption spectrum changes in a smooth
transition from the Franz-Keldysh type to the oscillatory pattern of the
magnetic type.
The theoretical picture has by and large been confirmed by magnetoabsorption measurements in parallel and crossed fields with small and large
ratio F / H .
Modulated magnetoelectroreflectance has been observed heretofore in
the parallel-field configuration only. This is simply a matter of experimental convenience and does not reflect any basic restriction. It can be
expected that modulated reflectance studies will soon be expanded to the
crossed-field configuration. The greater complexity of the crossed-field
case inherently provides a greater potential for the identification of initial
and final states at a critical point. Not only can the Landau ladders of
valence and conduction band be separated, but scanning through the
relative angular orientation of the electric and magnetic fields and modulating
in both the weak- and strong-field range also increases the volume ofinformation to be obtained from cross-field magnetoelectroreflectance.
V. Experimental Results
1 1. ELECTROREFLECTANCE
OF SEMICONDUCTORS
a. General Features
Semiconductors of carrier concentrations varying between 10 and

10 cm- form the largest group among the materials investigated by
electroreflectance. A surface field sufficiently strong to generate electrooptical effects facilitates modulation of reflected light that, as to the order of
magnitude, penetrates approximately as far as the field.
Early work established the responsibility of this surface field for the
generation of the reflectance m ~ d u l a t i o nSimultaneous
.~
measurement of the
surface conductance demonstrated that the phase of the optical response
inverted with the sign of the carriers accumulated in the surface, as one would
expect, and that there is no first-harmonic signal at the field-free flat-band
position.
52
B. 0.SERAPHIN
If the Fermi level at the surface is locked through the large density of
states present at a mechanically polished surface, the potential barrier cannot be modulated. Band swing, and therefore reflectance modulation, is
sufficient only if the surface recombination velocity is small as on etched or
virgin surfaces. If rectifying back contacts inhibit the flow of carriers in and
out of the space-charge region, the modulation of the potential barrier is also
small, even at an etched front surface.
Use of the space-charge field as a modulating agent is frustrated by distinct
disadvantages.
(1) It is difficult to define an effective field that enters a correlation of
electrical and optical modulation required for line shape discussions. An
external modulation voltage distributes itself among the various parts of
the sample cell according to the point of operation along the spectrum of
possible surface conditions. In the electrolytic version this distribution is a
function of time as well, showing hysteresis according to prepolarization
history.
(2) The space-charge field is nonuniform along the penetration path of
the light, its exact spatial distribution being given by the doping level and
conduction mechanism of the material. As a consequence, the reflected
light interacts with a wide range of field values, and the observed reflectance
modulation results from their superposition along the penetration depth.
This further complicates line shape interpretation.
(3) The extension of the field-affected region with respect to the penetration depth determines how a given spectrum must be reduced to a modulation of the optical constants. In the same material, various doping levels
can produce wide variations in the extension of the space-charge region
without affecting the penetration of the light, so that a different reduction
of data can apply.
(4) Distortion of the response with respect to the driving wave form can
result from the space-charge capacitance. A phase lag causes the optical
response to represent a time average of the electrical modulation, making
the correlation of the two quantities even more complicated. This time
average depends upon the penetration depth of the light and is therefore a
spectral function. Modulation is restricted to low frequencies if frequencydependent distortion or even inversion of the response is to be avoided.
For wave forms other than square wave modulation the output depends
upon changes in amplitude as well as shape of the optical response, since
phase-sensitive detection extracts only the first Fourier component of the
response.
Any one of these inherent features complicates line shape discussion of

spectra recorded by surface barrier techniques. The need for better experi-
53
mental methods is apparent, and improved techniques are gradually replacing the original ones. Dry sandwiches consisting of thin films of dielectric
and metal evaporated on the reflecting surface provide a stable configuration transparent into the far ultraviolet and usable at liquid helium temperat ~ r e . ~In~ recent
* ~ ~electrolytic
* ~ ~
work, surface conditions have been
carefully controlled through simultaneous capacitance and photovoltaic
measurement^.^^ An alternate approach, discussed in more detail in the
analysis section, searches for features of an electroreflectance spectrum
that are invariant to changes in sign and size of the effective field and extract
a signature characteristic for the symmetry of the correlated critical
point. 8 6
This second-generation effort will better realize the potential of electroreflectance for an ab initio identification. Until that time, the existence of
structure at certain photon energies-albeit observed with high resolution
and sensitivity-must be considered the basis of an analysis.
It seems worthwhile, however, to compare the spectra of the reflectance
R and the electroreflectance A R / R for matching structure. The result supports the view, stimulated by Kanes work on Si, that the critical-point
notation of reflectance structure is merely nominal, because such structure
results from extended regions of the Brillouin zone. There is apparently no
one-to-one correlation between structure in R and in ARIR. Coarse structure in R is usually accompanied by structure in ARIR, but there is no
fixed relation with respect to the spectral position, and there are a few
conspicuous cases of missing A R / R structure. In general, the modulated
spectrum shows more structure than the static trace.
Semiconductors of the diamond and zinc blende type are good candidates
for such a comparison. Similar reflectance spectra, characterized by three
coarse structural features called E , , E , , and E 2 in a notation first used by
Cardona, suggest band structures that are basically ~ i m i l a r . ~Three
*~~~~
major approaches to band structure calculations-mpirically
adjusted
first principle m e t h ~ d , ~pseudopotential
~.~~
method,20*90*91
and k . p
D. E. Aspnes and A. Frova, Phys. Reo. B2, 1037 (1970).
N. Bottka and B. 0.Seraphin, Bull. Amer. Phys. Sue. 14,415 (1969).
E. 0. Kane, Phys. Reo. 146,558 (1966).
F. Herman, R. L. Kortum, C. D. Kuglin. and R. A. Short. in Quantum Theory of Atoms,
Molecules and the Solid State: A Tribute to John C. Slater (P. 0. Loewdin, ed.), p. 381
8 9 F. Herman, R. L. Kortum, C. D. Kuglin, and J. L. Shay, in 11-VI Semiconducting Compounds (Proc. 1967 lnf. Conf., Providence)(D. G. Thomas, ed.), p. 503. Benjamin, New York
and Amsterdam, 1967.
90 J. C. Phillips, Phys. Rev. 112, 685 (1958).
9 1 D. Brust, J. C. Phillips, and F. Bassani, Phys. Rev. Lett. 9, 94 (1962).
85
86
54
B. 0.SERAPHIN
meth~d~.~~-onfirmthis similarity. Their band models, based on an

interpretation of coarse features in the reflectance spectrum, predict a
number of splittings as well as finer structural features not observed in all
R traces. Some of these predictions come out quite differently, so that their
experimental observation and identification could establish a basis for
preference among the various calculations.
Electroreflectance has been only partially successful in this respect.
The spin-orbit splitting of the fundamental edge E , has been resolved in
materials such as InSb and InAs, in which the large separation A. moves the
split-off transition into a region of high absorption. The similar splitting
of the Elpeak has been observed in all materials with increased precision,
and its relation to the Eo splitting has been determined. A splitting of the
E , peak, following from an assumed near degeneracy of two critical points,
is still uncertain, because it is observed in some materials but is absent in
others.
Results of diagnostic value can be expected from an unambiguous identimarginally observed
fication of the Eo structure. This weak response-nly
in reflectance-is supposed to be correlated to a transition at the center of
the Brillouin zone, leading into a higher conduction band. The various
calculations differ significantly in their predictions. As a common feature
of all band models, conduction and valence bands run nearly parallel through
extended regions of the Brillouin zone in the spectral region of the E,
transition. This leads to a predicted clustering of critical points in a narrow
range of photon energies. The potential of electroreflectanceto separate true
critical points from the strong background of a nearly flat interband energy
surface could be of particular value here.
Present techniques seem to have reached their limitation in the E, structure, however. Different authors report different results, the controversy
being particularly apparent for Ge. The weak response is richly structured,
and various values are being reported for the splitting of initial and final
states according to an assessment of peaks as satellites or main structure.
The location of correlated critical points cannot be determined. Improved
techniques are needed that combine sensitivity and resolution with reproducibility even in regions of weak response.
b. Silicon
Silicon seems to present a case of peculiar complexity when its fundamental optical spectra are being analyzed. There is no lack of detailed
information on the extrema of valence and conduction bands between which
92
E. 0. Kane, in Semiconductors and Semimetals (R. K. Willardson and A. C. Beer, eds.),

Vol. 1, p. 75. Academic Press, New York, 1966.
M. Cardona and F. H. Pollak, Phys. Rev. 142,530 (1966).
55
indirect transitions begin to connect at 1.1 eV. In the search for the first
direct transition edge, however, one seems to encounter a band structure that
places Si and possibly diamond in an exceptional position. All available
calculations agree that the edges of valence and conduction bands are nearly
parallel through large regions of the Brillouin zone, producing for the band
separation a contour that is nearly flat in k space, and on which a cluster of
critical points is expected.12~20*87~88~93-103
This near degeneracy of several
critical points may result in a first direct interband edge that is complex and
in many respects anomalous.
In general, calculations of the band structure have provided a good
picture of most interband transitions. The pseudopotential calculations by
Brust, Cohen, Phillips, and others were recently complemented by HeineAbarenkov calculations made by Kane,87 who adjusts the Fourier coefficients of the crystal potential in order t o achieve agreement with measured
cyclotron masses and the indirect gap. Herman and co-workers88.102in a
recent comprehensive review that challenges some existing views on the
band structure of Si away from the band edges, present an empirically
adjusted band structure, the starting point of which was a self-consistent
energy band calculation. By adjusting his solution to the indirect band gap,
Herman found that TzS-rl5
was lower than previous estimates by at least
0.5 eV. This result, ifcorrect, would have a bearing on current interpretations
of optical, electrooptical, piezooptical, and photoemission spectra, since
a change in I25r-r1
by even 0.5 eV would affect the structure of three of the
four lowest conduction bands in the central region of the reduced zone and
the detailed nature of interband transitions in the range between 2 and 4 eV.
The different approaches produce major structure relating to transitions
at X and X that satisfactorily reproduces the experimental observations above
4 eV. Below this energy, however, the three remaining principal transitions
are placed not only at different energies but also in varying sequence,
depending upon the theoretical approach. In contrast to the uniformity of
the calculated results above 4 eV, these discrepancies are caused by the pronounced sensitivity of the calculated critical-point spectrum to the smallest
T. Woodruff. Phys. Rev. 103, 1159 (1956).
F. Bassani, Phys. Rev. 108,263 (1957).
96 L. Kleinman and J. C. Phillips, Phys. Rev. 116, 880 (1959).
L. Kleinman and J. C. Phillips, Phys. Rev. 117,460 (1960).
9 8 L. Kleinman and J. C. Phillips, Phys. Reu. 118. I152 (1960).
99 J. C. Phillips, Phys. Rev. 125, 1931 (1962).
l o o D. Brust, M. L. Cohen, and J. C. Phillips, Phys. Rev. Lett. 9, 389 (1962).
D. Brust, Phys. Rev. 139,A489 (1965).
lo F. Herman, R. L. Kortum, C. D. Kuglin, and R. A. Short, Proc. Inr. Cot$. Phys. Semicond.,
Kyoto, 1966 ( J . Phys. SOC. Japan 21, Suppl.), p. 7. Phys. SOC. Japan, Tokyo. 1966.
94
95
56
B. 0.SERAPHIN
variations of the crystal potential and the choice of the experimental parameters used for its adjustment. A high-resolution study of the one-electron
spectrum of Si by Saravia and Brust'03 confirms this sensitivity. Drastic
changes in line shapes that depend upon the relative position of r25,-r15
and L3,-L, are found in the 3.4-eV region. They examine various models
and predict an extremely complex nest of critical points near the fundamental
edge from all of them.
A detailed discussion of the band structure of Si is outside the scope of
this review. However, the theoretical situation has to be outlined in order
to emphasize the potential of a high-resolution technique as well as the need
for particularly careful assessment of the experimental evidence. Static
experiments lack the resolution necessary to confirm or reject conflicting
features of the theoretical models. Although reflectance displays a broad
peak at 3.4 eV, even high-precision measurements fail to resolve further
structure. 6.6 6 . 6 7+ 1 04- 10 7 Electroreflectance, on the other hand, resolves
structure, indicating that more than one critical point is present inside the
energy interval covered by the static reflectance peak. Although the multiplicity is established, a basis for an assignment of the observed structure
cannot be provided. In the case of Si the need for unambiguous identification is probably more of a challenge to the experimentalist than in any other
material. Once obtained, this identification will make Si a testing ground
for concepts of interpretation and calculation that theory has recently
introduced.
(1) T h e Zndirect Edge at 1.1 el/. To date, no electroreflectance response
correlated to an indirect transition has been observed in any material. For
Si, this can be explained qualitatively. Electroabsorption107a~108~109superior in sensitivity to electroreflectance in regions of sufficient transmittance-has determined the field-induced changes in the optical constants at
the indirect edge. If inserted into the differential of Fresnel's equation, Eq. (2),
values for A R / R obtain that are typically one to two orders of magnitude
below those that can be detected by electroreflectance.
L. R. Saravia and D. Brust, Phys. Rev. 171,916 (1968).
J. Tauc and A. Abraham, Proc. Int. Conf. Phys. Semicond., Prague, 1960, p. 375. Czech
Acad. Sci., Prague and Academic Press, New York. 1961.
lo5 F. Lukes and E. Schmidt, Proc. Int. Conf Phys. Scmicond., Exerer. 1962, p. 389. Inst. of
Phys. and Phys. SOC.,London, 1962.
l o 6 M. Cardona and D. L. Greenaway, Phys. Rer. 125. 1291 (1962).
lo' U. Gerhardt, Phys. Status Solidi 11,801 (1965).
lo7'J. Lenz and E. Mollwo, Z . Phys. 176, 536 (1963).
M. Chester and P. H. Wendland, Phys. Reti. Lett. 13, 193 (1964).
l o 9 A. Frova and P. Handler, Phys. Rev. Lett. 14, 178 (1965).
lo3
lo4
57
(2) The Spectral Region u p to 3.2 el/. In view of Hermans band model,
the implications of finding structure, particularly between 2.6 and 3.2 eV,
would be of importance for an interpretation of band structure in general.
There is no report of such structure. Repeated runs at this laboratory
with a sensitivity of
did not reveal any response. Any hidden structure
must be smaller than 1/50 of the response at 3.4 eV.
(3) Structure in the Region 3.2-3.6 el/. A strong, highly structured response
has been observed in this spectral region in several independent measurements.l 5c,37,71,74,110-1 1 3
A sensitive reaction of sign and line shape to
variations in the surface conditions is reported in all studies. It is tantamount,
therefore, to determine and quantitatively control these surface conditionsa requirement that at present is met only by the field-effect technique.
Measurements of size and sign, shape, and spectral position of the 3.4-eV
structure have been performed with this technique as functions of surface
potential, crystal orientation, and temperature. From these field-effect
measurements it can be quantitatively established that the group of structure
consists of a t least two independent parts that behave quite differently as
various external parameters are changed. This conclusion is supported by the
piezoelectroreflectance measurements of Pollak and Cardona as well as
studies of the alloy system Ge-Si by Kline and co-workers.
We will first review the results obtained with the field-effect technique on
over 50 samples of both n- and p-type, varying in resistivity between 10 and
100 ohm-cm. Figure 20 shows that two peaks appear a t room temperature,
located with opposite sign at 3.34 and 3.45 eV. The slight shoulder between
them indicates the presence of a third peak, which is resolved at low temperatures and eventually overtakes the negative neighbor in size.
The temperature gradient of the wavelength position places the peaks in
two distinctly different classes: Peak I moves only slowly with temperature
eVfK.The two upper peaks I1 and 111 movemore
at (- 1.35 k 0.10) x
than twice as fast with temperature, their coefficients being ( - 3.25 f 0.45) x
and (- 3.40 & 0.45) x
eVfK. These values are approximately
representative for the two groups of transitions band structure analysis
describes as insensitive and sensitive to small changes of the crystal
potential. It is interesting to note that previous reflectance studies, not
able to resolve any structure within the one peak observed in this region,
eVfK to this peak,
assigned a temperature coefficient of -2.7 x
lo
I3
B. 0. Seraphin and N. Bottka, Phys. Rec. Lett. IS. 104 (1965).

B. 0. Seraphin, Phys. Rev. 140, A1716 (1965).
A. K. Ghosh. Phys. Leu. 23, 36 (1966).
J. S. Kline. F. H. Pollak. and M. Cardona, Hrlr. Phys. Acta 41,968 (1968).
58
B. 0.SERAPHIN
FIG.20. The field-induced change in the reflectance A R / R in the 3.4eV region of p-type Si.
for four different temperatures (a) 300 K:(b) 215K: ( c )145 K;(d) 95 K.(After Seraphin.'"1
which is the arithmetical mean of the coefficients of the three resolved

peaks.' l4
The two different values of the temperature shift-measured over many
more temperatures, as shown in Fig. 21, and found in all samples within the
given range-provide a clue as to the location of contributing areas in the
Brillouin zone. Coefficients as large as 3 x
eVpK are usually observed
for the L bands only. Pressure coefficients derived from Herman's calculations assume large values near L only, whereas between r and X much
14
M. Cardona, J . Appl. Phys. 32,2151 (1961).
59
100
150
200
Temperature
250
300
7-
( O K )
FIG.21. The spectral position of the three peaks shown in Fig. 20 as a function of temperature.
The + and - signs on the edges of the crosshatched areas indicate in which direction a dc bias
of this sign shifts the peak. (After Seraphin.'")
smaller values obtain. As a result, the temperature coefficients would not be

inconsistent with a mixture of contributions from the L region and regions
closer to the center and possibly aligned along A, as suggested by other
results.
The dependence upon the surface potential offers further evidence for
the separation of the three peaks into two separate groups. While the first
peak (I) is affected by the magnitude of the surface field in a normal manner,
the remainder (peaks I1 and 111) of the structure has one sign and shifts
into one direction with field increase for weak electric fields, and has the
opposite sign and shifts into the opposite direction for strong electric field.
This dissimilarity of the response is not a trivial surface effect, but probably
has its roots in the parameters of the band structure correlated to peak I
and peaks I1 and 111, respectively. Since the absorption coefficient rises by
a factor of three within the width of the structure, it is plausible that the
strong variation of the ratio of field penetration to light penetration contributes t o the dissimilarity of the response. It cannot explain the inversion of
the field shift, which is a parameter of fundamental significance based on
type and location of the correlated critical point.
If the response is obtained from reflecting surfaces of different crystalline
orientation, a further difference between peak I on the one hand and peaks I1
and I11 on the other emerges. Although peak I is nearly insensitive to this
orientation, peaks I1 and 111change size in a systematic manner as shown in
Fig. 22. Since the absolute peak height is the least reproducible parameter,
due to the strong dependence upon the surface potential, the absolute value
ofthe ratio ofthe height ofpeak I11 to the height ofpeak I is plotted in Fig. 22
60
B. 0. SERAPHIN
0
0
0
0
100
200
300
OK
FIG.22. The absolute value of the ratio of the height of peak 111 to the height of peak I in
Fig. 20 as a function of temperature for three different orientations of the reflecting surface.
0,
(100); V , ( I 10): 0,
( 1 11). (After Seraphin.)
as a function of temperature for a number of measurements on surfaces of

different crystalline orientation. It is evident from this diagram that the ratio
is greatest for the (1 11) direction, decreases slightly for the (I 10) direction,
and is on the average smaller by a factor of two for the (100) direction. The
temperature gradient of the ratio decreases in the same proportion.
This dependence of the height of peak 111 upon the crystalline orientation
provides support for the assignment of this peak to a saddle-point edge,
which has a principal axis oriented in k space in a certain direction, so that
the observed dependence upon the orientation of the reflecting surface can
result. The independence of peak I, on the other hand, must relate this
peak to an isotropic transition, suggesting an assignment near the center
of the Brillouin zone.
Pollak and Cardona have extensively investigated the 3.4-eV region in
piezoelectroreflectance. Scanning through the various directions of stress
for reflecting surfaces of different orientations, with the polarization either
parallel or perpendicular to the stress, they find stress-induced splittings of
peaks that can be understood qualitatively on the basis of A5-A transitions.
Interband effects alone, however, are not sufficient to explain the observed
splittings for (001) stress, on which the A assignment could be based. Intraband effects-f
considerable influence in a material with such a small spinorbit splitting-are required to explain the observed stress dependence. In
addition, polarization effects are observed for (1 11) stress that clearly indicate
the presence of contributions from regions other than along A. The greater
resolution and sensitivity of piezoelectroreflectance apparently improves
on Gerhardts static measurements, which did not show any polarization
effects for (111) stress.68 Pollak and Cardona conclude that their results
1.
61
ELECTROREFLECTANCE
2,
P
C
20
40
60
80
100
Atomic percent silicon
FIG.23. Composition dependence of structure in the reflectance spectrum of Ge-Si alloys.

(After Kline er a/.113)
suggest a predominant A symmetry. A self-consistent explanation cannot be

obtained on the basis of this assignment, however, so that contributions
from other areas are likely.
Studies of the electroreflectance of the system Ge-Si by Kline et ~ 1 . ~
confirm the multiplicity and mixed character of the 3.4-eV structure. The
E,, structure, only marginally observable in G e and over most of the alloy
range, can be followed more clearly in electroreflectance. The modulated
structure correlated to E, and E , merges near 80% Si (Fig. 23), indicating
contributions from the center and the A direction of the Brillouin zone. The
crossover near 80 % Si places the A contribution on the high-energy side of
the E, contribution, in agreement with the spectral sequence previously
derived from the field-effect results.
We have so far cited results that based a discrimination between separate
parts ofthe structure on its response to changes in some external parametertemperature, surface potential, uniaxial stress, and polarization or composition. Straight electrolytic electroreflectance lacks the potential of scanning
an extended range reversibly. On Si, an oxide layer permits some variation
of dc bias. The surface condition is mainly set by the Fermi level in the bulk,
however, and spectra of n-type or p-type are observed accordingly.
A strong electric field wipes out the differences between various parts of the
structure. Operating at a 10-V modulation voltage-a prohibitively large
swing from an electrochemical point of view-Ghosh
observed three
peaks in the 3.4-eV region that are probably one main peak at 3.50 eV with
accompanying strong-field satellites. The structure becomes better resolved
l1
E. Schmidt. Phys. Status Solidi 27, 57 (1968)
62
B. 0.SERAPHIN
as the swing is reduced, but variations with ac voltage are larger than the
differences between surfaces of different orientation. Cardona e t al. 5 c * 7 4
report a threefold structure similar to the field-effect results in spectral
position. However, the response to doping type and dc bias is strong and
apparently erratic, because the modulation operates in the blocking range
in which, according to Gobrecht and co-workers?' unreliable results are
obtained.
In the field-effect configuration, the region 3.3-3.6 eV was searched
carefully, with the necessary spectral resolution, for any indication of the
hyperfine structure observed in reflectance' O 5 and interpreted as phonon
assistance to direct transitions.'I6 The result was negative.' l o No indication
of a spin-orbit splitting was seen either, even though its value of 0.044 eV is
well within the resolution of the technique.
Summarizing the contribution of electroreflectance to an understanding
of the 3.4-eV region, we can point to experimental evidence for the multiplicity and the mixed character of the structure, not to be derived from previous measurements. At least two different components can be distinguished,
one probably related to a parabolic edge near the center of the Brillouin
zone and extending in the A direction, and a second contribution at slightly
high photon energy originating at a saddle point along A.
(4) Structure at 4.0 el'. By extrapolation of the concentration dependence
obtain a value of
of the direct edge Eo in the Ge-Si system, Kline et
4.00 eV for the r25,-r2,
transition in pure Si. Weak structure is seen at this
energy in Ghosh and Cardona's results, but is probably of satellite character
and inconclusive.
( 5 ) Structure ur Higher Energies. A near degeneracy of two saddle points
along X and C had previously been postulated by theory for an explanation
of the strong reflectance peak. Kane's work rendered this classification
nominal for the use of Si.87However, a splitting of this peak had been observed
that could be confirmed in electroreflectance. Ghosh reports an u p d o w n
sequence of peaks at 4.24.32 eV and a dip at 4.44 eV. Cardona reports
dips at 4.31 and 4.51 eV, their separation being in good agreement with the
splitting of the static reflectance peak. Field-effect measurements find the
first component at 4.2 eV, with a temperature coefficient of - 1 x
eV /"K. 110.1 1 1 The second component is beyond the spectral range of this
technique. The electrolytic technique used by Ghosh permits him to observe
further structure at 5.45 eV, usually assigned to an L,.-L, transition. None
of these results at higher energies improves in any way on the previous
findings of reflectance studies, nor can they offer additional information
that would secure the assignment more firmly.
'
l6
J. C. Phillips, Phys. Rev. Lett. 10, 329 (1963).
63
c. Germanium
Germanium occupies the position of a cornerstone in band structure

analysis. As a group IV elemental semiconductor with diamond structure,
it is a convenient theoretical model. An abundance of experimental results is
available that can be incorporated into the developing band model. AS a
result, Ge band structure has served as the proving ground for most concepts of band calculations, which have since been applied to numerous
other materials.
In view of the basic position of Ge in the theoretical frame, it is a matter
of concern that many of these concepts still lack direct experimental confirmation. Most experimental results above the fundamental edge are faithfully interpreted in terms of existing band calculations. They cannot verify
these calculations independently, however.
The various calculations do agree on the coarse features of the Ge band
model, but there are areas of disagreement. There is an urgent need for an
independent identification of optical structure that can establish a basis
of preference of one method over the other.
Areas of dispute involve (1) a postulated near degeneracy of L,.-L, and
A3-A, not resolved beyond doubt by experiment, (2) the sequence and type
of transitions in the 2.7-3.7 eV range, and (3) a postulated near degeneracy
of transitions at X and E that generates the strong reflectance peak at 4.4 eV.
Results in these areas automatically bear on fundamental concepts. Any
modification required by improved experimental data for Ge will extend to a
large number of other materials.
Electroreflectance has the potential to resolve near-degenerate transitions
and identify the ones in dispute. Some results are available (Fig. 24), but
they must be considered inconclusive with respect to the questions in debate.
To date, as in the case of Si, electroreflectance has only partially lived up
to its potential.
( 1 ) The Fundamental Edge. Electric-field modulation of the reflectance
was first observed at the fundamental edge of Ge.35 It served as a vehicle
to prove the responsibility of the surface field for the generation of the signal
by measuring the field effect of the surface conductance and the electroreflectance response ~irnultaneously.~
A large variety of line shapes can be
observed, according to the different surface conditions. Assignment of the
edge to any particular part of the structure results in ambiguity. This difficulty,
together with the variation in line shape, accounts for the spread of values
in the literature from 0.795 to 0.806 eV.5.36.4h*53.54
From a comparison of
calculated and observed line shapes over a range of surface fields, a value of
0.795 0.005 eV seems the best fit for 295"K,"' in agreement with magneto-
117
B. 0. Seraphin and N. Bottka, Solid Stute Commun. 7, 497 (1969).
64
B. 0.SERAPHIN
+2
4
1
T
2 322x
a
l
L
-8
3.65
2.109*
-6
-121
10
15
fi
20
25
30
35
40
45
Photon energy (evi
FIG.24. Electroreflectance spectrum of Ge recorded in the field-effect configuration. Values

with asterisks are 10 times greater than scale. (Alter Seraphin and H e s ~ . ~ ~ )
optical measurements. 5d The response shifts with a temperature coefficient

of -3.72 x
eV/K.35
It was established early that the line shape of electroreflectance could
be approximated by the Kramers-Kronig transform of the electroabsorption
line shape. In later work, this correlation was confirmed by Hamakawa
et
based on more complete electroabsorption data. Using the FranzKeldysh theory without lifetime broadening for the case of homogeneous
perturbation, the authors concluded that the experimental line shapes do
not quantitatively agree with this theory and consequently that the effect
must be of excitonic character. The argument has been invalidated by two
recent theoretical developments. First, Aspnes et a/. have shown that the
functional dependence of the complex argument in Eq. (25) upon the electric
field is such that the basic one-third power dependence can be expected only
in the case of very small relaxation energy r. Switching on lifetime broadening, the one-third power dependence of hR >> r gradually approaches a
quadratic dependence as hR << r. Consequently, an interpretation of spectra
observed with the electric field as a variable parameter must be based on a
variable ratio hQ/T, which influences the functional relationship between
electric field and electrooptical response. Secondly, homogeneous perturbation cannot be assumed if a quantitative interpretation of line shapes is
intended. As shown in Section 3, good agreement with surface-controlled
electroreflectance spectra can be obtained if the perturbation is assumed to be
~
65
inhomogeneous. Evangelisti and Frova' l 8 consider the nonuniformity of

the electric field in a manner different from Aspnes' solution of the wave
equation for inhomogeneous media,' 5 a but also agree with field-effect
controlled electroreflectance. They conclude that an integrated FranzKeldysh mechanism is responsible for the signal at the fundamental edge.
The situation is probably not that simple, however. Handler points out
that the line shape is determined by the energy range over which the electric
field affects the density of states."' The extent to which other broadening
mechanisms have already mixed exciton states with the continuum, and the
ratio of the field broadening to the broadening by these other mechanisms
and the exciton binding energy will influence the line shape.
Interband as well as excitonic contributions must probably be credited
in the interpretation of electroreflectance. At the present time, however, we
are not in a position to determine the fraction of either contribution on the
basis of quantitative line shape interpretation.
(2) Structure between 1.0 and 2.0 eV. Transitions from the lower valence
band to the bottom of the conduction band at k = 0 correlate to weak
structure observed at room temperature near 1.09 eV. With only one except i ~ n all
, ~studies
~
find a line shape similar to that at the fundamental edge
for a given surface condition. Differences can be explained on the basis of the
smaller penetration depth of 1.09-eV photons as compared to 0.8-eV
Despite past claims to the contrary, the fundamental gap can be observed
in reflectance, as McElroy'*' and Potterl'l have shown.
Potter12l a reports structure in a reflectance spectrum recorded in his
pseudo-Brewster-angle technique at 1.74 and 1.94 eV. In spite of careful
search, however, no electroreflectance response could be observed in this
spectral range. This in no way reflects on Potter's claim, since structure in
static reflectance is not necessarily present in modulated reflectance.
( 3 ) The Doublet at 2.112.3 el/. Strong peaks are observed at 2.109 and
2.322 eV at room temperature. Their exact line shapes depend, as usual, upon
surface conditions. The field-effect results3 agree approximately with electrolytic work in anodic
but disagree with electrolytic work in the blocking range,15.112,122.123 Th e energetic separation of the doublet, caused by
F. Evangelisti and A. Frova, Solid State Commun. 6,621 (1968).
P. Handler, Proc. ZX l n r . Conf Phys. Semirond.. Moscow. 1968, Vol. I . p. 380. Publishing
House "Nauka," Leningrad, 1968.
I Z o P. McElroy, Harvard Univ. Tech. Rep. HP-21. 1968. unpublished.
''I
R. F. Potter. Phys. Rea. 150. 562 (1966).
IZIaR.F. Potter, Proc. lnt. Con$ Phys. S e m i t m d . , Kyoto, I966 [Pfiys. Soc. Jclputi, Tokyo. Suppl.
21 (1966)l.
I *' A. K . Ghosh. Solid Srute Commun. 4. 565 (1966).
A. K. Ghosh, P h p . Ret.. 165,888 (1968).
'I8
Iy
66
B. 0.SERAPHIN
spin-orbit splitting off k = 0, well fits the predicted 2:3 ratio to the spinorbit splitting at k = 0. Between 100 and 300"K, the value of the splitting is
independent of the temperature within the experimental error of kO.002 eV
in determining the position of a peak.
The stress dependence of the response in polarized light suggests that the
doublet originates along the (11 1) direction, according to piezoelectroreflectance measurements by Pollak and Cardona7 and piezoreflectance
studies by Sell and Kane.lz4 Their measurements confirm that both components of the doublet relate to the same transition.
In contrast to these findings, Hamakawa et a1.5.47conclude from their line
shape discussion that the two components relate to entirely different transitions. Their claim must be considered questionable, however, until doubts
about line shape interpretation of electrolytic spectra in general are eliminated. In agreement with other electrolytic work, the authors report drastic
changes in line shape as the modulation voltage is increased. The claim
that one end of the modulation always touches the flat-band position as
long as the dc bias is kept at half the ac swing is suspect in view of recent
results by Gobrecht et
In addition, quantitative agreement at a multivalley critical point can never be expected unless the angular algebra of
superpositions from equivalent branches is considered."
For some orientations of the reflecting surface, Ghosh' 1 2 3 1 2 2 * 12 3 observes
weak shoulders on the red flanks of both components, at 2.05 and 2.24 eV.
A dissection of the structure into probable constituents indicates an M ,
character of the shoulders. This suggests their assignment to L,.-L,, which is
supposed to precede the stronger A3-A, transition by 0.1 to 0.2 eV. Based
on the line shape of cZ derived from their piezoreflectance measurement,
Sell and Kane assume a superposition of an M , edge slightly preceding an
M , edge.
No other electroreflectance results support Ghosh's observation. Potter's
sensitive method does not reveal any structure in static reflectance either.
The absence of structure in other measurements recommends caution in
drawing conclusions. At a multivalley critical point, contributions from
equivalent branches oriented differently with respect to the field direction
are superimposed. Shoulders can result from superposition of the large-field
satellites, which would agree with their observed presence in some and
absence in other crystalline directions. Unless some other method confirms
the existence of these shoulders+areful field-effect measurements have
failed so far-their assignment to the L3,-L1 transition must be considered
speculative.
Progressing further in the spectrum, a weak shoulder is observed in static
reflectance by Donovan et ~ 1 1 . " ~ at 2.47 eV. Potter does not confirm its
24
D. D. Sell and E. 0. Kane, Phys. Rev. 185. I103 (1969).

T. M. Donovan, E. J. Ashley, and H. E. Bennett. J . Opt. SOC. Amer. 53, 1403 (1963).
67
existence, nor has any electroreflectance response been reported in this

region.
(4) Structure between 2.6 and 3.7 e V . The various band models differ
markedly in this spectral region. They place the transition I - 2 5 J l 5 at
different energies ranging from 2.7 to 3.5 eV. All calculations predict contributions from A5-A1 and agree on the small strength of both types of transitions.
The four available electroreflectance spectra show rich structure in this
spectral region, which, however, is very weak.36.43-4,122,123
There is little
agreement among the spectra reported by different authors, and discrepancies exist even between results from the same g r o ~ p . ~ ~ , ~
When attempts are made to interpret the spectra in terms of existing
band models there is such a rich variety of peaks to choose from that the
required combinations of spin-orbit splittings can be accommodated in any
model. There are always a number of features left unaccounted for, however,
and the selection is ambiguous.
We d o not believe that the conflicting spectra presently available can
support a preference among the various band models. No excessive weight
should be attached to the existence of structure below 3 eV either. Caution
must be exercised because (1) the structure is very weak and approaches the
noise level in all methods if operated at reasonable modulation voltage :
and (2) the structure cannot be reproduced, results being very dissimilar on
materials of different doping, under variable surface conditions, or for
different modulation voltages.
We d o not believe that the spectra consist entirely of artifacts or satellites.
The region undoubtedly is rich in meaningful structure that will eventually
lead to an understanding of this complex and controversial region of the
Ge band structure.
Experiments superior to the existing ones are required, however. Reproducible results will probably be obtained under controlled surface conditions that are varied over a broad range to sort out main structure from
satellites. Once reproducible parts of the spectrum can be recognized,
polarization experiments by Ghosh
2 3 point the way for identification.
In an attempt to unmask overlapping features, multiple parts of the spectrum
around 2.93 eV have been found to be relatively insensitive to changes in the
polarization direction, whereas another multiplet centered at 3.0 eV is
polarization sensitive. A further effort to sort out various components by
varying the ac modulation is less convincing, in view of the difficulties of
line shape interpretation of measurements obtained in the blocking range of
the electrolytic cell and at extremely large ac voltages.
( 5 ) Structure around 4.4 el/. For certain operating conditions, a down-up

sequence of peaks at 4.25 and 4.45 eV seems to support the theoretical con-
68
B. 0.SERAPHIN
cept of contributions from X and C regions of the Brillouin zone.15cThis

line shape can be transformed into one peak only through the proper choice
of modulation voltage and surface condition^.^^.'^^ Observations in polarized light suggest, however, that actually two critical points of different
type contribute to the structure.23
More conclusive evidence for the composite nature of the 4.4-eV structure is provided by experiments in which the polarization and direction of
the modulating field are rotated at the same time. The two parts vary in
multiplicity upon full rotation of either parameter, indicating a different
symmetry character of the critical points related to the first and second
peak, respectively. Details are given in the analysis section of this chapter.
( 6 ) Srructure at Higher Energies. Ghosh12j reports structure at 5.35

and 5.52eV. In agreement with an interpretation of a similar doublet in
reflectance, he assigns this structure to the L3.-L3 transition, the spin-orbit
splitting of the L, being negligible.
Higher structure observed by Ghosh at 5.85 and 6.2eV is close to the
spectral cutoff of the technique and consequently is too weak to justify an
assignment.
d . Gray Tin and Selenium
The electroreflectance spectrum of gray tin has been studied between
195 and 273K by Cardona er
using electrolytes on an alcohol basis.
The spectrum is superior in structure to the room-temperature reflectance
curve.1o6At 80K, however, the number of structural features in R approximately equals those of the ARIR spectrum shown in Fig. 25, so that a basis
for comparison is obtained. 2o Considering the reported temperature coefficients, the coarse features E l , El A l , and E 2 seem to relate well if a
spectral mismatch of up to 0.08 eV is tolerated. This is well outside a match
within 0.03 eV usually observed in other materials. On the spectral scale,
R structure precedes ARIR structure in the El group, coincides with it near
E , , and again precedes it for higher photon energies.
eV/K for El and - 3.5 x
Temperature shifts in the order of -5 x
lOP4eV/K for E , are reported. The two components of the El doublet
converge noticeably upon cooling. This is in contrast to measurements on Ge
over a larger temperature interval that indicated a temperature-independent
spin-orbit ~plitting.~
Outside the coarse features, structure in ARIR and R is weak and their
correlation is less obvious as in Fig. 25. Extremely weak reflectance structure
could match peaks I and shoulder G, if the latter is taken seriously. There is
lz6
M. Cardona, P. McElroy, F. H. Pollak, and K. L. Shaklee. Solid State Commun. 4.319 (1966).
69
I
0
Y
-T
-4k
I
1.365
El
8 , (84+A)-AI(A6) I
no R correspondence to peak J. Points C and A match weak structure in the

reflectance if spectral differences in the order of 0.05 eV are tolerated. There
are two weak structures in R that have no counterparts in ARIR.
Several independent measurements of Ge have demonstrated how strongly
weak structure can vary: E l , El + A 1 , E 2 , and probably I and A can be
considered invariant to surface conditions. However, J, D, and C , not to
mention shoulder G, should be confirmed by other measurements or be
observed under a variety of conditions before their possible nature as
satellites or composites of satellites can be disregarded entirely.
In a n unfortunate analogy to Ge, it is again this weak structure that
could discriminate among the various band models if it could be reproducibly
recorded and properly identified.".'
The values of the spin-orbit
splittings, especially at the center of the zone, could be of diagnostic value.
In gray tin, the spin-orbit splitting is a considerably larger fraction of the
gaps between the bands than it is in materials composed of lighter atoms.
Spin-orbit split components of the same transition are likely to overlap
those of a neighbor transition, so that a sequence of peaks can actually
belong to different multiplets. Identifying structure as components of the
same transition is therefore more important here than in materials where
such components are bunched in separate multiplets. If identical multiplets
are measured over an extended range of surface potential or temperature,
2 7 9 1 2 8
12*
D. S. Bloom and T. K. Bergstresser, Solid State Commun. 6,465 (1968).

C. W. Higginbotham, F. H. Pollak. and M. Cardona, Solid State Commun. 5. 513 (1967).
70
B. 0.SERAPHIN
they can be sorted according to satellite pattern, temperature coefficient, or

field shift, and the reality of weaker structure can be established.
As we proceed in our review t o less popular materials, we will repeatedly
be forced to discuss one single spectrum taken at one condition only. We
must then recall the drastic differences in the weak parts of Ge and Si spectra
recorded under different conditions. We do not believe that one single
spectrum can upgrade the information we already have from the reflectance
of a material, and we must beware of overinterpretation of unreliable weak
structure.
This cautious view is supported by diverse results on Se reported by
various authors. Using the electrolyte technique, Chen129reports a very
complex spectrum taken in nonpolarized light on polycrystals. The trace
resembles the spectrum available for gray tin in the sequence of broad peaks
that produce a response for every photon energy and in which the correlation
t o reflectance structure seems coincidental. A thermoreflectance spectrum
by Lange and Henrion13' is claimed to agree with the electrolytic spectrum;
closer inspection, however, shows agreement only in that both spectra are
very complex.
The necessary separation of main structure and meaningless satellites is
accomplished by recording a spectrum over a wide range of experimental
conditions. Information that is more reliable can be obtained from spectra
such as reported by Weiser and S t ~ k on
e ~trigonal
~
Se single crystals. Using
transverse electroreflectance,60-61they measured the reflectance and the
electroreflectance spectrum over a wide temperature range. They further
investigated all the various orientations of polarization vector and field
vector not only with respect to each other, but with respect to the optical
axis as well. The resulting variety of spectra enabled them, through a
systematic pattern ofchanges, to classify a structure that is sharp and narrow
and is separated by large regions of zero response.
Reflectance and electroreflectance at 90K are compared in Fig. 26 for
the polarization vector E aligned parallel and perpendicular to the optical
axis c. There is no one-to-one correlation between structure in the two
spectra, indicating their different origin. Note the absence of structure in the
modulated spectrum above 3.5 eV in a region of strong reflectance structure.
The temperature dependence of the spectral position of structure is
plotted in Fig. 27. As in the case of Si, such diagrams suggest an affiliation
of structure with the same or different transitions. Structure a t 1.85 eV
responds to variations in sample thickness and probably relates to electroabsorption. The negative temperature coefficient of this edge-related
13'
J. H. Chen, Phys. Lerr. 23, 516 (1966).

H. Lange and W. Henrion. Phys. Sratus Solidi 23. K67 (1967).
1.
4I
45 J
7
0
+
-
71
ELECTROREFLECTANCE
y,x;o
-2
-4
0I{
3
Energy (eV)
dxlo
FIG.26. Transverse electroreflectance spectrum of trigonal Se single crystals. with the polarization vector E oriented parallel (a) and perpendicular (b) t o the c axis. Note the absence o f an
electroreflectance response (bottom) in the spectral region of the large reflectance peak (top)
at 4 eV, indicating the separate origin of static and modulated reflectance in extended and
localized regions of the Brillouin zone, respectively. (After Weiser and S t ~ k e . ~ ~ )
structure eliminates a previous contradiction between pressure and temperature coefficient. Hydrostatic pressure shifts the edge without changing its
slope. Decreasing temperature not only shifts the edge, but decreases its
slope, simulating a positive temperature coefficient.
A temperature coefficient similar in size, and of the same positive sign,
suggests an assignment of the structures around 2.0 eV and near 2.2 eV to the
same transition. Using band calculations by Treusch and Sandrockt3'
and satisfying the selection rules, they assigned this structure to transitions
at the edge of the Brillouin zone at H from bands spin-orbit split by 40 meV.
Again using the selection rules for polarization parallel and perpendicular
to the optical axis, they assigned the structure at 3.2 eV to a transition at the
center of the Brillouin zone. A mixture of excitonic and interband contributions are probably responsible for both groups of structure, but their respective fraction cannot be derived from the spectrum.
Rotating the electric field with respect to the crystal changes the size of
the response, in agreement with an anisotropy of the effective mass determined from measurements of the magnetoconductivity. 32
'
"'
13'
J. Treusch and R.Sandrock, Phys. Status Solidi 16.487 (1966)

H. Mell and J. Stuke, Phys. Sfatus Solidi 24, 183 (1967).
72
B. 0.SERAPHIN
3 124
(0)
2.00-
o-
I .96-
80
I00
120
Temperature
I40
160
I :0
(OK)
FIG. 27. Temperature dependence of structure in the electroreflectance spectrum of Se.

(a)
11 c at - 4 x 10-4eV/"K; (b) 1.5 x 10-4eV/"K; (c) B I c at 1 x 10-4eV/"K:
eV/"K. (After Weiser and S t ~ k e . ~ ~ )
(d) - 5 x
e. ZZZ-V Compounds
(1) Aluminum Antimonide. The electrolytic method is particularly suited
for recording the electroreflectance spectrum of AlSb. Cleaving a sample
inside a nonaqueous electrolyte prevents the tarnish that AlSb surfaces
quickly acquire upon exposure to water vapor in the air.
An indirect edge at 1.6 eV prevents an accurate determination of the first
direct edge by conventional optical methods, in analogy to Si. It shows up
clearly in an electroreflectance measurement, however, as seen in Fig. 28.'33
A value of 2.22 eV for the direct gap at room temperature can be derived from
the structure that moves at -3.4 x 10-4eVpK with temperature. The
transition from the spin-orbit split valence band is apparently hidden behind
the stronger structure at 3 eV, and no estimates can be made from a 3 rule
133
M. Cardona, F. H. Pollak. and K. L. Shaklee, Phys. Rev. Lett. 16.644 (1966).
1.
ELECTROREFLECTANCE
73
eV
FIG. 28. Electroreflectance spectrum of p-type AlSb at room temperature. (After Cardona
et
that does not hold well for materials in which the splittingof anion and cation
are too disparate.
The structure at 2.81 and 3.21 eV is assigned to the A3-A1 transition, with
a spin-orbit splitting A l = 0.4eV. Both components of the structure shift
with -3.1 x 10-4eV.
Structure at 3.72 and 3.99 eV is assigned to transitions in the (lOOIdirection,
near the center of the Brillouin zone. The dip at 4.25 eV precedes the reflectance peak at 4.36 eV, similar to many other materials of the zinc blende type.
( 2 ) Gallium Phosphide. As in similar materials, no electroreflectance
response is observed in G a P at the indirect edge so that the first direct edge
stands out clearly (Fig. 29) near 2.6eV.l Its spin-orbit split companion
could hardly be recognized, if it were not for the convergence of this doublet
in the series GaAs-Gap, studied by Thompson et al. 3 4 A value A. = 0.096 eV
agrees well with transmission data. 35
Strong structure appears between 3.4 and 4.0eV and could relate to
structure observed in reflectance near 3.7 eV. The S shape of the response
34
13*
A. G. Thompson, M. Cardona, and K. L. Shaklee. Phys. Rev. 146.601 (1966).

W. K. Subashiev and S. A. Abagyan. in Physics of Semiconductors (Proc. 7th Int. Cont),
p. 225. Dunod, Paris and Academic Press, New York, 1964.
74
B. 0.SERAPHIN
eV
FIG. 29. Electroreflectance spectrum of n-type Gap. (See text for details.) (After Cardona
et u / . ' 9
prevents resolution of a very small spin-orbit splitting A 1 . The two dips

at 4.75 and 5.74 eVare labeled &'and E 2 . The identification ofweak features,
leading to Aor = 0.06 eV and 6 = 0.465 eV, seems questionable.
(3) Gallium Arsenide. Electroreflectance has been studied extensively in
GaAs. The two main groups of structure at 1.4 and 3.0 eV fall into the spectral
range of field effect as well as electrolytic method and, for semi-insulating
GaAs, transverse electroreflectance can be used. The spectrum has been
recorded as a function of temperature, electric field, impurity content, and
various orientations of the reflecting surface and the polarization vector.
The results were compared with reflectance and photoluminescence spectra.
Such extended coverage bypasses difficulties of interpretation encountered
in materials for which only one spectrum recorded under one condition is
available. Only on such an extended basis can we use the sensitivity and
resolution of electroreflectance with confidence.
1.
ELECTROREFLECTANCE
FIG. 30. Electroreflectance spectrum of GaAs at two different temperatures: (-1

200K. (After Seraphin.'36)
75
300K :
(---)
Samples of intermediate resistivity and of both n- and p-type were studied

in the field-effect configuration.2*'36 Figure 30 shows the spectrum between
1.2 and 3.5eV for two different temperatures, as observed on an n-type
sample. For p-type samples, the sign of the response is inverted for all peak
groups. Field-effect studies show that this is to be expected, since virtually
no minority carriers are present, and the modulating field moves only the
majority carriers at the boundary of the depletion layer.'37*'38In p-type
material their motion is, of course, producing an effect of opposite phase.
This rather simple correlation between the internal and the external electric
fields makes GaAs a more promising candidate for a quantitative analysis
than Ge or Si, in which the balance of electric charges is more complicated
because of the presence of minority carriers in the surface.
Before discussing the two clusters of peaks separately, we want to point
out their temperature dependence. Although they both shift to greater photon
energies upon cooling, the group at 1.4 eV decreases slightly in size, whereas
the second group grows. As observed in Ge, the band swing for a given
modulation amplitude is reduced at low temperatures. This effect, however,
is overcompensated for in the high-energy peak group by the signal enhancement resulting from the reduced lifetime broadening at lower temperatures.' 3 9
Matching this temperature dependence to calculations of the electroreflectance response as a function of the Lorentzian broadening parameter4
produces values for this parameter considerably more precise than the orderB. 0. Seraphin, Proc. Phys. Soc. (London)87, 239 (1966).
I. Flinn and M. Briggs, Surface Sci. 2, 136 (1964).
138 M. H. Pilkuhn. J. Phys. Chem. Solids 25. 141 (1964).
139 D. T. F. Marple and H. Ehrenreich, Phys. Rer:. Lett. 8, 87 (1962)
13'
'"
76
9. 0.SERAPHIN
eV
100
200
300
O K
FIG.31. Spectral position of structure in Fig. 30 as a function of temperature. (After Seraphin.')
of-magnitude estimates obtained from the interpretation of the reflectance

curve.
A strong peak at 1.38 eV precedes the fundamental structure by approximately 30-40 meV. Its unusual dependence upon modulation voltage and
temperature sets it aside from the rest of the structure. Its association with
impurity levels has been demonstrated in simultaneous photoluminescence
m e a s ~ r e m e n t s . ' ~This
. ~ ~ proves
~ . ~ ~ that
~ impurity effects, beyond detection
in reflectance, can be seen in electroreflectance.
The up-down sequence of peaks starting at 1.40eV is related to the
fundamental absorption edge. Although precise values are given for the
location of the peaks, the exact position of the edge inside the width of the
double structure is uncertain. The edge is probably located between the
first peak and the crossover point. This is suggested (1) by comparison with
absorption spectra by S t ~ r g e , ' ~plotted
'
between the two peaks of opposite
14
14
E. W. Williams and V. Rehn, Phgs. Rev. 172. 798 (1968).

E. W . Williams, Solid State Commun. 7, 541 (1969).
M. D. Sturge, Phys. Rev. 127,768 (1962).
77
I'" 1l / j ~
0
0
0
- 300
6ooi
0
E,
0
0
FIG. 32. Field shift of structure in the electroreflectance spectrum of GaAs. Large positive
values of the dc bias represent the high-field condition in the space-charge layer at 200K.
(After Seraphin.')
sign in the temperature diagram of Fig. 31, (2) by comparison with electroabsorption spectra measured as a function of electric field, and (3) by the
fact that the first peak is less sensitive to changes in the electric field. as shown
in Fig. 32. According to theory, a peak shifts more strongly with field as it is
separated further from the edge in the oscillatory satellite pattern. The top
of Fig. 32 represents the high-field end of the surface potential barrier.
Transverse eiectroreflectance permits us to align the polarization vector
of the incident light parallel and perpendicular to the modulating field.62
No difference is observed at this parabolic edge of small anisotropy.
Differences in energy can be determined with high precision by comparing
equal parts in two groups of structure. The spin-orbit splittings A. = 0.348
0.002 eV and A l = 0.232 f 0.002 eV follow very closely a 3 : 2 ratio and are
found to be temperature
The further the high-energy partner is split, the more it is subject to line broadening by scattering. Consequently, the line width ratio of spin-orbit split companions increases as
they move apart.'40
The region between 2.0 and 2.8 eV, toward greater photon energies, was
searched with particular care. Previous reflectance measurement had shown
structure in this spectral region that was subsequently assigned to the
L,.-L, t r a n ~ i t i 0 n . No
l ~ ~response is observed in electroreflectance in this
14
D. L. Greenaway. Phys. Rev. Lett. 9 , 9 7 (1962).
78
B. 0.SERAPHIN
region. This is in line with the previous failure to detect the L,.-L, transition
in Ge unambiguously. The present result is even more puzzling, since in
GaAs this transition should be separated from the saddle-point edge following it by an energy at least 50 times the resolution of this method, so that no
explanation can be found in experimental restrictions.
The doublet of u p d o w n peaks clustered around 3.0eV shifts with a
temperature coefficient slightly larger than the fundamental structure as
seen in Fig. 31. The controversy about the location of the edge inside the
up-down structure must be resolved here without assistance from transmission measurements. The smaller field dependence suggests identification
with the first peak. The field shift results from a very complicated superposition of equivalent branches a t an off-center saddle point, however, and
cannot readily be evaluated. It is perplexing that the field shift is inverted
with respect to the fundamental edge and that the structure narrows toward
the high-field end. A smaller field dependence again suggests a position of
the edge near the low-energy peak. Evaluating the spectra of an alloy series
GaAs-Ids, Thompson and co-workers
suggest that the second
peak is related to the edge.
Transverse measurements by Rehn and Kyser6 display strong anisotropies upon rotation of the polarization with respect to the field vector.
Aymerich and Bassani derive the (1 11) symmetry of the correlated transition from these anisotropies. For agreement, they must assume a ratio of
longitudinal to transverse mass, however, which is inverted with respect to an
estimate derived from pseudopotential calculations.20 Orientation effects
on (110) surfaces can be interpreted by using the same c a l ~ u l a t i o n . ~The
.~~
crystal orientation does not noticeably influence the fundamental structure.
Both clusters of peaks shown in Fig. 30 have been studied under uniaxial
stress in the piezoelectroreflectance measurements by Pollak and Cardona.
The results are reviewed in Section 10a.
Structure at higher energies is weak and has been investigated much less
extensively. Electrolytic measurements have been performed on GaAs at
one end of the compositional coordinate in alloy studies. 34*44-146 In
agreement with previous electrolytic measurements, 5 c * 7 4 peaks are observed
at 4.46, 4.64, 5.00, and 5.35 eV. It cannot be decided on the basis of the
available results which of these are independent or which are components of
spin-orbit split multiplets. In his notation, Cardona tentatively assigns the
first group to the E, transition and the second to E , , deriving Ao = 0.18 eV
and 6 = 0.35 eV. The band structure relating to this spectral region is being
347144-46
144
145
146
A. G. Thompson and J. C. Woolley, Bull. Amer. Phys. SOC. 12, 639 (1967).
A. G. Thompson and J. C. Woolley, Can. J . Phys. 45.2597 (1967).
A. G. Thompson and J. C. Woolley. Can. J . Phvs. 45, 2557 (1967).
1.
1
I
79
ELECTROREFLECTANCE
I
4
eV
FIG.33. Electroreflectance spectrum of n-type GaSb. (After Cardona er a/."')
reevaluated, however.20*89*147*148
Th ere seems to be agreement that the
reflectance peak near 5.0 eV receives contributions from extended regions
of the Brillouin zone, as Kane" first showed for the related peak in Si.
Electroreflectance probably unmasks the critical points superimposed on
this strong noncritical background. Its structure must not be identified
on the basis of band models derived from a nominal correlation between
reflectance structure and critical points, however. Independent identification
of this weak structure at higher energies, of crucial importance in the assessment of conflicting band models, must await improved experiments in
electroreflectance.
(4) Gallium Antimonide. Lukes and Schmidts3 employ a thin-film variation of the electrolyte technique to record the direct transition a t 0.734 eV,
in agreement with absorption m e a s u r e m e n t ~ 'that
~ ~ give 0.725 eV. From
the small dip at 1.52 eV seen in Fig. 33, a spin-orbit splitting of A. = 0.79 eV
can be d e r i ~ e d . ' ~ '
The A3-A1 doublet at 2.185 and 2.655eV does not present the difficulties of interpretation encountered in GaAs. The structure consists of an
W. Sas1ow.T. K. Bergstresser,C. Y. Fong,and M. L. Cohen,Solid State Commun. 5,667 (19671.
F. Herman and W. E. Spicer. Phys. Rev. 174,906 (1968).
L49 W. M. Becker. A. K. Ramdas, and H. Y. Fan, J . Appl. Phys. 32, 2094(1961).
14
14
80
B . 0.SERAPHIN
+E2+Az
t
Eb+Ao
tR
eV
FIG.34. Electroreflectance spectrum of n-type InP at 297K. (After Cardona et al.15F)
unambiguous center dip surrounded by satellite^.^^ Consequently, the value

of A1 = 0.47 eV is reliable.'
Except for the dip labeled E 2 at 4.2eV, the structure at higher photon
energies is weak and will need confirmation by further results before the
identification is positive.
(5) Indium Phosphide. The room-temperature electroreflectance spectrum

'
of InP is shown in Fig. 34, after a measurement by Cardona ef ~ 1 . ' ~Agreement with absorption data is obtained15' by correlating the second part of
the fundamental structure to the direct edge at 1.34 eV. The first strong peak
probably relates to an impurity level. Unlike the impurity peak in GaAs,
however, there is no further experimental evidence to support such an
assignment.
The spin-orbit split companion of the fundamental transition is probably
hidden in the high-energy satellites of the fundamental structure. No data
from alloy series permit an extrapolation, as in the case of Gap. Lowtemperature spectra resolve a dip that could indicate a splitting of A. = 0.10
eV, smaller than the splitting A1 = 0.15 eV derived from the strong and
unambiguous doublet near 3.2 eV. Deviations from the Ao/Al = $rule are not
uncommon. Inversion of the 3 : 2 ratio would be unusual, however, and
150 W.
J. Turner, W. E. Reese, and G. D. Pettit, Phys. Rev. 136, A1451 (1964).
81
eV
FIG. 35. Electroreflectance spectrum of p-type InAs. (After Cardona et a1.'5')
measurements on the InP-InAs system are necessary before final conclusions

can be drawn.
The strong doublet near 3.2 eV presents difficulties of interpretation similar
t o those caused by the u p d o w n sequences of GaAs. No precise value for
the location of the edge inside the width of the structure can be given. However, the separation of 0.15 eV can be determined very precisely and agrees
well with low-temperature reflectance measurement^.^'
Cardona labels the two dips near 5 eV Eo' and E , . Their actual origin
must be considered uncertain; even more uncertain are the splittings A,'
and ti2.
( 6 ) Indium Arsenide. The fundamental absorption edge near 0.35 eV is
beyond the range of present electroreflectance techniques. The spin-orbit
split component has been observed near 0.8 eV by two different measurements. Two values for the splitting A. are reported that are different outside
the range of experimental error. The uncertainty of the edge location inside
a group of structure probably explains the disparity. Williams and Rehn14'
M. Cardona. J . Appl. Phys. 32,958(1961).
82
B. 0.SERAPHIN
find a value of 0.446 & 0.008 eV by subtracting results from an absorption

and an electroreflectance measurement on the same sample. Pidgeon et a[.40
report a value of 0.38eV from the convergence of the oscillatory pattern
observed in magnetoelectroreflectance at 1 SoK.
The strong structure between 2.4 and 2.9 eV varies in appearance according to the method used. Electrolytic spectra exhibit the positive swing shown
in Fig. 35, suggesting a straightforward i n t e r p r e t a t i ~ n . ' ~ ~Data
. ' ~ ~ taken
in the field-effect configuration show the u p d o w n sequence for which the
location of the edge is a r n b i g u o u ~ . ' Even
~ ~ considering the alloy series
GaAs-Ids, it is not possible to determine which peak represents the edge;
the consequences for the interpretation are discussed in detail by Thompson
and W ~ o l l e y . The
' ~ ~ peak separation, however, can be determined with precision, and a value of A 1 = 0.267 i 0.009eV results.
The peak at 4.44eV shifts little over the compositional range toward
GaAs. Its spin-orbit split companion can be followed over half of the alloy
range, but merges into the peak labeled E 2 toward the InAs end. As a consequence, the value for Ao' is uncertain.
Although the structure at 4.75 and 5.25 eV is very weak, it can be followed
through the whole compositional range, suggesting a value of 0.50 eV for
8.145
(7) Indium Antimonide. In a magnetoelectroreflectance measurement at

1.5"K, the fundamental edge is observed as a series of sharp symmetrical
lines that seem more characteristic of transitions to discrete exciton states
rather than of the broader asymmetrical lines one expects from transitions
between Landau sub band^.^^.^^ In the same measurement, structure is
observed between 1.05 and 1.20 eV that can be fitted to transitions from the
spin-orbit split valence band, separated from the higher valence band by
A. = 0.82 eV (Fig. 36).
Two electroreflectance spectra confirm this value, indicating that the
spin-orbit splitting is temperature independent over a large range. Cardona
et al.1*54find 0.82 eV at room temperature, using the electrolyte method;
Glosser and SeraphinlS2report the same value at 80K.
The separation of the two strong peaks near 1.88 and 2.38 e V approximately confirms the 3 rule by giving A, = 0.50eV. However, this value is
in contrast to an 0.58-eV separation of the related low-temperature reflectance peaks,I5 although A l derived from static and modulated reflectance
spectra agrees well in most other materials, and the separation of spin-orbit
split components can be determined precisely, irrespective of line shape.
Glosser and Seraphin, using dry sandwiches in the field-effect configuration,
Is
R. Glosser and B. 0. Seraphin, 2. Naturforsch. Ua, 1320 (1969).

M. Cardona and G. Harbeke. J . Appl. Phys. 3 4 . 8 7 3 (1963).
1.
83
ELECTROREFLECTANCE
1.000 1.050
1.100
1.150
1.200
Photon energy feV)

FIG. 36. Interband magnetoelectroreflectance in InSb for H
84 k G at T = 1.5"K with
e IH 1) F. Inset shows the spectrum of the split-off valence-band to conduction-band transition,
with the solid arrows showing the theoretical energies for these transitions. (After Pidgeon
et a1.4O)
observe an up-down sequence in contrast to the center dip of the electrolytic

technique (Fig. 37), but find a separation A, = 0.50 f 0.02 eV independent
of temperature and doping. Between 80K and room temperature, both
components move at a rate of - 5 x
eV/"K.
The structure labeled E,', Eo' + Ao', and E , in the electrolytic roomtemperature spectrum is also observed in the field-effect spectrum recorded
at 80 K.The first two peaks shift with -1 x 10-4eVPK, while the E ,
peak shifts with - 4 x
The line shape of E,' is quite different from the
line shape of E,' + A,', however, if it is recorded in the field-effect configuration, making the spin-orbit split interpretation questionable. A s in the case
of weak structure throughout, more and better results are necessary to make
the interpretation final.
f . 11-VI Compounds
The attention these materials previously received in static optical studies
extended to modulated reflectance as well. Most compounds are insulating
84
1.4
l1
20
- -I0
I .96 f
20
4 27
25
&
1
4 tI8
3t5 4
3:6
'
244t
I
2.50
B. 0.SERAPHIN
30
35
40
4.5
Photon energy (eV)
FIG.37. Electroreflectance spectrum of n-type InSb at 80K in the { 1 1 1 ) plane with 6 x lo6
carriers/cm3. The peaks to the left of the dotted line are 5 x larger than scale. (After Glosser and
Sera~hin.'~')
and photoactive so that all four versions of electroreflectancehave been used

-field effect, electrolytic, transverse, and photoreflectance. As with other
materials, however, most studies are preliminary ;their results are incomplete
and hardly go beyond what was already known from previous work.
Compared to 111-V compounds or the elemental semiconductors, the key
interband thresholds occur at higher photon energies in most 11-VI compounds. Consequently, the spectral range of present electroreflectancecovers
fewer structural features. Available spectra essentially show only the E ,
and E , structure. Structure beyond El-notoriously weak even if it is located
at smaller photon energies-is too close to the spectral cutoff to be interpreted with confidence.
Most 11-VI compounds can be prepared in the cubic and the hexagonal
modification. The similarity of the band structure, assumed to follow a
quasi-cubic model for the hexagonal modification, permits us to understand
anisotropy effects through a perturbation of cubic symmetry by a hexagonal
crystal field. Band structure analysis from reflectance studies on both
modifications could benefit from the similarity. Unfortunately, this is not so
for existing electroreflectancespectra that have been taken for each material
on one modification only (except for the structure related to the fundamental
edge of CdS). Future studies should fill this coincidental gap.
Reflectance studies could demonstrate that the optical processes at the
fundamental edge of 11-VI compounds are dominated by exciton effects.
The case was built through the interpretation of relative amplitudes, polariza-
1.
ELECTROREFLECTANCE
85
tion effects, and-probably most convincing-the observation of excited

states in structure components of identical line shape and proper spectral
separation.
Electroreflectance spectra show corresponding structure. It cannot be
said, at present, that this structure is also related to the excitons and not
just to the interband edge. The majority of the results are taken by the
electrolytic method at room temperature and are much too broad to resolve
details such as excited states. Results taken in the field-effect and transverse
configurations indeed show a dramatic sharpening of structure toward
lower temperature, supporting an exciton interpretation, but lack detail
that can be interpreted unambiguously as excited states.
To base a decision on line shape interpretation is hazardous for the
fundamental difficulties mentioned frequently in this review. We lack a
quantitative theory of exciton field decay from which a theoretical line
shape can be derived. In addition, it is not clear to what extent the modulating
field destroys the exciton or whether residual surface fields have already
accomplished this destruction before the modulation even starts. According to qualitative theories, modulating fields are usually much stronger
than required for this complete destruction. The response actually observed
is orders of magnitude smaller than predicted for complete destruction,
however. As in other materials, the relative fraction of excitonic and interband contributions cannot be determined at present.
In hexagonal crystals, anisotropies of the response are observed for
variations of the polarization direction that agree with selection rules
derived from previous reflectance studies. These effects add to the anisotropy,
induced by the electric field, even in cubic crystals. The modulation-induced
anisotropy-a significant advantage of modulated reflectance-is observed
in the few cases in which the electric field has been oriented either parallel
or perpendicular to the optical axis.
(1) Zinc Oxide (Hexagonal). A reflectance measurement by Hoffmannl 54.15 5 at the polar faces of vapor-grown ZnO prisms deserves particular attention as the only static electroreflectance spectrum. On these
polar faces atomic hydrogen and molecular oxygen produce an accumulation layer and a depletion layer, as determined through surface conductance.
In a simultaneous measurement, changes of up to 5 % in the reflectance at
the photon energy of the fundamental absorption edge at 3.4 eV are observed
in going from one surface condition to the other (Fig. 38).55*55b
This
reflectance change can be interpreted in terms of the surface field derived
B. Hoffmann, Z. Phys. 206,293 (1967).
B. Hoffmann, Solid State Commun. 5, 61 (1967).
155aE.
Mollwo, Reichsber. Phys. 1, 1 (1943); Z . Angew. Phys. 6, 257 (1954).
ISSbD.
G. Thomas, J . Phys. Chem. Solids 15,86 (1960).
154
155
86
B. 0.SERAPHIN
"c
a,
0
c m-'
104
c
9
*
102
v1
8
0
+
W
u
al
K
0.2
01
0
(C)
30
32
34
Photon energy (eV)
36
FIG.38. Reflectance of a ZnO prism face as a function of surface conditions, as adjusted by

fractional coverage with oxygen and hydrogen. The reflectance R, is that of the thermally
cleaned crystal, and R is that after generation of the surface conductivity Au. (a) 0- - 0:
crystal 176, Au = 3.5 x
ohm-': x - x : crystal 137, A u = 1 x 10-40hm-1. (After
x : single crystal. (After
H ~ f f m a n n . ' ~(b)
~ )Absorption constant. o - 0:thin layers; x
M o l l ~ o . ' ~ (c)
~ ' )Reflectance data. (After Thomas.'55b)
~
from the field-effect measurement, and agreement is found with electroreflectance as based on the Franz-Keldysh theory.
differs considerably
The differential spectrum taken by Cardona et d.15c
from the spectrum of CdS and CdSe, the other two hexagonal compounds
investigated in electroreflectance. A number of oscillations reminiscent of the
Franz-Keldysh theory are seen for both E Ic and 11 c . Both spectra are
identical except that the Ic spectrum is shifted to higher energies by
0.04 eV. No structure is observed at higher energies. The apparent existence
of only two transitions is in line with reflectance results'56 that make it
difficult to apply the quasi-cubic model to the valence band of ZnO. Lowtemperature measurements are desirable and will probably reduce the present controversies.
156
Y.S. Park, C. W. Litton, T. C. Collins, and D. C. Reynolds, Phys. Rev. 143.512 (1966).
87
(2.623 eV)
B'
(2578 eV)
2 50
B
I2 558 eV)
2 55
2 60
2 65
27
Photon enemy (eV)
FIG.39. Photoreflectance of a CdS platelet at 83K for polarization parallel (solid line) and
perpendicular (dotted line) to the optical axis. The point values are: A, 2.542 eV: B, 2.558 eV :
B', 2.578 e V ; C, 2.623 eV; C', 2.652 eV. (After Wang and Albers.")
(2) Cadmium Suljide (Hexagonal). With a photoreflectance technique

improved over their previous
Wang and co-workers report sharp
and detailed spectra at the fundamental edge at 83K that permit them readily
to identify structure correlated to the A, B, and C exciton structure of reflectance spectra (Fig. 39).57Their spectral separation agrees well with Thomas
and hop field'^'^^ values determined at 1.6"K. In addition, two peaks can be
recognized 20 and 29 meV above B and C, respectively, that might be associated with excited states of an exciton if their satellite character could be
ruled out beyond doubt. A possible excited state of A would overlap the B
structure.
A spectrum of similar quality, but restricted to the A, B, and C structure,
results from transverse measurements at 77"K.64 The response is inverted
with respect to photoreflectance, but otherwise is very similar in line shape.
In contrast to reflectance spectra, the weak C structure can be observed even
at room temperature. The A structure is missing when the polarization vector
coincides with the optical axis c, in agreement with reflectance spectra.
Compared to these two low-temperature measurements, two spectra
taken at room temperature with the electrolytic method are noticeably
e
15
D. G. Thomas and J. J. Hopfield, Phys. Rev. 116,573 (1959).
88
B. 0.SERAPHIN
(I)
P
x
6-
.-.
4-
20
20-
LL
-2 -
2-
- 02 -2-a - 4 x
LL
4-
-E
X
0-
- -4LL
-8
eV
FIG.40.Electroreflectance spectrum of n-type CdSe. (After Cardona et
d.lSc)
inferior in resolution and detail.1 5 c * 1 5 8 The two spectra look quite different,
their structure shifting as much as 0.1 eV with respect to each other and
responding strongly to changes in dc bias. In view of these shifts, a claim that
some structure precedes interband edges by 50 meV'58 and must therefore
be associated with excitons, is not very convincing. No structure is reported
at higher energies up to 6 eV.
In the single exception to an otherwise unfortunate gap, Cardona ec al.' 5 c
report a single peak at the fundamental edge of cubic CdS epitaxially
deposited on G A S .The correlation between the two modifications is not
discussed, nor is any further structure at higher energies observed on the
cubic sample.
( 3 ) Cadmium Selenide (Hexagonal). The electroreflectance spectrum of
CdSe is shown in Fig. 40 for three different orientations of the vectors of
E. Gutsche and H. Lange, Phys. Status Solidi 22,229 (1967).
89
,G-
dc retlectonce
(unnorrnalized)
1150
3200
3250
x (2
331
FIG.41. Electroreflectance spectrum of a nominally cubic ZnS crystal at 77K. The values
are for F 11 (1 10) and equal to 3 x lo4 V/cm. (-) f? 11 F ; (---) f? I F. (After Forman and Cardona.64)
polarization, modulation field, and optical axis with respect to each other,15'
taken at room temperature with the electrolytic method.
In the hexagonal lattice, the top level of the valence band is split by the
crystal field, giving rise to the A and B structure of optical spectra. However,
the first updown sequence in Fig. 40 cannot be considered split into an A
and a B component in this room-temperature spectrum, and rotation
of the polarization is of little avail in this case. Up is separated from down by
an energy that agrees with low-temperature reflectance spectra, but this must
be considered fortuitous. The C structure follows at an energy that also agrees
with the A-C separation of reflectance structure, but probably for a better
reason.
The splitting of the El structure into an A , and an A 2 component can be
caused either by spin-orbit splitting or, in the hexagonal lattice, by a lifting
of the degeneracy of eight equivalent branches of an (111)-critical point
0.SERAPHIN
8.
4450
>
\ \
4400
>
x (A,
4000
3900
3000
FIG.42. Electroreflectance spectrum of ZnSe at 77K. (After Forman and Card0na.6~)
by the hexagonal crystal field. In CdSe, spin-orbit splitting by 0.26 eV is held

responsible for the separation of A and A 2 .Note that this group of structure
is considerably stronger at a surface that contains the optical axis c than for a
surface perpendicular to c. This implies an anisotropy of the reduced mass
at the corresponding critical point. The doublet is not allowed for E 11 c.
An independent measurement also taken by the electrolytic method differs
considerably from the spectrum of Fig. 40, not only in line shape, but also
in spectral position of structure by amounts of up to 0.1 eV.lSaIt is difficult
to show preferences until the complexities of the present electrolytic method
are better controlled and understood.
(4) Zinc Sulfide (Nominally Cubic). The spectrum at the fundamental
edge of ZnS, taken in the transverse configuration at 7?K, is shown in
Fig. 41.64 The small polarization dependence, not expected for a purely
cubic crystal, is probably due to the presence of a small amount of hexagonal
stacking. The authors suggest the use of such polarization effects for determining the composition of mixed crystals. However, this will require the
careful elimination of all secondary polarization effects, difficult to avoid in
optical experiments.
A peak C is assigned to transitions from the spin-orbit split valence band
or its exciton. Its possible character as satellite structure should be ruled
out by further measurements, however.
91
eV
FIG.43. Electroreflectance spectrum of p-type ZnTe. (After Cardona et U I . ~ ~ )
( 5 ) Zinc Selenide (Cubic). N o polarization dependence is observed in the

transverse low-temperature spectrum of ZnSe shown in Fig. 42.64 The line
shape of the structure labeled n = 2 and spin-orbit is quite different
from the main structure n = 1, in contrast to all other optical structure
related to excited states or spin-orbit split companions. The authors blame
incomplete exciton destruction for part of the structure-not quite convincing for the magnitude of the fields.
The CdTe spectra taken with extreme spectral resolution at 6K show no
sign of excited-states structure.38 Further evidence for such structure in
other materials seems necessary before the question of exciton decay in
electroreflectance spectra can be settled.
(6) Zinc Telluride (Cubic). The electrolytic room-temperature spectrum
of ZnTe shown in Fig. 43 is similar to that of group IV elements and 111-V
c~mpounds.~
The direct edge Eo is separated from its spin-orbit split
component by 0.92 eV, as compared with reflectance data (0.9 eV) and intravalence band transitions (0.98 eV).5 9 Better agreement with the latter value,
but not with the reflectance spectrum, is obtained from a photoreflectance
spectrum, also taken at room t e m p e r a t ~ r e It
.~~
shows a dip at 2.18 eV,
70 meV below the peak believed to represent the edge in the electrolytic
N. Watanabe and S. Usui, Japan J. Appl. Phys. 4,464 (1965).
92
B. 0.SERAPHM
I0
Q
X
- 10
Photon energy (eV)
FIG.44. Electroreflectance spectrum of CdTe at 6K. (After Ludeke and Paul.")
spectrum. Unless such discrepancies are resolved in more complete investigations, a four-digit readout of spectral positions is meaningless.
The El and E , + A 1 structure is also located above the energies of reflectance and absorption structure. A claimed peak Eo' is too improbable to be
discussed.
(7) Cadmium Telluride (Cubic). The extremely sharp structural features
of the spectrum shown in Fig. 44 demonstrate the superiority of low-temperature spectra taken in the dry-sandwich configuration independently
developed by Ludeke and
and Pidgeon and grove^.^' At 6"K, the
total width of the fundamental structure, for example, shrinks to less than
6 meV, making a high-precision readout meaningful.
The sandwich consists of a quartz film of 5000 A vacuum deposited on a
previously etched CdTe bulk sample. A SnO, film serves as a transparent
electrode.
The results of a 6K run are shown in Fig. 44.As previously observed
in field-effect spectra, the structure is much sharper than electrolytic spectra
taken at the same temperat~re.'~"
The sign is inverted, probably due to the
cathodic bias preferentially used in present electrolytic work.
Between room temperature and 6"K, the fundamental structure sharpens
by a factor of 15, the spin-orbit split transition near 2.5 eV by a factor of
6, and the A3-A1 doublet by a factor of only 2.5, the decrease probably being
due to a spectrally dependent lifetime broadening. These factors are well in
line with observations on 111-V compounds62 and need not necessarily
point to an excitonic character.
The inflection point of the fundamental structure at 1.5952 f 0.0002 eV
at 6K is in good agreement with Thomas' value'60 of 1.5945eV at 20K
D. G. Thomas, J . Appl. Phys. 32,2298 (1961).
1.
93
ELECTROREFLECTANCE
eV
FIG.45. Electroreflectance spectrum of n-type HgSe. (After Cardona et al? 5 ' )
based on a n excitonic interpretation. However, any indication of excited

states is missing in this high-resolution spectrum reported by Ludeke and
Paul.
(8) Mercury Selenide (Cubic). No response related to the fundamental
edge can be seen in the electrolytic HgSe spectrum shown in Fig. 45. The wide
swing of structure is reminiscent of spectra observed on degenerately doped
materials. Cut-out effects due to the large variable background can make
the determination of peak positions such as the E , and E , A1 structure
less accurate.
O1-V-I
eV
FIG.46. Electrorefiectance spectrum of n-type HgT'e. (After Cardona er d.L5e)
94
B. 0.SERAPHIN
' t
Ill1
0.350
-t t
0.400
t t
I
0.450
Photon energy (eV1
FIG.47. Magnetoelectroreflectance spectrum of HgTe at 42 kG with T = 15 K and E IH 11 F.

(After Pidgeon and grove^.^')
(9) Mercury Telluride (Cubic). It is not clear why the spectrum of a

material known to be a semimetal looks more like a semiconductor than does
HgSe (Fig. 46).' 5 c No spectrally varying offset hides well-resolved structural
features that agree with reflectance and absorption spectra. It must be
suspected that the electrochemistry of the semiconductor-lectrolyte
interface-very complex and sufficiently known for Ge only-promotes
high resolution for one material and inhibits it for another.
Pidgeon and Groves41 find a broad, zero magnetic-field background that
they subtract from their magnetoelectroreflectance spectrum taken at 1.5"K
in the dry-sandwich configuration (Fig. 47). The oscillatory Landau pattern
can be matched by an inverted gap of E , = -0.3025 eV, based on twice as
many oscillations as are resolved in static magnetoreflectance.
g. IV-Vl Compounds
So far, few electroreflectance measurements have been performed on

IV-VI compounds. As for all other materials, the existing structure in static
optical measurements is enhanced ;however, the few available results indicate
that interpretation in terms of the band structure must be made cautiously.
In addition to difficulties of line shape interpretation encountered in other
materials, an unusually strong sensitivity of the electroreflectance spectrum
to changes in dc bias, carrier concentration, temperature, and modulation
amplitude and frequency is observed in most IV-VI compounds. A drastically
different appearance of the spectrum can be obtained through only minute
changes in any of these parameters.
95
The strong variations are probably caused by the predominance of bandfilling effects. Large carrier concentration and a high dielectric constant
further aggravate the difficulties.
In first studies on the lead salts23and on SnTe and GeTe,16 Aspnes and
Cardona observed the different character of IV-VI electroreflectance
spectra as well as the difficulties in measuring and interpreting them. In
a separate study, Aspnes and Frova 5 a explored the consequences of modulation by means of a space-charge layer extending over a small fraction of the
light penetration depth only. The spectral functions for the coefficients CI
and in the derivative of Fresnels reflection equation4 are then different
from the previously considered case of a space-charge layer extending
further than the light (Section 3). Since the light sees an electric field over
only a fraction of the penetration depth, the modulation is much smaller in
materials in which a large carrier concentration compresses the spacecharge layer. Reflectance modulations of only
are typical in the IV-VI
compounds. This is close to the detection level and requires careful experimentation.
The large dielectric constant causes phase lag between external modulation
and space-charge field, further complicating the correlation between electrical
input and optical output.
Band population effects, which Aspnes first postulated for the interpretation of the SnTe and GeTe spectrum, 6 seem to establish a fundamental
difference of the basic mechanism. Consequently, they were investigated on
two series of samples in which a drastic variation of such effects could be
expected. 6 2 First, the electroreflectance spectra at 200K-a temperature
sufficiently low to make changes of dc bias effective in the space-charge
layer-were recorded on a set of PbTe samples of carrier concentrations
~,
the point of degeneracy
varying from 2 x lo to 9 x 1019~ r n - passing
inside this range. Second, the spectra of five samples of the type Pb,Sn -xTe,
the PbTe sample x = 1 being the 9 x 1019cm-3 end of the previous series
and the carrier concentration increasing to 8 x 1020cm-3 at the SnTe
end, were measured.
In both series, the spectra consisted of well-resolved structure, broader
than in other materials, but distinct and without large background. The
influence of band-filling effects is apparent throughout both ranges, however,
and probably explains the strong variations in the appearance of the spectra.
Band-filling effects result when the charge screening the applied field
changes the occupancy of the degenerate valence band in the surface
region. Transitions involving this degenerate band will respond one way to
16
D. E. Aspnes and M. Cardona, Bull. Amer. Phys. SOC. 13, 27 (1965).

B.0.Seraphin, Proc. l n t . Con& Phys. IV-Vl Compounds, Paris, 1968, J . Phys. (Paris)29, C 4
96 (1968).
96
B. 0.SERAPHIN
a modulation operating around a band edge bending away from the Fermi
level, in a different way if the band edge bends toward the Fermi level and
crosses it near the surface, and, finally, in a third way if it bends toward the
Fermi level without crossing it. This explains the strong sensitivity of the
line shape to changes in quiescent potential as set by the dc bias.
For accumulation and depletion layers alike, population effects of three
different types can be expected accordingly.
(1) Inversion of the reflectance response (flip-flop) with inversion of the
dc bias of half the ac modulation amplitude results when the Fermi level
is riding on or is very close to the band edge involved in an optical transition.
(2) When the Fermi level has shallowly penetrated the band, structure
shifts to larger photon energies upon inversion of the dc bias from positive
to negative values.
(3) If the Fermi level lies deep inside the band or if the transition involves
a band far away from the Fermi level, the structure is insensitive to changes
of dc bias.
The dc bias effect will further be determined by the penetration depth of
the light : Large penetration depths will result in small dependence on dc
bias, expected in the near infrared and the ultraviolet for most IV-VI
compounds since their c2 peaks in the visible region of the spectrum.
The three categories of response to changes in dc bias-flipflop, blue shift,
or no response-are actually observed. In spite of the drastic variations of
the line shape, they establish a systematic pattern. The variations can be
interpreted consistently in terms of a shift of the Fermi level up or down,
as carrier concentration, fractional composition, or temperature is changed.
If one part of the spectrum first shows inversion of sign with dc bias inversion,
then shifts into the blue, and finally becomes insensitive, indicating a downward penetration of the Fermi level into the band, all parts of the structure
show similar behavior consistent with such a shift of the F e m i level. We
therefore believe that this establishes a criterion that indicates the location
of the initial band (all samples were p-type) with respect to the Fermi level.
We furthermore believe that this is presently the only band structure feature
that can be extracted from spectra that vary so strongly with a variety of
parameters.
The sensitivity of the line shape to the relative position of the Fermi
level inside the initial band plays a considerable role due to the peculiar
band structure of the IV-VI compounds. C a l c u l a t i ~ n s ' ~ ~predict
- ' ~ ~ three
valence band maxima inside the energy variation of the Fermi level as
163
164
165
P. J. Lin and L. Kleinman, Phys. Rev. 142,478 (1966).

D. L. Mitchell and R. F. Wallis, Phys. Rev. 151, 581 (1966).
P. J. Lin, W. Saslow, and M. L. Cohen, Solid State Commun 5, 893 (1967).
97
functions of doping, temperature, and fractional composition. Correspondingly, three groups of structure are observed in the two sets of samples
covering the two coordinates PbTe (low carrier concentration) --* PbTe
(high carrier concentration) and PbTe + SnTe. More thorough studies are
required to extract actual band model parameters from spectra varying in
such a complex manner. The following tentative conclusions seem permissible, however :
(1) A basically similar electroreflectance spectrum suggests a similar
band structure along the two coordinates.
(2) The position of the Fermi level with respect to the edge of the initial
band determines appearance of the electroreflectance spectrum and its
response to dc bias and temperature (band-filling effects).
(3) An inverted Burstein shift166in Pb,Sn,-,Te confirms the existence
of a second, lower, valence band at nearly constant separation from the
lowest conduction band edge. The position of the Fermi level inside this
lower valence band is determined by the number of states available in the
upper band above the Fermi level. Since this number varies strongly over
the compositional range, the separation of the Fermi level from the conduction band edge varies accordingly, probably overcompensating for the
simultaneous Burstein shift. If this is accepted, we must conclude from the
magnitude of the spectral shift that the density-of-states mass of the lower
valence band is comparable to or smaller than that of the upper
(4)The consistent behavior of structure between 4.0 and 4.5 eV suggests
that a third valence band could contribute to the generation of the spectrum.
With the Fermi level deep inside the valence bands for all samples of the
series Pb,Sn,-,Te, it cannot be expected that a possible closure of the
thermal band gap at some x of the compositional range would drastically
affect the electroreflectance spectrum. No evidence for or against such a
closure can presently be derived from the electroreflectance spectrum.
(5) The observations support existing band structure ~ a l c u l a t i o n s . ' ~ ~ - ' ~ ~
Two lower valence band maxima are predicted within a few tenths of one
electron volt of the highest valence band maximum at L, one along the 2and one along the A direction. Breaking of selection rules by the electric
field may enhance the oscillator strength of transitions from these bands.169
Movement of the Fermi level near these two lower maxima as determined
by the strongly variable upper maximum could explain most features of the
16
16
69
E. Burstein, Phys. Reu. 93,632 (1954).

W. E. Howard, R. Tsu, L. Esaki, and P. J. Stiles, Proc. I n t . ConJ Phys. 1V-Vl Compounds,
Paris, 1968, J . Phys. (Paris) 29, C4-61 (1968).
A. A. Andreev, Proc. lnt. ConJ Phys. IV-Vl Compounds, Paris, 1968, J . Phys. (Paris) 29,
C4-50 (1968).
M. L. Cohen, Y . Tung, and P. B. Allen, Proc. Inr. Conf. Phys. 1V-VI Compounds, Paris,
1968, J . Phys. (Paris) 29, C4-163 (1968).
98
B. 0.SERAPHIN
spectra. The calculations of Herman et a1.170 suggest a separation of these

maxima in going from PbTe to SnTe-in agreement with the postulated
upward shift of the Fermi level in the Pb,Sn, -,Te series for decreasing x.
(6) The observations seem to provide a probe for the location of initial
states with respect to Fermi level and band edge. Further conclusions with
respect to the nature and location of these initial states must await investigations more complete with respect to the range of carrier concentrations,
fractional composition, and temperature as well as modulation amplitude
and bias. The predominance of band-filling effects in degenerate IV-VI
compounds suggests that electroreflectance is probably restricted as a
critical-point phenomenon in these materials. Consequently, a critical-point
analysis of spectra can only be tentative at present.
h. Other Semiconductors
Electroreflectance measurements on semiconductors from groups other
than those previously discussed include a study on Mg,Si, Mg,Ge, and
Mg,Sn by Vasquez et al. 17 and investigations of excitonic features in PbI,
by Gahwiller and Harbekej3 and in Cu,O by Shestatskii and sob ole^.'^'
i. Semiconductor AUoys
Optical spectra of mixed-crystal series have in the past provided band

structure analysis with important clues. Spectral variation of structure
with alloy concentration in many cases verified the assignment in the constituent compounds on either end of the compositional range. Kinks in the
variation of the spectral position with composition indicate a crossover in
energy levels.
The value of following structure along the compositional coordinate is
often degraded by the lack of resolution in static reflectance measurements.
Electroreflectance has improved on previous reflectance measurements in
all systems investigated so far. In the Ga,In, -&,140*144 GaAs,P, - x , 1 3 4
InAs,Sbl-,,145 and Ge,Si, - x , l l 3 sharp spectra are observed over theentire
compositional range. This is not a trivial fact. The virtual crystal model
from which the electronic structure of alloys is derived predicts a tailing of
energy states into the adjacent forbidden regions, resulting in a smear-out of
transition threshold^.'^^*'^^ In the experiment, line width variations stayed
within a factor of two and could be attributed to field variations rather than
alloy broadening.
F. Herman, R. L. Kortum, I. B. Ortenberger, and J. P. Van Dyke, Proc. f n t . ConJ Phys.
IV-Vf Compounds, Paris, 1968, J . Phys. (Paris) 29, C4-62 (1968).
1 7 F. Vasquez, M. Cardona, and R. A. Forman, Bull. Amer. Phys. SOC.13, 387 (1968).
1 7 2 S. N. Shestatskii and V. V. Sobolev, Phys. Status Solidi 28, K131 (1968).
7 3 L. Nordheim, Ann. Phys. 9,607 (1931).
1 7 4 R. H. Parmenter, Phys. Rev. 97,587 (1955).
I7O
1.
oc
10
99
ELECTROREFLECTANCE
4-4
20
30
40
50
Photon energy ieV)
FIG.48. Electroreflectance spectrum of a thick Au film evaporated on an optical flat. The

reflectance of an identically prepared sample is shown for the left-hand scale. (After F e i r ~ l e i b . ~ ~ )
The virtual crystal model predicts a variation of energy gaps with composition that is linear in the first order and quadratic in second order. Unless
energy levels cross, the peak positions in the 111-V series follow a quadratic
dependence. The Ge-Si system can better be approximated by a linear
dependence, however.
Variations in the complex surface chemistry of alloys may change the
point of operation over the compositional range. Drastic changes often
observed along the compositional coordinate may simply reflect variations
in the quiescent surface potential, and caution is advocated in line shape
interpretation.
OF METALS
It is not immediately obvious that electroreflectance should be applicable
to metals. In a good conductor the modulating field is screened out within
the Thomas-Fermi screening length of less than 1 A, leaving a field-free
region over most of the penetration distance of the light. In Cu, for example,
the field penetration depth of 0.5A should reveal little about the band
structure to a depth of 100 A typically probed by the light.
In spite of these facts, electroreflectance spectra have been observed by
the electrolytic method in Au, Ag, and Cu. The first report by F e i r ~ l e i b ~ ~
confirmed that the spectra are closely related to structure in the static
reflectance curve of these metals (Fig. 48). The modulation mechanism is
not quite clear. It probably depends upon cooperation with field-induced
100
B. 0.SERAPHIN
changes in the optical constants of the electrolyte in the sense that these
changes act as a sensitive and amplifying probe for the discontinuities in
the slope of the metal reflectance curve. Prostak and H a n ~ e n ' ~claim
'
such
a cooperation is unnecessary. They interpret field-induced changes in the
attenuated total reflection spectrum of Au to be caused by changes in carrier
concentration, in the Fermi level, and hence in all interband transitions
involving the Fermi le~e1.I'~Consequently, the optical constants of the
metal will simply be shifted on the photon energy scale by the same fraction
that the carrier-density dependent plasma frequency shifts. The mechanism
seems to be oversimplified, however, and the numerical agreement with Au
and Ag spectra appears to be fortuitous. Parsons177can show that for Cu
no response is obtained at 2.1 eV where c2 steeply rises according to static
optical measurements and where, according to Hansen and Prostak's
proposal, the biggest effect should occur.
A change in the optical constants induced by the field modulation causes
a correlated change in the ellipsometric parameters b,t and A. Buckman and
Bashara' 78 first developed the analysis for modulated ellipsometry and
applied their results to Au and Ag. By measuring three quantities-A$,
AA, and AR/R-enough data are available for a direct calculation of the
complex dielectric function in the absence of the field, the field-induced
changes, and the depth into the sample to which the optical constants are
being affected. The results agree well with Feinleib's data for ARIR at normal
incidence, and the penetration depth is found to be of the same order as the
Thomas-Fermi screening length. Besides its apparent ability to show certain
features of structure in the modulated spectrum more clearly than a measurement of ARIR alone, the method has the advantage of not requiring a
Kramers-Kronig analysis. '79
OF FERROELECTRICS
Structure in the reflectance of a ferroelectric shifts markedly when the
material is cooled through its Curie temperature.'
This indicates that
the spontaneous polarization causes band structure effects resulting in the
change of the reflectance spectrum.' '8 2 Similar reflectancevariations could
be expected when an external electric field modulates the alignment of the
dipoles.
'9
'" A. Prostak and W. N. Hansen, Phys. Rev. 160,600(1967).
W. N. Hansen and A. Prostak, Phys. Rev. 174,500(1968).

B. J. Parsons, Phys. Rev. 174,801 (1968).
''' A. B. Buckman and N. M. Bashara, J . Opt. SOC.Amer. 58, 700 (1968).
1 7 9 A. B. Buckman and N. M. Bashara, Phys. Rev. 174,719 (1968).
M. Cardona, Phys. Rev. 140,A651 (1965).
l a ' J. D.Zook and T . N. Casselman, Phys. Rev. Lett. 17,960(1966).
"* J. R. Brews, Phys. Rev. Lett. 18,662(1967).
301
A,
15
2.5
-I 01
25
30
3.5
30
35
101
A2
40
45
50
40
45
50
55
hv (eV)
FIG. 49. Room-temperature reflectance of BaTiO, at zero electric field, with polarization
vector E parallel and perpendicular to the c axis with T = 25K (a). Corresponding electroreflectance spectra with a field of 6.7 kV/cm applied in transverse configuration parallel to the
c axis (b). (After Gahwiller.61)
Large effects were indeed observed in the electroreflectance of perovskite

ferroelectrics such as BaTiOJ, KTaO,: KNb03,61*183
and SrTi03.1S4
Reflectance changes of up to 45 % are distributed over the spectral scale in
broad, continuous bands of either sign. Magnitude and line shape suggest a
mechanism other than the Franz-Keldysh effect. Relative displacement of
oxygen and metal sublattices responsible for the ferroelectric properties are
probably the major cause for the optical effect as well. The displacement
changes the overlap integrals between pairs, which affects the band structure.
Electroreflectance of ferroelectrics is probably not a critical-point phenomenon. For the interpretation of his measurements on BaTi03 shown in
Fig. 49, Gahwiller6' must assume a field-induced increase of the band
separation by an amount independent of the k vector.
Frova and P. J. Boddy, Phys. Rev. Lett. 16. 688 (1966)
J. D. Zook. Phys. Reo. Lett. 20,848 (1968).
l E 3 A.
lE4
102
B. 0. SERAPHIN
The situation is different in rutile, investigated by Frova et a f . l S sA very

large ionic polarizability and a structure resembling the active constituent
of the perovskites makes rutile an almost ferroelectric. Its electroreflectance spectrum is also broad and large, but seems to relate to critical points.
At least a good theoretical fit to the experimental data is obtained by assuming
that the field-induced changes in the optical constants result from a strongly
lifetime-broadened Franz-Keldysh effect.
VI. Analysis of Electroreflectance Spectra

Semiempirical band models crucially depend on an accurate assignment
of structure in optical spectra to critical points in the band structure. Modulated spectra appear to be superior to static reflectance in this assignment
process mainly for two reasons. First, the modulated response originates in
the neighborhood of the critical point rather than in extended regions of the
Brillouin zone. Secondly,modulation by an electric field or a stress establishes
a preferred direction and lowers the symmetry of the sample crystal. Consequently, anisotropies of the reflectance response can be expected as the
modulation vector rotates relative to the crystal frame.
Such anisotropies are indeed observed, and their diagnostic value is
investigated in this section. Proper evaluation of directional experiments
leads to a symmetry analysis that, in principle, could identify a critical point
with respect to (1) its transition energy, (2) its location in the Brillouin zone,
and (3) its topographical class and orientation. In contrast to previous
analysis, the identification from symmetry analysis does not rely on the collaboration of existing band models. The general and obligatory nature of
symmetry arguments suggests an identification of electroreflectance structure in an a&initio manner.
14. SCOPE, INTENTION, AND PROBLEMS OF THE ANALYSIS
a. Parameters of a Critical Point
The following parameters must be known for the full identification of a

critical point: (1) the band separation at the critical point, its transition
energy, (2) its location in the Brillouin zone, (3) the topography of the interband energy surface at the critical points and, if hyperbolic, its orientation
in k space. Information on the relative curvature of the interband energy
surface, i.e., the reduced interband effective mass in the various directions,
is desirable.
The potential and the limitations of an analysis with respect to a determination of these parameters is discussed in the following sections.
A. Frova, P. J. Boddy, and Y. S. Chen, Phys. Rev. 157,700 (1967).
103
(1) Transition Energy. In the past, structure in static reflectance spectra

was widely associated with the transition energy of critical points. Recent
trends have deemphasized this association, however, suggesting that the
spectral position of modulated rather than static structure is correlated to
the transition energy of a critical point. However, the spectral sharpness of
such structure-peak positions can be read out to typically 1 meV-must
not give the impression that transition energies can be determined with
similar precision. The whole width of structure is typically 50 meV and the
location of an edge inside this width is uncertain. Only spectral differences,
such as temperature or compositional shifts and spin-orbit splittings, can
be read out with satisfactory precision. At low temperatures, the total width
may shrink to 10 meV o r less, easing the assignment quantitatively, but not
in principle.
Some guidance for the placement of the edge inside a group of structures
can be obtained by subjecting a spectrum to a Kramers-Kronig analysis,
using Eqs. (12) and (13). This dissects the spectrum into the field-induced
,
the problem onto the level of discussing A&
changes
and A E ~lifting
line shapes rather than A R / R line shapes.'" Progress is made on this level
only by presupposing some knowledge of the band structure and the modulation mechanism.
A different but equally restricted approach synthesizes the response from
an assumed mechanism such as the Franz-Keldysh effect. Transition energy
and type of a critical point are then determined from a n optimum match
of the experimental ~ p e c t r u m . ~
In certain cases, reasonable assumptions can be made, as for the necessarily
parabolic character of the fundamental edge. A variation of the surface
conditions leads to a systematic pattern of the line shape responke that can be
evaluated in terms of the transition energy.'5d As was shown in Section 3,
the transition energy at the fundamental edge of G e can be read out from
such an experiment with a margin much smaller than the width of the
structure.
(2) Location and Topographical Features of a Critical Point. In an
appropriate coordinate system using a parabolic approximation, we can
describe the separation of two bands n and n' at a critical point k, as a function of the wave vector by
The previously discussed transition energy appears here as En*ns(kc).

We will
now proceed to an analysis with respect to the location k, of the critical
point and the topographical features of the interband energy surface Eq. (26)
104
3 . 0.SERAPHIN
as described by the reduced interband effective mass

1
1 aZE,.
1 aZE,
i = x,y,z,
(27)
p i mti mhi A aki2 h2 aki2
where me*and mh*are the effectivemasses of electrons and holes, respectively.
Mass values of either sign are admitted in different directions, with a negative
mass corresponding to a maximum of the band separation.I6
Such an analysis has a precedence in the cyclotron resonance of semiconductors. We will therefore briefly sketch the analogies and differences of
the two techniques.
1 - 1
-
+*=-
b. ElectroreJIectanceversus Cyclotron Resonance
In cyclotron resonance, anisotropies of the resonance absorption are

observed as the magnetic field swings through principal trajectories in the
crystal frame. These anisotropies reflect the variations of the effective mass
in a direction perpendicular to the magnetic and the electric fields. As the
magnetic field swings through its trajectory, the values of the effective mass
in the various directions are being sampled. The observed anisotropies can
then be interpreted consistently by placing the correlated energy minimum
in a certain location of the Brillouin zone, giving the effective mass tensor
appropriate components.
The diagnostic value of this powerful technique rests on the directional
sampling of the effective mass by the magnetic field. It must be expected that
the modulating field in electroreflectance also establishes a preferred direction of sampling in an analogous manner. The differences are obvious. An
interband rather than a single-band phenomenon is being monitored. The
sampling will respond to a direction parallel rather than perpendicular to
the field direction. The correlation to the interband effective mass is probably
very complex.
The analogy, however, refers to the directional sampling. Without resorting to a specific mechanism, the electrooptical effect can be expected to
respond to the loss of translational symmetry of the crystal along the field
direction. In addition, the response must be correlated to the interband mass
through the curvature of the interband energy surface that determines the
character of the band separation-minimum or maximum-at the critical
point. The Franz-Keldysh theory establishes this correlation in a straightforward manner. However, the sampling of the reduced interband mass
along the direction of the electric field will be a necessary feature of any kind
of mechanism suitable to explain the electromodulation of optical properties
at critical points.
Once we accept the premise that electroreflectanceresponds to the reduced
mass along the field direction, we can follow the analogy to cyclotron reso-
105
nance one step further. Impressed by the power of symmetry analysis, we

will put much faith in directional experiments and the anisotropic results
they deliver. We must realize, however, that their analysis is not as simple
as in cyclotron resonance for which the mass tensor-necessarily ellipsoidal
at an absolute extremum of the band separation-has positive components
in all directions, and for which the effective mass relates to the experimentally
observed resonance frequency in a simple manner.
Electroreflectance aspires to explore critical points in the full width of
the intrinsic band structure, where at saddle points the components of the
interband mass tensor can assume opposite signs in different directions.
The main difficulty, however, arises from the complicated and largely
unknown manner in which the interband mass in field direction enters the
observed reflectance modulation.
In contrast to the singular absorption peak of cyclotron resonance, electroreflectance spectra consist of an oscillatory response that in its line shape
and its spectral frequency depends upon a number of parameters. Aside
from the optical constants, direction and magnitude of the electric field,
as well as lifetime broadening as expressed in a temperature dependence of
line width and spectral frequency, play an important role.
Again using the Franz-Keldysh theory as a demonstration only, we point
to Eqs. (20), (21), and (25), which establish the combination of interband
mass, electric field, and lifetime broadening in the argument of the electrooptical functions F and G of the Airy type.
Beyond the assumption of a special mechanism, it is sufficient, however,
to refer to the bulk of experimental evidence. Among other facts, the strong
dependence of the line shape upon surface conditions suggests that interband
mass and effective modulating field enter the argument of the oscillatory
spectral function not separately, but in combination.
Consequently, the question arises as to how to separate this combination
of interband mass and field strength, and to retrieve the parameter indicative
of the topography of the interband energy surface at a critical point.
Two approaches to this problem have been tried in the past. One consists
of a one-to-one correlation of the experimental spectrum with a matching
member of a family of spectral functions A R / R (AF,o) derived from an
assumed mechanism such as the Franz-Keldysh effect4 or exciton
A second approach uses a systematic variation of the electric potential
across the external terminals of the system in order to produce a similar
variation of the effective modulating field.5*45*46
Both approaches are based on the expectation that a correlation between
electrical and optical modulation can be established and that quantitative
interpretation of the line shape in terms of a certain value of the electric
field F is meaningful. The results are not convincing in the sense that they
106
B. 0.SERAPHIN
preclude alternate assignments. At the present state of experiment and theory

it is fair to state that line shape interpretations as one-to-one correlations
of experimental and calculated spectra have failed to unambiguously link up.
In the following section, we will outline some of the reasons for this failure
and emphasize aspects more promising than quantitative line shape interpretation.
c. Problems of Quantitative Line Shape Interpretation
Insufficient knowledge of the effective field is probably the most important

cause for the failure of line shape interpretation in providing one, and only
one, answer. Unless the modulation swing AF around a point of operation F
is known, the relationship between electrical and optical modulation cannot
be established. In present sample configurations, the actual field appearing
across the active region is a complex nonlinear function of the modulation
impressed onto external terminals. Assumptions on the voltage distribution
must be made with caution, are valid under certain conditions only, and
require strict control of the experiment. The following restrictions are of
importance :
(1) In all types of surface barrier electroreflectance, the fraction of the
external modulation passed on to the surface potential is a complicated
function of the point of o p e r a t i ~ n . ~ ' In
. ' ~the
~ electrolytic version in particular, chemical processes at the semiconductor-electrolyte interface are
subject to hysteresis, rendering the surface potential dependent upon prepolarization history, modulation frequency and amplitude, and other
parameters to be controlled reliably in a narrow range of electrode potential
only.48 Simultaneous measurement of some reference property determining
the value of the surface potential is mandatory if quantitative interpretation
of the line shape is intended.
(2) The nonlinear character of electrooptical effects distorts the wave
form of the optical response with respect to the wave form of the electric
field. Unless square-wave modulation operates field on/field off, a lock-in
amplifier extracting the fundamental Fourier component monitors the
shape change as much as the amplitude of the response.
In addition, time lags caused by the capacity of the space charge region
can distort the wave form. As a rule, the optical response is seldom in phase
with the driving voltage, and phase lags vary among materials according to
their dielectric constants and, for the same material, over the spectral range
due to variations of the light penetration depth.
(3) The strong inhomogeneity of the electric field in the surface barrier
configuration distorts the line shape of a response that originates as a superB. 0.Seraphin, Surface Sci. 13, 136 (1969).
lE6
1.
ELECTROREFLECTANCE
107
position from widely varying values of the electric field. In the most drastic
consequence, the ratio of light penetration to space-charge extension determines the formal analysis to be used, as described in Section 3. The ratio
of the field modulation, varying locally, to the quiescent value on which it
is superimposed, determines further whether the derivative of the electrooptical function or its actual value is to be used. The superposition tends
to smear out the oscillations of the response near its main peak. The main
peak itself, of field-dependent spectral position if lifetime broadened, is
observed a t an energy that represents an average over the field values present
in the potential barrier.
(4)Using the Franz-Keldysh theory as a demonstration, it must be
realized that the independent variable of the electrooptical function is not
the electric field itself, but the ratio of the characteristic electrooptical
energy hR to the relaxation energy determining the lifetime broadening.
Since lifetime broadening is practically always present, the theoretical
functional relationship between field and line shape will be modified considerably.
It follows that the external modulation goes a long and complicated way
before it enters the theoretical description as an effective field that determines the optical response in a complex manner, modified by field inhomogeneities and lifetime broadening. Accordingly, line shapes can be discussed
on a qualitative basis at best.
More confidence can be placed in an analysis that follows variations of
the optical response over an extended range of the modulation conditions,
the sample orientation, or the polarization of the incident light. By focusing
on features independent of an accurate knowledge of the effective field, such
an analysis bypasses some of the difficulties discussed in this section. In the
following sections, attempts of this kind will be reviewed and suggestions will
be made for further improvement.
15. FUNDAMENTALS
OF A SYMMETRY ANALYSIS
In view of the difficulties of identifying structure in electroreflectance
from line shape interpretation, we will now investigate the possibility of
extracting signatures from a spectrum that are characteristic of the
symmetry features of the correlated critical point.
Adopting an approach first used by Phillips,25 we will treat the problem
on two successive levels. We will first consider the effect of an electric field
on a singular critical point, either located at the center of the Brillouin zone,
or in an off-center position, one of the many symmetry-equivalent branches.
Except for a few basic assumptions, we will not prescribe a particular
mechanism for the electrooptical effect on such a singular critical point.
108
B. 0.SERAPHIN
Anisotropies of the response are expected that are nontensorial in character

and are particularly pronounced at saddle points.
Summation of the effect over the equivalent valleys considerably reduces
the influence of the orientation of the electric field, causing a loss in angular
contrast.
This is not of critical concern, however, since such a summation refers
to the electrooptical effect in the dark. As we sample the perturbed state
of the dielectric tensor by reflecting polarized light off the crystal, we must
consider the polarization-dependent oscillator strength of the various valleys.
This results in tensorial anisotropies of the optical sampling procedure that
are superimposed upon the nontensorial anisotropies existent in the dark
without sampling. Between these two levels of diagnostic anisotropies,
nontensorial in the electrooptical effect and tensorial in the optical sampling,
we expect to retrieve symmetry information on the location and character of a
critical point.
a. Anisotropies of the Electrooptical Effect
We first discuss the electrooptical effect at a single, nondegenerate

critical point located at the end point of a vector ki in the Brillouin zone.
If ki = 0, the critical point occurs at the center of the Brillouin zone and
no further summation is required. If ki # 0, the special point under consideration is a member of a symmetry-degenerate set of equivalent points located
at the ends of a vector star produced by the lattice symmetry. The total
electrooptical effect at such an off-center multivalley critical point consists
of the sum of all the partial effects at each equivalent branch, one of which we
first discuss separately.
There is no need to specify a particular mechanism for this electrooptical
effect D i . Experiment and the basic nature of the effect suggest the following
three assumptions, on which the symmetry analysis will be built :
(1) Among other parameters, the effect depends upon magnitude and
direction of the electric field F, as well as upon the reduced interband effective
mass pi [Eq. (27)] in field direction.
In its first part, this assumption reflects experimental fact. Its second
part rests on the perturbation of translational symmetry by the electric field
along its direction. It further postulates that the topography of the interband
energy surface, as described by the interband mass, can be explored by
directional experiments.
(2) Again following experimental fact, it is assumed that the effect cannot
distinguish between equal fields of opposite direction.
(3) At a saddle point, the effect disappears along l / p i = 0. If this line or
surface separates sectors of opposite sign of the interband mass, it is assumed
109
that the electrooptical effect in the two sectors is described by two different
branches of a functional relation.
This assumption, probably disputable, is suggested by a minimum of the
band separation along a direction of positive mass, and a maximum along
a negative-mass direction-features entering the electrooptical effect on a
fundamental level.
These three assumptions permit us to draw a few conclusions based on
symmetry arguments. We will define our terms as we proceed.
We describe the field direction by two angles 0 and a, which are counted
from the z and x axes, respectively, of a Cartesian coordinate system attached
in its origin to the tip of the vector ki with the z axis parallel to k i . We can
then write the first assumption
Di = Di[F(8, @), pi(8,a),. . .].
(28)
If ki is aligned along a direction of high symmetry such as A or A, cylinder

symmetry around k, can be assumed and Eq. (28) depends upon 8 only.
Directions of lower symmetry such as I:do not necessarily have rotational
symmetry around ki and dependence upon both 8 and @ must be retained.
The second assumption requires
for all values of @.

Parabolic topography at the critical point dictates the same sign for the
interband mass in all directions.
At a saddle point, however, opposite signs are assumed in sections that
are separated by cones on which l/pi = 0.
Accepting the third assumption, we expect two different branches of an
electrooptical function in these sections of opposite sign. We can define
Di(8 = 0, n ;a) = DiL
Di(8 = ~ / 2@; I ) = D i T , ;
Di(8 = ~ / 2 0;2 ) = D i T 2 ,
(31)
which are assumed with the electric field aligned either along ki or in two
special directions in a plane perpendicular to ki. For a parabolic critical
point, all three functions can belong to the same branch. At a saddle point
of rotational symmetry, DiTl= D i T 2 = DiT.
We can similarly define piLand piTI,piT2.Three components of the interband-mass tensor are required along directions of lower symmetry such as X.
110
B. 0.SERAPHIN
For high-symmetry directions, we can write the ratio piT/piL= c. Its

magnitude at a saddle point characterizes the topography of the interband
energy surface by determining the angle under which the cone l/pi = 0
opens around the principal direction k, .
This cone angle, determined by the ratio c of transverse to longitudinal
interband mass introduces a major degree of freedom into the analysis.
Different angular line shapes of the electrooptical response obtain for the
twocasesc> 1 andc < 1.
Band models sometimes provide guidelines for this ratio along directions
of high symmetry. An analysis ab initio must forego these suggestions, however, and consider both possibilities separately.
At a multivalley critical point located off the center of the Brillouin zone,
the total response is the sum of the partial effects at the separate branches,
aligned differently with respect to the electric field. Bottka and Roessler
have developed the angular algebra of this superposition and have calculated
the spectral line shapes for the principal locations of critical points.
We will bypass this stage, where the sample is still in the dark, and immediately proceed to the optical sampling of a multivalley star for which an
electric field has broken the cubic symmetry of the dielectric function. We
will investigate the effect of an electric field on off-center critical points
along the three principal directions, A, A, and C.If the field direction coincides with one of these three principal directions, symmetry establishes
relations of equivalence among the various Dis, that are listed in Tables I,
11, and 111. They simply result from the equality of the electrooptical effect
for equal angles between F and ki,the two principal directions in a plane
perpendicular to ki for a Z point. The trajectories in question are illustrated in
Fig. 50.
These equivalence relations simply reflect the symmetry of the cubic
lattice.Although they are an essential part of the complete symmetryanalysis,
alone they do not reveal more than the structural features of the sample
crystal. Only in a combination with the superimposed anisotropies of the
sampling process do they deliver information on the location of a critical
point.
In listing the equivalent branches of critical points along the principal
directions, A, A, and Z, of a cubic lattice, we have used the same subscript
for points at ki and -ki,and only points on one side of the (001) plane are
noted. For the X direction, two transverse components DiT, and DiTl are
listed. Throughout the following discussion, we use the notation of Eqs.
(32).
1
[loo]
A
2
[OlO]
(324
3
[OOl]
1.
ELECTROREFLECTANCE
1
2
3
4
[Ill]
[iii]
'
2
3
4
5
6
[I101
[iio]
[I011
[ioi]
[Oll]
[oil]
111
[mi
[iii]
b. Selection Rules
The field-perturbed dielectric function described by the Di is now probed
by reflecting polarized light off the sample crystal. This results in tensorial
anisotropies that are superimposed on the nontensorial anisotropies of the
electrooptical effect.
Depending upon specific selection rules, the incident photon is either
accepted or rejected by a pair of initial and final states near a critical point.
Among other parameters such as the character of this initial and final state,
the selection rule depends upon the direction of the photon polarization
with respect to the principal direction of the critical point. Consequently,
at a multivalley point the photon can be accepted by some and rejected by
other equivalent branches, depending upon the relative alignment of the
particular star vector with the direction of polarization. In the unperturbed
state, the various directions average out to a polarization-independent
isotropy of the optical properties in a cubic crystal. Under the directional
perturbation of the electric field, however, the various branches are no
longer equivalent. Depending upon their orientation with respect to field
and polarization, they are sampled with different weights by the incident
photon, resulting in anisotropies of the reflectance response.
The effect Di at the ith branch therefore contributes to the total effect a
fraction jiDi, where f, represents an oscillator strength
j;
cos2 9 ,
(33)
depending upon the angle 19between an allowed direction and the polarization vector e. We register Eq. (33) as the first assumption on the sampling
process.
Relating this allowed direction to the star vector k i requires a second
and more restrictive assumption. In writing
fi
1 - ( e .ki)2,
(34)
112
B. 0.SERAPHIN
FIG.50. Three possible trajectories of the field vector F and the polarization vectors el, ,e, on
which a symmetry analysis can be based. The vector triplet is fixed in its relative position as the
trajectory coordinate [ varies through its range.
we identify the allowed direction with the direction perpendicular to the

star vector ki. This second assumption holds for transitions between states
of p symmetry and states of s symmetry, a case of common occurrence in
semiconductors.
As a third assumption-again most disputable-we request that the
selection rule Eq. (34) be independent of the presence and strength of the
electric field. This assumes the electric field to break the symmetry exclusively
on the level of the electrooptical effect, leaving the optical sampling process
unaffected. This assumption can be accepted on a first-order approximation
only. It must be modified in a more refined treatment.
Adding the partial contributions of the various branches, we now obtain
We will next investigate this expression for several trajectories of the

electric field F and the polarization vector e.
c. Trajectories of Field and Polarization
As an incomplete sample of numerous other possibilities, we follow

Ac2(F, e) along three trajectories of the field vector, defining components of
ELEMENTS
OF THE ELECTROOPTICAL
RESPONSEEQ. (35)
Critical
point
direction
TABLE I
FUNCTION
OF THE FIELDDIRECTION
ALONG TRAJECTORY
I (FIG. SO),
THE TRAJECTORY
COORDINATE
AS A
Equivalence for field direction
Oscillator strengths
(100)
D,
Dz
DFSCRIBED
BY
n,(l), p i ( [ )
(110)
DT
D,
DT
D3 = D ,
D,
D3
Di = 0
D,
AS
<
D2
D,
P2 = P3 =
n,
D2
P1 = P 2 =
D4 = D ,
n I = n2 = $ 1
nz = 1 - n3 = sin2 5
= -D3
D,
A
PI = 0
Ps
P4
+ cos 5 sin 5 )
r
rn
2;a
%m
D , = D , = DT,
D 3 = D4 = D ,
D,
D6
D1
--
D 2 -- D3
D,
-D6
D4 = 0
D,
D,
=
==
nl
Tz
-D3
D, = D, = 0
-D4
n3 =
n2
$1
n4 = $1
+ sint)
+ cos2 5)
ns = +( 1
+ 2 sin 5 cos 5 )
nb = + ( I
2sin5cos5)
a For critical points along the principal directions A, A, and Z, the center columns list equivalence relations for the Di and their derivatives aDi/d(
at the given directions of the electric field. The oscillator strengths ni([)and p i ( [ )for the two directions of polarization e, and ell are listed on the
right as a function of The notation expressed in Eqs. (32) is used.
r.
TABLE I1
ELEMENTS
RESPONSEEQ. (35) AS
FUNCTION
OF THE FIELD
DIRECTION
ALONG TRAJECTORY
I1 (FIG.50), AS DESCRIBED
BY
THE TRAJECTORY
COORUINATE
5
A
Critical
point
direction
D , = D2
D3
D,
D,'
D,
D,
D3
D,
D,
D , = D3
D ' --D ' -
-D3'
D,
D,
D3
D2
D,
D,
D,' = 0
D,' = D,' = -D4'
p , = p2
D,
D2
D3
D,
P3 =
=0
n , = n2 = f(l
D.'
D,' = D,'
Dz' = -D4
Oscillator strengths ni(5),pi(5)

(110)
(111)
(100)
D,
D3
D2
D,
D,'
D,
+ sin2[)
n3
= cosz 5
PI
P3 =
P2
P4 =
ar
0
n, = n 3 = cosz [ + 3 sin2 [
n2 =
+ sin2 5) + +J2 cos 5 sin 5
D,' = 0
= - D4'
D2'
+ sin2 5 ) - +Jzcos 5 sin

p, =o;
p2 = 1
n3 = +(I
D , = D 2 = D,,
D3
D4
D,
D,
D,
D I' -- -D 2 ' = 0
D,'
D5' = -D3'
-D6'
D,
D,
D2
D4
D,'
D6'
-z
DT*
DI
DT,
D5
D,
D,
P3
D , = D,
D, = D,
n, = 1;
*TI < T < T2
D,'
Dz' = 0
D 3' -- D '6 - - - D 4 ' =
n3 =
-D5'
fl6
n - n
P4
PS
= P6
n2 = sinz[
+ cosz 5 - 2 4 cos 5 sin 5)

- L.+(2 + cos2 5 + 2 J 2 cos 5 sin 5 )
-
&2
a For critical points along the principal directions A, A, and Z, the center columns list equivalence relations for the D , and their derivatives aD,/d(
at the given directions of the electric field. The oscillator strengths ni(5) and p i ( 5 ) for the two directions of polarization e, and el, are listed on the
right as a function of [. The notation of Eqs. (32) is used.
kl
T
-
TABLE 111
ELEMENTS
RESPONSEEQ. (35) AS
Critical
point
direction
FUNCTION
OF THE FIELD
DIRECTION
ALONG TRAJECTORY
111 (FIG.50),
THE TRAJECTORY
CCORDINATE
t
A
(loo)
D,
(1 10)
D , = D , = 0,
D,'
D,
D,'
DESCRIBED
BY
Oscillator strengths ni(5j. pi(<)
(111)
D, = D 2 = D,
AS
'Dl
D,'
D3
=
=
p 3 = sinZ(
D,
D: = 0
D,' = 0
+ cos25j
p , = p , = $1
D,
n1
- n,
+ sin2[)
= +(I
n3 = cos' 5
D , = D,
D , = D4
D,
D,= D,'
D2'
D,
D3
= -Di
D,
D,
D,'
D 4' -- D , ' =
DT,
D, = D,
D, = 0
- D '3 - -- D g '
D,
D,
D,
D4
D,
D,
D,
D2
D,
Dl
D , = D , = D,
*T,<T<Tz
+ cos' 5 - 2 4 cos 5 sin 5 )

p4 = 21 + cos2 5 + 2J2 cos 5 sin 5 )
n , = n 3 = cos2 < + +sin2 5
+ sin2 r + 2J2 cos 5 sin 5 )
n2 =
n4 = 21 + sinZ[ - 2 J Z c o s 5 s i n 5 )
p 2 = +(I
D,' = -D4'
DT*
D,' = D,' = 0
p , = 1;
= DT,
p3 =
D2 = D ,
D,
D,
D,'
D,'=D,'=
D,
+ f cos2 (
p , = p , = sin'
D,
D,= D, = 0
D,' = 0
D ' --D ' - - -D4'
D, = D,
rn
D, = 0
-D,'=
D,
p6
$(2
p4 = p s = &2
n,
p2
1;
Ev
r
8
2z
E
cos2 5
+ sin2 5 + 2 J z
+ sin2 5
r
m
c,
cos 5 sin 5)
2 x 2 cos 5 sin 5 )
n2 = sin2 5
-D~ n , = n , = ~ ( 2 + c o s 2 ~ - 2 J z c o s ~ s i n ~ )
,-- n ,-- 1,(2 + cosz 5 + 2 J z cos 5 sin 5 )
For critical points along the principal directions A, A, and E, the center columns list equivalence relations for the D, and their derivatives aDi/dg
at the given directions of the electric field. The oscillator strengths ni(5) and pi(<) for the two directions of polarization e, and e l l are listed on the
right as a function of 5. The notation of Eqs. (32) is used.
01
116
B. 0.SERAPHIN
FIG. 51. Cylindrical Ge sample geometry generating trajectory I1 upon rotation, with the
electric field oriented radially.
the polarization parallel and perpendicular to a preferred direction. The

three selected trajectories are of experimental significance and form a basic
set for the investigation of others. They are plotted in Fig. 50 as functions
of a trajectory coordinate t, together with the definition of parallel and
perpendicular components of the polarization vector. In the first two cases
these components are defined with respect to the axis of rotation generating
the trajectory, and in the third case with respect to the field direction.
Note that in the first two trajectories the sampling light is incident along
the field direction, whereas in the third case the field vector is perpendicular
to the direction of light incidence. The three selected trajectories therefore
correlate to an experimental configuration of particular simplicity. Trajectories I and I1 are realized in longitudinal electroreflectance from a sample
of cylinder symmetry (Fig. 51) rotated around [OOl] and [l lo], respectively.
Trajectory I11 represents transverse electroreflectance from a (110) surface.
For a location of the critical point along the three principal directions,
A, A, and Z, the angular functions fi" = p,(<) and if = ni(<)of the oscillator
strength for the parallel and perpendicular components of the incident
light are listed for the three trajectories in Tables I, 11, and 111. Together with
the symmetry-derived equivalence relations for the Di and their derivatives,
the line shape of AcZ(F,e)can qualitatively be synthesized along a given
trajectory and compared with experiment.
1.
(AR/R) x
117
ELECTROREFLECTANCE
103
D r u m rotation
180"
0'
-E
-3.'
<Ill>
FIG. 52. Electroreflectance response at the 2.1-eV peak of Ge upon rotation of the cylindrical
sample of Fig. 51 through a full turn. (After Fischer et
d . Symmetry Analysis of a Spectrum

In order to record an electroreflectance spectrum that can be symmetry
analyzed on the basis of the information contained in Tables I, 11, and 111,
the experimentalist must select his mode of operation in two ways.
He must first decide on the experimental configuration as described by
one of the three trajectories.
He must then-and this is the more important decision-select the experimental quantity to be recorded along the trajectory. A variety of parameters
or their combinations can be chosen. The size of the most prominent peak(s),
(100)
(Ill)
(110)
(111)
(100)
Field direction
FIG. 53. Spectral position of a 4.4:eV peak in Ge upon rotation of the cylindrical sample of
Fig. 51 through a full turn. (After Fischer er
J. E. Fischer, N. Bottka, and B. 0. Seraphin, Bull. Amer. Phys. SOC. 14, 415 (1969)
118
B. 0.SERAPHIN
its spectral position, its shift with increasing field, and the ratio of its size
in parallel versus its size in perpendicular polarization, are a few of the
possible signatures of an electroreflectance spectrum. Different signatures
bring out the angular anisotropies to a varying degree. Invariance to field
variations along the trajectory is required and no assumptions about the
reduced effective mass ratio must be necessary for the symmetry analysis.
As shown on a few examples in the next section, the proper choice of the
signature determines the success of the analysis.
In following the selected signature S(t) through the trajectory, traces
similar to the ones plotted in Figs. 52-54 are obtained. These traces
necessarily reflect the symmetry operations of the lattice. Beyond this trivial
requirement, however, the signature displays features representative of
location and type of the correlated critical point. Lattice symmetry can
require, for example, that the signature is polarization independent in
certain principal directions. The ratio of the peak size for the two directions
of polarization must then go through one as the field lines up with these
directions. How this value one is approached from either side of the trajectory,
however, i.e., whether the derivative is zero, positive, or negative, reflects
information beyond the requirements of lattice symmetry. Similarly, the
sign of the signature, additional extrema, and zero crossings between
symmetry points along the trajectory are of diagnostic value.
To retrieve this information, the signature along the trajectory must be
synthesized from Eq. (35) and Tables I, 11, and 111. We obtain a general
expression that contains the Di in an unspecified form
S(0 =
S[oi(t),f;.(t),
<I.
(36)
The experimental information is inserted into this expression at the p points

for which the signature or its derivative assume simple values along the
trajectory. All the trigonometrical functions assume numerical values at a
given point of the trajectory, and we obtain a set of equations in the Di and
their derivative with respect to l.
S(tJ = S[Di(tq), (aDi/at)l<,J,
4 = 192,.
. .,P .
(37)
This set of equations is underdetermined. We can derive from Eq. (37) a

number m of relations between the Di and their derivatives at directions of
high symmetry.
n (ti) n
=
[Di(tj)y
(a~i/at)l,,I,
j = 172,. . - m .
7
(38)
These relations, Eq. (38), must be compatible with the equivalence relations
listed in Table I, 11, and 111, for a location of the critical point along A, A, or
E.If the relations, Eq. (38), derived from experiment are consistent with one,
and only one, of the three principal directions, the analysis has resulted in an
119
(100)
(1 I I>
(I 10)
(Ill)
(100)
Field direction
FIG.54. The ratio AR,/ARll determined along trajectory I I for the two components of the
4.4-eV structure in Ge. Note the different angular pattern for the two Components, indicating
different symmetry features of the correlated critical points. (After Fischer er a/,"')
unambiguous identification of the structure generating the signature. If the

experimental results, Eq. (38), are compatible with more than one location,
we must select a different signature or vary the trajectory in order to remove
the ambiguity.
We demonstrate this symmetry analysis by a simple example. We select the
experimental configuration of trajectory I11 and record along it the ratio
ARJAR,, of the electroreflectance response for two orthogonal directions
of polarization. In this procedure the same electrooptical effect is sampled
in two different ways. The ratio of the two readings is largely invariant to the
factors that complicate ordinary line shape interpretation, such as field
variations along the trajectory. Compared to the spectral line shape itself,
the ratio signature is nearly invariant to variations of the surface conditions.
As shown in Fig. 54, it assumes a wide range of values as the field swings
through the trajectory, and its value one at points of high symmetry can be
clearly recognized.
We can compare the experimental trace with a signature synthesized on the
basis of Eq. (2), Eq. ( 3 3 , and Table 111. Accepting only the symmetry assumptions described above, we obtain three general expressions S,(t), S,,(t), and
S,(t) for the signature along the trajectory, if the correlated critical point
is located along A, A, or Z. For the electric field along directions (loo),
(1 1l ) , and (1 lo), as described by the values 0, v/2, and 4 2 of the trajectory
coordinate 5, these three angular functions reduce to the expressions listed
in Table IV. In a mutually exclusive manner, the presence and location of
t4
0
TABLE I V
VALUESOF THE SIGNATURE
A R , , / A R , ASSUMED
ALONG TRAJECTORY
Ill AT THREE
VALUESOF 5 FOR THREE
LOCATIONS
OF THE CORRELATED
CRITICAL
POINTALONG THREE
DIRECTIONS'
Values of
V
2
1
H
-
z
~-
~~
~~~
The angle between two directions ( I I I ) is v , and cylindrical symmetry of the interband mass tensor is assumed for reasons of simplicity, even
for the Z point.
a
1.
ELECTROREFLECTANCE
121
value one of the signature classifies the critical point, unless degeneracies
of the electrooptical function cause accidental values of one in addition to
the symmetry points.
In this example the signature is discussed on a very simple basis. More
information can be obtained by evaluating the derivative of the signature
along the trajectory, using the relations between the derivatives of the
electrooptical function D along high-symmetry directions.I8*
16. SIGNATURES
SPECTRA
In this final section experimental aspects of the analysis are discussed.
The anisotropies on which the symmetry analysis is based stand out more or
less clearly along the trajectory, depending upon the proper choice of an
experimental signature. The factors that render spectral line shape interpretation useless also influence angular sweeps, but to a varying degree. Useful
signatures display symmetry-induced anisotropies even in the presence of
severe field variations along the trajectory, and no assumptions about the
interband mass ratio are required. We will inspect several signatures with
respect to their merits for a symmetry analysis.
Q.
Signature of the Size
The size A R / R of an electroreflectance peak is the fundamental building

block of any analysis. Unfortunately, this size is drastically affected by
field variations along the trajectory, rendering it useless as a signature.
The anisotropies induced by field variations can completely hide symmetryinduced features.
Results obtained by Fischer and co-worker~~
on a cylindrical Ge sample
(Fig. 51) demonstrate this point. The anisotropies shown in Fig. 52 are
observed as the 2.1-eV peak is recorded along trajectory 11. The drastic
angular variations of the size are not caused by interband effects exclusively,
however. Boddy and Brattain showed previously that the quiescent surface
potential of etched Ge surfaces of various orientation grows in the sequence
(loo), (1 lo), (1 11). The size variations plotted in Fig. 52 therefore reflect
the different slope of the master curve of the surface potential in the different crystalline directions rather than symmetry-induced anisotropies of the
electrooptical effect. This dominance of surface effects over interband
effects suggests rejection of the size signature for use in the symmetry
analysis.
Results such as those shown in Fig. 52 show that caution is necessary in
an interpretation of spectra recorded on samples of different orientation,
N. Bottka and J. E. Fischer, Phys. Rea. B3, 2514 (1971).
122
B. 0.SERAPHIN
even if it is etched in the same process. It is very likely that variations considered indicative of orientation effects are in reality due to surface effects.
b. Signature o j the Field-Induced Spectral Shift
The field-effect method permits modulation around variable values of an

average electric field in the surface. Most structure responds to such a variation by shifting in spectral position-some parts of a spectrum to smaller,
other parts to larger photon energies, spin-orbit split partners always in the
same direction. This field shift, typically in the order of 5 to 10 meV in the
field-effect technique, establishes a valuable experimental signature. The
superposition from equivalent branches of an off-center critical point of
saddle-point type averages out most of the anisotropies. * The position of
the oscillatory pattern with respect to the edge survives as a discriminatory
feature, however. Oscillations above, below, or on both sides of the edge
correlate to type and location of a critical point with respect to a given
field direction. Extracting this discriminating feature from an experimental
spectrum on the basis of the line shape is unreliable. However, the field
shift clearly separates the first main peak of the oscillation above the edge
from its counterpart below the edge, since they shift into opposite directions
as the average field is increased, the oscillatory pattern always stretching
away from the edge for such an increase. As an effect that correlates a
direction of change in the modulation to a direction of shift in the response,
the field shift is less sensitive to the point of operation or an integration
over the field inhomogeneities of the potential barrier.
c . Signature of the Spectral Position
As electric field and incident light beam vary their directions along the
trajectory, the contributions from the different branches of the star are
sampled with varying weights. Along the trajectory the total effect therefore
varies in fractional composition. As a consequence, the maximum of the
response occurs at different spectral positions as the trajectory is scanned.
This spectral variation is considerably larger than the spectral shift induced
at one particular photon energy by an increase in the field. As shown in
Fig. 53, the spectral position of the 4.4-eV peak recorded around the Ge
cylinder of Fig. 51, displays a characteristic angular pattern with an amplitude
of over 50 meV.
The experiment can be simulated using the Franz-Keldysh theory for the
electrooptical effect.63 The theoretical pattern, shown in Fig. 55 for two
hypothetical critical points along the directions A and A, resembles the
experimental trace in appearance and size. If variations of the electric field
are introduced into the calculation, the two patterns of Fig. 55 expand or
contract in a vertical direction, but inside wide limits do not wipe out the
123
0"
Eg
(100)
(111)
90"
l
(110)
100'
I
<Ill>
(~00)
Field direction
-I 0
FIG.55. Spectral position of the electroreflectance response of two hypothetical critical points
located along directions A and A in the Brillouin zone, as calculated from Franz-Keldysh
theory. (After Bottka and S e r a ~ h i n . ~ ~ )
characteristic shape. The discriminatory value of the spectral-position signature seems considerably more invariant to field variations than the size
signature.
Assumptions about the ratio of longitudinal to transverse interband mass
are necessary, however, to make Fig. 55 unambiguous. Inversion of this
ratio c transforms the A trace into the A trace and vice versa.
The signature of the spectral position is therefore of value in cases where
reliable information of this mass ratio is available. If an analysis on a strictly
ab initio basis is required, we must turn to the ratio signature discussed in the
next paragraphs.
d . Signature o j the Polarization Ratio

A signature of sufficient invariance to changes in the modulating field
as well as the mass ratio consists of the ratio A R J A R , , of the response to light
of the two polarizations e, and e,, (Fig. 50). The invariance results from the
fact that modulating field and mass ratio both enter on the level of the electrooptical effect. The situation that exists in the dark and is unperturbed by
the subsequent sampling procedure is then probed in two different ways and
the ratio of the two results is plotted along the trajectory. In our first-order
approximation that samples the nonequivalence of the various branches
124
B. 0.SERAPHIN
with a field-independent selection rule, this procedure should result in the

desired invariance.
We can again use the Franz-Keldysh theory as the vehicle of the electrooptical effect in order to prove this point. Drastic variations of the electric
field along the angular trajectory do not affect a characteristic angular
pattern of the ratio that discriminates strongly among various locations of
the assumed critical point. All parts of a structure, main peak and satellites,
are similar in appearance.88
Experimental results for the ratio signature are plotted in Fig. 54. On
the Ge cylinder of Fig. 5 1, the spectral line shape of the response near 4.5 eV
was recorded for the two directions of polarization of the incident light shown
under I1 in Fig. 50. The ratio of the peak sizes obtained for two positions
of the polarizer was then formed for the two parts of the u p d o w n sequence
of which the response consists in this spectral range. Note that the down
part of the structure near 4.44eV responds in an angular pattern that is
characteristically different from the angular line shape of the ratio for the
up part.*
The striking difference in the symmetry-generated angular line shape of
the two parts of the structure suggests their correlation to two separate
critical points with different symmetry character. This result, based on
symmetry arguments of wide validity, provides an experimental confirmation
of a basic theoretical concept of long standing. Band models for semiconductors of diamond and zinc blende structure assign the strong ultraviolet reflectance peak common to all these materials to a near-degeneracy
of two critical points of different symmetry character and location. The
strongly dissimilar angular pattern of the two components of the 4.5-eV
structure in Ge proves that they indeed relate to two separate contributions
of different symmetry character.
The ratio signature is superior to the other signatures because it delivers
symmetry information invariant to the influence of the electric field on
selection rules. This simply follows from the lower symmetry of the crystal
in the presence of the field. Transitions allowed in the unperturbed system
are still allowed under the field. However, previously forbidden transitions
may be allowed in the field-perturbed system. Switching on the field therefore
moves the sampling process into the direction of decreased selectivity.
Extreme lowering of the symmetry-occurring for fields in low-symmetry
directions-can result in a complete breakdown of the selection rules.
Sampling photons of parallel and perpendicular polarization are then
accepted with equal probability and fi = f;.
Defining a selectivity parameter E, we can write
fi 11 J(E)
= fill
-fd,
(39)
125
where E = 0 corresponds to the unperturbed crystal of high selectivity, and

E = 1 represents the complete breakdown of selection rules.
Writing the basic element of the ratio signature as
i
and introducing L(E)

from Eq. (39), it is apparent that the resulting equation
for E,
2 (L - fi ! ' ) D i=
i
(fi'
E
I
- J")Di,
(41)
can be satisfied only for
c(h' - fi")Di = 0
I
and
& =
1.
(43)
This means that symmetry points at which S = 1 are not affected by an

increase in E [Eq. (42)]. The signature between the symmetry points deflates
without crossing the line S = 1. The angular pattern is simply squashed in
the vertical direction, as the symmetry-breaking effect of the electric field
increases. For E = 1, the angular line shape shrinks into the line S = 1 for
the whole length of the trajectory.
The deflation of the angular pattern toward S = I without crossing this
line before E = 1 is reached, has a significant consequence. It means that
the symmetry information derived from the angular line shape is not influenced by the symmetry-breaking effect of the electric field on the selection
rule. No new structural features can be added as the symmetry is lowered.
Consequently, a symmetry analysis of the ratio signature can ignore the
influence of the electric field on the selection rules-bypassing analytical
difficulties of considerable complexity.
VII. Addendum
Electroreflectance (ER) has continued to expand rapidly during the I2
months since the manuscript of the preceding review was submitted in the
summer of 1969. The following addendum updates the review to August
1970 and includes papers presented at the International Semiconductor
Conference in Cambridge, Massachusetts, August 17-21, 1970.
During an initial period, much attention was focused on effects, on novel
applications, and on new materials. By using ER as a tool rather than as a
phenomenon in its own right, the existence and spectral position of structure
126
B. 0. SERAPHIN
was interpreted in terms of critical points. Qualitative measurements were

sufficient for this purpose.
Much of last years work still contributes on this level. However, the
most successful contributions probe the field in depth and approach solutions to problems that were still unsolved a year ago. Their objective points
to ER itself, to a quantitative understanding of the basic mechanisms as
expressed in the line shapes of the spectra. If successful, a detailed and
quantitative interpretation of the line shape will lead first to an unambiguous
identification of the critical-point spectrum, and second to a better understanding of the electrooptical process as well as of the interaction of the
electrons with each other and with the lattice.
Progress has been most gratifying in this respect. The basic factors determining the line shape of ER structure have been investigated theoretically.
Control of the experimental conditions has improved considerably. Contributions in both areas have moved the analysis a step further toward quantitative line-shape interpretation, to a point where the comparison of theory and
experiment is more justified than the complexity of the problem had led us
to suspect a year ago. Consequently, we will direct our attention to this
important aspect of the recent developments first.
17. ANALYSIS
SPECTRA
The preceding review pointed in at least four areas to problems that complicate quantitative line-shape interpretation. Progress has been made in all
of them, and we will discuss the results in sequence.
a. Control and Determination of Surface Parameters
A comparison of theory with experiments that use space-change modulation rests on the accurate determination of the surface field. In previous
work, conclusions on this key parameter were derived from external parameters such as the dc bias, or from field effect based on assumptions about the
surface mobility. Such determinations are limited in accuracy. For both
versions of space-charge ER, Aspnes and Frova overcome this limitation by
measuring two surface parameters simultaneously. This gives accurate
values for the surface field and proves previous determinations to be incomplete, as suspected.
A combination of Hall and field effect is used for the field-effect sandwich.* Continuous control proves a shift of the quiescent surface potential
that the dc bias component of the modulation causes through a net storage
of charge in the surface states. A variable modulation swing designed to be
clamped at one end of the flat-band position, will probably not do so unless
A. Frova and D. E. Aspnes, Phys. Rev. 182,795 (1969).
127
I X
II
4
CI
0.5
1.5
F, ( l O 5 V / c m )
FIG.56. Magnitude of ER peaks I, 11, and 111 of the fundamental response of Ge versus surface field F,. The dashed curves are calculated from the theory that neglects exciton and collision-broadening effects. The ordinates of all theoretical curves have been multiplied by the
same normalization factor, which equates the theoretical crossover magnitude with the experimental value. (After Frova and Aspnes.Ia9)
it is continuously checked by surface control. Without such control, the

frequently assumed operation between field-off and field-on is an empty
claim.
Little difference is observed between sine-wave and square-wave modulation. It must not be concluded, however, that the waveform of the modulation
is of no significance. The nonuniformity of the field profile simply overrides
other line-shape effects. A similar situation holds with respect to exciton
effects. as we will see later.
128
B. 0.SERAPHIN
In a quantitative study of the electrolyte technique, Aspnes and Frova

use a combination of surface capacitance and photovoltage for the accurate
determination of the surface field. A wealth of results on the electrochemistry
of the Ge-electrolyte interface is obtained. With respect to line-shape interpretation, the authors confirm Gobrechts4 preliminary finding that the
external dc bias bears no simple relationship to the space-charge parameters
and cannot be used for their control or determination. Modulation swings
in excess of 300 mV and/or operation in the cathodic range disrupt the
chemical balance at the interface and generate surface states that complicate
the correlation between ARIR and the driving voltage. As for the sandwich,
the modulation cannot be expected to stay clamped to the flat-band position
under variable dc bias operation.
The study clearly outlines the conditions that must be met for the quantitative interpretation of an electrolytic ER spectrum. Unfortunately, they disqualify most, if not all, previous studies. Their interpretation can state the
existence of structure in a certain spectral range, but cannot make any claim
on the significance of its particular line shape.
b. Nonuniformity of the Field P r o j l e
Knowing the surface field accurately, Aspnes and Frova find their nonuniform perturbation theory15 in good agreement with the ER spectra
taken under quantitative surface control. The three peaks of the fundamental
response of Ge follow the surface field as shown in Fig. 56. The theoretical
curves are based on one-electron theory and are normalized with respect to
the proper size crossover of peaks I1 and 111. Hence the agreement in size
of the response is arbitrary-a factor of significance, as will be shown later.
A nonuniform perturbation profile was used in several other investigations.
Aspnes 19192 determines the surface field during photoreflectance (PR) runs
at the Ge-electrolyte interface,and finds the PR response compatible with the
inhomogeneous perturbation theory of ER. Schmidt 9 3 formulates the
approximation more generally and derives some useful analytic expressions.
Del Sole94calculates the motion of electrons and holes in a localized field,
eliminating the assumption of a uniform Franz-Keldysh contribution in
every point of the nonuniform field profile. Evangelisti and Frova analyze
ER spectra of Ge taken in parallel and crossed magnetic fields by accounting
19*
Iq4
19
D. E. Aspnes and A. Frova, Phys. Rev. BZ,1037 (1970).

D. E. Aspnes, Bull. Arne?. Phys. SOC. 15,288 (1970).
D. E. Aspnes, Solid State Commun. 8,267 (1970).
E. Schmidt, J . Appl. Phys. 40,2671 (1969).
A. Del Sole, Ph.D. thesis, Univ. of Rome (1970), unpublished.
F. Evangelisti and A. Frova, Phys. Status Solidi 33. 623 (1969).
129
uB: 6 Accurnulotion
I02
103
lo5
104
Electric field
I 06
F,
FIG.57. The parameter R , indicating the nonuniformity of the field profile, versus magnitude
of surface electric field F, for four values of impurity concentration for Ge at 300K. Except
for the uB = 6 curve, only the depletion region is shown. Curves can be used for n- or p-type
material. Points A-C indicate the fields above which it is better to use a sample with the next
higher doping level shown. (After Koeppen and Handler.19')
for the nonuniform profile of the electric field. B ~ c k m a n can

' ~ ~interpret
his ellipsometric study of the electrolytic ER of Ge by considering the
nonuniformity of the optical properties in the reflecting surface.
how, by proper choice of the
Handler and c o - ~ o r k e r s '9~8 ~demonstrate
~'
doping level and operation in the depletion region, a given surface field
can be maintained more uniformly than in an intrinsic sample. Based on a
criterion for the validity of the uniform-field approximation, the optimum
doping level uB for a given surface field can be taken from Fig. 57. Note that
for optimum doping less inhomogeneity is encountered than for the intrinsic
sample. A comparison of accumulation and depletion for the case uB = 6
explains the familiar fact that ER spectra are so different on either side of the
flat-band position. In a subsequent experimental study, Handler and coworker~
prove
~ ~ their
~
point by observing as many as 11 half oscillations in
the fundamental ER response of a Ge sample of optimal doping level.
c. Lifetime Broadening oj'ER Spectra
In a transverse configuration (TER), Forman and c o - w o r k e r ~ demon'~~

strate the influence of collision broadening on the line shape observed in
196
19
19'
L99
A. B. Buckman, J . Opt. SOC. Amer. 60,416 (1970).

S. Koeppen and P. Handler, Phys. Rev. 187, 1182 (1969).
P. Handler, S. Jasperson, and S. Koeppen, Phys. Rev. Len. 23, 1387 (1969).
R. A. Forman, D. E. Aspnes, and M. Cardona, J . Phys. Chem. Solids 31,227 (1970).
130
B . 0.SERAPHIN
FIG.58. Fit of the evolution with reduced field E ( =F/F,) of the peak-to-peak amplitude of
GaAs spectra to the theoretical curve based on the electrooptical functions F(x, r)and G(x, r),
with a Lorentzian factor I? = 21 meV entering the field unit F,, = 10.9 kV/cm. (After Forman
et al.''')
high-resistivity Si and GaAs. The uniform transverse field is assumed to

dominate any space-charge field normal to the surface, so that lifetimebroadening effects emerge more clearly. The collision-broadened oneelectron theory satisfactorily reproduces peak location and separation as well
as peak-to-peak amplitude, as shown for the latter in Fig. 58. The fit is
obtained for a field normalization F, corresponding to a Lorentzian factor
r = 21 meV at 77K-in agreement with the 30 meV obtained at 200K.''
This effective broadening explains why exciton effects with a binding energy
of 3.3 meV in GaAs can be seen at liquid-helium temperature only."' At
77"K, the line shape is determined mainly by interband effects, and the use
of the one-electron approximation is justified.
It follows that for all but very low-temperature measurements, extremely
high fields, or wide-gap materials, the characteristic electrooptical energy
hQ, Eq. (21ktypically of the order of 10 meV-is smaller than the relaxation
*O0
J. L. Shay and R. E. Nahory, Solid State Commun. 7,945 (1969)
131
energy r,for higher interband transitions in particular. For this case, Aspnes
and Rowe201 find an asymptotic expression for the Airy function convolution of the zero-field dielectric function [Eq. (20)]
from which the dominant features of the field-dependent change in the

dielectric function of a crystal can be derived in terms of its one-electron
band structure E,,(k). Experimental features such as the rapid damping
of the oscillations are accurately reproduced, so that a straightforward
comparison between experiment and band structure calculation can be
expected on the basis of the approximation, Eq. (44), particularly for higher
interband transitions. Experimental criteria for the application of the
asymptotic expression follow from (1) the invariance of the line shape with
field, and (2) the scaling of the observed size of the response with F 2 .
d. Excitonic Eflects
In its simplest form, the one-electron approximation cannot reproduce
experimental ER line shapes. A popular conclusion once blamed the missing
Coulomb interaction for the discrepancies. At that time such a conclusion
could not conflict with quantitative comparison, because an electrooptical
theory including exciton effects was only slowly emerging.
Considerable progress has been made in this respect, which is reported in
another chapter of this volume.6 We review here the work that discusses the
line-shape effects of Coulomb interaction and compares the results with
spectra taken under improved conditions.
Inclusion of the Coulomb interaction in all the various theoretical approaches indeed predicts drastic effects on the line shape. Some common
features evolve : Excitonic ER is much larger than in the one-electron approximation. It is particularly enhanced near and below the gap, and the oscillations are damped and of wider swing. In common with nonuniformity and
lifetime broadening, excitonic effects on the line-shape are so strong that
critical points can never be uniquely identified without some information
on the strength of the exciton interaction.
This is shown explicitly by the work of Rowe and Aspnes202 who used a
Slater-Koster contact i n t e r a ~ t i o n ~as
.~~
an~ approximation for the
Coulomb potential. Although it is a noticeably poor approach for the hydrogenic bound states, this approximation works well for the electron-hole
201
02
03
204
D. E. Aspnes and J. E. Rowe, Solid State Commun. 8, 1145 (1970).

J. E. Rowe and D.E.Aspnes, Phys. Rev. Lett. 25, 162 (1970).
B. Velicky and J. Sak, Phys. Status Soiidi 16, 147 (1966).
J. Hermanson, Phys. Rev. 166,893 (1968).
132
B. 0.SERAPHIN
continuum states. Since lifetime broadening usually exceeds exciton binding

energies, the detailed shape of the electron-hole potential is unimportant,
and the Slater-Koster approach is justified.
In the framework of the effective-massapproximation, Rowe and Aspnes
can show that the electric-field modulation Ac0 of the dielectric function in
one-electron description changes to
A&= (1 g&O)- AEO,
(45)
where g characterizes the strength of the interaction. As g advances the phase
of
by an increments, the one-electron line shapes are mixed as shown in
Fig. 59. An M o line shape progresses toward M 2 as the interaction grows in a
manner that is qualitatively different from the mixing due to inhomogeneous
fields,15abut is not less destructive from the viewpoint of a line-shape interpretation that ignores the actual interaction strength. The results can be
fitted well to ER data taken by Nishino and HamakawaZo5on a Ge heterojunction surface barrier at 24K. Over the entire range of the experiment, the
data are probably affected strongly by the field inhomogeneity. However,
Rowe and Aspnes use the small range of field strengths only, for which the
doping of Nishino and Hamakawas sample reduces the inhomogeneity,
according to Handlers criterion.
A successful fit to the recent spectra taken by Handler and co-workers
under improved condition^'^^*^^^ is obtained on the basis of a numerical
calculation of the final-state electron-hole interaction. Dow and coworkers,206as well as Weinstein and c o - w o r k e r ~compare
, ~ ~ ~ their results,
valid in the uniform-field approximation as well as the one-electron theory,
with Handlers experimental trace shown in Fig. 60.
e. Quantitative Line Shape Interpretation
The recent work can be condensed into two conclusions: First, the surface
field as the basis of a comparison of theory and experiment can accurately be
determined by proper experimentation. Second, three factors-field inhomogeneity, lifetime broadening, and the admixture of excitonic effects to the
one-electron mechanism-affect the line shape drastically. The individual
fraction of their interference must be known before conclusions can be
drawn from a given line shape.
Our ultimate concern is the identification of critical points and answers
to such questions as Exciton or Franz-Keldysh effect?208 However,
before differences indicative of the critical-point character or the basic
T. Nishino and Y. Hamakawa, J . Phys. Soc. Japan 26,403 (1969).

J. D. Dow, B. Y. Lao, and F. C. Weinstein, Proc. 10th Int. ConJ Phys. Semicond., Cambridge,
Massachusetts, 1970, p. 183. USAEC Div. Tech. Information, Oak Ridge, 1970 (availableas
CONF-700801 from Nat. Tech. Information Serv., Springfield, Virginia 22151).
07 F. C. Weinstein, J. D. Dow, and B. Y. Lao, Phys. Status Solidi 43, KlOS (1971).
2 0 8 P. Handler, Proc. IX Int. Conf: Phys. Semicond., Moscow, 1968, p. 380. Nauka, Leningrad,
1968.
205
lo6
1.
ELECTROREFLECTANCE
133
FIG. 59. The progression of Franz-Keldysh line shapes for

phase-angle increments, calculated for a uniform electric field oriented in a positive-mass direction. The lifetime broadening
energy r for these curves is taken equal to h0. For a field oriented in a negative-mass direction.
the energy axis is reversed and the sequence relabeled (from top) M , , M,, and M , . (After
Rowe and Aspnes.)
mechanism can clearly emerge from the line shape, they must not be masked
by the dominating presence of other line-shape factors. In the past, much
controversy simply reflected our ignorance of these factors at that time.
In evaluating the relative strength of the line-shape factors with
respect to each other, we follow the conclusions of Aspnes and coWOrkerS.190,201.202,209
(1) If the nonuniform perturbation is included in the theory, it suppresses
the differences between one-electron and excitonic approximation, i.e., the
inhomogeneity determines the line shape irrespective of the basic mechanism.
This explains the good agreement of some spectra with inhomogeneous oneelectron theory-an inconclusive result if it is based on the qualitative
features of the line shape.
09
D. E. Aspnes and J. E. Rowe, Proc. 10th lni. ConJ Phys. Semicond., Cambridge, Massachusetts,
1970, p. 422. USAEC Div. Tech. Information, Oak Ridge, 1970 (available as CONF-700801
from Nat. Tech. Information Serv., Springfield, Virginia 221 51).
134
B. 0.SERAPHIN
-0.40L
0.70
0.80
0.90
1.10
1.20
Photon energy (eV)
FIG.60.Fit of the fundamental response of Ge'97.'98

to one-electron theory and to a theory
including exciton effects. (-) experiment; (---) theory (excitons): (. . .) theory (no excitons).
and Weinstein et a[.''')
(After Dow et
(2) Although the qualitative features of a line shape produced by a nonuniform field are insensitive to the inclusion of the Coulomb interaction, the
magnitude of the response is not. Calculating this magnitude for the known
surface field of their experiment on the basis of a continuum exciton theory,
Aspnes and F ~ o v a predict
' ~ ~ a fundamental response of Ge several times
larger than the one-electron result. The comparison with experiment-now
possible on a quantitative basis-learly
favors the excitonic theory with
respect to size of the response-a result of considerable significance.
(3) The effect of the lifetime-broadening correction on the Coulomb interaction can be considered in the framework of the approximate treatment cited
below.209 A general theory that includes both effects has not yet been
developed to a stage where comparison with experiment is meaningful.
If r is larger than the exciton binding energy, however, interband effects
will dominate, and the one-electron theory is a good approximation.
We conclude that the line shape cannot discriminate among various
mechanisms, let alone the characteristics of critical points, unless the masking
hw
135
(ev)
FIG.61. Line shape of the fundamental response of Ge, as calculated on the basis ofa simplified
convolution integral including Slater-Koster exciton interaction (after Aspnes and FrovaZu9),
with experimental data dots (after Nishino and Hamakawazo5).
interference of nonuniformity and/or lifetime broadening either is negligible

or is properly taken into account.
Aspnes and RoweZo9demonstrate proper procedure in a line-shape analysis of the E l transition of Ge. Lifetime broadening is considered by using the
simplified convolution integral, Eq. (44).Exciton effects are treated approximately using the Slater-Koster interaction, Eq. (45). A nonuniformity cor~
entering Eq. (45).
rection according to Eq. (1 7) could be added to A E before
This would then consider all the principal factors determining the line shape,
the result depending upon their relative weight.
By variation of r and the band structure parameters entering E&) in
the calculated line shape is fitted to the spectra of Nishino and
Eq. (a),
Hamakawa. The fit shown in Fig. 61 is generated by a pair of critical
points of type M,, and M I , separated in energy by an amount less than the
lifetime broadening and located along the A direction in a range of nearly
constant interband energy extending over a large fraction of the Brillouin
zone. Besides proving the potential of a properly executed lineshape analysis,
the result resolves difficulties of interpretation discussed in Section 11.c.
f. Symmetry Analysis of ER Spectra

Quantitative interpretation of the line shape requires surface measurements
of considerable difficulty and complexity. Future work must either take on
136
B. 0.SERAPHIN
this additional complication or turn to approaches that rely on symmetry

arguments rather than on line-shape interpretation.
Bottkal" has expanded the basis of the symmetry analysis given in
Section 15d by including field effects on the transition matrix elements
and describing the conditions under which they can be distinguished from
interband effects.
Forman and c o - ~ o r k e r s investigate
'~~
the E , and E , structures taken in
TER in Si and GaAs from the viewpoint of symmetry analysis. N o polarization dependence is observed, in agreement with the assignment of these
structures. Unfortunately, the field was not applied in directions for which the
optical selection rule predicts a polarization effect. Near the 3.5-eV peak in
Si, polarization effects suggest a minimum of two different symmetry characters, but the evidence falls short of a definite identification.
The Ge spectrum is searched in TER for polarization effects by Fischer
and co-workers.211--213 The results are symmetry compatible with the previous assignments. Deviations are interpreted in terms of field effects on
the matrix elements.
If we evaluate the situation at this point, it seems obvious that matrix
element modulation and field effects of secondary order mask the symmetry
information. It is because of this complication of the initial approach that
the data reported so far, however promising, fall short of realizing the full
potential of a symmetry-based analysis. Truly unambiguous identification
will require sets of data that are improved over existing results in the following three aspects.
(1) Signatures must respond more strongly to variations of the trajectory
parameter, i.e., the direction of field or polarization. Polarization effects
in the order of 10% can be generated by causes unrelated to symmetry.
This is particularly true for weak responses such as E,' or Eo + Ao, in
relating the polarization dependence (or its absence) of a weak structure
and a strong one, or in evaluating polarization effects in satellites.
(2) As function of the field direction, signatures must be recorded for as
many entries of the symmetry table as possible. No conclusions should be
drawn from a single field direction, especially if no polarization dependence is
predicted for this direction. Several trajectories must be investigated in a
systematic manner, and the results must be consistent with respect to symmetry character and interband-mass ratio. It is against the objective of the
210
211
I2
213
N. Bottka, Ph.D. thesis, Tech. Univ. of Berlin, 1970 (unpublished).

J. E. Fischer, D. S. Kyser, and N. Bottka, Solid State Commun. 7 , 1821 (1969).
J. E. Fischer and N. Bottka, Phys. Rev. Lett. 24, 1292 (1970).

J. E. Fischer, Proc. 10th Int. Con$ Phys. Semicond., Cambridge, Massachusetts, 1970, p. 427.
USAEC Div. Tech. Information, Oak Ridge, 1970 (available as CONF-700801 from Nat.
Tech. Information Serv., Springfield,Virginia 22151).
137
projected symmetry analysis to explain inconsistencies by field effects of

second order.
(3) Experimental configurations should be designed in which such
secondary effects can be bypassed, kept constant along the trajectory, or
evaluated in their effect on the symmetry character so that the symmetry
information emerges unmasked.
A novel way of identification is reported by Glosser and co-workers.2'4-217
In response to variations of the dc bias, a spectral shift of some peaks in the
spectrum of InSb is observed that results from band-filling effects in the
space-charge layer. In the manner of the Burstein-Moss effect, the existence
and direction of this spectral shift distinguishes among transitions that end
at the Fermi level, start from it, or bridge it. By evaluating the shifts of peaks
A/A' and BIB' shown in Fig. 62, position and splitting of the higher conduction bands Ts and r7can be determined. A similar effect has been found in
the ER spectrum of GaSb.218
g . Linear Electrooptical Efects
Linear electrooptical effects can be expected in crystals for which the

point group does not contain the inversion. A response in the fundamental
frequency for symmetric modulation around the zero line indicates their
presence, contrasting effects even in the electric field such as Franz-Keldysh
effect and exciton quenching.
Two harmonics of the reflectance modulation, correlated to a linear and
in
a quadratic Stark effect of excitons, were first observed by Mohler219*220
the TER of CuCl. The observations were confirmed by Daunois et
The linear effect that is due to a field-induced splitting of the valence bands
is superimposed on the regular even effects. Mohler suggests a method to
separate the two components in the analysis of the line shape.
On a phenomenological basis, Kyser and Rehn222derive the linear effect
in noncentrosymmetric crystals that is due to piezoelectrically induced
piezoreflectance. Depending upon the direction of field and polarization, the effect occurs in logitudinal and transverse geometries alike. The
I4
I5
16
I7
"*
*I9
''O
'"
"'
R. Glosser and B. 0. Seraphin. Z. Natur/orsch. Ua, 1320 (1969).

R. Glosser and B. 0. Seraphin, Phys. Rev. 187, 1021 (1969).
R. Glosser and B. 0.Seraphin, Bull. h e r . Phys. Soc. 15,288 (1970).
R. Glosser, J. E. Fischer. and B. 0. Seraphin. Phys. Rev. B1,1607 (1970).
H. Piller, S. A. Khan, and B. J. Parsons, Bull. Amer. Phys. Soc. 15.288 (1970).
E. Mohler, Phys. Status Solidi 29, KSS (1968).
E. Mohler. Phys. Status Solidi 38, 81 (1970).
A. Daunois, J. L. Deiss, and S. Nikitine, C. R. Acad. Sci. Paris 268, 977 (1969).
D. S. Kyser and V. Rehn, Solid State Commun. 8, 1437 (1970); Bull. Amer. Phys. Soc. 16, 373
(1 971).
138
B. 0.SERAPHIN
,
eV
337
375
R0
-a
[L
QII
-I
I96t
I
20
2 441
I
25
30
Photon energy (eV1

(0)
-I
35
-2
Wave vector
(bl
FIG. 62. (a) ER spectrum of an InSb n-type MOS-sample at liquid-nitrogen temperature

80K. in the (111) plane at 6 x 106cm-3. (b) Band structure of lnSb near the center of the
Brillouin zone. (After Glosser et d.214--217
1
calculations are in good agreement with experiments on GaAs, and provide

a satisfactory explanation for the first-harmonic components of the TER
response observed in compound semiconductors,60-62 but absent in Ge
and Si. The relative contribution of linear electrooptic and linear piezoelectric effects is determined by, and characteristic of, a particular experimental configuration, with the connection made via the piezoelectric tensor.
However, it follows from Kyser and Rehns results that piezoelectric lineshape effects must be taken into account before polarization dependences
can provide information on the critical-point symmetry.
At the close of the analysis section, a comment is in order on the lineshape interpretation of wavelength modulation spectra that are found to be
of the same magnitude as ER response^.'^^^^'^ A strong surface field is
ordinarily present in semiconductors. A wavelength modulation scan
necessarily follows the profile of a static reflectance that has ER contributions
superimposed. For the case of ZnO it can be shown that static and
dynamic ER correlate well. This static-ER component must be deducted
from the wavelength modulation trace before conclusions on basic mecha223
224
225
A. G. Thompson, J. E. Rowe, and M. Rubenstein, J . Appl. Phys. 40,3280(1969).
R. R. L. Zucca and Y. R. Shen, Bull. Amer. Phys. SOC.14, 1159 (1969).

B. Hoffmann, Z.Phys. 219, 354 (1969).
139
nisms can be based on the line shape. No confidence should be placed on

quantitative line-shape interpretations if the wavelength-modulation spectrum responds to variations of the surface field.
18. EXPERIMENTAL
RESULTS
a. Semiconductors
(1) Si. The TER results by Forman and c o - w o r k e r ~ are

~ ~mentioned
in the analysis section. Volfson and Subashiev226study the effect of heavy
doping on the ER spectra of Si and Ge and find the results compatible with
a narrowing of the gap.
(2) Ge. Nishino and Hamakawa205 investigate the region 0.6-2.6 eV in a

heterojunction configuration that permits operation between 24 and 300K.
The interpretation confirms the valid assignments. TER studies of the complex Eo structure by Fischer and ~ o - w o r k e r s ~suggest
~ ~ - ~a ~tentative
~
identification of r6-- Ts+ at 3.00 f 0.05 eV and of Ts- - r6-at 0.191 f.
0.005 eV, both values at 85K.
In their study designed for optimal uniformity of the field, Handler and
c o - ~ o r k e r s observe
~~
destructive interference between higher oscillations
that is caused by the superposition ofcontributions from the light- and heavyhole band. Fischer and Bottka support this interpretation by observing a
polarization dependence consistent with the selection rules of the degenerate bands. If field effects on the matrix elements can be ignored, such a
polarization dependence at r points indicates the degenerate character of the
bands involved, and thereby promotes the identification.
(3) Gap. Kyser and c o - w o r k e r ~ ~report

~ the first observation of indirect
transitions in E R . Structure between 2.3 and 2.8 eV recorded in TER coincides to better than 1 meV with phonon emission and absorption thresholds
previously observed in optical absorption. Transition and phonon energies
are determined for three separate indirect edges. They all lead through the
T6intermediate state, so that no polarization dependence is observed.
(4) GaAs. Bendorius and Shileika228determine pressure coefficients and
hydrostatic deformation potentials for the r lSv-rlc
and the A3-Al transition.
At 24K at the fundamental edge, Nishino et
observe a threefold
structure that is repeated weakly at the spin-orbit transition and that they
correlate to the interband edge, the exciton. and a localized state.
A. A. Volfson and V. K. Subashiev. P h w Starus Solidi 33. 149 (1969).

227
228
229
D. S. Kyser. V. Rehn, and V. 0. Jones. Bull. Amer. Phys. SOC.15,288 (1970).

R. Bendorius and A. Shileika, Solid Stare Commun. 8. 1 1 1 1 (1970).
T. Nishino, M. Okuyama, and Y. Hamakawa. J . Phys. Chem. Solids 30.2671 (1969)
140
B. 0. SERAPHIN
Dzhioeva and S t ~ p a c h i n s k i i question

~~'
the nature of the impurity peakotherwise well established-because they observe a back-reflection signal
in front of the edge. Forman et
see the same back reflection without
arriving at conclusions about the impurity peak. Studies by Vorob'ev and
Z h a r k ~ v a and
~ ~ lby S h a l d i are
~ ~ of~ conventional
~~
character.
(5) GaSb. Parsons and Piller233,234a
observe within the Eo' structure the
level known from the fundamental
recurrence of the A. splitting of the rI5"
edge. This provides the key to assignments for the higher conduction band
= 3.160 eV; rav-TSc
= 3.375 eV; and r7v-I'8c
= 4.1 10
as follows: r8v-r7c
eV. This assignment is consistent with selection rules and provides accurate
data for a crop of existing band calculations diverging on this point by as
much as 1.5 eV.
(6) ZnSb. The spectral shifts caused by variations of the band filling permit
Glosser and co-workers2 4-2 to identify interconduction band transitions,
on the basis of which r7c
and Tsc can be assigned to 3.4 and 3.8 eV, respectively.
(7) Other Semiconductors. Shay and c o - w o r k e r ~as~well
~ ~ ~as~Kava~
liauskas et aL234dinvestigate the polarization selection rules determining the
ER spectrum of the chalcopyrite crystal CdSnP, ,the ternary analog of InP.
The interpretation requires an unusual ordering of the valence bands that
results from the assumption of a negative crystal-field splitting. Accordingly,
the valence bands can be regarded as an equivalent to those that would occur
in a strained version of the binary analog InP. On this basis, the polarization
dependences in the fundamental as well as in the E , structure can be quantitatively explained by a quasi-cubic model. The occurrence of the negative
crystal-field splitting is credited to the interaction between the valence band
maxima and new states that occur at r in the chalcopyrite structure owing to a
Brillouin zone that is smaller than that in the zinc blende structure. The
transformation of the unit cell relative to zinc blende also explains the transS. G. Dzhioeva and V. B. Stopachinskii, Fiz. Tekh. Puluprov. 3, 386 (1969) [English Transl.:
Sou. Phys.-Semicond. 3, 328 (1969)l.
2 3 1 Yu. V. Vorob'ev and T. N. Zharkova, Ukr. Fiz. Zh. 14, 1890 (1969).
232 Yu. V. Shaldin, Fiz. Tuerd. Tela 11, 3633 (1969) [English Transl.: Sou. Phys.-Solid State 11,
3049 (1970)l.
233 B. J. Parsons and H. Piller, Solid State Comrnun. 9,767 (1971).
234aB.J . Parsons and H. Piller, Program and abstracts of 3rd Materials Res. Syrnp. Electron.
Density States, Gaithersburg, 1969. Nat. Bur. Stand., 1969, p. 125.
234bJ.L. Shay, E. Buehler, and J. H. Wernick, Phys. Rev. Lett. 24, 1301 (1970).
234cJ. L. Shay, R. F. Leheny, E. Buehler, and J. H. Wernick, Appl. Phys. Lett. 16. 357 (1970).
2346J. Kavaliauskas, A. Shileika, N . A. Goryunova, E. 1. Leonov, and V. M. Orlov, Phys. Lett.
33A, 49 (1970).
230
141
formation of indirect transitions in the latter into pseudo-direct transitions

in the chalcopyrite structure. Much additional structure in the CdSnP,
spectrum is attributed to these pseudo-direct transitions.
LUthz3 observes electric-field modulation of the reflectance near both
edges of the Reststrahlen band of ZnO. Electric Grueneisen constants are
determined from the field-induced shift of the eigenfrequencies.
The ER spectrum of Ni0236is dominated by three peaks between 3 and
5 eV. If assigned to critical points, their interpretation in conjunction with
photoconductivity measurements favors a band model in which a narrow
3d band makes substantial contributions to the interband density of states
above the 3.7-eV absorption edge.
In a short note, GhoshZ3reports measurements of ER spectra on SrTiO,,
together with other photoelectronic effects.
(8) Semiconductor Alloys and Impurity Eflects. Vishnubhatla and cow o r k e r ~investigate
~ ~ ~ , ~the~ variation
~
of principal gaps with composition
in In(As, Sb), In(As, P), and (Ga, 1n)Sb mixed-alloy systems. The nonlinearity
of the compositional gap shifts is consistent with a predominance of effects
due to the disorder of the lattice. Williams and RehnZ4 present a consistent
interpretation of their previous ER spectra taken on (Ga, 1n)As that is in
good agreement with recent theoretical calculations. Transition energies
and spin-orbit splittings and their dependence on sample composition were
determined by Shileika (Sileika) and co-workers on the system Ga(As, P)241
and In(As, P).242
Williams
on heavily doped GaAs further confirms the impurity
association of the peak near 1.36 eV at 300K. The Mn, Cd, and Si impurities
can be discerned in the ER spectrum near this photon energy. In this context
also see the work of Nishino et al.,229as well as observations on heavily
doped Si and Ge.226
b. ER Structure Credited to Excitons
Quantitative line-shape analysis clearly requires the admission of Coulomb interactions into the electrooptical theory. We will review here some
H . Liith, Phys. Status Solidi 33, 267 (1969).
J. L. McNatt, Phys. Rev. Lett. 23, 915 (1969).
23 A. M. Ghosh, Solid State Commun.7, 1125 (1969).
238 S. S. Vishnubhatla, B. Eyglunent, and J. C. Woolley, Can..
I
Phys.
. 47, 1661 (1969).
239 S. S. Vishnubhatla, Ph.D. thesis, Univ. of Ottawa, 1970 (unpublished).
240 E. W. Williams and V. Rehn, Solid State Commun.7, 545 (1969).
2 4 1 A. E. Irzhikyavichyus, Yu. F. Kavalyauskas, and A. Yu. Shileika, Litor. Fiz. Sbornik 9 , 5 3 5
(1969).
2 4 2 J. Kavaliauskas and A. Sileika, Phys. Status Solidi 38, K73 (1970).
2 4 3 E. W. Williams, Solid State Commun. 7, 541 (1969).
235
236
142
B. 0.SERAPHIN
recent work in which contributions of excitonic effects are claimed on a

different basis. Such contributions can be firmly established if the static
optical properties are dominated by exciton effects and the ER structure
clearly correlates to the static spectrum. However, excitons should no
longer be the sole scapegoat for all deviations of a line shape from the oneelectron prediction. The complexities of the various line-shape factors have
now been established too firmly to let such an argumentation carry any
weight in the future.
Following preliminary work by Daunois and c o - w o r k e r ~ Gahwiller
,~~~
and Ha~-beke,~measure both reflectance and ER on PbI,. The first three
lines of the hydrogenic exciton at the fundamental edge are well resolved in
reflectance.They correlate accurately to ER structure that is interpreted as a
Stark shift of the exciton. Beyond the fundamental edge, the existence of
several metastable exciton states is suspected to give large contributions to
the ER spectrum.
Spectralmatch within 0.5 meV between structure in staticand in modulated
reflectance is observed for the light and dark blue exciton lines of
Cu20.246-249A reduced effective mass of 0.29 is derived from the saturation
field.
Upon cooling of the sample, the appearance of additional peaks located
in proper position in front of an edge, is sometimes interpreted as evidence
for an excitonic character of such structure, as in GaAs229and in ZnSe.2sos251
However, conclusions based on plain line-shape discrepancies such as those
observed in Ge252and in CdTe253must be supported by quantitative surface measurements before the excitonic contribution can be established
beyond doubt.
c. Band Population Effects
Band population effects, first qualitatively discussed by CardonaI6la

and A ~ p n e s , ~ have
* l ~ ~been quantitatively established in InSb by Glosser
and c o - ~ o r k e r s . ~ ~
The
~ - observed
~~
shifts of ER structure with dc bias
A. Daunois, J. L. Deiss, Y.Dolisi, and S. Nikitine, C. R. Acad. Sci. Ser. B 268,930 (1969).
Ch. Gahwillerand G . Harbeke, Phys. Reu. 185, 1147 (1969).
246 S. N. Shestatskii and V. V. Sobolev, Fiz. Tuerd. Tela 11, 2708 (1969) [English Transl.: SOC.
Phys.-Solid Sfare 11, 2196 (197O)l.
S. N. Shestatskii and V. V. Sobolev, Phys. Status Solidi 28. K131 (1968).
2 4 8 S. N. Shestatskii and V. V. Sobolev, Phys. Status Solidi 32, K109 (1969).
249 J. L. Deiss, A. Daunois, and S. Nikitine, Solid State Commun. 8, 521 (1970).
K. Ikeda and Y. Hamakawa, Phys. Leu. 288,647 (1969).
2 5 1 S. Fujiwara, K. Hattori, and M. Fukai, Phys. Lett. 318,258 (1970).
2 5 2 T. Nishino and Y. Hamakawa, J . Phys. SOC.Japan 26,403 (1969).
2 5 3 V. S. Vavilov, S. G. Dzhioeva, and V. B. Stopachinskii, Fiz. Tekh. Poluprou. 3, 727 (1969)
[English Transl. : Sou. Phys.-Semicond. 3,617 (1969)l.
244
245
143
Emox (eV)
3 551
3 50)
3 45;
11
3 20i
..
3 I5
lo'
I 901
851
I80C
-~
-I
+I
vdc
FIG. 63. Spectral shift with bias of structure associated with transitions starting from the
Fermi level (upper two plots). as compared to reference structure associated with a transition
bridging the Fermi level (lower plot) for lnSb at 2 x 10" cm-' and N at 300 K.Circles represent positive and squares negative extrema of the response. Arrows point in the direction of
increasing peak magnitude. All data are taken by the electrolyte technique. (After Glosser and
co-workers.' ''-2'7 1
provide evidence for their participation in the ER response of heavily doped

semiconductors. The direction of the shift classifies the correlated transitions
according to their involvement with the Fermi level. In Fig. 63 is plotted
the spectral shift with dc bias of an intraconduction band transition starting
from the Fermi level, calibrated against structure originating in a transition
that bridges the Fermi level. The shift is in quantitative agreement with
effective mass data and field-effect results, clearly establishing its origin in
band-filling effects.
Band-population effects provide an additional mechanism in the generation of ER responses. In heavily doped semiconductors such as the IV-VI
compounds, they can dominate, so that an interpretation in terms of critical
points may fail.
144
(eV)
2.4-
2.32.2-
0.7
2.1-
100 200 300 400 500
(OC)
Ts
FIG.64. (a) Spectral position E,, of four peaks (0,positive; V, negative) in the ER of Ge
films deposited onto Ge substrates of various temperatures 6 . Arrows indicate the direction of
increase of the response. (After Piller er 0 1 . ' ~ ~ )(b)
. Same as (a) except for the fundamental edge
E , and its spin-orbit-split companion Eo + Ao. Bars below 200C indicate approximate position
of weak structure.
d. Amorphous Materials
In contrast to integral properties receiving contributions from the entire

Brillouin zone, ER monitors localized discontinuities of the electronic
structure that can be expected to react sensitively to a loss of the long-range
order of a crystal. Such loss is gradually introduced in a set of Ge films
evaporated onto substrates of progressively lower temperature until the
transition to the amorphous phase is passed at a temperature that depends
upon the evaporation conditions. Piller and c o - w o r k e r ~recorded
~ ~ ~ the ER
spectrum on such a set of Ge films and find the results shown in Fig. 64.
Structure correlated to transitions off the center of the Brillouin zone disappear at the transition temperature of 225C (Fig. 64a) whereas the center
transitions stay on [Fig. 64(b)]. Both shift toward the red through the amorphous range, the fundamental response being slightly washed out and the
spin-orbit split companion sufficiently resolved. The results are in agreement with conventional models of the electronic structure of amorphous
solids, which predict that a center transition will be less affected by the loss
254
H. Piller, B. 0.Seraphin, K. Markel, and J. E. Fischer, Phys. Reo. Lett. 23,775(1969)
1.
ELECTROREFLECTANCE
145
of order than an off-center transition, and a p-type band edge more than the
s-type edge of the conduction band on which both fundamental transitions
terminate.
A weak ER signal is observed on amorphous Se films by Weiser and
S t ~ k below
e ~ ~the
~ electrical band gap and the photoconduction edge.
The structure is much broader than the nearby exciton response in trigonal
Se. Its temperature shift is of opposite sign. The authors correlate the ER
response to a Frenkel-type exciton originating at the disordered ring molecules of the amorphous phase.
e. Metals
Ishibashi and Stadler 5 6 investigate the reflectance modulation of evaporated Au films caused by a reversal of the ferroelectric polarization of the
BaTiO, substrates. The metal film is sufficiently affected to display a response
similar to the spectrum observed at a gold-electrolyte interface.44 Since
the cause of this modulation is probably very complex, identical observations by Grant257and Parsons2s8remain unpublished. The piezoreflectance
component inherent in the modulation of the ferroelectric polarization is not
as easily separated from the ER part as these authors believe. More work is
required before this configuration can contribute to the still disputable
problem of ER in metals.
McIntyre and A s p n e ~ approach
~~
the problem by showing that the
primary features could arise from an electric-field modulation of the freeelectron contribution to the dielectric function of the metal in the surface
region. Rigid-energy shift of the optical constant or Fermi-level modulation
of interband transitions (causes previously considered) are incompatible
with the experimentally observed differences between piezo- and electroreflectance of the noble metals.
19. EXPERIMENTAL
METHODS
a.
Field-Effect Technique
The dry-sandwich configuration mentioned briefly in the preceding review

was developed f ~ r t h e r~233,234
.~
Interference effects are avoided by a
200-A thickness of the A1203 spacer, withstanding more than lo6 V-cm-
and capable of low-temperature operation. Ni is recommended as a field
255
256
257
258
259
G. Weiser and J. Stuke, Phys. Starus Solidi 35. 747 (1969).

Y. Ishibashi and H. I. Stadler, J . Phys. Chem. Solids 30,2113 (1969).
P. Grant, personal communication(1967).
B. J. Parsons, personal communication(l967).
J. D. McIntyre and D. E. Aspnes, Bull. h e r . Phys. SOC. 15, 366 (1970).
146
B. 0.SERAPHIN
electrode because of its small light absorption at the onset of conduction.

These sandwiches can be used up to 7 eV.211-z13
Hamakawa and C O - W O ~ developed
~
~
~ a Sheterojunction
~
~
~
~con-~
figuration between antimony-doped SnOZ and the sample, using vacuum
deposition of tin and subsequent thermal oxidation. A film 2000-,4 thick
has a resistivity of 80 ohm/square, is transparent up to 3.1 eV and introduces
use
acceptor states at the interface with Ge. Shileika (Sileika) ef al.241.242
this configuration on GaAs.
In their quantitative surface work, Frova and Aspnesl 8 9 used sandwiches
with epoxy/Mylar spacers, which resembles the old wet techniquez6
rather than the dry configuration.
b. Electrolyte Electroreflectance
Aspnes and F r ~ v a demonstrate

~
that the electrolyte technique is a
valid method for obtaining quantitative information about space-charge
parameters and ER spectra, provided proper care is used in measuring and
interpreting experimental data. In their refined version, the electrode
potential is controlled by a potentiostat that controls the platinum electrode
through a driving amplifier, receiving feedback from the calomel electrode
through a buffer amplifier. Capacitance measurements can be performed with
a I-psec resolution. The characteristic is displayed on a two-beam oscilloscope, together with fast photovoltage response. Both measurements
determine the field profile accurately through knowledge of the flatband
condition and the doping in the surface region. A 0.10-molar solution of
K2S04 indistilled water, buffered to pH = 6.86 and cleaned by gettering
with Ge crushed in situ, was used. No surface states were observed in the
measurements. Most of Aspnes and Frovas findings are supported by the
results Thu1lZ6obtained in his thesis work.
B ~ c k m a n studies
~ ~ the growth of unwanted contaminations a t the interface of G e with a 1 N KC1 electrolyte. Without more than touching the surface
of a promising field, Seliger262investigates the possibility of an internalreflection spectroscopy in conjunction with a phase-correlated modulation
a t both electrolyte interfaces of an ATR plate.
c . Transverse Electroreflectance
Compensation raises the resistivity of some semiconductors sufficiently
to make TER operation feasible at low temperature. Forman et ~ 1 .
used this possibility on GaAs compensated by Cr doping, and on Si doped
Y. Hamakawa and T. Nishino, Proc. I X Int. Con$ Phys. Semicod., Moscow 1968, p. 384.
Nauka, Leningrad, 1968.
2 6 1 B. 0. Seraphin, Surface Sci. 13, 136 (1969).
laR. Thull, Ph.D. thesis, Tech. Univ. of Berlin. 1970 (unpublished).
2 6 2 H. Seliger, Optik 31, 72 (1970).
260
147
by Au diffusion. A conformal mapping method is presented for the calculation of the effective field in common TER geometries.
Fischer et al. irradiate Ge with 6oCogamma rays at a dose of l o L 8cm-.
Deep acceptor levels introduced into the lattice under the assumption that
there is no damage, raise the resistivity to lo6 ohm-cm under illumination.
The etched surface is rinsed in CuSO, to minimize surface barrier effects.
A 500-AAlZO3layer beneath the evaporated Au electrodes reduces leakage
currents.
d . Other Techniques
Independent of earlier work by McCoy and W i t t r ~ , Broser
~~
and cow o r k e r ~modulated
~~~
the reflectance of Ge by a chopped electron beam.
Although their predecessors believe in a gap reduction due to screening by
the excess carriers, the present authors can interpret their results as a mixture
of thermoreflectance, dominating at low frequencies and high beam intensities, and Franz-Keldysh effect, if a low-intensity beam is modulated
rapidly.
The reflectance modulation induced by current variationsz65is not a band
structure effect, but could interfere with thermoreflectance at direct heating.
The theoretical study outlines the effect for the case of InSb.
20. PHOTOREFLECTANCE
Of the four mechanisms that may be present in PR, thermal effects have
been more firmly ruled out by a study by Nilsson.z66The remaining threepotential barrier modulation, exciton screening, and band filling-ach
contributes a fraction that depends upon material and conditions of the
experiment, band filling effects probably contributing the smallest part.
Potential barrier modulation (photo-flattening of the bands) dominates
for moderate light levels at the Ge-electrolyte interface, as established under
controlled surface conditions by Aspnes. l 9
The PR response vanishes
with the surface field and is consistent with inhomogeneous-field ER outside
the flatband condition. In Si, Cerdeira and CardonaZ6 find polarization
effects at 3.4 eV that suggest an ER interpretation. Proper dc bias increases
the PR response, while a secondary light beam photoquenches the ER
signal, thereby establishing a reciprocal relationship between PR and ER.
2b3
264
265
267
J. H. McCoy and D. B. Wittry, A p p l . Phvs. Lerc. 13, 272 (1968).

I . Broser, R.-A. Hoffmann, and H.-J. Schulz. Solid State Commun. 8. 587 (1970)
C. V. Hodge and C. A. Baumgardner, Phys. Rev. B 1,3347 (1970).
N. G. Nilsson, Solid State Commun. 7,479 (1969).
F. Cerdeira and M. Cardona, Solid Stare Commun. 7, 879 (1969).
148
B. 0.SERAPHIN
h w (eV)
FIG.65. Line shape. of the B-exciton transition in CdS (dashed line after Wang er ~ 1 . ' ~with
)
a calculation based on exciton screening. (After Albers et ~ 1 . ' ~ ' ~ ' ~ ' )
Shay et
rule out band-filling effects in the magneto-PR of InSb
by observing the regular oscillatory structure due to Landau levels, of which
the higher members are not populated. A similar argument applies for PR
structure at transitions that bridge the Fermi level, such as the El structure
in GaAs. The lifetime in the final state is much too short to have bandfilling effects operate. At the Eo edge of GaAs, PR can also be correlated to
ER, as Shay269shows in studies as a function of doping, temperature, and
excitation intensity. For ultrapure material and high intensity, the
correlation fails, and there may be room for an explanation on the basis of
band filling.269a
Last but not least, exciton effects play the dominant role under favorable
conditions. Cooling GaAs from 77 to 2"K, Shay and Nahory2" find a two-
'" J. L.Shay, R.E. Nahory, and C. K. N. Patel, Phys. Rev. 184,809 (1969).
'" J. L. Shay, Bull. Amer. Phys. Soc. 15, 288 (1970).
269nJ.L. Shay, Phys. Rec. B2,803 (1970).

"O
J. L. Shay and R.E. Nahory, Solid State Commun. 7,945 (1969).
1.
ELECTROREFLECTANCE
149
hundredfold increase in the PR response, which, together with line-shape

arguments, supports an assignment to a bound exciton.
suggests free-carrier screening of the Coulomb interaction
on bound states of excitons as an alternative explanation of modulated
reflectance in general. He investigates ground-state energy and oscillator
strength of a bound-exciton state within the effective-mass approximation,
using a screened Coulomb potential. An evaluation of the results shows that
free-carrier screening is probably negligible in the ER of Ge, but that screening could be the dominant factor in the PR of CdS. Figure 65 compares the
line shape calculated on the basis of exciton screening with the experimental
PR trace55 for which band-filling effects gave a poor fit.56 An exciton
screening mechanism for CdS is further suggested by the rapid temperature
variation of PR. In GaAs, however, thermal broadening and field effects
dominate the temperature variation.273
ACKNOWLEDGMENTS
In the course of writing this review I have indispensably profited from stimulating and helpful
discussions with my co-workers N. Bottka, J. E. Fischer, R. Glosser, and B. J. Parsons. The
analysis section in particular reflects in numerous points their original contributions to the
subject.
272
273
W. A. Albers, Phys. Reo. Lett. 23,410 (1969).

W. A. Albers, E. Y. Wang, and C. E. Bleil, Solid State Commun. 7 , 81 1 (1969).
B. 0.Seraphin, Proc. Phys. SOC.(London)87, 239 (1966).
CHAPTER 2
Modulated Interband Magnetooptics*

R . L . Aggarwal
I . INTRODUCTION. . . . . . . . . . . . . . . .
THEORYOF INTERBAND
TRANSITIONS
I N A MAGNETIC
FIELD . . .
1. Simple Two-Band Model . . . . . . . . . . . .
2 . Direct Edge in Germanium and Ill-V Compounds . . . . .
111. MODULATION
TECHNIQUES
. . . . . . . . . . . . .
3 . Sensitivity Considerations . . . . . . . . . . . .
4 . Fractional Noise-Equiident-Power . . . . . . . . . .
5. Wavelength Modulation . . . . . . . . . . . . .
6. Stress Modulation . . . . . . . . . . . . . .
7. Magnetic-Field Modulation . . . . . . . . . . . .
8. Electric-Field Modulation . . . . . . . . . . . .
9 . Temperature Modulation . . . . . . . . . . . .
1V . EXPERIMENTAL
RESULTS. . . . . . . . . . . . . .
10. The Direct Edge in Germanium . . . . . . . . . . .
I I . The Indirect Edge in Germanium . . . . . . . . . .
12. The Fundamental Edge in Gallium Antimonide . . . . . .
13 . The Split-Ofl Valence-to-Conduction Band Transitions in Gallium
Antimonide . . . . . . . . . . . . . . . .
14. The Fundamental Edge in Gallium Arsenide . . . . . . .
I 5 . The Stress- Modulated Magnetoreflectancefor the Split-Of Valenceto-Conduction Band Transitions in Gallium Arsenide . . . . .
16. The Fundamental Edge and the Split-Off Edge in Indium Antimonide
17. Modulated Magnetorejlectance in Indium Arsenide . . . . .
18. Stress-Modulated Magnetoreflectance in Lead Telluride . . . .
19. Conclusions . . . . . . . . . . . . . . . .
11.
151
154
154
169
187
188
189
197
199
203
204
206
207
207
216
222
229
233
236
24 1
247
251
255
I Introduction
Since the first successful observation. by Zeeman' in 1897. of the influence
of magnetic field on the nature of light emitted (or absorbed) by a substance.
Zeeman studies of the atomic spectra have played a very important role in
elucidating the electron structure of atoms. Similarly. Zeeman experiments
in solids have been equally important in the study of their electron energy
* This chapter was prepared at Francis Bitter National Magnet Laboratory. a center for research
I
operated by Massachusetts Institute of Technology with the support of the U.S. Air Force
Office of Scientific Research .
P . Zeeman Versl. Kon . Akad . Wet . Amsterdam 5. 181. 242 (1897); Phil . Mag . 43. 226 (1897).
151
152
R. L. AGGARWAL
bands. In particular, the Zeeman studies in semiconductors and semimetals

provide information on the location and symmetry of the band edge extrema
or critical points in the Brillouin zone, the effective mass and g-factor at
and in the vicinity of the critical points, and the energy gaps between the
band extrema. Excellent reviews of these and other magnetooptical phenomena such as Faraday effect in semiconductors, semimetals, and metals
have been given by Lax and coworker^,^-^ Bagguley and Owen,6 Moss,
Dresselhaus and Dresselhaus: and Gabriel and Piller. This list of review
articles is by no means complete for an extensive subject such as this. A
bibliography of magnetooptics of solids compiled in 1966 by Palik and
Henvis contains more than 1200 references to original articles.
In this chapter we will review the Zeeman experiments in semiconductors
for the last five years. Over the last 10 years a number of differential techniques
of electric field, I-
tress,'^." temperature,** w a ~ e l e n g t h , ~ *and
~
photo modulation have been reported for the observation of optical
M. Faraday, Faradays Diary. Bell and Sons, London, 1932; Ann. Phys. Chem. 68, 105
(1946).
B. Lax, in Proc. Int. School Phys. Enrico Fermi Course XXII (R.A. Smith, ed.), p. 240.
B . Lax and S . Zwerdling, Progr . Sernicond. 5,221 (1960).
B. Lax and J. G. Mavroides, Solid State Phys. 11, 261 (1960); in Semiconductors and Semimetals (R.K. Willardson and A. C. Beer, eds.), Vol. 3, p. 321. Academic Press, New York,
1967; Appl. Opt. 6,647 (1967).
D. M. S. Bagguley and J. Owen, Rep. Progr. Phys. 20, 304 (1957).
T. S. Moss, Phys. Status Solidi 2, 601 (1962).
* G. Dresselhaus and M. S. Dresselhaus, in Proc. Int. School Phys. Enrico Fermi Course
X X X W , (J. Tauc, ed.), p. 198, Academic Press, New York, 1966.
C. J. Gabriel and H. Piller, Appl. O p f .6,661 (1967).
l o E. D. Palik and B. W. Henvis, Appl. Opt. 6,603 (1967).
T. S. Moss, J. Appl. Phys. Suppl. 32,2136 (1961).
l 2 Q. H. F. Vrehen and B. Lax, Phys. Rev. Lett. 12,471 (1964).
I B. 0. Seraphin, in Physics of Semiconductors, (Proc. Int. Conf.),p. 165. Dunod, Paris and
l4 A. Frova and P. Handler, in Physics of Semiconductors (Proc. 7th Int. Conf.), p. 157.
Dunod, Paris and Academic Press, New York, 1964; Phys. Rev. 137, A1857 (1965).
K. L. Shaklee, F. H. Pollak, and M. Cardona, Phys. Rev. Lett. 15, 883 (1965).
l6 W. E. Engeler, H. Fritzsche, M. Garfmkel, and J. J. Tiemano, Phys. Rev. Lett. 14, 1069
(1965).
l7
l9
2o
G. W. Gobeli and E. 0. Kane, Phys. Rev. Lert. 15, 142 (1965).

B. Baa, Solid Stare Commun. 4, 241 (1966).
I. Balslev, Phys. Rev. 143, 636 (1966).
A. Perregaux and G. Ascarelli, Appl. Opr. 7,2031 (1968).
E. Y. Wang, W. A. Albers, Jr., and C. E. Bleil, in 11-VI Semiconducting Compounds
(Proc. 1967 Int. Conf., Providence) (D. C. Thomas, ed.), p. 136. Benjamin, New York and
Amsterdam, 1967.
2.
MODULATED INTERBAND MAGNETOOPTICS
153
spectra of solids. Since these techniques of modulation spectroscopy provide

several orders of magnitude enhancement in the sensitivity for the observation of resonant transitions, modulated magnetooptical experimentsz2 have
yielded new information on some of the energy band parameters such as
the effective mass and g factor of the spin-orbit split-off (r;;?)
valence band
in g e r m a n i ~ mand
~ ~ several
~ ~ 111-V compound s e m i c o n d u c t ~ r s . ~ ~ ~ ~ ~
Even though optical modulation spectroscopy is hardly ten years old,
modulation techniques have long been used in several other areas of physics.
For example, magnetic field modulation has been successfully employed
for over 30 years in paramagnetic resonance experimentsz9 in which a small
magnetic field oscillating at audio frequencies modulates the splitting of
the spin states caused by the application of a large static magnetic field.
This technique of magnetic field modulation was later used for observing
broad (or weak) cyclotron resonance absorption in solid^.^^,^ We believe
that the recent popularity of modulation s p e c t r o s c ~ p yhas
~ ~ come about
as a result of relatively inexpensive phase-sensitive amplifiers which became
commercially available in this country after 1955.
Modulated interband magnetoabsorption was first reported by Vrehen
and Lax in 1964 for the direct transition r;i? + r2.in germanium. These
experiments were performed to test Aronovs theory33 of magnetoabsorption
in the presence of an electric field normal to the magnetic field. Two years
reported their preliminary observation
later Aggarwal, and Mavroides et
of stress-modulated magnetoreflectance for the direct transition in Ge and
InSb. They also observed weak structure in modulated magnetoreflectance
due to the split-off transition r;;?-+ rz.in Ge. Similar experiments were
A review of the early modulated magneto-optical experiments was given by J. G. Mavroides,
in Physics of Solids in Intense Magnetic Fields, Chapter 8, p. 206.Plenum Press, New York,
1969.
23 J. G. Mavroides, M. S. Dresselhaus, R . L. Aggarwal, and G . F. Dresselhaus, J. Phys. SOC.
JapanSuppl.21,184(1966);R.L.AggarwalandB.
Lax,Bull.Amer. Phys.Soc. 11,828(1966).
2 4 S. H.Groves, C. R. Pidgeon, and J . Feinleib. Phys. Rev. Lett. 17,643 (1966).
2 5 R. L.Aggarwal, Bull. Amer. Phys. SOC.12, 100 (1967).
2 6 C.R. Pidgeon, S. H. Groves, and J. Feinleib, Solid State Commun. 5, 677 (1967).
2 7 M. Reine, R. L. Aggarwal, and B. Lax, Solid State Commun. 8, 35 (1970).
M. Reine, R. L. Aggarwal, B. Lax, and C. M. Wolfe, Phys. Rev. B2,458 (1970).
2 9 See for example, NMR and EPR Spectroscopy, by the NMR-EPR Staff of Varian Associates. Macmillan, New York, 1960.
30 R. N. Dexter and B. Lax, Phys. Rev. 100, 1216 (1955).
3 D. M. S. Bagguley, J. A. Powell, and D . J. Taylor, Proc. Phys. SOC.
(London) A70,759(1957);
D. M. S. Bagguley, R. A. Stradling, and J. S. S. Whiting, ibid. A262,340 (1961).
3 2 For a review of modulation techniques see M. Cardona, Solid State Phys. Suppl. 11, Modulation Spectroscopy (1969).
3 3 A. G. Aronov, Fiz. Tverd. Tela 5, 552 (1963)[English Transl.: Sou. Phys.-Solid State 5, 402
( 196311.
22
154
R. L. AGGARWAL
reported soon after by Groves et

who used the electrolyte electric field
modulation technique of Shaklee et a1.I5 to study magnetoreflectance in
Ge, I d s , and InSb at 300K. Later on Pidgeon et aLZ6reported results for
modulated magnetoreflectance in InAs and InSb at 1.5"K measured with
the dry electric field modulation technique of Seraphin.'
The major contribution of modulated magnetooptical experiments is the
significant increase in the energy range, above the fundamental energy gap,
over which optical transitions between Landau levels could be observed
with conventional magnetospectroscopy. This increase in the spectral range
for the observation of oscillatory magnetoabsorption or magnetoreflection
has made it possible to determine nonparabolicity for some of the bands
not feasible p r e v i o u ~ l y Before
. ~ ~ discussing the modulated magnetooptical
experiments, we will give a brief outline of the theory of interband transitions
in a magnetic field in Part 1I.A summary of the various modulation techniques
will be presented in Part 111. Finally, the experimental results for Ge, GaSb,
GaAs, InSb, InAs and PbTe will be given in Part IV.
11. Theory of Interband Transitions in a Magnetic Field
1. SIMPLE
TWO-BANDMODEL
a. Landau Levels
Consider a simple band structure consisting of two bands for which the
energy momentum relations in the vicinity of k = 0 are given by
gC= gg
+ (h2kz/2m,),
and
" = -(h2k2/2mv),
where the indices c and v are for the conduction and valence band, respectiveiy, ggis the energy gap between the conduction and valance band extrema
at k = 0, m, and m, are the electron and hole effective masses, respectively.
On the application of a dc magnetic field H, the Hamiltonian for the motion
of the electron (neglecting spin) in the conduction band is
9 = [p
+ (e/c)AlZ/2m + V(r),
(3)
where p = hV/i is the momentum operator, A is the vector potential of

the dc magnetic field, m is the free electron mass, and V(r) is the periodic
potential energy of the electron in the crystal. In the effective mass approximat i ~ nthe
, ~Hamiltonian
~
becomes
+f = [p
34
35
+ (e/c)AI2/2m,.
R. L. Aggarwal, M. D. Zuteck, and B. Lax, Phys. Rev. 180.800 (1969)

J. M . Luttinger and W. Kohn, Phys. Rev. 97, 869 (1955).
(4)
2.
I55
The above Hamiltonian is similar to that for a free electron in a magnetic

field except that the effective mass appears in place of the free mass. The
problem of a free electron in a uniform magnetic field was originally solved
by Landau36 who showed that the motion of an electron in the plane perpendicular to H becomes quantized whereas the motion along the direction
of H remains unaffected. Following Landau, Luttinger and K ~ h solved
n ~ ~
the effective mass Hamiltonian of Eq. (4). To lowest order, the wave functions
for the conduction electron are
vcw = 4(r).LW7
(5)
where u,(r) is the periodic part of the Bloch function for k = 0, and fc(r)
is a slowly varying function of position compared to the Bloch function u,(r).
The eigenvalues and the functions fc(r) are determined from the solutions
of the Schrodinger-like equation
[;v + (e/c)A]2fc(r)/2mc
18c -
QfcW
(6)
To solve the above equation we consider a crystal in the form of a rectangular

parallelepiped with sides L,, L,, and t,along the x,y, and z coordinate axes
with the origin at the center of the crystal. If the magnetic field is taken along
the z axis, and the vector potential A = Hxg, where 9 is the unit vector along
the y axis, the eigenfunctions fc(r) are obtained as
f&) = ( L L ) - 112 e i ( k y y + k z z )
CPAX - x0L
(7)
Y
where xo = hck,/eH, and q nis the function for a qne-dimensional harmonic

oscillator of order n ; n is any positive integer including zero. For a given
value of n, the eigenvalue of Eq. (6)is
so that
8,- gg= (n + #oc
+ (h2kz2/2m,),
gC(n)= + ( n +)hot (hzkz2/2rn,),

(8)
where o,= eH/rn,c is the cyclotron frequency of the electron. Equation (8)
contains a very important result, viz., the splitting of the three-dimensional
band by the applied magnetic field into a series of one-dimensional subbands
separated by hw, . These magnetic subbands are known as Landau levels.
The Landau level index n is called variously orbital quantum number,
magnetic quantum number, or Landau quantum number.
Treating the valence band in the same manner as the conduction band,
the wave functions for electrons in the valence band are obtained as
T@)
= k(r)fv(d,
36
19)
See for example, L. D. Landau and E. M. Lifshitz, Quantum Mechanics Addison-Wesley.

Reading, Massachusetts, 1958.
156
R. L. AGGARWAL
where u,(r) is the periodic part of the Bloch wave function for the valence
band at k = 0, and f,(r) = f,(r) as given in Eq. (7) since f(r) does not depend
upon the effective mass. The energy eigenvalues for the Landau levels of
the electrons in the valence band are given by
&,(a)
-[(n
+ f ) h o , + (h2kz2/2mV)],
(10)
where o,= eH/m,c is the cyclotron frequency for the holes.

b. Dielectric Constant in the Absence of Modulation
To calculate the dielectric constant due to interband transitions in a
magnetic field, we consider the excitation of electrons from the Landau
levels in the valence band to the Landau levels in the conduction band. The
i t 2 due to
imaginary part c2 of the complex dielectric constant E =
these transitions is given by
where o is the angular frequency of the electromagnetic radiation and V =

L,L,L, is the volume of the crystal, the primes refer to the conduction band,
and
(12)
on,.= wg (n +)ov (n
+)oc,
+ +
+ +
where wg = 8Jh. Here Print is the matrix element,
where C is the unit vector in the direction of the electric field of the electromagnetic radiation. Using Eqs. ( 5 ) and (9) for Yc(r) and YV(r),the matrix
element can be written as
which yields
on the assumption that uc(r) and u,(r) are orthogonal to each other and that
they are normalized to unit volume ;SZ is the volume of the unit cell, ucell
stands for unit cell and entcry stands for entire crystal. The condition
that the integral
2.
157
is nonzero yields the selection rules An = n - n = 0, and Aky = Akz = 0.

Hence the matrix element for allowed transitions in a magnetic field is the
same as that for direct transitions in zero magnetic field at k = 0 which is
u,*(r)(p . C)u,(r)d r .
Substituting for the matrix element into Eq. (1 l), c2(o, H) for allowed
transitions is given by
c 2 ( o , H ) = (4x2/V)
IPC,I2S[ h o - h a , - ( h 2 k Z 2 / 2 p ) ] ,
(16)
n,k,.k,
with
on= wg
+ (n + +)o,
(17)
where op= w, o,is the sum of the cyclotron frequencies for the electron
and hole, and p = m,rn,/(m, + m,) is the electron and hole reduced mass.
On performing the summation over k, and k, in Eq. (1 6), we obtain
ho - ho, - h2k,i) dk,. (18)

2P
To perform the integration, we note that
in which x o is a root of f ( x ) , and the sum includes all roots in the interval
from a to b. In the present case, g = 1, andf = hw - h a , - h2kZ2/2p,so
that the integral
Substituting the above value of the integral in Eq. (18), we obtain
Using Eq. (20) and multiplying by a factor of 2 to take into account the
spin degeneracy, ~ ~ H
() 0
is given
,
by the expression
&2(W,
H ) = (CoJ2w2)
c
n
(0-
on)-
(21)
where
[2e2(2p)32/m2h52]
lp,,I2,
(22)
158
R. L. AGGARWAL
30r
1000
( w -w" ) / w
FIG.1. The individual line shape g z ( o - om)

for the imaginary part of the dielectric constant
due to direct allowed interband transitions between nth Landau levels for the simple two-band
model as a function of (o- w,)/w for several values of o ~ .
and
pcv = R-'
ucell
u,*(rj(p. C)u,(r) dr.
(23)
Equation (2 1j shows that ~ ( wH)

, has a series of infinite singularities occurring
at w = onfor each value of n corresponding to transitions between Landau
levels at k, = 0. These infinite singularities of eZ(w,H) are obtained only in
the ideal case of an infinite relaxation time. Following Roth et aL3' broadening effects due to finite relaxation time z may be introduced phenomenologically by making the substitution w -+ w - (i/rj. In this manner we have
Q(W,
3'
H ) = (Cw,/2w2)
1Re[w - w, -
(i/7)]- lit.
L. M. Roth, B. Lax, and S. Zwerdling, Phys. Rev. 114.90 (1959).
(24)
2.
159
is the line shape of an absorption peak for a transition between nth Landau
o as a function of (o- o,)/o
levels. In Fig. 1 we show a plot of ( ~ ) ~ g ~- (on)
for several values of oz.
The real part of the dielectric constant can be obtained from the KramersKronig relation
EI(W)
-2
E1(0)
-I
+ -P
do ,
2 70
(W.W)/W
FIG.2. The individual line shapeg,(w - wn) for the real part of the dielectric constant due to
direct allowed interband transitions between nth Landau levels for the simple two-band model
as a function of (w - w,)/w for the same values of W T as in Fig. I .
R. L. AGGARWAL
160
where P denotes the principal value of the integral. Substituting for c,(w, H)
from Eq. (21) into Eq. (27) and evaluating the principal value integral, we
obtain the following expression for cl(w, H) in the ideal case of an infinite
relaxation time :
E~(w,H
= )~ ~ ( 0(Cw,/2w2)
)
2 [-hi + (w + w,)1/2
If we make the substitution w

broadening effects, we obtain
E~(Q
where
g,(w
- w,)
lz
-(w
12].
(28)
+w -
( i / z )in the above equation to include
H ) = ~1(0)+ (Cw,/2w2)
= -204-
+ Im(o - con)-
1g,(O - O n ) ,
(29)
+ (0+ w,)- l/.

- w,) + [(w -
w,)2
+ (l/T2)]1/2
2[(0 - C%J2+ (l/T2)1
12
(30)
In Fig. 2 we have plotted (o)1/2gl(o

- w,) as a function of (w - w,)/w for
the same values of OT as in Fig. 1.
c. Effect of Modulation on the Dielectric Constant
(1) Stress Modulation. To obtain the stress-induced change in cl(w, H)

and c2(w,H), we assume that the effect of stress on the parameter C defined
in Eq. (22) is negligible. This implies that the band masses m,, m,,and the
momentum matrix element p,, are not affected by the applied stress. This is
a very good approximation for small strains of the order of
which are
obtained in stress modulation experiments. It is further assumed that 7 is
independent of the applied stress. Using these approximations it follows
from Eq. (25) that the stress-induced change in c2(w,H) is given by
where Awn = Amg which is the change in the energy gap produced by the
applied stress. Using Eq. (26) for the line shape g , ( o - w,,), we obtain the
derivative of g 2 ( 0 - on)with respect to w, as
-
W,)
awn
-
[(w - o,) - 1 / ~ +~ (O
] - o,)[(o- 0,)+ l / ~ ~ ] /
+ 1/T2]112F
(2)[(O - 0,) f ~ / T ~ ] ~ / {-( w
0,)
+ [(O -
(32)
2.
161
5 x lo3
i0:
300
500
-5
-2
Y
-10
I
-I
( w - w ) /w
2L
FIG. 3. The derivative of the line shape g,(w - wn),shown in Fig. 1, with respect to the transition frequency w, as a function of (w - wJw for the same values of w~ as in Fig. 1.
In Fig. 3 we have plotted (w)~ dg,(w
- w,)/dw, as a function of (w - w,)/w

for 0 7 = 100, 300, 500, and 1000. Since dg,(w - w,)/dw, is strongly peaked
at w,, at least for large values of at,the line shape for the Ae2(w, H) spectrum
in the vicinity of a given Landau level transition will bear close resemblance
to dg,(w - w,)/i?o, as shown in Fig. 3. However, for small values of 07, the
contributions from the tails of the other transitions could make an appreciable
change in the line shape as can be seen in Fig. 4.
R. L. AGGARWAL
162
FIG.4. The theoretical spectrum for the stress-induced change A E ~ ( wH, ) in the imaginary
part of the dielectric constant due to interband transitions between Landau levels for the simple
two-band model for several values W,,T with w,, = 0.01 w g .
The stress-induced change in the real part of the dielectric can be written as
where Awn = Amg, and
[(W
[(W
- 0,)2
- 0,)-
l/Tz]
+ 1/T213/2{-(w
(W
- W,)[(O
+ 1/T2]12
+ 1/T211/2p223/2
- 0,)
+ [(w -
(34)
In Fig. 5 we show a plot of ( ~ 0 ) a~g, ( o - w,)/aw, as a function of (w - w,)/w
for several values of wz. As one would expect, a g , ( o - w,)/aw, is strongly
( ~ ,
peaked in the vicinity of w, for large values of wz. Therefore, the A E ~ H)
spectrum will show structure around each w,. The line shape of this structure
will be similar to the line shape of a g , ( o - w,)/aw,.
2.
163
I000
-2
-I
(w-w") / w
FIG.5. Thederivativeofthelineshapeg,(w- shown in Fig. 2, with respect tothe transition

frequency w, as a function of ( w - w.)/w for the same values of W T as in Fig. 2.
(2) Magnetic Field Modulation. To calculate the change in the dielectric

constant due to a change AH in the magnetic field, we assume, as in the case of
stress modulation, that the parameter C and the scattering time T are constants which are independent of magnetic field. With this approximation, the
change in c2(w,H) would be given by the expression
R. L. AGGARWAL
164
Equation (35) shows that there are two contributions to A E ~ ( OH,) , one having
the normal line shape and the other the derivative line shape ag2(w - con)/
do,. It is interesting to compare the relative magnitude of these contributions.
is proportional to z l i 2 and that of ag(o - un)/
The peak height 0fg2(w - 0,)
do,is proportional to r3I2.The contribution of the derivative line shape is,
therefore, (n &~,r times as large as that of the normal line shape. This
shows that for wPz >> 1 the contribution of the normal line shape g2(w - on)
is negligible. In this case Eq. (35) can be written as
where
Awn = (n
+ $)w,(AH/H).
(37)
Since d g 2 ( 0 - o n ) / d o n is the same for all transitions, the contribution of

individual transitions to As2(w, H ) is proportional to Am, which increases as
( n + *). In a typical interband magnetooptical spectrum the spectral peaks
due to low quantum number transitions are strong and sharp, and they
become progressively weak and broad with increasing n. In view of this
feature of the interband magnetooptical spectrum, one would like to use a
modulation technique which provides small Awn for low n numbers and
large Awn for high n values. The magnetic field modulation is therefore ideal
for interband magnetooptical experiments since Awn increases at least
qualitatively as the linewidths of the corresponding transitions. Consequently it should be easier to observe high n transitions with magnetic field
modulation than with other modulation techniques such as stress modulation
for which Awn is independent of n.
The magnetic field-induced change in the real part of the dielectric constant
is obtained by differentiating Eq. (29) with respect to H . The result is
which yields
for w,z >> 1. The above equation is similar to Eq. (36) for Ac2(o, H ) .
(3) Electric Field Modulation. The calculation of the optical absorption

for direct transitions between simple bands in crossed electric and magnetic
fields was originally made by A r ~ n o vin ~the
~ framework of effective mass
approximation. According to Aronovs theory the application of a transverse
2.
165
electric field affects magnetoabsorption between Landau levels in two ways :

First, the selection rules are relaxed in that the electric field induces the
normally forbidden transitions corresponding to An = _+ 1, _+ 2, etc., whereas
the absorption due to allowed (An = 0) transitions decreases. Second, all
transitions are shifted to lower energies by an amount equal to &mc
m,)F2cZ/H2,where F is the magnitude of the applied electric field. For low
electric fields such that a2,as defined by
= (m, + mV)2c3F2/eAH3,
(40)
is much smaller than unity, Vrehen38 has obtained the following expression
for the imaginary part of the dielectric constant in crossed fields.
where
and g 2 ( 0 - w,,.) is obtained by substituting on,.for w, in Eq. (26). By the

Taylor series expansion of c2(F, H) in powers of F, we find the electric fieldinduced change in c2 to second order in F as
Ae2 = c2(F,H ) - ~ ( 0H,)
where
(d2c/dF2),=o = Cw,(m,
= g(a2&2/dF2)F=0F2,
+ m,)2c3~2G2(w)/02heH3
(43)
(44)
with
It is obvious from the above equations that the lineshape of the cross-fieldmodulated spectrum is determined by G2(w).To study the influence of the
parameters m,, m , , H , and T on G2(w),V ~ - e h e calculated
n~~
G,(w) for several
values of these parameters. The results for O,T = 1,3,9,27 and m, = 2m, or
38
Q . H. F. Vrehen, Phys. Reo. 145, 675 (1966).
R. L. AGGARWAL
166
-1
V
W
(b)
W-Wg
a,
FIG.6. The derivative lineshape function G,(w) defined in Eq. (45) for absorption between
two simple bands in crossed electric and magnetic fields for m, = 2m,. The calculated position
and relative intensity of the lines in the differential spectrum are shown in the bottom part (e) of
the figure. Positive lines correspond to An = 1 forbidden transitions, negative ones to An = 0
allowed transitions. (a) R,r = 27; (b) R,r = 9 ; (c) R,r = 3; (d) R,r = 1. (After V ~ h e n . ~ ' )
~
m, = im, are shown in Fig. 6. These GJw) versus (w - w,)/wpcurves bring

out the following features of the cross-field-modulated spectrum : First, the
forbidden transitions are resolved only for U+,T > 9. The cross-field-modulation, therefore, cannot be used for a determination of individual band masses
for lower values of wpz.Secondly, the contribution of the derivative lineshape
dg(w - wn,)/dwnn
is appreciable for O,T = 27 but can be neglected for lower
values of wpz.It should be noted that this term arises from the electric fieldinduced shift of Landau level transitions to lower energies.
Using Kramers-Kronig relations we obtain the real part of dielectric
constant in cross fields as
E ~ ( FH, ) = ~ ~ ( 0 (cw,/2w2)
)
[I
+ I)a21g1(w -
mnn)
2.
167
where g,(w - w,,.) is obtained by making the substitution w, + on,.in Eq.

(30). The electric field-induced change in e 1 ( w , H )to second order in F is
given by the relation
A E , = Cw,(m,
+ m,)2c3F2r
2G1(~)/2w2heH3, (47)
where G , ( w ) is obtained from Eq. (45) by replacing g,(w - w,,) by

gl(w - wnn,).
So far we have considered electric and magnetic fields which are mutually
perpendicular. In the parallel-field case the electric field affects only the
component of electron momentum in the direction of the fields, whereas the
magnetic field has the effect of quantizing the electron momentum in the
transverse plane so that the electron motion along the field direction remains
unaltered by the magnetic field. Thus the effects of parallel electric and
magnetic fields on the optical absorption (reflection) can be considered
separately. Using a method analogous to that of Tharmalingam39 for the
F r a n ~ ~ - K e l d y s heffect,
~ ~ Reine et aL4 calculated the optical absorption
due to direct transitions between simple bands in parallel fields. Their result
for the imaginary part of the dielectric constant in parallel fields is
e 2( F, H ) = (Cw,/w2B1i2) lAi(x,,)12,
(48)
where B
(e2F2/2pLh)1/3,
and Ai(x,) is the Airy function of argument x,
(w, - a)/&
Equation (48) shows that the effect of a parallel electric field is to
modify the lineshape for allowed transitions, but it does not induce any forbidden transitions. The change in F~ due to an on-off electric field is then given
by the expression
A F=
~ EZ(F,H ) - EZ(O, H )
=
3;
[2B-iAi(?)l
g2(w - w,) .
(49)
The corresponding change in the real part of the dielectric constant can be
obtained by means of the Kramers-Kronig relations.
d. Modulated Magnetooptical Spectra
(1) Magnetoabsorption. The absorption coefficient CI is related to the

imaginary part of the dielectric constant by the expression
c(
39
40
41
(wine)&,,
(50)
K . Tharmalingam, Phys. Reu. 130,2204 (1963).

W. Franz, Z . Nuturforsch. 13~1,484(1958).
L. V. Keldysh, Zh. Eksp. Teor. Fiz. 34. 1138 (1958) [English Trunsl.: Sou. Phys.-JETP 7, 788
(195811.
42
M . Reine, Q. H . F. Vrehen, and B. Lax, Phys. Rev. 163, 726 (1967).
R. L. AGGARWAL
168
where n is the refractive index of the medium which is related to the dielectric
constant as
and
n2 - k 2 =
(51)
2nk = e 2 ,
where k is the extinction coefficient. Solving Eqs. ( 5 1) for n and k, we obtain

El
and
n=[
(E12
E22)I/2
ll2
so that Eq. (50) becomes
Differentiating Eq. (53) we obtain the modulated absorption
where
and
The ratio of auJaE, to ~
is
U J ~ E ,
In the vicinity of the direct gap in semiconductors such as Ge and 111-V

compounds, the absorption coefficient u v lo4 cm- and n 3-4 so that the
E ~ We may, therefore, neglect the term
ratio l ( a ~ i / a ~ , ) / ( a cv~ E~ ~~) I / ~ 0.05.
containing Acl in Eq. (54) to obtain the following approximate expression for
modulated magnetoabsorption.
Aa(o, H ) N ( o / c n )Ac2.
(58)
This shows that the line shape of modulated magnetoabsorption is very

similar to the line shape of the change in e 2 ( o ,H ) due to the applied modulating perturbation as discussed in the previous section.
2.
169
(2) Magnetorejection. We consider the reflectance at normal incidence.

Using Maxwells equation, the normal reflectance is given by
[(n- 1)2
+ k 2 ] / [ ( n+ 1)2 + k2].
(59)
Substituting for n and k from Eqs. (52) into Eq. (59), R can be written as
R=
+
1+
1
(El2
(E12
+ Ez2)I2
212[E1
E 2 2 ) 112] 112
(El2
+ E22)12 + 21/2[E1 + ( E 1 2 + E 2
(60)
2 1/2 112
By differentiating the above equation, we obtain the fractional modulated

reflectance
ARIR
where
1 aR
A=--=
212[2&, - 1
- (c12
(E12
+BA E ~ ,
+ (El2 +
E22)2][E,
+ E22)2[(E1
(61)
- 1)2
E 2 2 ) 112 112
E22]
(62)
and
1 aR
B=--=
R a&,
(E12
212E2[2E, - 1
E22)1/2[E,
(E,2
+
E2
(E12
E22)12]
2 112 112
- i)2
+ E221
(63)
Equations (62) and (63) give the ratio
which yields
B/A
c2/2&,2: 0.05
for c2 0.1cl, which is the case in the vicinity of the direct gap in germanium
and IIILV semiconductors as discussed before. We can, therefore, neglect the
term containing B in Eq. (61) to obtain
A R / R ( o ,H ) 2: [2/n(n2 - l)]A c l ( o , H ) .
(65)
Equation (65) shows that except for a constant scaling factor, the modulated
magnetoreflectance spectrum is the same as the spectrum for A E ~ ( wH,) .
2. DIRECT
EDGEIN GERMANIUM
AND 1II-V
COMPOUNDS
a. Landau Levels
In germanium and 111-V compounds, the direct edge is due to vertical

transitions between valence- and conduction-band extrema at k = 0. The
E versus k curves in the vicinity of k = 0 for all these materials are similar
170
R. L. AGGARWAL
FIG.7. A schematic of the b ( k ) versus k curves in the vicinity of k = 0 for the conduction
2 0.75 eV. (After Reine4)
and valence bands in GaSb for tp2 0.81 eV and A
to those shown in Fig. 7 for GaSb. The conduction band is very similar to the
simple conduction band considered in the previous section. But the valence
band is degenerate at k = 0. The top of the degenerate valence band edge
consists of light- and heavy-hole bands. At energy A below the top lies the
spin-orbit split-off valence band extremum. All the three valence bands
belong to p-like atomic orbitals whereas the conduction band is s-like.
The problem of energy levels and wave functions of a degenerate band in a
magnetic field was investigated by L ~ t t i n g e rand
~ ~ Luttinger and Kohn3
among others. A more complete treatment for the calculation of the energies
of Landau levels for germanium-like conduction and valence bands at k = 0
is due to Pidgeon and Brown44 who treat the conduction band together with
43
44
J . M . Luttinger, Phys. Rev. 102, 1030 (1956).

C. R . Pidgeon and R. N. Brown, Phys. Rev. 146, 575 (1966).
2.
171
three valence bands. In the PB scheme the effective mass Hamiltonian (including spin) is written in the form of 8 x 8 matrix. For the magnetic field H in
the (110)plane, the matrix Hamiltonian D can be written as the sum of two
parts
Do
+ D1,
(66)
where D is a small part arising from the anisotropy of the valence band. The
large part Do which also contains part of the anisotropy can be solved exactly.
For the case of k , = 0 which is of most interest to us in magnetooptical
experiments, Dodecouples into two 4 x 4 matrices which satisfy the following
eigenvalue equations in matrix form:
D, - &,If,
0,
and
(67)
D, - ~ b l f h = 0 ,
where E,, &b are the eigenvalues, and fa, f b are the effective mass wave functions
which are linear combinations of the harmonic oscillator-type functions cp,, .
In matrix form
fb
L C7(Pn+ 1 ,
C6(Pn - 1
3
C4Vn+ 1
CsVn- 1
where c l , c 2 ,. . . etc., are the eigenvectors. The complete wave functions are of
the form
= CIU1(Pn
+ C3U3(Pn- 1 + C5U4(Pn+ 1 + C7U7(Pn+l
The u's are linear combinations of the s-like and p-like band edge Bloch
functions
u1 =
st,
u3 =
(2)-"2(x
u2 =
+ iY)?,
u5 = (6)-'''[(X -
iY)?
Sl,
u4 = 42)-
+ 2211,
u7 = i(3)-'12[-(x
- iY)t
lQ(X - i Y ) l ,
i(6)-'12[(X +
(70)
iY)l - ZzT],
+ z J ] , us = (3)-'12[(x + i Y ) l + 271,
=
172
-1-
ii
I N
R. L. AGGARWAL
-IN
-IN
N^
II
I1
"-I+-
" 9
.-IW
4"
IN
.
+
-- *
-
G
I
57
IN
+
-
2.
173
where 1and t stand for the spin-up and spin-down functions, respectively, S is
the atomic s-like conduction-band function, and X , Y, and Z are the atomic plike valence-band functions. For the effective mass wave functionsf, and fb
given by Eqs. (68), the determinantal equations for the eigenvalues of the u
and b sets are given by Eqs. (71) and (72) on p. 172; here s = rieH/rnc is the
cyclotron energy for a free electron; E , is the interaction energy between the
conduction and valence bands defined as4'
where pcv = (SlplX) = (SlplY) = (SlplZ) is the momentum matrix element

between the conduction and valence band; F represents the interaction of the
conduction band with the higher bands;46 y,, y 2 , y 3 , and ti are the valence
band parameters due to the higher-band contributions
y1 =
Y1
yz =
yz
L
L
q 3 4 ,
EP/6&,
73 =
hL- Ep/6ggr
K = tiL -
Ep/6&g,
where y l L , y2=, y3L, and K~ are the valence-band parameters defined by

L ~ t t i n g e ry. ~and
~ y" are given in terms of y 2 , y 3 , and the angle 0 between the
magnetic field H and the crystal z axis and A is the spin-orbit splitting energy
for the valence band.
The determinants in Eqs. (71) and (72) contain imaginary terms. These
determinantal matrices are of the form
[ a
ic
1-i~
-ib
ib
d l
ig
i:]
-ig
-ik
(73)
The matrix M can be made real by performing a unitary transformation on

the matrix M' which is obtained on interchanging columns 3 and 4 followed
by an interchange of rows 3 and 4,so that
r a
46
ib
H. Ehrenreich, J . Appl. Phys. Suppl. 32, 2155 (1961).

E.0.Kane. J . Phys. Chern. Solids 1, 249 (1957).
ic1
174
R . L. AGGARWAL
If we take the unitary matrix

l + i
(75)
then
1-i
., .I:
which is real. Interchanging rows 3 and 4, and then columns 3 and 4, we

obtain
a
b
c
d
MreaI
[:
i,
(77)
From a comparison of the matrices M and M,,,,, the determinantal equations

(71) and (72) can be written in the real form as given in Eqs. (78) and (79) on
p. 175. For a given set of band parameters r f g , E,, F , ylL, yzL, yjL, K ~ and
,
A, energies of Landau levels for the a and b set can be obtained from the
solutions of Eqs. (78) and (79) for a given value of the magnetic field. Since
general analytical solutions of these quartic equations are not possible, they
are usually solved numerically. In the absence of exact analytical solutions,
it would be useful to deduce analytical expressions for the eigenvalues of
Landau levels to given order in s which is proportional to the magnetic field
H. This has been done by Reine and co-worker~.~
We will follow this work
closely. We note that both the determinantal Eqs. (78) and (79) are of the
form
rifg + sA - I
s1C
sD
sE
47
M. Reine, R. L. Aggarwal, and B. Lax (to be published); M. Reine, Ph.D. thesis, Massachusetts Institute of Technology, 1970 (unpublished).
2.
-1m
t+
52
+
-
,.
.
i-
?
.
+
-
0 IN
r.l I N
G?
I
'0
>
.
- l a
- --
175
176
R . L. AGGARWAL
where for the a series
-(2)IZ[yf(
i)
71,
-K +
L,
= - [3n(n
and for the b series

=
L2 = - (yl
(:):I
+ 7) n +
- -K
L,
+ l)]zy,
-[?in ;)+ +;I,

-
-[3n(n
+ 1)] 2y .
Expanding the determinant in Eqs. (80) and rearranging the terms, we obtain
2.
177
+s2(L3 - L 1 L 2 ) ( b- bg)(&+ A)
+ s(E2 - sAB)
+s[(C + D 2 ) S A W , + L2)1&(&+ A)
+ s 3 [ B ( L 1 L ,- L3) F2L2 - G 2 L , + 2FGL,](& - gg)
-
+ C F ) - B(C2+ 0) - E2(Ll + L2)]&

+ s 3 [ A B ( L 1+ L 2 ) - A(GZ + F2)]
+s2(2CDL3 - C 2 L 2- D 2 L l ) ( b+ A) + s3A(L,L2 - L32)(&+ A)
+s3[B(CZL2+ D 2 L l ) - 2BCDL3 - 2DEGL, - 2 C E F L ,
-(CC - DF) + 2(CG + DF)EL3 + E2(LlLz- L 3 2 ) ] } .
(83)
+s2[2E(DG
To obtain expressions for eigenvalues to a given order in s, we expand d in

a power series in s:
& = &o
(&o
+ s3g3 + . .. .
(84)
Substituting Eq. (84) into Eq. (83), and equating terms containing equal
powers of s on both sides, we obtain equations for the coefficients o, b l ,
etc.
For the zeroth order in s, we obtain the equation
s1
s2&z
8g)602(+ o
A)
0,
(85)
which has four solutions: do = ggfor the conduction band, &, = 0 for the
degenerate light- and heavy-hole bands, and &o = - A for the split-off band.
The equation for the first order in s is
w o - 4$02
=
+ 2(0 -
g) o( o
+ A) + &02(o + 4 1 4
+ Lz)(bo- 4)o(&o + A) + A&02(o + A) + B(o - gg)&o2

+ Ezg0 + (C2 + D2)o(o + A).
(86)
(L1
This is a simple equation for the coefficient &, . By setting go = g, and -A,
we obtain the coefficient for the term linear in magnetic field for the conduction
and split-off band respectively. Since o is a common factor we do not have
an equation for the light- and heavy-hole bands from Eq. (86). Factoring out
Go and neglecting terms containing (Go - &g)(&o + A) which is zero for
do = Ggor A, Eq. (86) can be written as
[(cY0 - &J + (
+ A)],
A(8
+ A) + B(&o - 8;)+ E 2
+ (C2 + D2)(o + A)
0
(87)
178
R. L. AGGARWAL
Substituting o = &g in Eq. (87), we obtain the following equation for the
conduction band
&:=A+--
E2
4 + A
+ (C2 + 0
4
)
9
where the superscript c denotes the conduction band. Substituting for A , E,

C, D from Eqs. (81) and (82) into Eq. (88), we obtain the coefficient for the
linear term in s for the a and b series.
ET,,
(n
;);+
j1g , ,
where
m
mc
and
It should be noted that the above expression for the conduction-band

effective mass m, differs from that of Kane46 only in that it contains an
additional term (2mjh)F. Kane considers only the mutual coupling of the
conduction and valence bands. Therefore, the band parameter F which
represents the interaction of conduction band with other bands would be
zero in Kanes model. Equation (92) for the conduction band g factor g,
is the same as that given by Roth ef aL3
We now consider the linear coefficient for the split-off band. Substituting
&o = - A in Eq. (87), we obtain
This yields
ay,
forn= -l,O,l,...,
(94)
2.
179
and
where the effective mass and the g-factor for the split-off band are given by
the expressions
and
g,,=
-2
2 K +
Ep
3Wg
1.
+ A)
(97)
It should be pointed out that the sign of g,, is consistent with that of g, since
for the split-off band the a series is J = i, M , = -$, and the b series is
J = i , M = i. In terms of Luttingers parameters, Eqs. (96) and (97) for
msoand g,, can be written as
and
i 11
2KL + 1 - 2
3 4 4 +A A
~
(99)
For weak spin-orbit coupling (A << gg),Eqs. (98) and (99) simplify to
and
g,,
-2(2tiL
+ 1).
Using Eq. (9b) of L ~ t t i n g e r one

, ~ ~obtains g,, = 3(2Km - 1) = - ( 2 x L + 1)
for the case of weak spin-orbit coupling. Luttingers expression for g,, is in
error by a factor of 2 introduced in transforming from the ( L , S ) representation to the ( J , M,) representation for the split-off band. Note that our result
for g,, agrees with that deduced from Eq. (1 3) of Evtuhovs paper.48
48
V. Evtuhov, Phys. Rev. 125, 1869 (1962)
R. L. AGGARWAL
180
Let us now consider the second order terms in s. Equating s2 terms on both
sides of Eq. (81), we obtain
{[(a- &,)goZ + a g o - g p O ( 8 0 + A) + goZ(ff0+ 4 1 8 2

+ [ 2 ( & gg)&o+ 20(&0 + A) + (80 - 4)(&0+ A) + Go2]422)
= {(L,
+ LJ[(&O- 4180 + & O V O + 4 + ( 8 0 - g g w o + 414
+ B [ 2 ( 4 - &)go
+ 02]1+ A[02 + 20(80 + A)]&,
+ G 2 - B(L1 + Lz)](&o- gg)&o

- L,L,)(&O - J(o + A) + 2E2&081
-AB&02 + (C2 + D2)[o + (80 + A)]&,
A(L1 + L2)0(&0+ A)
+[FZ
+(L12
+[2E(DG
+ C F ) - B(CZ + 0
+(2CDL3
CzL2 - D2L1)(o
)- E2(L1 + L2)]8o
+ A)).
( 1 02)
Substituting go = 0 in the above equation, we obtain a quadratic equation

for the linear coefficient g1for the light- and heavy-hole bands. For go= ,
-A, we have a simple equation for the nonparabolic coefficient g2for the
conduction and split-off bands.
First we consider the light- and heavy-hole bands. Letting go= 0 in Eq.
(102), we obtain the following quadratic equation in 8,.
+ (L2-;)]&,-[(L3-$)
.P;-[(L1-$)
I):
( p:(
- L
--
L --
This yields
L3
=O.
y)2}12>
--
where the superscripts I, h denote the light- and heavy-hole bands, respectively; the upper sign is for the heavy-hole band and the lower sign is for the
light-hole band. Substituting the expressions given in Eqs. (81) and (82) for
L , , L,, L,, C, and D into Eq. (104) we obtain the following relations for the
linear coefficient in terms of Luttingers band parameters.
8 1 I. h
.a
- -[(.
;)?,L
?L
+ &I
+3n(n + l ) ( y L ) 2 ) 1 z ,
([?,L
- (n -
2 1
- k-L]z
(105)
2.
181
and
&O
1.b -
-[(n - $)?IL
f YfL
+ 3n(n + l ) ( y L ) Z }
iKL]
([ylL
+ (n - $)IJfL
KL]
( 106)
where for the light-hole band n = - 1,0,1,2,. . . , and for the heavy-hole
band n = I , 2,3,4, . . . . Equations ( 105) and (1 06) are identical to Luttingers
expressions for the light- and heavy-hole levels.
If we substitute &o = &g in Eq. (102), we obtain the following equation for
the nonparabolic coefficient g2for the conduction band.
gg2(gg A)&. = { -[gg2 2 8 3 4
+ A)](&1) + [(Ll + L2)4(gg + A)
+ B)4 + 2A&g(&g+ A) + 2E.8

+(C2 + D2)(28,+ A)]&,c - ABgg2 - A ( L , + L2)8,
x
+ A) + [2E(DG + C F ) - B(C2 + D 2 ) - E2(L + L2)]g
+ [ZCDL, - C 2 L 2- D 2 L 1 ] ( 4+ A)}.
(1 07)
+(A
(g
After some algebraic manipulations, Eq. (107) yields

&2c
A + B
&+A+[6,--(
(&ICY
= - ___
+B
-___
f&+A
2E(DG
C2
+ D2
)]
&IC
+ L l c 2+ L , D ~
Cfg2
+ C F ) - B(C2 + 0) 2CDL,
+-. 4
&Yg + A)
(108)
This is a complicated expression. An approximate result for the mean value of

for a and b series is obtained from Eq. (108) as
&2c
&2c =
3&g2 4A&g 2A2 m

-(n + :I2 m
2y3 . (109)
~ ( ~ - 1 ) [ ( 8 g + A ) ( 3 & g + 2 A ) ( ~ + y 1 )
In the derivation of Eq. (109), we assumed y = y = y 2 = ^ y 3 , i.e., warping

effects have been neglected. It is interesting to compare the above expression
for gZcto that obtained from the Kane model46 which neglects the interaction
of the conduction and valence bands with other bands. By letting y l = - 1,
and y 3 = 0 in Eq. (l09), we obtain the second order nonparabolic term for the
Kane model
which is identical to that derived by Vrehen.49 In terms of Luttingers

49
Q . H.F. Vrehen, J . Phys. Chem. Solids 29, 129 (1968).
182
R . L. A G G A R W A L
parameters, Eq. (109) can be written as
+ 4A4, + 2A2
Vg+ A ) ( 3 4 + 2A)
3g2
34
+ 2A
To obtain the nonparabolic coefficient
&2
for the split-off band we let
o = - A in Eq. (102). On simplifying the resulting equation, we obtain the
following approximate result for ? averaged over the a and b series.
In the case of the Kane model, Eq. (1 12) simplifies to
In order to obtain an expression for 2 of the light-hole band, we have to

consider the third order terms ins. The algebraic expressions are very complicated in this case. Therefore, we considered a simpler case of the Kane model
for which the nonparabolic coefficient is given by the expression
In the classical limit of large n, we have

1' = - ( n + -
:)(ylL
( n = 0, 1 , 2 , . . .)
2Y3L)
( 1 15)
assuming spherical symmetry for the valence band. Substituting Eq. ( 1 15)into
Eq. ( I 14), we obtain
N
(n
fi2=
(?IL
+ 2Y,L)z.
b. Selection Rules
Using the zeroth order wavefunctions Y'(n) and Y ' ( n ' ) for the initial and
final states, respectively, the matrix element for dipole transitions is given by
(Y'(n')lp elY'(n)> =
1[(P,,.- e)(fjf(n')lfj(n)>+ e
ij'
(fjz(n')lpljJn))bjj.]
,(I 17)
2.
183
where P
,. = ( u j p l u j . ) is the matrix element between the bands j and j at
k = 0. The first term on the right-hand side of Eq. (117) gives the allowed
transitions at k = 0. The second term, which is small compared to the first
term, gives the forbidden transitions at k = 0. The latter transitions are
analogous to those observed in cyclotron resonance. For the allowed valenceto-conduction band transitions, (fj.(n)lfi(n)) vanishes unless n = n & 1.
This selection rule of An = f 1 corresponds to the selection rule An = 0, - 2
derived by Roth et
The apparent difference in these selection rules is only
0
be
30-
a+
b+
b-
FIG.8. The Landau levels for the conduction band and the light- and heavy-hole valence
bands of Fig. 7 (not to scale).The Landau quantum number adjacent to each level is that obtained
in the coupled band scheme. The lowest energy allowed interband transitions are indicated by
vertical arrows for the Faraday configuration, right circularly polarized (RCP) and left circularly polarized (LCP) and by tilted arrows for the Voigt configuration. In this figure, E denotes
the electric field direction. (After Reine er ~ 1 . ~ )
R. L . AGGARWAL
184
artificial. This is due to the fact that in the coupled-band scheme we obtain a
set of envelope functions A's different from those obtained in the decoupled
scheme used by Roth et ~ 1 . ~In' addition to the selection rule for An, the
change in the total angular momentum AM, must be 0, -t 1. In the Voigt
configuration in which light propagates along a direction normal to the
appliedmagneticfield H, A M , = OfortheelectricvectorEIIHand AM, = f 1
for E IH. In the Faraday configuration in which light propagates parallel
to the magnetic field, only transitions corresponding to AM, = k1 are
allowed with AM, = + 1 for left circularly polarized (LCP) radiation and
AM, = - 1 for the right circularly polarized (RCP) radiation. In Fig. 8, we
have shown the Landau levels and allowed transitions appropriate for the
coupled-band scheme of Pidgeon and Brown.
c. Effect of Stress
The effect of homogeneous strain on the band extrema in zero magnetic

field can be obtained in the framework of the deformation potential theory.
The strain Hamiltonian for the k = 0 conduction band edge can be written as
where D,' is the conduction band deformation potential, and e,,, eyy.e,, are
the strain components. For the degenerate valence band edge, stress not only
changes its energy but also splits it into a pair of Kramers' doublets. Kleiner
and RothS0 have constructed a strain Hamiltonian in terms of the angular
momentum operator J to describe the splitting of the J = 3 valence band
edge,
+ ezz)+ $D,[(J,*
2:' = Ddv(exx eyy
+ cp]
- 3JZ)exx
where Ddv,D,, and D,. are the valence band deformation potentials ;Ddvgives
the shift of the center of gravity of the entire valence band; D, and D,. define
the valence band splitting for uniaxial stress along the [loo] and [ l 1 11
directions and are related to the corresponding Pikus-Bir' deformation
potentials b and d as5' D, = -3b and D,, = -(3"'/2)d. By cp is meant a
cyclic permutation of x, y , and z , referring to the crystallographic axes. It
should be pointed out that Eq. ( 1 19) is valid only for small stresses such that
the stress induced changes in energy are small compared with the spin-orbit
50
W. H . Kleiner and L. M . Roth, Phys. Rev. Lerr. 2, 334 (1959).
'' G. E. Pikus and G . L. Bir, Fiz. Tverd. Tela 1, 1642 (1959) [English Transl.: Sou. Phys.-Solid
Stare 1, 1502 ( 1960).
52
H. Hasegawa, Phys. Rev. 129. 1029 (1963).
2.
185
splitting A. The eigenvalues of 3;are found to be
+ eyy+ ezr)f {$Du2[(exx- eyy)2+ cp] + $D;.(e:, + C P ) } ~ .
= Ddv(eXX
( 120)
The last term in Eq. (120) represents one-half the strain splitting of the lightand heavy-hole bands, and the first term gives the shift for the center of
gravity of the split valence band edges.
The strain Hamiltonian for the spin-orbit split-off valence band edge is
given by
=
+ ezz)
DdY(eXX eYy
(121)
for the case of small stresses. Equation (120) shows that the position of the
split-off band edge relative to the center of gravity of the split light- and heavyhole bands is not altered by the applied stress. The relative motion of the four
band edges with the applied stress is shown in Fig. 9.
CONTRACTION
EXPANSION
STRAIN
FIG.9. The position of the four bands of Fig. 7 at k = 0, relative to the center of gravity of the
stress-split light- and heavy-hole valence band edges, is plotted as a function of a uniform twodimensional strain in the plane of a thin sample. (After Reine et 0 1 . ~ )
R. L. AGGARWAL
186
In order to find the effect of stress on the four bands in the presence of
magnetic field, we have to solve the total Hamiltonian
Ji? = #k
+ Se,
(122)
where Zk
= D is the Hamiltonian in the absence of stress as discussed in
Section 2(a). Equation (122) may not be soluble for an arbitrary stress. But
there are some particular stress configurations for which Xeis diagonal in the
(JM,) representation. For these special stress conditions, solutions of Eq.
(122) can be easily obtained by including the stress terms in the diagonal
elements of the matrix Hamiltonian D, and Dbprovided the magnetic field is
parallel to the stress axis and the stress is small enough to neglect the coupling
between the a and b series. Then Xe is found to be diagonal for uniaxial
stress along a [loo] or [ l l l ] direction, and
is also diagonal for twodimensional stress in a (100) or (1 1 1) plane provided the resulting strain is
isotropic in the stress plane, and the stress axis is taken to be the normal to the
stress plane.
The effect of a small stress TllH on the Landau levels can be seen more
explicitly by considering the decoupled band scheme. The stress-induced
change in energy for the light- and heavy-hole Landau levels can be written as
c,.((.)
Ddv(exx + eyy+ eZz)f
=
for the a series and

e,.(n) =
Ddv(exx
[C3(n) -
cs2(n)]b
+ eyy+ ezz)+ [c42(n) - c6(n)]d
(123a)
(123b)
for the b series. Here cg, c4, cg, and c6 are the eigenvectors obtained for zero
stress, and
d = $Du(ezz- exx),
for T11[001],
(124)
B = 2Du,exy,
for TII[111].
For high quantum numbers, Eqs. (1 23) reduce to
4 2: Ddv(exx + eyy + ezz)f $8,
(1 25)
where the + and - signs are for the light- and heavy-holes respectively.
Equation (125) shows that for high quantum numbers the stress-induced
change in energy is the same for all Landau levels.
Blinowski and GrynbergS3have also considered the effect of stress on the
light- and heavy-hole bands in a magnetic field. They take into account the
coupling between the a and b series so that their results are valid even for large
stresses. They have shown that in terms of the four-component wave functions
stress does not change the structure of the wave functions for the four ladders
J. Blinowski and M.Grynberg, Phys. Status Midi 20, K107 (1967).
2.
187
but only the amplitude of each component. Therefore, the selection rules for
interband transitions in the presence of stress are the same as in the case of
zero stress.
For the split-off and conduction bands, stress shifts all Landau levels by the
same amount, which is
c" = Ddv(exx + eyy + ezz)
for the split-off band, and
8
:
D:@,,
+ eyy +
f 127)
%2)
for the conduction band. It follows from Eqs. (126) and (127) that stress
changes the energy for the split-off valence-to-conduction band transitions by
h&:'+'
(DdC- DdV)(exx
+ eyy
+ ezz),
where (DdC- DdV)

is the deformation potential for the change in the energy
gap for isotropic strain. Equation (128)shows that the effect of stress modulation for the split-off transitions is the same as discussed previously for the two
band model. For the light- and heavy-hole transitions the shift in the transition energy due to stress can be obtained from Eqs. (123) and (1 27). In the high
quantum limit, this is
h&;*"'
= (Dd' - DdV)(exx
+ eYY+ ezs) f (8/2),
(1 29)
where the upper sign is for the light-hole transitions and the lower sign for the
heavy-hole transitions. Due to the term f &/2 in the above equation, the effect
of stress modulation for the light- and heavy-hole transitions is not the same
as for the split-off transitions. In addition, the effective modulation in energy
for the light- and heavy-hole transitions will not be the same for all transitions
involving Landau levels with small n.
111. Modulation Techniques
All these modulation techniques may be divided into two groups (a)
internal modulation and (b)external modulation. For internal modulation, a
small periodic perturbation is applied t o the specimen under study. This
results in a modulation of some physical property of the specimen which, in
turn, modulates the optical constants of the material. Temperature modulation,'
stress modulation,'6,' ' magnetic-field modulation, electric-field
modulation,'
and photo modulation" fall in the category of internal
modulation techniques. The only example of external modulation is the
wavelength modulation technique, since the sample remains unmodulated in
this case. Wavelength modulation may be preferred over internal modulation
methods since the interpretation of the wavelength-modulated spectra
'-"
188
R. L. AGGARWAL
should be a simple matter. An analysis of the lineshape observed with

internal modulation techniques could prove to be a difficult problem
theoretically. But from an experimental point of view, internal modulation
has an advantage over external modulation. The former modulates only the
optical structure associated with the specimen whereas the latter modulates
the optical structure resulting from the rest of the optical system as well,
which can become comparable to or even larger than the structure due to the
specimen. Before getting involved in the detailed comparison of the different
modulation techniques we would like to raise a fundamental question as to
how and when the use of a modulation technique enhances the sensitivity for
the observation of an optical transition in reflection or transmission.
3. SENSITIVITY
CONSIDERATIONS
In an attempt to answer the above question, let us consider, for example,

measurement of reflectance R. Suppose the frequency dependence of R is
given by
+ [B/(w- w0) + v 2 ] ,
( 130)
which implies that there is a peak in R at the frequency w = wo with a Lorentzian line shape of halfwidth (i.e., fullwidth at half maximum) equal to 2v.
Differentiating Eq. (130) with respect to o,we obtain
aR/aw
= -2qw
- wo)/[(w-
wo)2
+ ,212.
(131)
If A w represents the amplitude of w-modulation, the modulation in R would

be given by
AR
dR/aw A w .
( 1 32)
Substituting Eq. (13 1) into Eq. (132), we have

AR
= - 2B(w -
wO)
Ao/[(w - ~ 0 )
+ v].
( 1 33)
In order to obtain the true derivative lineshape, the amplitude of modulation

Aw should be infinitesimally small compared with the linewidth. From the
point of view of signal-to-noise ratio (SIN), one would like to use the largest
possible amplitude of modulation without affecting the lineshape seriously.
An amplitude of modulation equal to one-tenth of the linewidth usually
provides a derivative spectrum without distortion in lineshape. With Aw =
- v/5, Eq. (133) gives
AR
= - 2B(w - Wo)V/5[(W
w0)
+ ,I2.
(134)
2.
189
It can be easily shown by differentiation of Eq. (133) that the maximum

value of AR will occur at w - w o = - v. This is
AR(max) = B/10v2.
(135)
This should be compared with the maximum value of the w-dependent

contribution in R
R(too) = B / v 2 .
( 136)
Thus the maximum value of the modulated reflectance is only one-tenth the
peak value of the w-dependent contribution in R. At first sight, it would seem
therefore, that the signal-to-noise ratio for the modulated spectrum should be
worse compared with that for the unmodulated spectrum obtained with the
conventional technique of chopped light. The real answer to the question
hinges upon another consideration, viz., the value of R(o,) in relation to A . If
R(wo)is of the same order of magnitude as A or larger, modulation offers no
significant advantage. When R(wo) << A , we will have a small peak on a
large background in the conventional spectrum. In order to see the small
peak clearly, one needs to suppress the large background. This is where the
difficulty lies. Any instability in the system due to fluctuations and drift of the
light source, detector, amplifiers, and ofthecircuit for bucking the background
will contribute to noise which could become comparable to or even larger
1 % instability of the system is
than R(w,). For example, if R(wo)/A
sufficient to block the observation of R(wo) by conventional spectroscopy.
The situation is quite different in the case of the modulated spectrum. For
we obtain from Eqs. (130) and (135)
R(wo)/A =
AR(max)/R =
As we will see later, it is possible to observe modulated AR/R as small as lo-.
In view of this, ARIR 2
will be observed with a signal-to-noise ratio of
100. Thus we see that the modulation techniques will provide two orders of
magnitude improvement in the signal-to-noise ratio for the observation of
weak structure in the presence of a large background.
4. FRACTIONAL
NOISE-EQUIVALENT-POWER
Now we will consider the limitations on the smallest fractional modulated

signal, say, ARjR which could be observed with a signal-to-noise ratio of I.
A determination of ARjR at a given wavelength I. involves the measurement
of two signals : A1 due to the modulated radiation power AP incident on the
detector, and I due to the total radiation power P incident on the detector. It
is the ratio of these two signals which determines AR/R. That is
ARIR
Aljl
or
ARIR
APjP.
(137)
190
R. L. AGGARWAL
Equations (137) are valid only if the value of P does not exceed the limit
above which the detector response becomes a nonlinear function of P. The
smallest observable value of A R / R will be determined by the smallest value of
AP to which the detector will respond, say with the signal-to-noise ratio of 1,
in the presence of a large unmodulated or unchopped radiation power P
incident on the detector. It should be emphasized that the noise-equivalentpower (NEP) in the presence of the background radiation P is always larger
than that in the absence of background radiation. The dark NEP is
important for conventional spectroscopic experiments. But it is the fractional
noise-equivalent-power (FNEP) of the system which is meaningful in
modulation experiments.
To emphasize the significance of FNEP for an optical system let us suppose
we have an ideal photodetector, a device which produces a noise-free electrical
signal when exposed to a constant flux of photons. But there is no such thing
as an ideal radiation source which will emit a constant flux of photons. To
determine the noise in an ideal photon detector due to the random emission
and consequently the random arrival of photons at the detector, let us
consider that the source of radiation is a black body at temperature T. The
root mean square fluctuation n in the average rate of arrival N at the detector
of photons of wavelength A is given by
n,2
N,
exp(hc/AkT)
exp(hc/AkT) - 1
where h is Plancks constant, c the velocity of light and k the Boltzmanns

constant. For an average monochromatic radiation power P , incident on the
detector,
N , = (A/hc)P,.
(139)
Substituting Eq. (139) into Eq. (1 38), we obtain
This fluctuation in the photons arriving at the detector produces a fluctuation

in the generation of the current carriers. The root mean square noise equivalent radiation power p , due to these fluctuations has been shown to bes4
exp(hc/AkT )
- 1
where Af is the electrical bandwidth and &I

is)the quantum efficiency of the
54
P. W. Kruse, L. D. McGlauchlin, and R. B. McQuistan, Elements of Infrared Technology,

p. 356. Wiley, New York, 1962.
2.
191
photon detector. For our ideal photon detector q(A) = 1. Therefore, FNEP(E.)
for an ideal photon detector is
Bp*
2hc
exp(hc/).kT) Af
exp(hc/i.k T) - 1
q]
li2
In modulation experiments, the smallest fractional modulated signal which

could be observed must be larger than or equal to FNEP. The photon noise
limited fractional detectivity FD(A) defined as the reciprocal of FNEP(A) is
shown in Fig. 10 as a function of PA.The curve for = 0.5 p is for a black body
source at 2500K. The curves for A < 0.5 will lie below it. The upper curve for
1 = 10 p was computed for T = 1500"K, which is close to the temperature of
an infrared source, viz., globar used commonly for the spectral range 2-80 p.
The curves for 3, < 10 p will lie below that for I = 10 p, and those for l > 10 p
will lie above it. Since F D is proportional to (PA)1i2,
PA should be as large as
possible for the best signal-to-noise ratio.
The maximum value of PAfor a given resolution AA/J. is determined by (1)
the temperature and emissivity of the source, (2) the effective transmission
T, of the monochromator for monochromatic radiation, (3)the fraction of the
source radiation passing through the entrance slit of the monochromator,
and (4)the transmittance (or reflectance) T, of the specimen. For a black body
source at temperature T, Pi is given by
L)
Pi
= ( WJnf ')lwT,T,
AA,
(143)
where W, is the spectral radiant emittance of the source, fthef-number of the

monochromator, I the slit height, M the slit width, and A), the spectral width.
Since w and A2 are related to each other, w can be expressed in terms of A l .
Let us consider, for example, a grating monochromator equipped with a
blazed grating. In the case of a single-pass grating monochromator operating
in the first order
A2
(w/F)(4d2- A2)1'2,
( 144)
where d is the spacing of the grating grooves, and F is the focal length of the
monochromator. Substituting for w from Eq. (144) into Eq. (143), we have
When a blazed grating is used at wavelength near the blaze wavelength,
(4d2 -
1/22.
( 146)
Using Eq. (146) we can write Eq. (145) in the following approximate form
PA N (AW2'/2nf2)FTmT,(AA/A)2.
( 147)
Total Monochromatic Radiation Power Incident on the Detector PA (pW)

FIG. 10. Fractional detectivity as a function of the monochromatic radiation power PA (in microwatts) incident on the detector for a variety of
optical detectors. (1) l o p 7 1500K; (2) 0.5 p, 2500K; (3) S-20 Photomultiplier ( 0 . 4 2 ~ )(4)
: S-1 Photomultiplier (0.8 p); (5) Si Photodiode, 295K
(0.9p); (6)PbS, 295K (1-2 p); (7) PbSe, 77K ( 2 4 p); (8) Ge:Au. 77K (3-7 p).
2.
0.1
1
Wavelength X ( c ( )
193
FIG.11. The spectral variation of the radiation power P A incident on the detector. The curves
have been calculated from Eq. (147) for the black body source at 1500K and 2500K. The
) ~ / TF , T
=, 300 mm, 1 = 12.5 mm, f = 4.5,
equation used was PA = ( I W , F / / ~ ~ ~ ~ ~ ) ( A I / Lwith
and AI/A = l o - ?
In Fig. 1 1, we show the spectral variation of PAobtained for T = 1500K and

2500K. The curves of Fig. 1 I were computed for AA/A =
T, N 20 %
and T, = 30 % which is a typical value for the reflectance of elemental, and
111-V compound semiconductors near the direct absorption edge. In addition, we used 1 = 12.5 mm, f = 4.5, and F = 300 mm which are typical of
several grating monochromators used for infrared spectroscopy. The above
194
R. L. AGGARWAL
values of I,f, and F are actually those for the Perkin-Elmer monochromator
model 98G.
The spectral variation of the photon noise limited F D can be obtained from
Fig. 10 when used in conjunction with the results of Fig. 11. This is shown in
Fig. 12 for a black body source at 1500K and 2500K. It is interesting to note
that photon noise limited FD is larger than lo5 over a large spectral range
0.4-60 p. In practice, however, it is not possible to achieve such large values
for FD on account of detector noise. There are several sources of detector
noise ; in a semiconductor device, these are current noise, generation-recombination noise, and thermal noise. The current noise, which is the dominant source of noise in semiconductors at low frequencies, is commonly
referred to as l / f noise due to its frequency dependence. Several sources of
current noise have been suggested. All of them are associated with the presence of potential barriers which may exist at rectifying electrodes, at dislocations, at the semiconductor surface, or at p-n junctions, e t ~In. most
~ ~ serniconducting photodetectors, the detectivity is essentially determined by the
current noise. Likewise, the fractional detectivity is also limited by the current
noise for low levels of total radiation power P incident on the detector. Since
the current noise does not depend upon P , FD increases linearly with P as
can be seen from the initial slope of the F D versus P curves for PbS, Si, PbSe,
and Ge :Au detectors shown in Fig. 10.
Wavelength
A(p)
FIG. 12. The photon noise limited fractional detectivity as a function of wavelength for a
black body source at 1500 K and 2500K.
2.
195
For sufficiently high values of P at which the current noise limited F D

approaches the photon fluctuation limited FD, the generation-recombination
(g-r) noise becomes important. The g-r noise has its origin in the statistical
fluctuation of the number of charge carriers in a semiconductor. In photon
detectors it is intimately associated with photon fluctuation noise arising
from the random generation and recombination of charge carriers due to the
randomness of the incident photon flux. Like the photon noise, the g-r
noise is white due to its flat frequency dependence. According to van Vliet55
photon noise and g-r noise contribute almost equally to the performance of
photodetectors. Therefore the largest possible F D which can be obtained
experimentally is approximately 2 - ' I 2 or 0.7 times the photon noise limited
FD. As shown in Fig. 10, Si and PbS detectors approach this ideal limit for
large values of P.
Thermal noise, also known as "Johnson noise," arises from the thermal
motion of charge carriers in a conductor or semiconductor. It is considerably
smaller than the current noise or the g-r noise. We have therefore neglected
it completely in our calculations for F D vs P curves shown in Fig. 10.
In a multiplier phototube there are two sources of noise : (1) dark current
noise, and ( 2 ) shot noise. The dark current noise is produced by the photoelectrons thermally excited from the photocathode. This noise can be
reduced by cooling the phototube with dry ice or liquid nitrogen. The
cooling is especially important for photocathodes with S-1 response which
are sensitive in the near infrared. The dark current noise is the limiting factor
for FD a t Iow values of P as can be seen in Fig. 10 which shows FD versus P
curves for S-1 and S-20 tubes. With increasing P the tube performance becomes limited by shot noise.
Shot noise in a photomultiplier tube is associated with the statistical
fluctuation in the release of photoelectrons from the photocathode when
exposed to a constant flux of photons. The fluctuation in the photons arriving
at the photocathode contributes an additional noise. The shot noise is
analogous to the g-r noise in a semiconductor. In fact, many authors use the
term shot noise to describe the g-r noise as well. To determine the shot
noise in a multiplier phototube, let us assume that there is no fluctuation in
the photon flux incident on the photocathode. The random noise current i, ofa
dc photocurrent 1, emitted from a photocathode is given by the basic shot
iaw56
(148)
where e is the electronic charge, and Af the electrical band width. Therefore,
ik2
ik/Ik
55
56
= 2e1, Af.
(2e Af/Ik)"2.
K . M. van Wet, Proc. Insf. Radio Eng. 46,1004 (1958).

For a derivation of this formula see, for example. K r u ~ ep., ~242.
~
( 149)
1%
R. L. AGGARWAL
Equation (149) for the fractional cathode noise current is very similar to Eq.
(142)for the photon noise as I,/e represents the average rate at which electrons
are released from the photocathode. Since the quantum efficiency q(A).
defined as the ratio of the number of electrons released from the photocathode
to the number of photons ofwavelength L incident on it, is less than unity, the
fractional shot noise is always greater than the fractional photon noise
provided the factor
exp(hv/kT)
exp(hv/kT) - 1
is not much different from unity. This is indeed true in the case of all the
known photocubes when used with conventional black body radiation
sources. In this approximation, the fractional shot noise is [q(A)]times
greater than the photon noise. The fractional shot noise appearing at the
anode of the photomultiplier is further increased by a factor [a/(a - 1)~]/,
where cr is the mean gain per stage due to secondary emission process, and E
is the collection efficiency of the first dynode. Therefore, the random anode
noise current i, in the average anode current I , is given by
idla= [ 2 0 Af/(a
l)q(A)~Nl~/,
( 150)
where N is the rate at which the photon flux arrives at the photocathode.
Expressing N in terms of PA,the shot noise limited FNEP will be given by
The first term equal to unity inside the square brackets is due to photon noise
whereas the second term is due to shot noise. A computation of FNEP(A)for a
given phototube requires a knowledge of the tube parameters cr, q(A), and E .
Typical values for cr and E are approximately 3.557and 0.3,* respectively, for
most tubes. But ?(A) shows a wide variation among photocathodes having
different spectral response^.'^ For example, q(A) at the wavelength of peak
response is as large as 1&20 % for S-20 photocathodes, and as small as 1/40/,
for S-1 photocathodes. But ./(a - l)q(L)~>> 1 for all tubes. This implies that
the photon noise is negligible in comparison with the shot noise. In this
approximation, the fractional noise equivalent power for the photomultiplier
tubes is given by
FNEP(L) 5
[ ~ ~ C Af/lPA(o
C J
-
Deduced from manufacturers data sheets.

58
l)q(A)~]~
R. Foord, R. Jones, C. J. Oliver, and E. R. Pike, Appl. Opt. 8, 1975 (1969).
(152)
2.
197
Therefore, the shot noise limited fractional spectral detectivity is

(153)
In Fig. 10 the FD versus PA curves corresponding to the wavelengths of
peak response for the S-1 and S-20 photomultipliers were shown. These
curves of Fig. 10 showed two distinct slopes. The larger slope for low values of
PA is due to the dark current noise, and the smaller slope obtained for large
values of P is determined by the shot noise according to Eq. (153). At intermediate values of PA, however, both the dark current noise and the shot
noise contribute to FNEP to limit FD.
A final remark about the choice of a photodetector for modulation experiments: It is well known that the best detector for a conventional optical
experiment for a given wavelength is the one which has the largest fractional
detectivity. Since F D is a function of the total power PA incident on the
detector, the selection of the best detector for a modulation experiment
requires a knowledge of the largest possible value of PAwhich may, in some
cases, be limited by the maximum power rating of the detector. Let us, for
example, consider the choice of a detector for use at 0.5 p. An S-20 photomultiplier is the obvious choice for a conventional experiment at this wavelength. However, an examination of Figs. 10 and 11 together with the spectral
response curves and other specifications for the maximum power ratings
shows that silicon photodiode is the best choice for modulation experiments
at 0.5 p.
FD(II) v [iq(A)&(a- 1)PL/2hcoAf] .
5. WAVELENGTH
MODULATION
Wavelength modulation is an external modulation technique. The wavelength of the radiation incident on the sample is usually modulated inside
the monochromator which is used for obtaining monochromatic radiation
from an incandescent source. To appreciate the technique of wavelength
modulation, suppose the intensity of radiation of wavelength 3. incident on the
detector can be represented by P(II + AII sin at),where AII is the amplitude of
wavelength modulation and w is the frequency of modulation. By Taylors
series expansion
dP
P(A + AA sin or) = P(3.) + -(A].
dA
or
P(E.
+ AII sin w t ) =
{[
[
P(II)
sin cot) +
1 d2P
-(A).
2 dR2
sin wt)
.] [ai,+ . . .]
2P
+ 41 d7(Ai)2
+ .. +
dl.
~
+ . . .,
--+ d 2 P . . . cos 2wt

4 diL2
dP
sin or
198
R . L. AGGARWAL
Equation (1 54) shows that for a small amplitude of modulation, wavelength

modulation techniques provide a first-order derivative signal due to the
term AA (dP/dA)sin wt at the frequency of modulation, whereas the term
[(AA)/4] (dzP/dA2)cos 2wt yields a second order derivative signal at twice the
frequency of modulation. Thus, the wavelength-modulated spectrum is
simply the first or the second derivative of the conventional spectrum. In
contrast, the lineshapes observed with internal modulation techniques such
as electric field, stress or temperature modulation may be quite complicated,
and theoretical considerations are used to unfold the true lineshapes. In view
of the simplicity of the lineshape for the wavelength-modulated spectra,
wavelength modulation can be used very profitably to study the effect of a
perturbation such as magnetic field,59 electric field, temperature or
s t r e ~ s , ' ~ applied
, ~ ~ , ~ to
' the material under investigation. Another advantage
of wavelength modulation technique is that there are no special requirements
as to the sample dimensions and/or its material properties as is usually the
case for internal modulation. For example, in the stress modulation technique
of Engeler et a l l 6 thin samples are essential so that the applied stress or
strain is uniform throughout the whole sample.
There is one serious drawback, however, in the wavelength modulation
technique. It is obvious from Eq. (154) that wavelength modulation enhances
the wavelength-dependent optical structure present not only in the sample
but also in the rest of the optical system between the source and the detector.
This includes atmospheric absorption due to water vapor, carbon dioxide,
etc. The background structure may be quite unobtrusive in conventional
optical measurements but can become comparable to or even larger than
the structure due to the sample in wavelength modulation. It is possible
to separate the desired sample structure from the background structure
through the use of a double-beam instrument with the sample placed in the
path of one of the two beams. But one has to contend with the usual problems
of double-beam spectroscopy. For instance, complete cancellation of the
background structure is not achieved if the path lengths of the two beams
arenotequai or ifthespectral responseisnot identical for both the detector^.^'
Several methods have been suggested for modifying a monochromator
so that it could be used for wavelength modulation. Depending upon the
particular monochromator at hand, each investigator devised his own
scheme for this modification. Most of these devices usually called "wavelength wobblers" are very restrictive in their use since they can be inserted
59
R. L. Aggarwal and M. Reine (to be published).
J. E. Rowe, F. H. Pollak, and M. Cardona, Phys. Reo. Lett. 22,933 (1969).

6 1 L. D. Laude, F. H. Pollak, and M. Cardona, Phys. Rev. B3, 2623 (1971).
6 2 G. Bonfiglioli, P. Brovetto, G. Busca, S. Levialdi, G. Palmieri, and E. Wanke, Appl. Opt.
6, 447 (1967).
6o
2.
199
or installed only in the same type of monochromator for which they were
intended originally. Gilgore et a/.h3have described a wavelength wobbler
which is adaptable toany monochromatorwherethereisroom for it. It consists
of a transparent refracting plane disk attached to a shaft driven by a synchronous motor. As the shaft rotates, a ray of light passing through the disk is displaced in a circular path. When this device is placed in front of the exit slit of
the monochromator, the wavelength of the radiation passing through the slit
is modulated at the rotation frequency of the shaft. Being a mechanically
driven system, the rotating disk wobbler cannot be operated at frequencies
much higher than 60 Hz. Also the amplitude of wavelength modulation for a
given wobbler cannot be varied since it depends only upon the refractive
index of the disk, its thickness and the angle which it makes with the shaft.
The wavelength wobbler reported by Perragaux and AscarelliZ0is much
more versatile than the rotating disk modulator. It consists of a blade of
transparent material fastened to a bimorph piezoelectric transducer. The
amplitude of wavelength modulation obtained with this device can be varied
by simply varying the voltage applied to the transducer. This is a very useful
feature since the optimum amplitude of modulation is determined by the
line width ofthe transition to be studied. It is necessary to use small amplitude
of modulation for sharp lines whereas a correspondingly large modulation
can be used for broad lines in order to obtain good signal-to-noise ratio.
Another wavelength modulation technique applicable to any conventional
monochromator has been reported by Braunstein rt al.h4This requires a
replacement of the diagonal mirror before the exit slit with a mirror which
can be made to oscillate with a piezoelectric transducer. The chief advantage
of this setup is that it is equally good for any wavelength in the spectral
range of the monochromator.
6. STRESSMODULATION
The optical properties of a solid are, in general, sensitive to the presence
of an external stress. Therefore. the application of oscillating stress to the
sample should modulate its reflectance or transmittance at the frequency of
the applied stress. The stress-modulated reflectance or transmittance is
extremely useful for obtaining information about the band structure and
' ~ the first
other fundamental properties of the material. Engeler er ~ 1 . were
to report a simple but elegant method for modulating the reflectance of a
solid with stress. Gobeli and Kane" used a somewhat different method for
stress modulation of reflectance. But this method is not quite as convenient
to use as that of Engeler et ~ 1 . 'Since
~
a number of magnetooptical
63
h4
A. Gilgore. P. J . Stoller, and A. Fowler, Reu. Sci. Inst. 38,1535 (1967).

R. Braunstein. P. Schreiber. and M . Welkowsky. Solid Stare Commun. 6, 627 (1968).
200
R. L. AGGARWAL
Vacuum Grease
FIG. 13. The sample and transducer arrangement for stress-modulated reflectance experiments at low temperatures.
experiments to be discussed later have employed the stress-modulation

technique of Engeler et ~ 1 . it
' ~is discussed below in detail.
In the stress modulation technique of Engeler et ~ 1 . 'the
~ mechanical
stress is applied to the sample by means of a lead-zirconate-titanate
(PZT-4)65 piezoelectric transducer shown in Fig. 13. A thin (-0.5 mm)
sample is mounted on one face of the transducer approximately 2.5mm
thick with grease, which provides a rigid bond between the sample and
the transducer at temperatures below the freezing point of the grease. An
important advantage of using grease as a cement is that it minimizes the
chances of introducing inhomogeneous strains in the sample during the
process of cooling. For experiments to be performed at temperatures at
which the grease does not provide a rigid bond between the sample and the
transducer, a thin layer of any glue or epoxy may be used instead. To avoid
oxidation of the sample, it is preferable to use a glue or epoxy which hardens
at room temperature. Duco cement is found to be quite satisfactory for
this purpose.
65
A product of Clevite Cop., Bedford, Ohio.
2.
201
To determine the strain introduced in the sample by the transducer, let us

first discuss the oscillation mode of the transducer. The PZT-4 is supplied
by the manufacturer in the form of a disk for radial mode operation. This is
the mode in which a disk retains the shape of a disk when it is excited with
the application of an electric field across its thickness. We prefer to describe
this mode as the breathing mode for the following reason: If the disk is cut
into another shape, say, a rectangle, the transducer retains its rectangular
shape when in operation. Algebraically the breathing mode can be defined
in terms of the strain components as follows. Let us choose a Cartesian
system of coordinates (x, y, z) such that x and y are in the transducer face
on which the sample is mounted, and z is parallel to the thickness of the
transducer which is also the direction of the electric field in the transducer.
If ex,x, and eYfYf
are the diagonal strain components along the
and y-axes,
respectively, then for the breathing mode
XI-
( 155)
e x s x=
f eY,,,,= S ,
where S is the isotropic strain in the xy-plane.

Since a thin sample is mounted on the xy-face of the transducer, it is
also subjected to the isotropic strain S in the xy-plane. In fact, the strain
tensor is diagonal in the (x, y, z) coordinate system. The three nonzero
diagonal components of the strain tensor for the sample are
e:,
and
el,, = S
e;, = AS,
( 156)
where A is determined by the condition that there is no stress on the sample

in the z-direction and can be expressed in terms of the elastic constants of
the crystal. For cubic crystals, Kleiner and Roth obtained the following
expressions for 2 in the case of three principal crystallographic directions.
for z 11 [OOl], (157a)
2c,,/c11
where e l l , c 1 2 ,and c44 are the elastic stiffness constants. To find the effect
of the above strain on the optical properties of the crystal, it is often convenient to express the strain tensor relative to crystal axes. This is easily
done by following the usual method for the transformation of a second rank
tensor. For example, a strain component in the crystal system
eij
Ca,iulje;l,
kl
(15 8 )
R. L. AGGARWAL
202
where e;, is a strain component in the primed system and uki, a I j , .. . are
components of the matrix for transforming a vector in the crystal system to
the primed system.
For stress modulation experiments with radiation transmitted through the
sample Engeler el
used a three-post yoke. The sample forms the central
leg of the yoke and two matched PZT-type transducers form the other two
legs of the yoke. In this setup the sample is subjected to uniaxial stress
instead of the two-dimensional stress obtained with the arrangement of
Fig. 13. A simpler technique for stress modulated transmission experiments
has been used by Aggarwal et al.34 In their arrangement shown in Fig. 14
a rectangular slot is cut in the middle portion of the transducer. A long thin
sample is mounted on this slot in the transducer. If the width of the sample
is smaller than the width of the slot so that the sample is cemented at its two
short ends only, then it is subjected to uniaxial stress along the length of
the sample.
To obtain the components of strain tensor for the setup of Fig. 14, let us
choose an orthogonal set of axes x, y, and z such that y is along the length
of the sample, and 2 is normal t o the sample face as in Fig. 13. As in the case
of two-dimensional stress discussed already, the strain tensor for the sample,
except for the ends, is uniform and diagonal in the (x, y, 2) coordinate
system. The strain component e;, = S , where S , as before, represents the
isotropic strain in xy plane of the transducer. The strain components e:,
and e:, are determined by the condition that there is no stress on the sample
in the
and 2-directions. For cubic crystals the uniaxial stress T = Tl,,
for principal crystallographic directions is given by
XI-
S/S,,
for Y11[0011,
( 159a)
2S/(SIl
for y)1[110],
(159b)
for yI)[111],
( 159c)
+ S , , + is,,)
T = 3S/(S,, + 2SI2 + S,,)
where S , , , S , , , and S,, are elastic compliance constants. In terms of T,

the strain components relative to the crystal axes are given below for the
above three orientation^.^,
66
W. E. Engeler, M . Garfinkel, and J . J. Tiemann. Phvs. Rev. 155. 693 (1967).
2.
PZT-4
Transducer
203
Sample
FIG. 14. Alternative sample and transducer arrangement for stress-modulated transmission
experiments at low temperatures. (After Aggarwal Ct
7.
MAGNETIC-FIELD MODULATION
Magnetic-field modulation is perhaps the oldest modulation technique.

It has been extensively used for nuclear and electron paramagnetic resonance
experiments for more than 30 years. In 1955 Dexter and Lax3 extended
the use of magnetic-field modulation for the observation of weak cyclotron
for a
resonance absorption in Bi. Later on it was used by Bagguley et
study of cyclotron resonance absorption in p-type germanium at high
temperatures around 100K at which the conventional measurements may
not have had enough sensitivity for the observation of weak absorption.
More recently Iwasa6 has employed magnetic-field modulation for the
observation of interband magnetooptical transitions in semimetals.
67
S. Iwasa and A. Javan, Bull. Amer. Phys. SOC.14, 116 (1969).
R. L. AGGARWAL
204
As discussed in Section l(c), magnetic-field modulation has an important

advantage over wavelength or stress modulation for the observation of
interband magnetooptical transitions. There is, however, one serious drawback to the magnetic-field modulation technique. It cannot be used to
observe the zero-field spectrum because in the absence of a dc magnetic
field, the modulating field could affect the zero field edge only if the cyclotron
frequency uccorresponding to the modulating field is such that mcr > 1.
Usually this condition will not be satisfied for the small modulating fields
employed in the experiments.
Experimentally the modulating field can be generated either by the same
magnet which provides the dc field or by a separate coil placed around the
sample. In the former case a small ac current is superimposed upon the dc
current through the magnet. In this manner a maximum peak-to-peak
amplitude of approximately 3 kG at
10-15 Hz can be generated in the
100-kG Bitter magnets at the Francis Bitter National Magnet Laboratory. But the amplitude of modulation falls off very rapidly at higher
frequencies.
Finally, we will consider the magnitude of Am,, . Let us assume m p 0.04 m
which is within a factor of 2 or so of the k = 0 conduction band mass for
germanium and several III-V compound semiconductors. For this value of
m,,,
Eq. (37) gives h Am,, = ( n + 4)(0.3 meV/kG). This may be compared with
h A o , 0.4meV obtained in stress modulation experiments for the same
class of materials. Thus we should expect comparable results from these
two techniques.
8. ELECTRIC-FIELD
MODULATION
Several methods have been employed for applying ac electric fields to a
semiconductor sample. The simplest method of all is, of course, the direct
application of a high voltage to the sample. Since an electric field F lo4 V/cm
or higher is usually required to obtain appreciable modulation of reflectance
or transmittance, the direct method is limited to materials which are or can be
made very highly insulating. Even then it is difficult to obtain high electric
fields in the sample. Moss,'' for example, was able to obtain a maximum
field of only 5 x lo3 V/cm in insulating GaAs of unusually high resistivity
(> 10' ohm/cm).
To obtain electric fields much higher than 5 x lo3 V/cm in a semiconductor,
the method employed by Frova and Handler14 is very useful. By applying
a reverse dc bias voltage to a germanium diode they were able to achieve
electric fields of about lo5 V/cm in the space charge region of thep-n junction.
In order to modulate the transmission of the diode in the presence of these
high electric fields, a small ac voltage is superimposed upon the dc bias
voltage, and the resulting change in transmission is detected at the frequency
2.
205
of the modulating voltage. Even though the diode technique can be applied
to any semiconductor in which a p-n junction can be formed, it is of limited
application in the sense that it just cannot be used for any particular
sample of a given material. In f x t this is a very serious limitation of this
technique.
Seraphin developed an elegant technique for applying electric fields
lo5 V/cm to the surface of a semiconductor by using the principle of a
parallel plate condenser. In this method, usually known as the transparent
electrode technique, the modulating voltage is applied between the sample
acting as one of the two electrodes and a transparent electrode, consisting of
a transparent conductive coating on glass, separated from the sample surface
by a 10-p-thick insulating spacer of Mylar. An optical matching material is
used between the electrode and the insulator in order to avoid a large
unwanted wavelength independent signal caused by interference of light
reflected from the insulator-sample and electrode-insulator interfaces.
It was pointed out by Pidgeon et ~ 1 that. the~ electrode
~
sample assembly
of Seraphin is not suitable for low-temperature experiments, since most
optical fillers crack and become opaque when they are cooled to temperatures below 77K. To overcome this problem, Pidgeon et
developed a
mechanically integrated thin film package shown in Fig. 15. The insulating
spacer consists of 1-p-thick layer of Kodak Photo-Resist material KPR,
which is spin coated on the etched sample surface. A 65% transmitting
Ni film was deposited on the KPR layer to act as the transparent electrode.
This package has been used for temperature down to 1.5K.
Another method for applying high electric fields to the surface of a semiconductor was reported by Shaklee et ~ 1 . In~ this method, known as the
electrolyte technique, the sample is immersed in a dilute solution of KCl in
water and the ac voltage is applied between the sample as one electrode and
a platinum plate, also immersed in the KCl solution, acting as the other
electrode. The sample is dc biased so as to form a blocking contact, and the
ac voltage is put in series with the bias voltage.
The great advantage of the electrolyte method is its simplicity. For
example, it does not require accurately flat and smooth surfaces which are
essential for the transparent electrode method. But it cannot be used for
low temperature experiments due to the freezing of the electrolyte. It has
been pointed out, however, by Shaklee et ~ 1 . that
~ a suitable low-temperature
electrolyte such as propyl alcohol could be used down to 146K. Another
limitation of the electrolyte method is that it cannot be used in the infrared
region where the electrolyte begins to absorb strongly. According to Groves
et al.24the long wavelength cutoff is about 3 p for an electrolyte consisting
of a dilute solution of HCl in methyl alcohol provided the light path through
the electrolyte does not exceed a fraction of a millimeter.
206
R. L. AGGARWAL
V (mox)
- 40 V
540 H r
FIG.15. Mechanically integrated thin film package for electric field modulation. This can be
used for temperatures down to 1.5"K. (After Pidgeon et 0 1 . ~ ~ )
On the basis of photoreflectance experiments it has been suggested by

several authors21,68that the surface electric field in semiconductors can be
influenced by exposing the surface to an intense beam of highly absorbing
radiation so that it is absorbed in a very small depth below the surface.
Supposedly the free carriers produced by the light beam neutralize the
built-in surface field; this results in modulation of the surface field at the
chopping frequency of the intense light beam. This light modulation technique has been used successfully for magnetoreflectance experiments in
InSb.69
9. TEMPERATURE
MODULATION
Temperature modulation is based on the fact that the optical absorption
or reflection of a substance is, in general, changed by temperature. One or
more of several temperature-dependent parameters such as phonon population, energy gap, electron-phonon coupling, etc., could influence the optical
response of crystals to a change in temperature. For example, temperatureinduced changes in absorption at the indirect edge have been shown to arise
primarily from the modulation of phonon population.'' O n the other hand,
thermoreflectance spectra for the direct edge in germanium" and silicon' I
have been interpreted successfully in terms of the shift of the energy gap
with temperature. In this respect, the temperature modulation of optical
R . E. Nahory and J. L. Shay, Phys. Rev. Left. 21, 1569 (1968).
J . L. Shay, R. E. Nahory, and C. K . N . Patel, Phys. Rev. 184,809 (1969).
'' C. N. Berglund, J . Appl. Phys. 37, 3019 (1966).
'' A . Balzarotti and M. Grandolfo, Solid Srure Commun.6, 815 (1968).
68
69
2.
207
absorption or reflectance due to direct transitions is similar to wavelength

modulation of this structure.
The temperature of a specimen can be easily modulated by passing an
ac current through it.18 In order to keep the average temperature of the
specimen close to that obtained in the absence of current flow, the specimen
should be either immersed in a liquid refrigerant or a good thermal contact
must be provided with a cold finger which is in direct contact with the refrigerant.
Not considering its simplicity, temperature modulation is, in many cases,
inferior to other modulation techniques such as stress or electric-field
modulation for the following reasons. Firstly, it is difficult to obtain large
enough amplitude of modulation for frequencies exceeding 10-15 Hz.
Secondly, the linewidths of temperature modulated spectra are considerably
larger than those obtained with stress or electric field. For this reason, the
temperature modulation is incapable of resolving fine structure which can be
readily seen with other modulation techniques. In view of this limitation,
temperature modulation technique is not considered to be very useful for
magnetooptical experiments. To be sure the temperature modulated magnetoreflectance in InSb provided a very poorly resolved spectrum.
IV. Experimental Results

10. THE DIRECT
EDGEIN GERMANIUM
a. Electric-Field-Modulated Magnetoabsorption and Magnetoreflectance
The first modulated interband magnetooptical experiments were reported

by Vrehen and Lax on the direct edge in germanium. They used crossed
electric-field modulation to study magnetoabsorption in thin samples at
room temperature and at 77K. In Fig. 16 is shown the 77K cross-field
magnetoabsorption spectrum obtained by V r e h e ~The
~ . ~negative
~
peaks in
the differential spectrum of Fig. 16 have been interpreted by Vrehen as arising
from the electric field induced decrease in magnetoabsorption due to the
allowed transitions; the positive peaks have been identified as due to the
normally forbidden transitions. Since a large number of allowed as well as
forbidden transitions are predicted from theory, it is not certain if the
forbidden transitions were actually observed in the cross-field spectrum of
Fig. 16. The uncertainty stems from modulated magnetoreflectance measurements in InSb by P i d g e ~ n . He
~ compared the cross-field spectrum with the
parallel-field spectrum and found them to be nearly identical. Since only
J. Feinleib. C. R . Pidgeon. and S. H . Groves. BUN.Amer. Ph.w SOC.11. 828 (1966)
C. R. Pidgeon, private communication (1969).
R. L. AGGARWAL
208
880
920
960
1000
1040
PHOTON E N E R G Y ( r n e V )
I( 80
FIG. 16. Magnetoabsorption and cross-field differential absorption in strain-free germanium at 77K and 96 kOe for H 11 [110] and RCP(u_) radiation. (a) magnetoabsorption
spectrum, (b) calculated relative absorption intensities, (c)cross-field differential spectrum with
Edc = lo00 V/cm, and E,, = 250 V/cm (rms), and (d) calculated differential spectrum, positive
lines corresponding to forbidden transitions, negative ones to allowed transitions. For clarity of
presentation the strengths of heavy-hole transitions are shown on a scale 1/10 those of light(6)
ladder; x (b) ladder:
hole transitions in the calculated spectrum (d). A, (a) ladder; 0,
0 ,( b - ) ladder. (After V r e h e ~ ~ . ~ ~ )
the allowed transitions are expected for the parallel fields, Pidgeons magnetoreflectance experiments in InSb seem to indicate that only the allowed
transitions are seen in the cross-field configuration as well. O n the other hand,
the cross-field and parallel-field magnetoreflectance spectra obtained by
Evangelisti and F r ~ v are
a ~not
~ the same. This lends support to Vrehens
interpretation that forbidden transitions contribute to the cross-field
differential spectrum.
Another aspect of Evangelisti and Frovas work concerns the lineshape
analysis of the surface electric field-modulated magnetoreflectance spectrum.
They have shown that the reflectance lineshape cannot be explained satisfactorily in terms of the change Acl in the real part of the dielectric constant
l4
F. Evangelisti and A. Frova, Phys. Status Solidi 33, 623 (1969).
50
8
-50
=!
0 750
0 800
0 850
0 900
0 950
I000
I050
I 100
I150
I200
PHOTON ENERGY ( e v )
FIG. 17. Interband electroreflectance in germanium for H = 0 (dashed line) and H = 92.4 kG (solid line) in the parallel electric and magnetic
transitions
field configuration, at T 1 300K. Theoretical energies and relative strengths are shown for allowed light-hole ( x ) and heavy-hole (0)
up to 1.03 eV. Above this energy the positions of the principal light- and heavy-hole transitions are indicated by small arrows. The relative positions
of all the allowed split-off transitions are shown by heavy arrows. A schematic diagram of the experimental arrangement is shown (insert). (After
Groves et a1.*")
N
0
\o
210
R . L. AGGARWAL
1.050
0
O
0
12
3
;
>-
1.000
2
0
5
a
0.950
0.900
0.850
FIG. 18. Plot of the photon energy of magnetoelectroreflectance minima as a function of

magnetic field. The circles show the experimental points. The crosses give the positions of the
magneto-absorption peaks (i.e., transmission minima) of Zwerdling et (11. for H = 35.7 kG.
and the solid triangles, those of Vrehen for H = 96 kG (S indicates strong feature and W, weak
feature). The solid lines give the theoretical energies for the principal allowed light- and heavyhole transitions labeled 1-13. The split-off transitions are labeled Sl-S4. The values are for
Ge[ 11 13 and E IH 11 F. (After Groves et dZ4)
2.
21 1
10
00
% I2
- IE
- I0
- 20
09
10
11
12
I3
Phaton Energy ( e V )
FIG.19. Stress-modulated magnetoreflectance spectrum for the light-, heavy-, and split-offhole transitions in germanium at T 3OK, observed in the Faraday configuration with RCP
radiation and magnetic field H = 84.9 kG applied along a [110] direction with AS = 2.5 x
lo-. The strong minima in R - AR/AS are identified with lines under them which have a
characteristic symbol at the top end indicating the type of transition. A, a + + uc ; 0,
o + uc:
0 ,b- + b; m, h -+ b. The length of a given line is proportional to the oscillator strength
of the transition it represents. The positions of the lines are obtained from Eqs. (12) and f13) of
Aggarwal with the following parameters: 6, = 0.888(5)eV, A = 0.296 eV, E , = 26.8 eV,
( m / h 2 ) F = - 1.1. y l L = 13.38, ;2L = 4.30, 7,. = 5.68. tiL = 3.41. 8,= -0.0015eV, and
66, = 0.0056 eV. (After Aggarwal.)
alone, as it would be if the electric field were uniform. Both the real and
imaginary parts of the dielectric constant are needed to describe the line
shape observed with nonuniform fields.
In Fig. 17, we show the room-temperature magnetoreflectance spectrum
in Ge obtained by Groves et d2*
with the electrolyte electric field modulation
technique in the parallel-field configuration. The usefulness of the magnetoelectroreflectance for observing Landau levels high into the bands is quite
apparent. At about 1.1 eV transitions from the light- and heavy-hole bands
merge with those from the split-off valence band. A plot of the photon
energies for the magnetoelectroreflectance minima as a function of the
applied magnetic field H is shown in Fig. 18 in which the solid lines give the
theoretical energies computed from the coupled band scheme of Pidgeon
and Browna4 discussed in Section 2. I t is apparent from Fig. 18 that the
magnetoelectroreflectance data is consistent with the conventional lon-field
R. L. AGGARWAL
212
Photon Energy ( e V 1
FIG.20. Stress-modulated magnetoreflectance for LCP radiation (also see Fig. 19) for H =
84.9 kG and AS = 2.5 x 10- . The minima in R - I ARIAS with a question mark occur at the
same energy where there is strong structure in the RCP spectrum. These minima in LCP are,
therefore, presumably due to incomplete polarization of the circular polarizer. A, a+ + a :
X , b
b ; 0,
a - + a;
b - --t b; 0,
am + a. (After A g g a r ~ a l . ~ ~ )
e,
magnetoabsorption data of Zwerdling et ~ 1 . and

~
with the cross-field
magnetoabsorption data of Vrehen.38 The experimental data are also in
good agreement with theory. However, no attempt was made to obtain
the best fit between experimental and theory by adjusting the band parameters.
b. Stress-Modulated Magnetorejlectance
The stress-modulated magnetoreflectance for the direct edge in germanium
was first observed by Aggarwal et ~ 1 . and
~ Mavroides et aLZ3These preliminary room-temperature experiments which actually preceded the electric
field-modulated magnetoreflection measurements of Groves et
provided
spectra similar to those of Fig. 17 for magnetoelectroreflectance. The main
contribution of the room-temperature work was that it established the
usefulness of the stress modulation technique for the observation of Landau
levels high into the band. But the room-temperature data were not subjected
to any detailed analysis for the evaluation of band edge parameters.
76
S. Zwerdling, L. M. Roth, and B. Lax, Phys. Rev. 108, 1402 (1957).

R. L. Aggarwal, L.Rubin, and B. Lax, Phys. Rev. Lerr. 17,8 (1966).
2.
213
24 6? eV
OL
23 8
I
24 2
I
250
I
24 6
254
PP (eV)
FIG. 21. Root mean square deviation of the observed energies for the heavy-hole transitions
from those calculated from Eqs. (12)and (13) of A g g a r ~ a as
l ~a~ function of JP,with F = 0 and
the remaining parameters being the same as for Fig. 19. The following twelve transitions were
used in thecalculation of therms deviation : a-(3)aC(2),
b-(3)bC(2),a-(4)aC(3),b-(4)bC(3),a-(6)aC(5),
b-(6)bC(5),a-(2)aC(3),b-(2)bC(3),a-(3)aC(4),b-(3)b'(4), a-(5)aC(6),and b-(5)bC(6)for H = 53.1
and 84.9 kG.(After A g g a r ~ a l . ~ ~ )
The stress modulation technique was then adapted for low-temperature

experiments by A g g a r ~ a l .In~ ~Figs. 19 and 20, we show the stressmodulated magnetoreflectance spectra obtained at a temperature of 30"K.'7
These spectra were observed with the specimens in the Faraday configuration
in which the direction of propagation for the radiation is parallel to the
applied magnetic field. The stress-modulated reflectance R ARIAS
shown in Figs. 19 and 20 exhibits the following features: Beginning on the
low energy side, the R - ARIAS structure associated with a given transition
consists of large negative spike which is followed by a smaller positive spike.
As we go to higher energies the size of the positive spikes decreases faster
than that of the negative spikes. Above 1.0eV only the negative spikes
are observed. For this reason we chose to use the minima of R - ' ARIAS
for the transition energies. At about 1.2 eV transitions from the light- and
heavy-hole valence bands merge with those from the split-off valence band.
The experimental data have been analyzed in terms of the coupled band
theory of Pidgeon and Brown for the energies of the Landau levels as discussed
in Section 2. In this analysis we used the valence band parameters yiL, yZL,
;13L,
and K~ as determined by Hensel and Suzuki'* from cyclotron resonance
in p-type germanium. With values for Lfg and A as deduced from the analysis
7'
78
R. L. Aggarwal, Phys. Rev. BZ, 446 (1970).

J . C. Hensel and K . Suzuki, Phys. Rev. Leu. 22,838 (1969); 21,983 (1968)
214
R. L. AGGARWAL
FIG.22. Root mean square deviation of the observed energies for the light-hole transitions
from thosecalculated from Eqs.(l2)and(l3)0fAggarwaI,~~
withc$andFsuchthat m, = 0.0038 m,
and the rest of the parameters being the same as for Fig. 19. The following 10 transitions were
used in calculating the rms deviation : a+(3)aC(2),a+(4)aC(3),a+(5)aC(4),a+(6)aC(5),a+(7)aC(6),
b+(1)bc(2), b+(2)b'(3), b+(3)b'(4), b+(4)bC(5),b+(5)b'(6) for H = 53.1 and 84.9 kG. (After
Aggarwal.")
of the zero-field stress-modulated spectrum together with the analysis of the

data for the split-off transitions on the basis of the decoupled band scheme,
we calculated the photon energies for the allowed heavy-hole valence-toconduction transitions for many values of the parameter 8pwith F = 0.
In Fig. 21, we show the root mean square deviation of the calculated energies
from the experimental values for a number of transitions observed at intermediate and high fields. The minimum in the root mean square deviation
occurs at gP = 24.67eV. But this value of c"p along with F = 0 does not
provide an equally good agreement for the light-hole valence-to-conduction
band transitions. However, if we choose a small but negative value for F
and at the same time increase EPin such a manner that the conduction bandedge mass as given by Eq. (91) remains unchanged, the agreement between
experimental and calculated values improves. This behavior is shown in
Fig. 22 which is a plot of the root mean square deviation for the light-hole
valence-to-conduction band transitions. In this manner, we find that
F = ( - 1.1 f 0.2)h2/m,and dP = (26.8 _+ 0.4)eV provide the best fit for the
experimental data. Thiscan be seen in Figs. 23 and 24 which show the photon
2.
215
energy as a function of the applied magnetic field. Except for a small deviation
for the low quantum transitions, presumably due to exciton effects neglected
in this analysis, the experimental data are in excellent agreement with the
computed results shown by the solid curves. With the band parameters used
in these computations the following values for the band-edge masses and
g-factors are obtained: tnc = (0.0380 k 0.0005) m, rn, = 0.042 m, 4, =
0.34m. and g, = -3.0 f 0.2. With these values of m, and g c , we deduce
20
13
I9
I7
I5
12
I4
>
-
I3
?
W
11
0
c
S
0
6
5
I0
3
2
09
I
20
I
40
Magnetic
60
a0
I no
Fleld i k G )
FIG.23. Plot of the photon energy versus magnetic field ror a number oftransitions allowed in
the Faraday configuration for the RCP radiation. The solid fines are the theoretical curve5
obtained from Eqs. (12) and (13) of Aggarwa17' with the same parameters as for Fig. 19.
The numbers next to each curve denote the following transitions: 1.
'Ll)u'(O),K ( 1 ) M O ) :
2. u + ( I ) d ( O ) ;3. a - ( 2 ) a ' ( l ) , b ~ ( 2 ) b C ( l 4.
) : aC13)uc(2),b-(3)6'(2): 5 . a + ( 2 ) u " l I ) : 6. u-(4)trc(3),
b-(4)hC(3); 7. a+(3)aC(2);8. a - ( 6 ) a C ( 5 K
) , ( h ) b ' ( 5 ) :9. a'14)0'(3): 10. u-(7)uC16),h - ( 7 ) h c ( 6 ) :
I I . a-(8)aC(7),h-(8)bC(7):12. u + ( 5 ) a C ( 4 ) 13.
: u + ( 6 ) u c ( 5 ) :14. t r + ( 7 ) u C ( 6 )15.
: u+(X)rr'(7): 16.
a'(9)aC(8):17. h""(l)b"(O): 18. hs0(2)h'(l):19. hs0(3)h'(2):20. h'"(4)hC(3).A.u' + d : 0.K -t t f :
0 . h - + b';
b" + h'. (After Aggarwal.")
..
216
R . L. AGGARWAL
20
60
40
80
I00
Mognetic Field ( k G )
FIG.24. Plot of the photon energy versus magnetic field for a number of transitions allowed
in the Faraday configuration for the LCP radiation. The solid lines are the theoretical curves
obtained from Eqs. (12) and (13) of A g g a r ~ a lwith

~ ~ the same parameters as for Fig. 19.
The numbers next to each curve denote the following transitions: 1. b + ( - l ) b c ( 0 )2.
; a+(O)a'(l);
3. b+(O)b'(l); 4. K(1)aC(2),b - ( l ) b c ( 2 ) ;5. a-(2)ac(3),b-(2)bC(3);6. b+(l)b'(Z); 7 . a - ( 3 W ( 4 ) ,
; a-(7)aC(8),b - ( 7 ) b C ( 8 ) :
b-(3)bC(4);8. b+(2)bC(3);9. a-(5)ac(6),b - ( 5 ) b C ( 6 ) ;10. b + ( 3 ) b C ( 5 )11.
12. b+(4)b'(5);13. b+(5)bC(6);14. b+(6)bC(7);15. b+(7)bC(8);16. do(-I)a"(O): 17. ~'"(O)a'(l);
18.a'"(l)aC(2);19.a'"(2)aC(3).A , a + + a c ; x , b + + b C : O , a - + a c ; e , b - + b e ; U , a " - r u C .
(After A g g a r ~ a l . ~ ~ )
rnso = (0.095 ? 0.007) m and g,, = - 10 & 3 from the data for the split-off
valence-to-conduction band transitions.
11. THEINDIRECT EDGEIN GERMANIUM

The indirect absorption edge in germanium is due to transitions between
the valence-band maximum at k = 0 and the conduction-band minima at
the L points which lie along the ( 1 11 directions at the zone edge. Such
transitions occur via an intermediate state with the emission or absorption
>
2.
-8
217
-6
-4
-2
8~10.~
(l-w"3"2/wl
FIG.25. Plot of the lineshape function ~ [ +l ( w - W , , , ~ ) ~ T I~, ]for

- the indirect transition
in magnetic field. versus (I - conInJo>)
for the relaxation time T = 0.2 x 10- l 2 (- -), 0.5 x
lo-'' ( - . - . ) . a n d 1.0 x lO-"sec (- ). (After Aggarwal et
-
of a phonon in order to conserve total momentum in the initial and final

states. A calculation of the absorption coefficient for these phonon-assisted
transitions for the zero-magnetic field case was originally made by Bardeen
er ~ 1 . ' This
~
was modified by Macfarlane and Roberts" to include the
temperature dependence of the phonon population. The absorption coefficient
in the presence of magnetic field was obtained by Roth er d3'Assuming
simple conduction and valence bands and neglecting exciton effects, they
obtained the following expression for the absorption coefficient in magnetic
field.
a ( H ) = 2c'k(h2(~>c10~c2)
S ( h - hWnln2),
(161)
nlnz
79
J . Bardeen, F. J. Blatt, and L. H. Hall. in "Photoconductivity Conference" (Proc. Atlantic

City Conference) (R. G . Breckenridge, B. R. Russell, and E. E. Hahn. eds.) p. 146. Wiley,
New York and Chapman & Hall, London (1956). Phys. Rec;.95, 559 (1954).
G. G. Macfarlane and V. Roberts, Phy3. Rev. 97, 1714 (1955); 98, 1865 (1955).
R. L. AGGARWAL
218
4 x I0
4
3
Photon Energy ( m e V I
FIG. 26. Magnetopiezotransmission spectra for the indirect transition in germanium at

T 30K for H (1 T /I[ 1 1 1 ] with the direction of propagation q /I [ I T O ] . (a) E (1 H lj [ I I I]:
(b) E IH : (-)H = 88.9 kG; (---)H = 0. (After Aggarwal et
4
with
2 ) a unit step function, wcI and oc,are the appropriate

Here S(hw - h 0 f l , f 1 is
cyclotron frequencies for the two bands with their anistropy taken into
account, n 1 and n, are the respective Landau quantum numbers. g , and g,
are the appropriate spin g-factors and M , and M 2 are the spin angular
momenta; ggis the indirect energy gap and gPph
is the energy of the phonons
which are involved in the absorption process. C, = D exp( +JPph/kT)
where
D is a constant determined by the phonon and direct-transition matrices,
the density of states associated with the conduction and valence bands, and
219
z o x1 0 ' ~
- (a1
15 -
I
I
10 -
-j
5-
0-
-51
Photon E n P t g y ( r n e V I
FIG. 27. Magnetopiezotransmission spectra for the indirect transition in germanium at

T 30 K for H /I T j j [ I 101 with the direction of propagation q 1) [Ool]. (a) E /I H /I [110];
(b) E iH : (-)H = 86.3 kG:f- --)ff = 0. (After Aggarwal et ~ 1 . ' ~ )
-.
a factor for multiple conduction band minima. Due to phonon participation

there are no selection rules for ti, and n , . However, the selection rules for
the change in spin anguIar momentum are the same as for the transitions
without phonons, i.e., AM = Ofor E /I Hand AM = I for E 1H. According
to Eq. (161), the magnetoabsorption spectrum for the indirect transitions
should consist of a series of steps or absorption edges occurring at photon
frequencies o = a,,,,
. ,Such magnetoabsorption spectra were indeed
observed by Zwerdling et dS1
and Halpern and Lax.82
81
'*
S . Zwerdling, B. Lax, L. M . Roth, and K . J . Button, Phys. Rev. 114, 80 (1959).

J . Halpern and B. Lax, J . Phys. Chem. Solids 26, 91 I (1965).
220
R. L. AGGARWAL
The stress-induced change in the absorption coefficient due to the strain

AS is obtained from Eq. (161) as
1 6(hw - h o , , , , ) ( d & , d S ) A S ,
Aa(H) = 2C~(h2w,,wc,)
(162)
n1nz
provided the stress-induced changes in w c , ,(ucz,cFPbhand C, are neglected.

Equation (162) predicts that stress-modulated magnetoabsorption should
exhibit strong singularities at photon frequencies w = w,,,, in contrast to
the steps observed without modulation. However, if we take into account
the finite relaxation line T , the step function S(x) + arctan x where x =
(w - w n l n z )Therefore,
~.
in Eq. (162), 6(x) -, T[I
(w - o , , , , , ) ~ T ~ ] - '. Thus
the stress-modulated magnetoabsorption for each transition will show a
peak having the lineshape given in Fig. 25.34
In Figs. 26 and 27, we show the spectra observed by Aggarwal er d4
for
the stress-modulated transmission AT/T in germanium at T 30K for
two orientations of the magnetic field with uniaxial stress T I/ H. If we neglect
contributions due to multiple internal reflections in the specimens, we may
write34
for a specimen of thickness r. Of the three terms contributing to ATIT, the

first is relatively small and the third term merely produces a background
proportional to U. The spectral structure observed in ALYis caused by the
applied stress. The spectra of Fig. 26 and 77 for A T / T are consistent with
this interpretation.
An important aspect of the stress-modulated magnetoabsorption spectra
is the observation of structure over a spectral range which extends all the
way to the direct gap. In the conventional magnetoabsorption experiments,
structure was seen only in a relatively small spectral region lying close to
the indirect gap. The observation of Landau levels high into the bands has
made it possible to study the nonparabolicity of the indirect conduction
band minima. The variation in the transverse mass m,of the ellipsoidal band
as a function of electron energy & relative to the bottom of the band is shown
in Fig. X3' Experimentally, the increase in m,with energy was obtained from
the corresponding decrease in the energy separation, in the spectrum of
Fig. 26, between large peaks which have been ascribed to transitions from
the same Landau level in the valence band to successive Landau levels in
the conduction band ellipsoid with its major axis along the [ I 1 I] direction.
The theoretical curve shows the effective-mass variation obtained from the
2. MODULATED
221
INTERBAND MAGNETOOPTICS
following expression for the cyclotron effective mass:
m,(&) = m,(0)[1
+ 28/<(1,3')]-',
( 164)
where gg(1,3') 'c 2.2 eV is the energy gap between the L , and L,. conduction
TABLE I
SUMMARY OF THE BANDEDGEPARAMETERS IN GERMANIUM
Band
L,
L,-
m,/m
m,/m
r2.= r7-
Cyclotron
resonance
(4.2"K)
Parameter
m,lm
0.0819 0.0003"
0.082 & 0.00ld
1.64 rt 0.03"
1.58 k 0.04d
Magnetoabsorption
Stressmodulated
magnetoabsorption
(reflection)
(30K)
0.079(1.7K)b
0.079 f 0.001'
1.74 (1.7K)b
1.54 f 0.06'
0.038 (300K)'
0.0380
f0.0005J
0.037 f 0.00Ih
(4.2"K)
- 2.5 (4.2"K)h
-2.0 (5K)'
gc
EP
(mlh *)F
I-;$
ra+Y I L
Y2L
hL
KL
I-;$:
r7+m,,h
13.38'
4.30'
5.68'
3.41
'
I 3.25h
4.20h
5.56h
3.27h
~ "
'
0.042 & 0.005'

(300K)
0.037 (77K)'
f 0.2l
26.8 & 0.4 eVf

- 1.1 f 0.21
3.3 0.7l
0.095 +_ 0.007f
- 10
gsa
Dexter et
Halpern and Lax.82
Aggarwal et a/.34
Dresselhaus er ~ 1 1 . ~
' Burstein er u / . * ~ '
Aggarwal."
- 3.0
Electric
fieldmodulated
magnetoabsorption
(reflection)
* 3J
0.084 k 0.025*
(300K)
Groves er a/.24
Roth et a/.37
Vrehen.38
Johnson.a3d
Hensel and S u z ~ k i . ~ '
83aR.N. Dexter, H. J. Zeiger, and B. Lax, Phys. Rev. 104, 637 (1956).
83bG.Dresselhaus, A. F. Kip, and C. Kittel, Phys. Rev. 95, 568 (1954); 98, 368 (1955); C.
Kittel, Physicu 20, 829 (1954).
83cE.Burstein, G. S. Picus, R. F. Wallis, and F. Blatt, Phys. Rev. 113, 15 (1959).
J. Johnson, in Proc. Int. Conf. Phys. Semicond. Moscow, 1968. Vol. I, p. 276. Nauka,
Leningrad, 1968.
222
R. L. AGGARWAL
007
002
004
006
008
010
F (evl
012
FIG.28. Plot of the transverse effective mass m,, for the L, conduction band in germanium at
T 30"K, as a function of the electron energy 8 relative to the bottom of the band. The circles
denote the experimental points for H = 88.9 kG with E 11 H 11 [ l 1 11. The experimental curve
is a least-squares fit of the data points to a straight line. The dashed part of this line is to indicate
the data points not included for the fit. The theoretical curve (-.-.) shows the effective mass
variation as obtained from Eq. (164) which was deduced from the use of the ( k . p) perturbation
theory. (After Aggarwal et a1.34)
band edges. Equation (164) has been deduced from the use of the (k p)
perturbation theory. Figure 28 shows that the observed increase in mass is
linear only for large values of 8,and can be understood if the observed
transitions correspond to the creation of exciton states in a magnetic field.
If the Coulomb binding energy decreases with increasing n, the effective mass
deduced from the observed spectra should approach the true effective mass
for large n. Since the exact variation of the exciton binding energy is not
known, the mass at the bottom of the band has been determined by extrapolation of the line obtained for large d In this manner, we obtain rn,(O) =
(0.079 f 0.001) m. This is to be compared with the value of 0.082 m obtained
from the cyclotron resonance experiments. This discrepancy may partly be
due to the neglect of Coulomb binding energy which could be appreciable
even for large n.
In Table I, we summarize the band edge parameters for the L , conduction
band, the k = 0 conduction and valence bands in germanium as obtained
from various experiments.
12. THEFUNDAMENTAL
EDGEIN GALLIUM
ANTIMONIDE
There have been only a few magnetooptical experiments for the fundamental
edge in GaSb. The first interband magnetooptical experiments in GaSb were
2.
223
0.40
R
0.33
5 0 k (c)
I AR
--
R AS
a76
Y7
4
aao
0.84
PHOTON ENERGY (eV)
aaa
FIG. 29. Comparison of the wavelength-modulated and the stress-modulated magnetoreflectance spectra with the computed derivative spectrum AR/A& for the fundamental edge
in GaSb at T r 30K. (a) RCP reflectivity, H = 88.6 kG. (b)derivative, A& = 1 meV. (c) i-modulated, A1 = 0.06 A. (d) stress-modulated, AS = 5 x lo-. (After Aggarwal and Reine.59)
reported by Zwerdling et a1.83e who observed magnetoabsorption with

magnetic fields up to 40 kG. The Zeeman effect of the exciton and impurity
exciton complexes has been studied by Johnson and Fan84 with magnetic
fields below 20 kG. Halpern extended the magnetoabsorption measurements to higher magnetic fields up to 100 kG, but his data remain unpublished.
Groves et al.24used the technique of electric field modulation to examine
the magnetoreflectance at room temperature. In addition to the sharpening
83eS. Zwerdling. B. Lax, K. J. Button, and L. M. Roth, J. Phys. Chem. Solids 9, 320 (1959).
84 E. J. Johnson and H. Y. Fan, Phys. Rev. 139, A1991 (1965).
85
J. Halpern, private communication (1968).
224
R. L. AGGARWAL
PHOTON ENERGY ( e V )
FIG 30. Stress-modulated magnetoreflectance spectra for the fundamental edge in GaSb at
T z 30K, observed in the Faraday configuration with magnetic field H = 88.5 kG applied
along a [Ool] direction. The strong minima in 1/R ARIAS, AS = 2.5 x
are identified
with vertical lines under them which have a characteristic symbol at the top end indicating the
HH(AV). The length of a
type of the transition. A : LHA; 0 : HHA; x : LHB; 0 : HHB; 0 :
given line is proportional to the oscillator strength of the transition it represents. The positions
of the lines are obtained from the solutions of Eqs. (78) and (79) for the following parameters:
&g = 0.810(2)eV, A = 0.749eV, m,/m = 0.0418, (rn/h2)F = -1.5, y I L = 13.3, yzL = 4.4, yJL =
5.7, and K~ = 3.5. The numbers below the vertical lines represent the transitions listed in Table 11.
(After Reine et d4')
of the zero-field structure, they observed only one satellite peak even at a
high field of 92.4 kG. The failure to observe more interband Landau-level
transitions in the magnetoelectroreflectance spectra is presumably due to
short relaxation time at room temperature. A considerably large number of
transitions were observed in the low-temperature stress-modulated magnetoreflectance experiments of Aggarwal.86
Aggarwal and Reine' have compared the stress-modulated magnetoreflectance with the wavelength-modulated magnetoreflectance and with the
computed derivative of the conventional magnetoreflectance at the fundamental edge in GaSb. A comparison of these spectra obtained with an (001)
86
R. L. Aggarwal, unpublished.
2.
225
TABLE I1
EXPERIMENTALLY
OBSERVED
TRANSITIONS'
FOR GaSb
I N THE FARADAY
CONFIGURATION^
RCP
LCP
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
1n.
19.
20.
21.
22.
23.
24.
25.
26.
a
Depicted in Fig. 30.
After Reine et
sample in the Faraday configuration is shown in Fig. 29. The results of

Fig. 29 indicate that the lineshapes for all three differential spectra are almost
identical. This supports the interpretation of the stress modulation in the

framework ofthedeformation potential theory. In fact,Gavini and Cardonas7
have used the zero-magnetic field stress-modulated spectra to deduce the
deformation potentials for a number of materials including GaSb.
A detailed study of the stress-modulated magnetoreflectance in GaSb has
been carried out by Reine and c o - w o r k e r ~ He
. ~ ~has observed transitions
involving Landau levels as high as 18th conduction band level. In Fig. 30,
we show a typical stress-modulated magnetoreflectance spectrum obtained
87
A. Gavini and M . Cardona, Phys. Rev. 77, 1351 (1969).
226
R. L. AGGARWAL
as
1.0
1.1
PHOTON E N E R G Y ( e V )
FIG.31. Same as for Fig. 30 but H 11 [ l l l ] . (After Reine et
a/?)
by Reine for the fundamental edge in GaSb at T 30K. The spectrum of

Fig. 30 is for the Faraday configuration with the magnetic field H )I [loo]
and with the incident radiation either right- or left-circularly polarized. The
experimentally observed transitions are summarized in Table 11. Figure 3 1
shows the corresponding spectra for H I( [I 111. The zero-magnetic field
spectrum is shown in Fig. 32 for comparison.
The lowest energy negative peak in both spectra of Fig. 30 is the y excitonimpurity transition which has been shifted to higher energy by 6 meV by
a magnetic field of 88.5 kG.The &impurity transition was not present when
these spectra were taken, indicating possibly a lower sample temperature
than indicated in the figure, which is consistent with the exceptional sharpness
and strength of the structure in the spectrum. The 6 impurity was present
when the (1 11) spectra were taken, as shown in Fig. 31, and was shifted
to higher energy by 6 meV by a magnetic field of 88.5 kG.
Apart from the impurity and exciton-impurity structure, the dominant
features of the spectra of Figs. 30 and 31 are the negative peaks which
correspond to structure in the sample reflectance due to optical transitions
from the Landau level of the light- and heavy-hole valence bands to those
of the conduction band. The peaks are quite sharp ( - 2-3 meV wide) and
2.
SUMMARY
OF
mhh/m(100)
( 1 101
(1 11)
YIL
YIL
KL
gc
Stressmodulated
magnetoreflection"
0.042 f 0.001
mJm
?IL
TABLE 111
BAND-EDGE
PARAMETERS
FOR THE k = 0 CONDUCTION
BAND.
LIGHT-AND HEAVY-HOLE
VALENCEBANDSIN GaSb
THE
THE
Parameter
- hL
227
0.29 2 0.09
0.36 k 0.13
0.40 k 0.16
13.3 k 0 4
5 7 0.2
13
0.2
3.5 k 0.6
-7.8 f 0.8
*
*
Cyclotron
resonance
Magnetoabsorption
0.047 0.003*
0.04 1
0.045"
0.04I *
f4.5d
4.9
2.7'
- 6.5'
- 9.4"
- 6.6"
Other
experiments
0.048 5 0.002'
0.049 2 0.W41
0.052 & 0.004'

0.046 f 0.001'
0.26 2 0.04'
0.37 + 0.04'
0.36 2 0.03'
11.0'
4.4'
i .4'
Reine et aL4'
f Piller.88c
Zwerdling et aLS3'
% Higginbotham er
Lax and Mavroides.*
* Bordure.88d
Adachi.88a
Stradling.88'
' Bordure and Guastavino.8Bb
0.004
0.007*
0.33 2 0.013k
1.8 f 0.4'
Theory
O.04Ss
0.040h
0.049%
0.38h
0.45x
0.55%
1 1.2%
4.98
1 .o"
3.1g
- 6.7'
Ir
'
Cronburg and Button.'"

Walton and Mishra.88g
Seiler and Becker.88h
Johnson er al.8si
intense at energies just above the energy gap (8 x 0.81 eV) and become
weaker and broader with increasing energy. Similar features are also observed
in the modulated magnetoreflectance spectra for the direct edge in Ge.
In fact, this is the usual behavior for interband magnetooptical spectra and
reflects the decrease in the lifetime of the photoexcited electron with increasing
Landau quantum number. The data of Figs. 30 and 31 are about 20 to 40
""E. Adachi, J. Phys. Chem. Solidr 30,776 (1968).
'BbG.Bordure and F. Guastavino, C. R. Acod. Sci.B (France) 267, 860 (1968).

'"H. Piller. "Physics of Semiconductors" (Proc. 7th Intern. Conf.) p. 297. Dunod, Paris and
Academic Press. New York, 1964.
aMdG.
Bordure, Phys. Srutus Sulidi 31. 673 (1969).
s8eR.A. Stradling, Phys. Left. 20,217 (1966).
asrT.Cronburg and K. J. Button, private communication.
88*A.K. Walton and V. K. Mishra, J. Phys. C . (Proc. Phys. SOC.)1, 533 (1968).
88hD.G. Seiler and W. M. Becker, Phys. Reu. 183, 784 (1969).
"'E. J. Johnson, I. Filinski, and H. Y.Fan, Proc. I n t . ConJ Phys. Semicond. Exeter, 1962. p. 375.
Institute of Phys. and the Phys. SOC.,London, 1962.
228
R. L. AGGARWAL
0 72
0 80
0 88
FIG.32. The zero-magnetic field stress-modulated reflectance spectrum at the fundamental

edge of GaSb for T = 30K (solid line) and 77K (dashed line), with H = 0 and AS = 2.5 x 10- 5 ,
(After Reine et ~ 1 . ~ )
times more intense than the corresponding data of A g g a r ~ a l for

~ Ge and
represent the best stress-modulated magnetoreflectance data yet obtained.
In the (100) RCP spectrum, for example, evidence of transitions persists
as far as 1.25 eV, or about 450 meV above the energy gap.
The experimental data of Figs. 30 and 31 have been fitted to the coupled
band theory of Pidgeon and Brown, discussed in Section 2. To obtain the
best agreement between experiment and theory, Reine and co-workers4
have developed a computer program which seeks the set of band parameters
that minimizes the rms deviation of the experimentally observed transition
energies from the values computed theoretically. The parameter-finding
computer program, compared with the trial and error method used in the
past, is not only time-saving but is also very reliable as to the accuracy of
the values for the band-edge parameters. The effectiveness of the parameterfinding program in obtaining the best set of band parameters is illustrated
in Fig. 33 which shows the convergence properties of the iterative program
used to analyze the experimental transition energies.
In Figs. 34 and 35 are shown plots of the photon energy for the negative
peaks of the stress-modulated magnetoreflectance spectra of Figs. 30 and 31
and similar spectra for lower magnetic fields, as a function of the applied
magnetic field. The experimental points for the lowest four or five transitions
in Figs. 34 and 35 lie several meV below the theoretical curves and have
slightly different slopes; this is presumably due to the stronger influence of
2.
229
I02
10-2
RMS DEVIATION (meV1
FIG.33. Illustration of the convergence properties of the pararneter-finding program used

to fit the experimental energies of the Landau-levels transitions for the direct edge in germaniumlike semiconductors to the coupled band theory of Pidgeon and Brown. 0: m,; 0:
ylL; A : y 3 L ;
0 : mlh; A : mhh.(After Reine et a[?)
excitons on these transitions. With the exception of these transitions, the

theoretical fit is quite good for the heavy-hole transitions, and somewhat
less so for the light-hole transitions.
The values for the band-edge parameters obtained from the stressmodulated magnetoreflectance have been compared in Table 111 by Reine
with the values of these parameters as determined from other experiments
and from band-structure calculations for GaSb by Bordure,88dand Higginbotham ef a/.89
13. THESPLIT-OFF
VALENCE-TO-CONDUCTION
BANDTRANSITIONS
IN GALLIUM
ANTIMONIDE
Landau-level transitions between k = 0 spin-orbit split-off valence band
and the conduction band have been observed recently by Reine et d2with
89
C. W. Higginbotham, F. H. Pollak, and M. Cardona, Proc. IX Int. Con$ Phys. Semicond.,

Moscow, 1968, Vol. 1, p. 57. Publishing House Nauka, Leningrad, 1968.
t
/=/
0.8'
'
'
50
MAGNETIC FIELD (kG)
/ 25
(b)
l9
l7
'
I00
FIG.34. Plot of the photon energy versus magnetic field for the transitions observed in the (100) GaSb spectrum of Fig. 30 for (a) the RCP
radiation, (b) the LCP radiation. The theoretical values are represented by the solid lines with the experimental points indicated by the symbols :
A, LHA: x , LHB; 0 ,HHA; 0 ,HHB. (After Reine et d4')
2.
231
stress-modulated rnagnetoreflectance. In fact, this represents the only

magnetooptical study of the split-off valence-to-conduction band transitions
in GaSb. However, the zero-field spectrum for these transitions has been
reported previously by Cardona et a/.90 who observed them with electric
field-modulated reflectance at room temperature.
The stress-modulated magnetoreflectance obtained by Reine et a/." is
shown in Fig. 36. The spectra of Fig. 36 are for the Faraday configuration
with the magnetic field along a [ 1001 direction. The structure in these spectra
is quite weak, about three orders of magnitude smaller than the structure
in the fundamental edge spectra given in Fig. 30 for the sample. By comparison
the background is quite large, as can be seen from the RCP spectrum. There
is only a slight indication of the structure in the H = 0 spectrum at 1.56 eV.
In the H = 88.6 kG spectra, however, several minima are discernible. In
view of the low signal-to-noise ratio for the spectra of Fig. 36, and the fact
that only the lowest several transitions are observable, data have been
analyzed in terms of the simple model consisting of parabolic conduction
and split-off valence bands separated by the energy ' + A.
On the basis of this simple model, the difference in the transition energies
gnRand nL for the R C P and LCP spectra is due to the spin-splitting of the
two bands. In this manner, the sum of the g-factors for the two bands has
been determined as: g, + g,, = - 12 k 6. Using a value ofg, = -7.8 k 0.8
deduced from the stress-modulated magnetoreflectance for the fundamental
edge, we deduce g,, = - 4 k 7 for the value of the split-off band g-factor.
If the quantity &g, + gso)s,s being equal to heH/mc, is added to the RCP
tran'sition energies and subtracted from the LCP transition energies, a plot
of the resulting transition energies versus ( n + i)s should yield a straight line.
This is shown in Fig. 37 in which the straight line is a least squares fit to the
experimental data. The slope of this line has been used to deduce a value
for the split-off hole mass m,, = 0.17 k 0.03m which is larger than the value
of 0.12 k 0.01 predicted by the Pidgeon and Brown theory on the basis of
the band parameters obtained from the analysis of the stress-modulated
magnetoreflectance data for the fundamental edge in GaSb, given in the
previous section. However, it is in good agreement with the theoretical
value of 0.164~1
predicted by Higginbotham et
From the intercept of the line at s = 0 in Fig. 37, a value for the spin-orbit
splitting A = (0.749 k 0.002)eV has been obtained. This value for A is
about 50meV below the previously reported values. Kosicki and Paul"
found a value between 0.80 and 0.8 1 eV by measuring the intervalence band
absorption spectrum for p-type samples under large hydrostatic pressure,
9"
91
M . Cardona, K. L. Shaklee, and F. H . Pollak, Phys. Rev. 154,696 (1967)

B. B. Kosicki and W . Paul, Bull. Amer. Phys. SOC.11, 52 (1966).
/ 2o
MAGNETIC F I E L D ( h G )
1.1
i
-
MAGNETIC FIE1.D I k G l
Ftc. 35. Plot of the photon energy versus magnetic field for the transitions observed in the ( 1 1 I ) GaSb spectrum of Fig. 31 for (a) the RCP
radiation, (b) the LCP radiation. The theoretical values are represented by the solid lina with the experimental points indicated by the symbols:
A. LHA; x . LHB: 0. HHA: 0. HHB. (After Aggarwal er a/.")
2.
233
3
1
FIG. 36. Stress-modulated reflectance spectra for the split-off valence-to-conduction band
transitions in GaSb at T z 30K and AS = 5 x lo- for the Faraday configuration. The
spectra for H = 0 (top) and for LCP at H = 86.3 kG (middle) have been displaced upward for
clarity. The RCP spectra, at H = 86.3 kG,are at the bottom. (After Reine ef ~ 1 . )
and Cardona et ~ 1 . ~ quoted
the value of 0.80eV on the basis of roomtemperature electroreflectance data. We believe that the value of A obtained
from the stress-modulated magnetoreflectance data is considerably more
reliable.
14. THEFUNDAMENTAL
EDGEIN GALLIUM
ARSENIDE
There have been only two modulated magnetooptical studies of the fundamental edge in GaAs. The first one is by Vrehen who examined the crossfield magnetoabsorption, but his data remsins unpublished. The other is due
to Reine et d4who applied the technique of stress modulation to epitaxially
grown GaAs of a much higher purity than that used in the magnetoabsorption experiments of Vrehen. The stress-modulated magnetoreflectance
spectra obtained by Reine are shown in Fig. 38. These spectra were observed
in the Faraday configuration with H // [I 121. Transitions as high as 200 meV
above the energy gap can be seen in the spectra of Fig. 38. By way of comparison, Vrehens magnetoabsorption studies49 on thin ( 4 p ) samples
234
R. L. AGGARWAL
.,
FIG.37. Analysis of the split-off valence-to-conduction band transition energes for GaSb at
T 2 30K on the basis of the parabolic band model. The straight line is a least-squares fit to
the experimental points. The equations used were S:,= 8; + (s/4)(gC + g,,), S:, = BnL- (s/41
(g, + g
,) and g, + g, = - 12. The point symbols are: for H = 86.3 kG ( 0 ,RCP, 0 , LCP):
for H = 75.8 kG (0,RCP,
LCP); for H = 65.3 kG (a,
RCP, A,LCP). (After Reine et a/.)
were limited to a spectral region of about 100 meV above the energy gap.
The lines for the GaAs spectra of Fig. 38 are appreciably broader than those
for the stress-modulated magnetoreflectance spectra of the fundamental
edge in GaSb, shown in Figs. 30 and 31. The reason for the broad lines of the
GaAs spectra is not understood, especially in view of the high purity of the
epitaxial material used in Reines experiments.
The data of Fig. 38 have not been subjected to a detailed quantitative
analysis for the determination of band-edge parameters of GaAs on account
of the broadness of the structure and the presence of a large dc strain in the
specimen. The analysis of the Landau level transitions is further complicated
by the exciton effects which are more important in GaAs than in Ge and
GaSb. The recent photoluminescence studies by Gilleo ef
on epitaxial
GaAs established the zero-field exciton energy as (4.7 & 0.4) meV which is
more than twice the value of 2.2 meV expected for GaSb. Hobdens magneto-
M . A. Gilleo, P. T . Bailey, and D. E. Hill, Phys. Rev. 174,898 (1968).
2.
~
235

I
1.5
1.6
1.7
FIG. 38. Stress-modulated magnetoreflectance spectra for the fundamental edge (21 1) in
observed in the
epitaxially-grown high-purity GaAs at T 30K, with AS = 5 x
Faraday configuration with magnetic field H 11 [112] and H = 88.6 kG. The number directly
below each prominent transition refers to the complete identification of the transitions sumHH(AV).(After Reine ef aL4)
marized in Table IV. A, LHA; x , LHB;
o,
absorption study93 of the lowest two transitions showed clearly their

found it necessary to
excitonic nature. Also, Vrehen49 and Narita et
correct all of the transition energies observed in magnetoabsorption.
Unfortunately, there has been no theoretical work on the effect of excitons
on transitions involving Landau levels other than the lowest one. In the
absence of such a theory, Vrehen and Narita had to use approximate correcand Elliott and L o ~ d o n . ~ ~
tions inferred from the work of Yafet ef
A qualitative identification of the structure in Fig. 38 is indicated by means
of a symbol and a number directly below each prominent minimum. The
M. V. Hobden, Phys. Lett. 16, 107 (1965).
S. Narita, M. Kobayashi, and N. Koike, Proc. Int. Cony. Phys. Semicond.. Moscow, 1968,
Vol. 1, p. 347. Publishing House Nauka, Leningrad, 1968.
Y. Yafet, R. W. Keyes, and E. N. Adams, J. Phys. Chem. SolidF 1, 137 (1956).
96 R.J . Elliot and R. Loudon, J. Phys. Chem. Solids 15, 196 (1960).
93
94
236
R. L.
AGGARWAL
TABLE IV
EXPERIMENTALLY
OBSERVED
TRANSITIONS
FOR GaAs I N THE FARADAY
CONFIGURATIO~
RCP
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
LCP
a -(I )ac(0),
a-(2)ac(l),
a-(3)aC(2),
a+(l)ac(0)
a- (4)aC(3),
a+ (2)ac(1)
a-(6)ac(5),
a-(7bc(6),
a-(8)aC(7),
b-( l)b'(O)
b-(2)bC(l)
b- (3)bC(2)
a- (9)ac(8),
a - ( 10)aC(9),
b (9)bC(8)
b - ( 1O)bC(9)
b-( 1 I)V(10)
b - ( 12)b'( 1 1)
b - ( 13)bC(12)
b - ( 14)V(13)
b-( 15)bC(14)
b-( 16)b'( 15)
a-(1 l)ac(lo),
a - ( 12)ac(1I),
a - ( 13)aC(12),
a - (14)a'( 13),
a - (15)a'(14),
a-(16)uc(l3,
b- (4)bc(3)
b-(6)bC(5)
b - (7)b"(6)
b (8)bC(7)
a + ( - l)d(O),
a+(0)ac(l)
b+(O)b'(1)
a-(2)aC(3),
b'(l)b'(2)
a -(3)0'(4),
bC(2)b'(3)
a-(5)aC(6),
a-(6)aC(7),
a-(7)ac(8),
a -(8)aC(9),
a - (9)a'( lo),
a-(lO)a'(ll),
a - ( 1 l)ac(12),
a - ( 12)aC(
13),
a - ( 13)a'( 14).
b+( - I)b'(O)
b - (2)bC(
3)
b-(3)bC(4)
b - ( 5)bC(6)
b (6)bc(7)
b ( 7)bC(8)
b - (8)b'(9)
b (9)bC(10)
b-(lO)b'(lI)
b-( 1 l)b'( 12)
b - ( 12)b'( 13)
b-( 13)b'( 14)
After Reine et aL4'
symbol denotes the nature of the valence band level involved and the number
refers to the complete identification of the transitions summarized in Table
IV.
15. STRESS-MODULATED
MAGNETOREFLECTANCE
FOR
THE SPLIT-OFF
VALENCE-TO-CONDUCTION BANDTRANSITIONS
IN GALLIUM
ARSENIDE
The stress-modulated magnetoreflectance for the split-off valence-toconduction band transitions in GaAs has been reported by Reine et d 2 *
In fact, this is the only magnetooptical study of these transitions in GaAs to
date. In Fig. 39, we show the stress-modulated magnetoreflectance spectra
obtained for the high purity epitaxial GaAs sample in the Faraday configuration with H 11 (1121. As many as five Landau level transitions can be
seen in the spectrum of Fig. 39. By way of comparison the GaAs spectrum
of Fig. 39 for the stress-modulated magnetoreflectance is about ten times
stronger than the corresponding spectrum for GaSb given in Fig. 36. On
comparing the GaAs spectrum of Fig. 39 with the stress-modulated magnetoreflectance spectrum for Ge in Fig. 19 we find that the effect of the overlap
of the light- and heavy-hole transitions on the split-off transitions is negligible
in the GaAs spectrum even though the spin-orbit splitting in Ge and GaAs
is about the same.
2.
237
I80
1:
I90
Photon Energy
2 00
(ev)
FIG.39. Stress-modulated magnetoreflectance spectra for the split-off valence-to-conduction

in the Faraday configuration for
band transitions in GaAs at T Y 30K with AS = 5 x
the same sample as for Fig. 38. The zero-field spectrum is displaced upward for clarity. For
bottom curve, H = 88.6 kG,RCP is solid line and LCP is dashed line. (After Reine et dZ8)
The magnetoreflectance data of Fig. 39 for H = 88.6 kG and similar data

for lower magnetic fields have been analyzed in terms of the simple two-band
model. From the difference in the energy for the corresponding minima in the
RCP and LCP spectra, we obtain the value for the sum of theg-factors for the
conduction band and the split-off valence band as g,
g,, = -4.7 ? 1.0.
The conduction band g-factor has not been measured in spite of two attempts
by electron spin resonance experiment^^',^' in n-type material. According to
Eq. (92), we estimate g , z 0.2. Using this value of g, we obtain g,, =
-4.9 f 1.0.
The reduced mass for the conduction electron and the split-off hole has
been obtained from the slope of the straight-line fit to the experimental data,
given in Fig. 40 which is a plot of the energies corresponding to the minima
in the spectra, as a function of ( n + #I eH/mc. The point for H = 0 in Fig.
40 is the inflection point of the H = 0 spectrum in Fig. 39. The fact that the
97
98
W. Duncan and E.E. Schneider, Phys. Lerr. 7 , 23 (1963).

S. Haraldson and C. G. Ribbing, J . Phys. Chem. Soliris 30,2419 (1969).
238
R. L. AGGARWAL
FIG.40.Analysis of the split-off valence-to-conduction transitions for GaAs at T 1 30K on

the basis of the parabolic two-band model. The straight line is a least-squares fit to the experimental points. The equations used were B:,= CR+ (s/4)(gC + g,,), fin = CL- (44)
(g, - g,,), and g, + g,, = -4.7. The points plotted are: A,H = 0; +, H = 88.6 kG,LCP;
0 ,H = 88.6 kG, RCP; 0,H = 78.2 kG, RCP: x, H = 67.8 kG, RCP. (After Reine ef d z 8 )
least-square fit passes through the H = 0 point is consistent with the empirical
criterion given by MavroidesZ2 that the transition energy in the stressmodulated spectrum corresponds to the inflection point for H = 0, and to
the minimum for H # 0. The slope of the straight line fit in Fig. 40 gives the
following value for the reduced mass
(m/m,)
+ (m/m,,)
= 21.5
0.4.
On the basis of the recent magnetospectroscopic studies of shallow donors

in epitaxial GaAs samples similar to the one used in the stress-modulated
magnetoreflectance experiments, Stillman et aL9 have determined the conduction band effective mass m, = (0.0665 k 0.0005)m.This value is in agreement with Vrehens magnetoabsorption value49 of (0.067 +_ 0.002)rn as
well as with the recent cyclotron resonance value of0.0648 f 0.0015 obtained
by Chamberlain and Stradling. l o o Using Stillmans value, we obtain mso =
(0.154 & 0.010)m. This is the first experimental value of mso for GaAs. It is
99
G. E. Stillman, C. M. Wolfe, and J. 0. Dimmock, Solid State Comrnun. 7, 921 (1969).

J. M. Chamberlain and R. A. Stradling, Solid State Commun. 7, 1275 (1969).
loo
239
2. MODULATED INTERBAND MAGNETOOPTICS

TABLE V
VARIOUS EXPERIMENTAL
AND CALCULATED
VALUES"
FOR VALENCE-BAND
PARA METERS^
Calcuiated
Source
mlh
mhh
Reflectivity and
Faraday rotationC
Magnetoabsorptiond
Cyclotron resonancee
Magnetoabsorption'
0.068 f 0.015
0.082 0.006
0.087 0.005
0.1
0.50 0.02
0.45 & 0.05
0.475 f 0.015
0.38
+ g,,
y I L Y~~
K~
msu
t~
8.4
7.2
6.8
6.4
1.9
1.1
1.0
0.8
0.133
0.159
0.170
0.185
- 7.6
3.2
2.5
2.4
1.8
- 4.4
- 4.0
-3.3
The effective mass values are in units of the free electron mass
'After Reine et 01.4'
Walton and Mishra.'"
Vrehen49
Stradling.'*'
Narita et d.""
lower than Ehrenreich's estimate'" of 0.2 on the basis of Kane's expression

for mso.
From the intercept of the straight line fit on the H = 0 axis in Fig. 40,
Reine et a/." have deduced the value of 0.341 eV for the spin-orbit splitting
A for GaAs. There have been several values of A reported with which this
can be compared. On the basis of intervalence band absorption in p-type
GaAs, Braunstein"' estimated a value of 0.33eV. SturgeIo3 found A =
(0.35 k 0.01) eV from the absorption edge for the split-off valence-toconduction band transitions observed in the conventional absorption experiments on thin samples. Seraphinlo4 showed that A was independent of
temperature in electroreflectance measurements between 200 and 375K
and found the value of (0.348 f 0.002)eV. In electroreflectance experiments
on GaAs-GaP alloys at room temperature, Thompson et ~ 1 . ' ' ~obtained
A = (0.339 k 0.003)eV, and Williams and Rehn'" found the value of
(0.339 f 0.004)eV. Recently, Nishino et ~1."' determined the value of
(0.350 f 0.004)eV in electroreflectance studies over a temperature range of
25 to 300K. The value of 0.341 eV obtained in the stress-modulated
H. Ehrenreich, Phys. Rec. 120, 1951 (1960).
R. Braunstein, J . Phys. Chem. Solids 8. 280 (1959).
M . D. Sturge, Phys. Reo. 127,768 (1962).
B. 0. Seraphin, J . Appl. Phys. 37, 721 (1966); Proc. Phys. Soc. (London)87, 239 (1966).
In' A. G. Thompson, M. Cardona. K. L. Shaklee, and J . C. Woolley, Phys. Rev. 146,601 (1966).
The error estimate given for A was deduced from Table I and Fig. 11 of this reference.
ln6
E. W. Williams and V. Rehn, Phys. Rev. 172, 798 (1968).
l o 'T. Nishino, M. Okuyama, and Y. Hamakawa, J . Phys. Chem. Solids 30,2671 (1969).
In'
In*
240
R . L. AGGARWAL
magnetoreflectance experiments agrees well with the values of Thompson

et ~ 1 . " ~and of Williams and Rehn.Io6
It is interesting to compare the value for mso and g,, obtained from the
stress-modulated magnetoreflectance experiments with the values to be
obtained from Eqs. (96) and (97) for the band parameters E , , gg,A, ylL, and
K~ as determined from other experiments. Of these five band parameters,
ggand A are accurately known, at least for the purpose of the present
calculation. Also E , can be deduced from Eq. (91) for the conduction band
mass m, if we assume F = 0. Using GT~= 1.520eV, A = 0.341 eV, and
Stillman's value of 0.0665 for m,/m, we obtain E, = 22.3 eV, which is larger
than Ehrenreich's estimate"' of 20eV and y I L can be obtained from the
light- and heavy-hole masses. In Table V are listed the results for the lightand heavy-hole masses from Walton and Mishra's experiments"' on free
carrier reflectivity and Faraday rotation, Stradling's cyclotron resonance
experiment^,'^' and the magnetoabsorption studies of Vrehen49 and of
Narita et al.' l o Only one value for the heavy-hole mass is given in view of the
small anisotropy, which is a measure of the difference in the values of y3L
and y z L ; y3L = y z L is the condition for isotropic valence bands. Vrehen
failed to observe any anistropy in his magnetoabsorption studies. Recently,
Balslev"' has found (y3L - yzL) = 0.6 on the basis of intervalence band
piezoabsorption in p-type GaAs. This value of (y3L - yzL) is small enough
so that the isotropic band approximation will not introduce an appreciable
error in the determination of yL's from the light- and heavy-hole masses. The
values of y l L and yzL listed in Table V have been obtained from the quoted
masses in the isotropic band approximation. Narita er aI."' treated K~ as
an independent variable, and his quoted value is given. On the other hand,
Vrehen4' obtained K~ from the approximate relation
with y3L = yzL, and this approximation has been used to obtain values for
K~ from the results of Walton and Mishra'"
and of Stradling."' The last
two columns of Table V list the values for msnand (gc + gs0)calculated from
Eqs. (96), (92), and (97). As can be seen from these two columns, the experimental values for mso = (0.154 k 0.010)m, and (g, gso) = -(4.7 ? 1.0)
agree quite well with the values predicted from Vrehen's results and also with
those predicted from Stradling's results.
A. K. Walton and U. K . Mishra, J . Phys. C (Proc. Phys. Soc.) 1, 533 (1968).

R. A. Stradling, Electronic Components, October 1968.
110 S. Narita, M. Kobayashi, and N . Koike, Proc. Inr. Conf. Phys. Semicond., Moscow, 1968,
Vol. 1, p. 347. Publishing House "Nauka," Leningrad, 1968.
I. Balslev, Phys. Rev.177, 1173 (1969).
lo*
lo9
2.
v)
241
n
a
n
-4 I
240
2 60
280
PHOTON ENERGY ( m e V )
300
FIG.41. Low-energy part of the stress-modulated magnetoreflectance spectrum for the fundamental edge in InSb at T = 30"K, observed in the Faraday configuration with H I( [ l I I]and
H = 88.9 kG.(After Aggarwal.86)
16. THEFUNDAMENTAL
EDGEAND
IN INDIUM ANTIMONIDE
THE SPLIT-OFF
EDGE
a. Stress-Modulated Magnetorejectance
The stress-modulated magnetoreflectance for the fundamental edge in

InSb was first reported by Mavroides et a / . 2 3who observed an impressive
enhancement of the structure in magnetoreflectance due to Landau-level
transitions from the light- and heavy-hole bands to the conduction band.
These initial experiments of Mavroides et
which were made on InSb
samples at room temperature, served to establish the power of the stressmodulated magnetoreflection technique for the study of magnetooptical
transitions.
The low-temperature spectra for the stress-modulated magnetoreflectance
in InSb have been obtained by Aggarwal.86In Fig. 41, we show a typical spectrum for a (111) sample at T % 30"K, obtained in the Faraday configuration.
In the first set of three lines around 260 meV, there are only two principal
allowed transitions. It appears that the second and the third minima at 259.8
R. L. AGGARWAL
242
a
U
-2.0
1.000
1.050
1.100
1.150
1.200
1.250
FIG.42. Part of the stress-modulated magnetoreflectance spectrum which shows the split-off
valence-to-conduction band transitions in lnSb at T z 30K, observed in the Faraday configuration with H 11 [lll]. (After A g g a r ~ a l . ~ )
and 261.4meV correspond to the two allowed transitions, and the first
minimum at 257meV may be due to the impurity exciton complex. The
remaining lines in the spectrum of Fig. 41 correlate well with the principal
allowed transitions as can be seen from this figure.
Only a small portion of the observed spectrum has been given in Fig. 41.
Actually, transitions as high as 1 eV above the energy gap have been observed.
Part of the spectrum between 1.0 and 1.2 eV is shown in Fig. 42 in which a
number of lines have been identified with the split-off valence-to-conduction
band transitions. The Landau quantum number n of the conduction band
levels for these transitions is given under the corresponding lines in Fig. 42.
When the energy values for the A R / R minima in Fig. 42 identified with the
split-off transitions are plotted as a function of the applied magnetic field,
we obtain the fan chart shown in Fig. 43. The solid lines in Fig. 43 are the
theoretical curves obtained from the solutions of Eqs. (78) and (79) for the
coupled band theory with the values of band-edge parameters obtained from
the magnetoabsorption studies of Pidgeon and Brown44 for the light- and
heavy-hole transitions. But the value of the spin-orbit splitting A was
adjusted so as to obtain the best fit for the experimental data. In this manner,
2.
243
n.2
I l 5 0 E
Magnetic Field ( k G )
43. Plot of the energy values versus magnetic field for the split-off valence-to-conduction
band transitions in lnSb at T E 30K in the Faraday configuration with H 11 [ l l l ] . (After
Aggarwal.86)
FIG.
a value of (0.803 f 0.005)eV for A is obtained from the convergence point

of the computed curves at H = 0 after subtracting off the energy gap
g = 0.235eV. This value of A is lower than the previously estimated
value of0.9 eV but it is consistent with the recent results of Pidgeon et
obtained from electric-field-modulated magnetoreflectance in InSb. From
the overall fit of the experimental data to the computed curves in Fig. 43,
we find the effective mass for the split-off valence band ms0 = (0.10 f 0.01)m.
This value of m,, is lower than the value of 0.144 m as determined by Higginfrom the band structure calculations.
botham et
h. Etecfric-Fieid-Moduluted Mugnetorejertrrnce
The first attempt to observe the electric-field-modulated magnetoreflectance in InSb was made by Groves et
who used the electrolyte technique
at room temperature. In their electroreflectance spectrum for the range
0.8-2.2 eV, they observed negative structure peaked at 0.97 eV, and positive
structure in the vicinity of 1.9 eV. They have attributed the 0.97-eV structure
as due to the onset of split-off valence-to-conduction band transitions, and
the 1.9-eV as due to the transitions at the 2 point in the Brillouin zone. Subtracting off the room-temperature energy gap of 0.18 eV from 0.97 eV, the
value of the spin-orbit splitting A at room temperature was found to be
0.79 eV. Magnetooptical structure associated with these transitions was not
R. L. AGGARWAL
244
20.0
yr)
-*
a.
10.0
(L
-10.0
*
c
10.0-
a0
a 10.0I
0.300.350 0.360 0.370 a380
PHOTON ENERGY ( e W
FIG.44. The electric-field-modulatedmagnetoreflectancein lnSb for H = 84 kG at T = 1.5"K

with E IH 11 F. Inset shows the spectrum for the split-off valence-to-conduction band (so + c)
transitions, with the solid arrows indicating the theoretical energies for these transitions. (After
Pidgeon et
observed in the room-temperature electroreflectance, probably because of

the lifetime broadening.
The low-temperature magnetoelectroreflectance in InSb has been reported
by Pidgeon er aLZ6who developed the integrated thin-film package of Fig. 15
that could be immersed in liquid helium. The magnetoelectroreflectance
spectrum for the light-, heavy-, and the split-off-hole transitions observed at
1.5"K with this technique is shown in Fig. 44. A comparison of the lowenergy part ofthe spectrum between 250 and 280 meV with the corresponding
stress-modulated magnetoreflectance spectrum given in Fig. 41 shows that
the magnetoelectroreflectance spectrum has more lines than the number of
principal allowed transitions.
Recently, Pidgeon and Groves' have shown that the additional structure
in the magnetoelectroreflectance spectrum of Fig. 44 is caused by the warping
and the inversion-asymmetry of the valence band in InSb. These additional
transitions occur for H /I (1 11) or (1 12) but are absent for H /I (100) and
''
C. R. Pidgeon and S. H. Groves, Proc. In[. Cony. Phys. Semicond., Moscow, 1968 Vol. I ,
p. 307. Publishing House "Nauka," Leningrad, 1968.
2.
245
10
FIG.45. The electric-field-modulated magnetoreflectance in lnSb for (a) H 11 [I 1 I ] and (b)

H // [I001 in the Faraday configuration, with H = 84 kG and T = 1.5"K.The warping-induced
and the linear k-induced transitions are labeled by w and k, respectively. The symbols cL (solid
line) and uR (dashed line) denote LCP and RCP radiation, respectively. (After Pidgeon et a / . L 1 z )
(1 lo), as can be seen in the spectra of Fig. 45. For H 11 (1 11) or (1 12) a
strong warping interaction (absent for H I1 (100) and (1 10)) is present
between certain nearly degenerate levels of the a and b series. For example,
warping interaction strongly mixes the wave function of the lowest heavyhole level for the a series with the lowest light-hole level of the b series. This
mixture in the wave functions gives rise to extra transitions labeled w in the
spectra of Fig. 45. In addition, the linear k interaction mixes the lowest heavyhole level of the a series with the second heavy-hole level of the b series. This
gives rise to inversion-asymmetry-induced transition labeled k in Fig. 45.
It should be pointed out that structure identical to that in the magnetoelectroreflectance spectrum of Fig. 45 has also been observed in the normal magnetoreflection spectra.Il3 This shows that the extra transitions are not caused by
the electric field applied to the sample. Therefore, the reason for the absence
of these extra transitions in the stress-modulated magnetoreflectance spectrum given in Fig. 41 is most likely the presence of a dc stress in the sample.
The effect of the stress is to increase the energy separation between the interacting levels which are nearly degenerate in the absence of stress. This would
'I3
C. R. Pidgeon and S. H. Groves, Phys. Rev. 186, 824 (1969)
246
R. L. AGGARWAL
Photon Energy ( e V )
FIG. 46. The magnetophotoreflectance spectrum in lnSb at T z 50 K. observed in the

Faraday configuration with H 11 [ I 121 for H = 0 (dashed line) and H = 19.8 kG (solid line).
(After Shay et ~ 1 . 6 ~ )
reduce the mixing of the wave functions for the coupled levels; in turn, this
should reduce the strength of the extra transitions.
From the energy separation between the relative strength of the allowed
and w- and k-transitions, Pidgeon and Groves' have determined the valence
band anisotropy (y3L - yzL) = 1.2 f 15%, and the Dresselhaus inversion
asymmetry parameter' C = 6.6 x
atomic units or 9.3 x 10- eV . cm
f30%. The above result for (y3L - yzL) is in good agreement with the cyclotron resonance work of Bagguley et a!.' l 4 and not with the more recent
work of Tohver and Ascarelli."' However, the value of C is about an order
of magnitude smaller than those of the experimental values obtained by Bell
and Rogers,"' and Robinson.' It is also a factor of 5 smaller than the theoretical estimate of Kane.46
'
''
c. MagnetophotoreJlecrance
The magnetoreflectance for the direct edge in InSb has been reported by
Shay et
The spectrum obtained in the Faraday configuration with a
magnetic field of 19.8 kG applied along a [112] direction is shown in Fig. 46.
Structure as high as 150 meV above the band gap can be seen in the spectrum
of Fig. 46. From the change in the energy values for the observed structure
with magnetic field up to 50 kG they established that the structure in Fig. 46
D. M. S. Bagguley, M. L. A. Robinson, and R. A. Stradling, Phys. Lett. 6. 143 (1963).
H. T. Tohver and G . Ascarelli, Proc. I n t . Con$ Phys. Semicond., Moscow, 1968, Vol. 1,
p. 326. Publishing House "Nauka." Leningrad, 1968.
I6 R. L. Bell and K. T. Rogers, Phys. Rev. 152, 746 (1966).
'" M. L. A. Robinson, Phys. Rev. Leii. 17,963 (1966).
14
2.
247
is due to interband Landau-level transitions. On the basis of this result,

have concluded that the physical mechanism responsible for
Shay et
the photoreflectance effect is not band-filling as proposed by Gay and
Klauder,"' since the higher Landau levels have no significant population.
Instead, the magnetoreflectance in InSb confirms the initial suggestion of
Wang et al." that the photoreflectance is due to the modulation of the built-in
electric field at the surface by the electron-hole pairs created by the secondary
light beam used in the photoreflectance experiments.
d. Summary of the Band-Edge Parameters for the k
Valence Bands
0 Conduction and
In Table VI we summarize the band-edge parameters for the k = 0 conduction and valence bands in InSb. In the first column are given the results
of interband magnetoabsorption studies of Zwerdling et ~ 1 . " and
~ of Pidgeon
and Brown44 along with the more recent results of the interband magnetoreflectance work of Pidgeon and Groves' 1 2 , 1 l 3 who observed the warpinginduced and the linear k induced transitions. In the second column are given
the values obtained from the cyclotron resonance experiments of Dresselhaus
et u1.,''
Palik et a/.,1z1 Bagguley et a1.,l14 Robinson,''7 Tohver and
1
Ascarelli,l's and the most recent study of p-type InSb by Button ef ~
using submillimeter wavelengths and high magnetic fields up to 170 kG.
Button et al. have shown that the cyclotron resonance absorption lines
observed in p-type material at microwave frequencies represent the envelopes
of several absorption peaks some of which are resolved a t higher frequencies
corresponding to the submillimeter wavelengths. In view of this, they have
given a range of values as quoted in Table V1 for the light- and heavy-hole
masses in the classical (large n) limit. In the last column are given the results of
the theoretical work of Higginbotham et
17. MODULATED
MAGNETOREFLECTANCE
IN INDIUM ARSENIDE
The modulated magnetoreflectance spectra for the fundamental edge in
InAs have been obtained by Aggarwals6 and by Pidgeon er aLZ6 with the
techniques of stress modulation and the electric field modulation respectively.
In Fig. 47 is shown the stress-modulated magnetoreflectance spectrum in
InAs at T = 30"K, observed in the Faraday configuration with H 11 [ 1113.
I9
lZo
J. G . Gay and L. T. Klauder, Jr., Phys. Rev. 172, 81 I (1968).

S. Zwerdling, W. H. Kleiner, and J. P. Theriault, J . Appl. Phys. Suppl. 32, 2118 (1961);
Proc. Int. Con$ Phys. Semicond., Exrter, 1962 p. 455. Inst. of Phys. and Phys. SOC., London,
1962.
G. Dresselhaus, A. F. Kip, C. Kittel, and G . Wagoner, Phys. Rev. 98,556 (1955).
E. D. Palik. G. S. Picus, S. Teitler, and R. F. Wallis, Phys. Rat. 122,475 (1961).
K. J. Button, A. Brecher, and B. Lax, private communication (1970).
248
R. L. AGGARWAL
TABLE VI
SUMMARY OF THE k = O CONDUCTION AND VALENCE
BAND-EDGE
PARAMETERS
IN InSb
Source
Parameter
Interband
magnetooptics
Cyclotron
resonance
0.0145 f O.ooO3"
0.0145 f 0.0006'
- 48%'
0.0149 f O.ooO3"
0.0160 f 0.006'
0.0157J
0.30'
0.273 f 0.005J
0.0013 f 0.001'
0.0145 f 0.00ld
0.021 f 0.005g
0.016 2 0.002h
0.0143 - 0.0181'
0.34 f 0.03'
0.32 f0.03*
0.317 - 0.353'
0.42 f 0.03'
0.412 - 0.467'
0.45 2 0.03g
0.34 f 0.02h
0.412 - 0.467'
0.42b
0.332 k 0.005/
0.44'
0.358 f 0.005J
C(lO-"eV.cm)
0.10 0.01'
21.92'
21.21J
36 k 1"
32.5'
33.51J
14.5 & 0.4"
14.3'
14.48/
16.2 f 0.5"
15.4b
15.65J
13.4'
13.47J
0.4 i 0.2/
9.3 2.8/
+-
"Zwerdling ef a1.119
Pidgeon and Brown.44
Dresselhaus et a1.120
Palik et 0 1 . ' ~ '
Higginbotham et
J Pidgeon and Groves.LL3
'
Theory'
0.0178
--
36.1
0.0195
0.52
0.60
0.70
0.144
17.5
25'
26.49
103
12.05
1 1 9
12.70
71 f 42'
Bagguley et
Tohver and A s ~ a r e l l i . ' ' ~
Button et
' A g g a r ~ a land
~ ~ Pidgeon et
Robinson."'
'
2.
249

1
Faraday Configuration
400
500
600
700
Photon Energy (rneV)
FIG.47. The stress-modulated magnetoreflectance spectrum for the fundamental edge in

lnAs at 7" 2 30"K, observed in the Faraday configuration with H I/ [l I 1 3 and H = 88.9 kG.
(After AggarwaLB6)
All the prominent lines in the spectrum of Fig. 47, with the exception of the
line at 0.415 eV, correlate well with the principal allowed transitions observed
in the magnetoabsorption experiments of Pidgeon et
The 0.415-eV
line in Fig. 47 corresponds to the line in the zero-magnetic-field spectrum
(not shown) at 0.403 eV which is about 7 meV below the energy gap. The
origin of this line is not clear as yet. It is possible that this additional line
may be associated with some impurity-exciton complex similar to those
observed in the stress-modulated magnetoreflectance spectra of GaSb
shown in Figs. 3Ck32. However, the GaSb samples were p-type whereas the
InAs sample was n-type.
The electric-field-modulated magnetoreflectance spectrum obtained by
Pidgeon et ~ 1 for. InAs
~ at~ 1.5"K is shown in Fig. 48. The magnetoelectroreflectance spectrum is very similar to the stress-modulated magnetoreflectance spectrum of Fig. 47, but the extra transition below the gap was not
observed in electromagnetoreflectance. This discrepancy in these two
spectra may be due to the difference in sample temperatures in the two experiments. Further work is needed to clarify this point.
The inset in Fig. 48 shows the magnetoelectroreflectance spectrum for the
split-off valence-to-conduction band transitions for left- and right-circularly
123
C. R . Pidgeon, D. L. Mitchell, and R . N . Brown, Phys. Reo. 154, 737 (1967).
R. L. AGGARWAL
250
6.0
4.0
2.0
fl
a ? O.O
-2.0
-4.0
-6.0
0.400
0.500
0.600
PHOTON ENERGY (eV)
0.700
FIG.48.The electric-field-modulated magnetoreflectance spectrum in InAs for H 11 [ 1 1 I ] and

= 84 kG and T = 1.5"K. The inset shows the
spectrum for the split-off valence-to-conduction band transitions for left- and right-circularly
polarized light. The experimental arrangement of the electroreflectance package is also shown
in the inset. (After Pidgeon et
E IH 11 F in the Faraday configuration with H
polarized light. A plot of the energy values of the magnetoelectroreflectance

minima for the split-off transitions as a function of magnetic field is shown in
Fig. 49. The solid lines give the transition energies computed from Eqs. (78)
and (79) using the band-edge parameters which retain a good fit to the
and provide a reasonably good
magnetoabsorption data of Pidgeon et
fit for the split-off transitions. In this manner they obtained the following
values for the band-edge parameters of the split-off band
(0.38 f O.Ol)eV,
mso = (0.14 f 0.01) m,

g,, = - 13 f 1.
2.
25 1
0 980
0960
0 940
0 920
--2 0900
&
80880
zz
P
9
0860
a
0 840
//"
0 820
0000
0 780
10
20
30
40
50
60
70
00
90
100
H (kG)
FIG. 49. Plot of the photon energy of magnetoelectroreflectance minima for the split-off
valence-to-conduction-band transitions in lnAs at T 2 1.5"K as a function of magnetic field
oR).The solid
strength with E IH 11 F. The circles show the experimental points ( 0 ,oL: 0,
lines give the theoretical energies for the allowed transitions. (After Pidgeon e t a / . 2 6 )
A summary of the k = 0 conduction and valence band-edge parameters

obtained from interband magnetooptical experiments is given in Table VII
which includes the results of cyclotron resonance in n-type InAs by Palik
and S t e ~ e n s o n , and
' ~ ~ the theoretical values of Higginbotham et ~ 1 1 . ~ ~
18. STRESS-MODULATED
MAGNETOREFLECTANCE
I N LEADTELLURIDE
The stress-modulated magnetoreflectance for the fundamental edge in
PbTe has been reported by Aggarwal et a / . ' 2 5Figure 50 shows the spectrum
'24
lZ5
E. D. Palik and J . R. Stevenson, Ph-vs.Rev. 130. 1344 (1963).

R. L. Aggarwal, U. Smith, and B. Lax, Proc. I n t . Conf: Phys. Semicond., Moscow, 1968,
Vol. 1, p. 337. Publishing House "Nauka," Leningrad, 1968.
R. L. AGGARWAL
252
TABLE VII
SUMMARY
OF THE k = 0 CONDUCTION
AND VALENCE
BAND-EDGE
PARAMETERS
IN InAs
~
Source
Parameter
Interband
magnetooptics
Cyclotron
resonance
0.024
m,/m
Theory'
~~
0.024*
0.001"
-15
1"
0.026 f 0.002"
0.4"
0.14 k O.0ld
-13
Id
19.8"
20.5"
9.0"
8.0"
gc
mllm
mhlm
m.Jm
gs.3
E , (eV)
?IL
fL
KL
a
Pidgeon et al.Iz3
'Palik and S t e ~ e n s o n . " ~
0.026
- 13.2
0.030
0.95
0.108
- 13.9
18.3
17.05
8.1
' Higginbotham et a/.89

Pidgeon et aLZ6
I .o
I I\
-10-
P
v
220
240
260
vv
280
300
320
340
Photon Energy (meV1
FIG. 50. The stress-modulated magnetoreflectance spectrum for the fundamental edge in
p-type (n,, = 3 x 1018/~m3)
PbTe for H 11 [ l l I] in the Faraday configuration, with H = 88.7 kG
and T 2 30K. (After Aggarwal et al.lZS)
2.
253
I80 o
20
40
60
a0
loo
Magnetic Field ( k G )
FIG.51. Plot of the photon energies for the light mass transitions in PbTe at T = 30K as a
function of the applied magnetic field H 11 [ l l l ] showing the experimental points (0)
and the
theoretical curves (-). (After Aggarwal rt
obtained for a p-type ( =3 x 1018/cm3)sample in the Faraday configuration

with magnetic field parallel to a [11 I] direction. The gross features of the
spectrum have been interpreted in terms of the direct interband transitions.
The PbTe spectrum is different from that of the 111-V compounds discussed
in the preceding sections in that the conduction and valence band edges in
PbTe do not occur at k = 0 but they occur at the L points which are at the
zone edges along the (1 11) directions. Therefore, the cyclotron effective
mass for a given conduction or valence band ellipsoid is determined by the
transverse mass m,,the longitudinal mass m, and the direction of the applied
magnetic field as
m,(i)
mI[mt/(ml
cos
+ m, sin @))I~,
(166)
where Oci) represents the angle between the magnetic field and the longitudinal axis of the ith ellipsoid. In views of Eq. (166), two series of interband
transitions are to be expected for H I( [I 111, one series corresponding to the
254
R. L. AGGARWAL
TABLE VIII
THEREDUCED
TRANSVERSE
EFFECTIVE
MASSp, FOR
ABSORPTION EDGEIN PbTe
THE
FUNDAMENTAL
Technique
Effective
mass
PJm
Cyclotron
resonance
(1.8K)
Shubnikovde Haas
(4K)
Magnetoemission
(10K)
Magnetoabsorptiond
(4.2K)
Stressmodulated
magnetoreflection
(30K)
0.013
0.01 1
0.014
0.013
0.012
~ i 1 2i9
Cuff er a!.
Butler and Calawa.128
Mitchell et ol. 3 0
Aggarwal er a/.
light mass equal to m, and the other corresponding to heavy mass

equal to 3m,[l
8(ml/ml)]-12. In the spectrum of Fig. 50, the strongest
(negative) peak at 234.5 meV is identified as the n = 0 line for the light-mass
series. The relatively broad peak at 219 meV is considered to be the n = 0
heavy-mass line. The peak at 297.5 meV is interpreted as the n = 1 lightmass transition. The remaining lines in the spectrum (except for the sharp
line at 230.0 meV) seem to be related to the heavy-mass series. The origin
of the 230.0-meV line is not understood.
The data for the light-mass transitions in Fig. 50 and similar data for
lower magnetic fields have been successfully interpreted in terms of the Lax
two-band model,126 assuming that the g-factors for the conduction and
valence bands in PbTe are equal in m a g n i t ~ d e ~but
opposite in sign.128
This is shown in Fig. 51 which is a plot of the photon energies for the lightmass transitions as a function of magnetic field. The circles denote the
experimental points and the solid lines are the theoretical curves obtained
from the two-band model for the reduced effective mass p = 0.012 m. As can
be seen in Table VIII, this value of the reduced effective mass is in good agreement with those obtained from other measurements, viz., cyclotron resonance
12
12*
lL9
B. Lax, J. G . Mavroides, H. J. Zeiger, and R. J. Keyes, Phys. Rev. Lett. 5,241 (1960).
K. F. Cuff, M. R. Ellett, C. D. Kuglin, and L. R. Williams, in Physics of Semiconductors
(Proc. 7th Int. Conf.), p. 677. Dunod, Paris and Academic Press, New York, 1964.
J. F. Butler and A. R. Calawa, in Physics of Quantum Electronics (P. L. Kelley, B. Lax,
and P. E. Tannenwald, eds.), p. 458. McGraw-Hill, New York, 1966.
R. Nii, J. Phys. SOC.Japan 19,58 (1964).
D. L. Mitchell, E. D. Palik, J. N. Zemel, in Physics of Semiconductors (Proc. 7th Int.
Conf.), p. 325. Dunod, Paris and Academic Press, New York, 1964.
2.
255
absorption by Nii,12 Shubnikovde Haas experiments by Cuff et d.,

magnetic-field dependence of the radiation emitted from a diode laser by
Butler and Calawa,128 and magnetoabsorption in epitaxial films by
Mitchell et
19. CONCLUSIONS
Modulated interband magnetooptical experiments have proven to be
extremely useful for the observation of Landau-level transitions deep into
the bands. An important objective of many of these experiments has been to
look for the effect of magnetic field on the transitions between bands with
energy gap larger than the fundamental gap. In this respect, positive results
have been obtained for the spin-orbit split-off valence band to conduction
band transitions in Ge and 111-V compound semiconductors with similar
band structure. But attempts to observe the effect of magnetic field on interband absorption (reflection) for the other higher transitions have not been
successful, presumably due to short relaxation times.
In the interpretation of the experimental results for the modulated magnetooptical experiments, little attention has been given to the analysis of the
observed lineshapes and the influence of exciton effects, which affect not only
the transition energy but also the lineshape. Clearly, further work along these
lines is needed for a proper understanding of the observed spectra.
ACKNOWLEDGMENTS
The author wishes to express his appreciation to Professor Benjamin Lax, Drs. M. Reine,
U. Smith, and C. R. Pidgeon, K. J. Button, Drs. S. H. Groves, F. H. Pollak, and E. J. Johnson for
many stimulating discussions regarding this work. He would like to thank K. Kinney and C.
Barbay for typing the manuscript, and E. Taylor for proofreading the pages.
CHAPTER 3
Electroabsorption
Daniel F . Blossey and Paul Handler
I . INTRODUCTION
. . . . . . . . . . . . . . . .
I1 . THEEXCITON
IN A UNIFORM ELECTRIC
FIELD. . . . . . . .
1 . General Concepts, History. and Theory . . . . . . . .
2 . Calculaiion of Optical Absorption by Wannier Excitons in an Electric
. . . . . . . . . . . . . . . . .
Field
3. Weakly Bound Exciton Limit . . . . . . . . . . .
4 . Comparison of Theory and Experiment . . . . . . . .
I11 . EXPERIMENTAL
RESULTS. . . . . . . . . . . . . .
5. Experimental Methods . . . . . . . . . . . . .
6 . Cuprous Oxide . . . . . . . . . . . . . . .
7 . Direct EdgeofGermanium . . . . . . . . . . . .
8 . Gallium Arsenide
. . . . . . . . . . . . . .
9 . Cadmium Sulfide . . . . . . . . . . . . . . .
10. Indirect Edge of Silicon . . . . . . . . . . . . .
11 . Indirect Edge of Germanium
. . . . . . . . . . .
12. Titanium Oxide . . . . . . . . . . . . . . .
13. Lead Iodide . . . . . . . . . . . . . . . .
14. Defects, Impurities, and Miscellaneous . . . . . . . . .
IV . SUMMARK
. . . . . . . . . . . . . . . . . .
APPENDIX
. . . . . . . . . . . . . . . . . .
257
261
261
268
283
288
290
290
293
295
302
302
305
306
307
308
309
311
313
I Introduction
In this chapter we will discuss only one facet of the field of modulation
spectroscopy. electroabsorption . While the subject has been treated in other
chapters of this book as well as by other^^.^ we plan to review some experimental and theoretical work which has not been previously emphasized.
Electroabsorption has turned out to be useful for the study of the lowest
* This work was supported in part by AdvanEd Research Projects Agency. Office of Naval
Research and Army Research Office (Durham).

For example. see Chapter 6. this volume. by Aspnes and Bottka .
M . Cardona. Soiid. State Phys. Suppl . 11 (1969).
B.0.Seraphin. Modulated Reflectance in Optical Properties of Solids (F.Abeles,ed.). NorthHolland Publ., Amsterdam. 1971.
257
258
DANIEL F. BLOSSEY A N D PAUL HANDLER

Absorption
c0efficient.a
Photon-induced
electronic
transition
/I
- - 7-
' .t
Wave vector
(a 1
(b)
Absorption
coefficient, a
Light energy
Light energy
(C)
(d)
FIG. 1. Typical electroabsorption spectrum and its correlation with band structure : (a) twoband semiconductor, (b) absorption spectrum, (c) finite- and zero-field absorption spectra,
(d) modulated electroabsorption spectra.
direct energy gap and also for any indirect edges which lie below the direct
gap. In addition the technique is useful for the study of defects and impurities
which have strong absorption cross sections which lie in the forbidden gap
of the material under study. Figure 1 illustrates the type of data obtained.
Figure l(a) shows a simple two-band model in momentum space. Figure l(b)
indicates the typical optical absorption resulting from a thermally broadened
absorption edge. Figure l(c) shows how an external electric field modifies
the absorption edge. The oscillatory result arises from the fact that the wave
functions, which describe the electron-hole pair in the presence of an external
electric field, are oscillatory in both spatial dependence and as a function
of energy. The absorption coefficient which is proportional to the probability
of creating an electron-hole pair shows these electric-field-induced oscillations. Below the absorption edge there is an exponential like tail which
represents the photon-assisted tunneling between bands. Figure l(d) shows
the type of experimental data obtained. It is electroabsorption spectrum
which is the difference in value between the two curves shown in Fig. l(c).
The exact shape of the curve shown in Fig. l(d) depends upon a number of
3.
ELECTROABSORPTION
259
factors. The most important factors are the degree of ionicity, the crystal
structure of the compoun,d, the relative strength of the external electric field
with respect to the strength of the coulomb (electron-hole) interaction, and
the mechanisms involved in thermal broadening. We will show how each
of these factors plays its role.
Since the effect of the electric field on the optical spectra can be quite
large, one may wonder about the absence of early observations in the literature. Clearly, workers looking at the spectral response of reversed biased
photodiodes must have noticed the enhanced production of electron-hole
pairs for photons of energy hw < E , as the electric field was increased.
The effect was not understood because it occurred in combination with or
was attributed to a combination of phonon and impurity effects. The first
observations were probably made by Harrick4p5 who used the electric field
to modulate the number ofcarriers in the space charge region ofsemiconductor
surfaces. At photon energies close to the band edge he observed large effects
which could not be explained by free carrier absorption and so they remained
unpublished. A few years later, Franz6 and Keldysh predicted photonassisted tunneling between bands and presented a theory for absorption in
an electric field, explaining the electric field effect as being a shift of the band
edge toward the red. The first published experimental attempt appeared in
1960 approximately two years after Franz and Keldyshs theory. The early
work on CdS and GaAs was interpreted as a shift to lower energies of an
exponential absorption edge. At the Paris Conference on Semiconductor
Physics in 1964, Seraphin presented his first electroreflectance observations
and Frova and Handler their first data on electroabsorption in a p-n
junction. The first work which showed the transformation of the direct edge
into an exponential edge was shown by Frova and Handler on germanium. -I3 It is interesting to note that both Seraphin and Handler were
originally interested in looking for surface states by modulation techniques.
The potential of these techniques in studying band structure, phonons,
N. J . Harrick, Phys. Rev. 103, I173 (1956).
N. J . Harrick, Phys. Chem. Solids 14,60 (1960).
W. Franz, Z . Naturforsch. 13, 484 (1958).
L. V. Keldysh, Zh. Eksper. Teor. Fiz. 34. I138 (1958) [English transl. : Sou. Phys. J E T P 7,
788 (1958)l.
R. Williams, Phys. Rev. 117, 1487 (1960).
T.S. Moss, J . Appl. Phys. 32.2136(1962).
l o B. 0. Seraphin, in Physics of Semiconductors (Proc. 7th Int. Conf.), p. 165, Dunod, Paris
A. Frova and Paul Handler, in Physics of Semiconductors (Proc. 7th Int. Conf.). p. 157,
Dunod, Paris and Academic Press, New York, 1964.
A. Frova and P. Handler, Appf. Phys. Lerf.5, 1 1 (1964).
l 3 A. Frova and P. Handler, Phys. Rev. 137, A1857 (1965).
260
structural defects, as well as surface states, has yet to be fully realized.

Surface states have now been seen by Chiarotti et d . l 4 and interface
states by McNatt and Handler using a spatial modulation technique.
The later work of Seraphin16 and Seraphin and Hess17 showed that the
higher band edges could be easily seen and so stimulated the ensuing work
in electromodulation,8-76 p i e z o r n ~ d u l a t i o n ~and
~-~
temperature
~
modulati~n.~-~
At this point in time, it is now necessary to look back at all the theoretical
andexperimental electroabsorption work and ask what has been accomplished
and what remains to be done. At first the experimental data obtained at
the direct edge were interpreted as photon assisted tunneling which produced
free electron-hole pairs without any coulomb intera~tion.~.It was felt
that at room temperature, thermal broadening was so large as to ionize any
bound electron-hole pairs. Straightforward absorption measurements
tended to strengthen this viewpoint since the peak associated with the
exciton could not be observed at room temperatures. Experimentalists
using modulation techniques also attempted to force fit the data to the
available one electron theory with some success. However, in 1966,
Hamakawa et a/. suggested that exciton effects were the dominant cause
of discrepancies between electroabsorption theory and experiment. Later
in 1968, they showed that only one of the six possible predictions of singleparticle electroabsorption theory was confirmed by experiment.20Additional
work on CdS,66*67in which exciton absorption is known to dominate
the absorption spectra, showed that the single-particle theory was inadequate. Attempts to take the effect of the electron-hole interaction into
account were made by several people, but the first complete calculation
for both bound and continuum states was made by Blos~ey.~
The results
of these calculations will be reviewed in Part I1 with a presentation of
experimental electroabsorption data in Part 111. A summary of the contents
of this chapter will be given in Part IV.
G. Chiarotti, G. Del Signore, A. Frova ,and G . Samoggia, Nuovo Cimenro 26,403 (1962).
J. L. McNatt and P. Handler, Phys. Rev. 178, 1328 (1969).
l 6 9. 0. Seraphin, Phys. Rev. 140, A1716 (1965).
9.0.Seraphin and R. 9. Hess, Phys. Rev. Leu. 14, 138 (1965).
Y. Hamakawa, F. A. Germano, and P. Handler, Proc. lnt. Con$ Phys. Semicond., Kyoto,
1966, J. Phys. SOC.Japan Suppl. 21, p. 111, Phys. SOC.Japan, Tokyo, 1966.
Y. Hamakawa, P. Handler, and F. A. Germano, Phys. L e r r . 25A,617 (1967).
Y. Hamakawa, F. A. Germano, and P. Handler, Phys. Rev. 167,703 (1968).
-See Appendix at end of this chapter for these general references.
b b B. B. Snavely, SolidState Commun. 4, 561 (1966).
6 B. B. Snavely, Phys. Rev. 167,730 (1968).
68-94 See Appendix at end of this chapter for these general references.
9 5 D. F. Blossey, Ph.D. Thesis, Dept. of Physics, Univ. of Illinois, 1969; Phys. Rev. B2, 3976
(1970); Phys. Rev. B3, 1382 (1971).
l4
l5
3.
ELECTROABSORPTION
261
11. The Exciton in a Uniform Electric Field
1. GENERAL
CONCEPTS,
HISTORY,
AND THEORY
Excitons, in their most general sense, are elementary excitations of a

crystal produced when a crystal strongly absorbs light of a given wavelength.
Over the past 30 years, excitons have been categorized into one of two types,
either as excitons of the Frenkel type or of the Wannier type. Whether an
exciton is a Frenkel exciton or a Wannier exciton depends on the type of
theoretical approach that is applicable to the crystal in question. The type
of theoretical approach is, in turn, dependent on how much an electron is
shared among the various lattice sites of the crystal, or, in other words, on
the type of chemical bonding in the crystal. In highly ionic or molecular
crystals, the electrons are tightly bound to the lattice sites. These crystals
exhibit highly localized excitations known as Frenkel excitations. On the
other hand, in covalently bonded crystals, the electrons are shared among
many lattice sites. Covalently bonded crystals thus exhibit excitations
extending over many lattice sites ; these excitations are categorized as
Wannier excitons. The localized exciton theory is most applicable to
alkali halide, molecular, and rare gas crystals whereas the nonlocalized
approach is most applicable to group IV semiconductors. The 111-V and
11-VI compounds are considered to be intermediate cases but there has
been considerable success in treating their exciton wave functions as linear
combinations of nonlocal (Bloch)
The localized exciton theory was first proposed by F ~ - e n k e l ~and
*.~~
These treatments
PeierlslOOand subsequently improved by Overhauser.
considered the excitation to be atomic or molecular in nature, including
the crystal only as a small perturbation on the atomic or molecular energy
levels. The possibility of either singlet or triplet exciton spin states has
added to the understanding of phosphorescence which is due in part to the
long lifetime of the triplet exciton state. The Frenkel theory is based on the
tight-binding theory of crystals in which only nearest neighbor and possibly
next nearest neighbor effects are considered.
The nonlocalized exciton theory was first proposed by Wannier. l o *
D r e s ~ e l h a u s introduced
~~
effective masses into Wanniers treatment and
J. 0. Dimmock, in Semiconductors and Semimetals (R. K. Willardson and A. C. Beer,
eds.), p. 259ff, Vol. 3, Academic Press, New York, 1966.
R. S. Knox, Solid State Phys. Suppf. 5 (1963).
98 J. Frenkel, Phys. Rev. 37, 17 (1931).
99 J. Frenkel, Phys. Reu. 37, 1276 (1931).
l o o R. E. Peierls, Ann. Phys. 13,905 (1932).
l o A. W. Overhauser, Phys. Rev. 101, 1702 (1956).
G. H . Wannier, Phys. Rev. 52, 191 (1937).
I o 3 G. Dresselhaus, Phys. Chem. Solids 1, 14 (1956).
96
262
E l l i ~ t t ~ used
~ , ~Dresselhaus
~
results to calculate the optical absorption
spectra for Wannier excitons. Using the effective mass approximation, the
Wannier exciton is simply an electron-hole pair bound together by their
attractive Coulomb potential. This electron-hole pair is a hydrogenic atom
differing from the hydrogen atom only in effective masses and dielectric
constant of the medium. The bound states of the electron-hole pair occur
in the forbidden gap of semiconductors and insulators at energies given by
En = E , - R/n2,
where E, is the energy gap, R is the effective Rydberg energy, and n is an
integer specifying the state. The intensities of the absorption lines for transitions to bound exciton states are proportional to n - 3 . For light energies
greater than the energy gap of the material, the absorption spectrum is a
continuum. The effective Rydberg R is given by
pe4/2h2~02
= 13.6(pfrn~,) eV,
(2)
where p is the reduced mass of the electron-hole pair, m is the normal

electron mass, and E~ is the static dielectric constant of the material. The
radius (effective Bohr radius) of the exciton is given by
a = h2eo/pe2 = 5.29 (meo/p) x i O P 9
cm.
(3)
A typical exciton radius is 50A and a typical binding energy (effective

Rydberg) is about 20meV. Considering that a typical value for the width
of a unit cell in a crystal is 5 A, the typical exciton does span many unit cells
thus making the Wannier approach quite feasible.
There have been only a few published calculations of the effect of an
electric field on Wannier type excitons. The first calculations of this type
were performed to explain the Stark effect in hydrogen.lo6-* These calculations were performed in the context of perturbation theory. In the case
of the hydrogen atom, perturbation theory is quite adequate as the field
necessary to ionize the ground state is very high (Si= 2.59 x 109V/cm).
This ionization field corresponds to a potential drop of one Rydberg across
a Bohr radius. As long as S / 4 < 0.5, the 1s hydrogenic level can be considered to be a discrete level with little mixing with other levels and the
continuum. But if S/gi > 0.5, the ground state of the exciton becomes
appreciably mixed with the higher states and the continuum ; and, conse04
lo
lo6
lo
R. J. Elliott, Phys. Rev. 108, 1384 (1957).

R. J. Elliott, in Polarons and Excitons (C. G. Kuper and G. D. Whitfield. eds.), p. 2698.
Oliver and Boyd, Edinburgh and London, 1963.
C. Lanczos, Z . Phys. 62,518 (1930); 68,204 (1931).
H. Rausch von Traubenberg and R. Gebauer, 2.Phys. 54,307 (1929); 56, 254 (1929); 62,
289 (1930); 71,291 (1931).
3.
263
ELECTROABSORPTION
TABLE I
ENERGYGAPS, RYDBERGENERGIES.
A N D kINlZATlON FIELDS FOR SELECTED
SEMICONDUCTORS
Energy gap (eV)

Material
-~
Pblz
Ge
GaAs
GaSb
InP
InAs
InSb
AlSb
CdS
CdSe
CdTe
ZnS
ZnSe
ZnTe
a
2.55
0.80
1.41
0.8 13
1.29
0.360
0.2357
1.6
2.5831
1.8415
1.606
3.9115
2.818
2.30 1
Effective Rydberg
energy (eV)
Ionization field
Rlea (V/crn)
0.073
0.0014
0.005 1
0.001 8
0.0065
0.0018
0.0005
0.0075
0.0294
0.01 57
0.0100
0.0401
0.0 190
0.01 30
4.6
5.5
5.7
1.0
7.8
7.0
7.6
1.2
1.4
6.0
3.1
2.0
105
x lo2
x
lo3
x 103
lo3
lo2
x 10
x
x
x
lo4
105
lo4
lo4
x 105
7.5 x 104
4.7
lo4
Exciton from highest energy split-off valence band.
quently, the spectra become continuous rather than discrete. The value of
bivaries from material to material ; and, since fields of the order of lo5 to
lo6 V/cm are attainable in semiconductors and insulators, the electric field
in these materials cannot be treated simply as a perturbation but must be
treated on an equal footing with the Coulomb field. In Table I, there is a
listing of energy gaps, binding energies, and ionization fields for various
semiconductors and insulators calculated from tabulated values of effect
masses and dielectric constants.08-13
The perturbation treatment of the hydrogenic atom in an electric field
was the only approach published until 1966, when Duke and AlferiefflL4
lo*
lo9
lL1
l2
I
I4
J. R. Oppenheimer, Phys. Rev. 31.66 (1928).

R. A. Smith, Semiconductors, pp. 347. 350. 367,410, Cambridge Univ. Press. London and
New York, 1961.
C. Hilsum, in Semiconductors and Semimetals ( R . K. Willardson and A. C. Beer. eds.).
Vol. I , p. 9. Academic Press, New York, 1966.
J. 0. Dimmock, in Semiconductors and Semimetals ( R . K . Willardson and A. C. Beer,
eds.), Vol. 3, p. 314. Academic Press, New York, 1966.
0. Madelung, Physics of 111-V Compounds, p. 101. Wiley, New York, 1964.
B. Segall and D. T. F. Marple, in Physics and Chemistry of 11-VI Compounds (M. Aven
and J. S. Prener, eds.), pp. 335, 344. Wiley, New York. 1967.
C. B. Duke and M. E. Alferieff, Phys. Rev. 145, 583 (1966).
264
DANIEL F. BLOSSEY AND PAUL HANDLER
FIG.2. Coulomb potential for zero- and finite-electric fields.
treated a simplified model of the coulomb plus electric field. The coulomb
potential with and without electric field is shown in Fig. 2. Duke and
Alferieffs model assumed that the coulomb potential is zero outside a
critical radius and that the electric field is zero inside this critical radius.
With these assumptions, the problem is analytically solvable. The model
was reasonable but it predicted incorrect Stark shifts of the excitons lines
with electric field. To improve on this approach, numerical integrations
of the effective mass differential equation have been accomplished by
Ralph,''5 Dow and Redfield,' l 6 and one of the authors.95The calculations of
Ralph and Dow and Redfield are limited to the 1s exciton level and do not
show the electric field induced oscillations in the continuum density of states.
B10ssey~~
was the first to numerically calculate the electric field effect on the
higher bound exciton levels and to show that the electric field did indeed
induce oscillationsin the exciton's continuum. Blossey has also demonstrated
that the electron-hole interaction enhances the electric-field-induced oscillations near an M , type critical point and quenches these oscillations near an
M , type critical point. Enderlein'" has also made an attempt to solve the
problem of the hydrogenic atom in an electric field using a Green's function
approach. Recent calculations' l6 have shown that one of his assumptions is
115
H.I. Ralph, J. Phys. C (Proc. Phys. Soc.) Ser. 2 1,378 (1968).

J. D. Dow and D. Redfield, Phys. Rev. B1, 3358 (1970); J. D. Dow,Phys. Status Solidi 34,
K71 (1969).
R. Enderlein, Phys. Status Solidi 26,509 (1968).
3.
265
ELECTROABSORPTION
TABLE I1
DEFINITION
OF SYMBOLSAND UNITS
Quantity
Symbol
Effective Rydberg
Effective Bohr radius
Ionization field
Electric field
Reduced mass of
electron-hole pair
Electrooptical energy
R
a
pe4/2hZeo2
h2co/pe2
Ria
4
fl
h0
MKS units
m,mh/(m,
+ mh)
(hZe28/2p)
Atomic units
One energy unit
One distance unit
1
814
(8/4)23
invalid and that his calculations are only valid in the limit of weak electronhole binding. In the following, the notation used will be consistent with that
used by Dimmock in Chapter 7, Volume 3 of this series. The derivation
presented by Dimmock will be reviewed briefly here and will be used as a
starting point for calculations of optical absorption by Wannier excitons in a
uniform electric field. Several quantities that will be used frequently in the
text are defined in Table 11.
a. Theory of the Wannier Exciton in an Electric Field

From the band theoretical point of view, the absorption of light by a
crystal is accomplished by creation of an electron-hole pair. The ground
state of the crystal is assumed to be the state in which the valence band is
completely filled and the conduction band is completely empty. The electron
and hole in the final or excited state may interact via the attractive coulomb
potential. This electron-hole interaction breaks the translational symmetry
of the crystalline potential and mixes the Bloch waves. The excited state
of the crystal may be approximated by a linear combination of Bloch
electron and hole wave functions as
ynsk(rerh) =
3
C C
c.ke V,kh
A::t(ke kJ$c,k,(re)$v, - kh(rh)

9
(4)
where n and k (k = ke + kh)are used to label the excited state, and $& and
$v,kh are the electron and hole Bloch wave functions. The energy difference E
between the excited state Yn,and the ground state Yo of the crystal may
be determined from the following set of equations.
266
DANIEL F. BLOSSEY A N D P A U L HANDLER
where E,(ke) and E,(k,) define the energy bands for the conduction and
valence band states and V(re - r h ) is any potential energy which is a function
of the distance between the electron and hole; in our case, this means the
Coulomb potential and the electric field. If the Coulomb potential is screened
by a medium with dielectric constant .so and an external electric field is
applied, then the electron-hole pair sees the combined potential energy
V(r) = - e2/&,r - e& * r ,
(6)
where r = re - rh and d is the electric field. This potential was shown in

Fig. 2 for z e r w and finite-electric field. The major effect of the electric
field is to lower the lip of the potential well which causes the bound levels
to be mixed and broadened into a continuum. A secondary effect ofthe electric
field is a slight widening of the coulomb well which causes a shift of the 1s
level to lower energies which produces the well-known phenomena of the
second order Stark shift.
As an aside, it should be noted that the Coulomb potential is not quite
an accurate representation of the electron-hole interaction. This is due
to the fact that the electron and hole are not truly point particles but, in
effect, have the dimensions of a unit cell of the crystal. This means that if
the electron and hole are located in the same unit cell, their charge clouds
are overlapping and the potential well has a bottom on it instead of singular
point at r = 0. Using the Coulomb potential as being the electron-hole
interaction causes overestimation of the binding energy of the lowest bound
exciton level. In materials where more than two bound levels are observable,
it has been shown that the 1s level deviates slightly from the (En= E , - R/n2)
rule. *
The effective mass equation of Dresselhaus O 3 is obtained by introducing
the Fourier transform of A;$(ke, kh) which is defined as
@$(re, rh) =
C 2 exp(ike re)eXp(ikh rh) A$(ke, kh) .

*
ke
kh
(7)
If we assume that V(r) varies slowly over the distance of a unit cell and that
the energy bands are nondegenerate, then @$(re, rh) satisfies the differential
equation
{ E,( - iV,) - E,( - ivh) + V(r) - E}@E;t(re,rh) = 0 .
(8)
Using the effective mass approximation and assuming that the bands are
isotropic near the band edge gives
S. Nikitine, J . Burckel, J . Biellman, and R . Reiss, C. R . Acud. Sri. Paris 251,935 (1960)
3.
267
ELECTROABSORPTION
where En = E - E,, E , is the energy gap at the band edge, and

defined by the equation
@;:!(re, rh) = exp(ik R)4,,(r),
4,(r)
is
(10)
where r is the relative coordinate, R is the center-of-mass coordinate, p is the

reduced mass of the electron-hole pair, and M is the sum of the electron
and hole masses. Equation (9) is the equation that must be solved to determine the wave function for the Wannier exciton in an electric field, but
before we seek a solution let us find the relationship between the optical
absorption by Wannier excitons and +"(r).
b. Direct Excitons, Allowed and Forbidden Transitions
I f we include both bound and continuum exciton levels, then it may

be stated that the entire absorption spectrum is due to the formation of
excitons. Actually, what we mean by this statement is that the single-particle
optical density of states is altered by the electron-hole interaction not only
in the region directly below the energy gap but throughout the entire
spectrum. Thus we will be interested in calculating absorption by not only
the bound exciton states but also the continuum exciton states.
The matrix element that determines the transition rate for optical transitions between the ground state 'Poand the excited state 'P"," is given by
where A = A t exp(iq r - i o t ) is the vector potential of the electromagnetic

wave. Using F kfrom Eq. (4) and neglecting the momentum of the photon
hq relative to the crystal momentum hk, the matrix element M",' may be
expressed as
where R is the volume of the unit cell of the crystal. The function uk is
defined in the normal manner as the part of the Bloch wave possessing the
crystalline translational symmetry, i.e., $k = N - ' I 2 exp(ik r)uL.Combining
Eqs. (7)and (10)and assuming that the integrals in Eq. (12) are slowly varying
functions of k, gives the r e ~ u l t ' " ~
268
where Pcvand Ucvare defined by the integrals
and
For allowed transitions, u, and uv are antisymmetric and U,, 2 0 ; for

forbidden transitions, u, and u, have the same point group symmetry and
Pc, N 0. The imaginary part of the dielectric constant is related to M"*' by
the relation
Thus for allowed transitions, E~ is given by
k,n
and for forbidden transitions is given by
ho).
(17)
The imaginary part of the dielectric constant is proportional to the

absorption coefficient o! (c2 = nccc/u, where n is the index of refraction).
The imaginary part of the dielectric constant is also related to the reflectance
R through a Kramers-Kronig transformation. (See Chapter 6 by Aspnes
and Bottka on dielectric properties of solids in an electric field.)
2. CALCULATION
OF OPTICAL
ABSORPTION
BY WANNIEREXCITONS
IN AN ELECTRIC
FIELD95
In the previous section, it was shown that the imaginary part of the
dielectric constant E~ is proportional to a sum over the amplitudes 1$n(0)12
times an interband momentum matrix element squared. If we assume that
the interband momentum matrix element P,, is a slowly varying function
of k near the band edge, then c2 may be expressed as
where the function +(O)
is the probability that the electron and hole are
3.
269
ELECTROABSORPTION
found at the same point in the crystal. Mathematically, c$~(O)is given by
4(0) = 47rZRa3 n 14,(0)l26(E, + En - ho),
(19)
where n represents the three quantum numbers that specify the hydrogenic
wave function $,,(r).
a. Hamiltonian and Separation into Parabolic Coordinates
The assumption of direct transitions requires that k = k, kh = 0.

Thus knowing that only solutions with k = 0 are needed, the differential
equation for C$,,(r)reduces to
where the electric field 8 is taken to be in the z direction. This is the

Schrodinger equation for the hydrogenic atom in an electric field with p
being the reduced mass of the electron-hole pair and E~ the static dielectric
constant of the crystal. As mentioned previously, the externally applied
electric field in the crystal can be large enough so that it is not simply a
perturbation on the coulomb field. Fields on the order of 105V/cm are
sufficient to ionize excitons in most crystals which means that the electric
field can be comparable if not stronger than the Coulomb field. Thus, in the
following, we will not treat the electric field as simply being a perturbation
on the coulomb field but will treat both equally. Our approach is to solve
Eq. (20) by separation into parabolic coordinates, followed by a numerical
integration of the resulting differential equations.
Because of the linearity of the electric field potential, Eq. (20) is separable
in parabolic coordinates. Parabolic coordinates, in fact, are useful in the
treatment of all kinds of problems in which a particular direction in space
is distinguished by some external force. l 9 The parabolic coordinates [, v],
and cp are defined as
[=r
+ z,
r - z,
and
cp = tan- (ylx).
(21)
The surfaces [ = constant and v] = constant are paraboloids of revolution

about the z axis having the origin as focus. The volume element is given by
I9
H. A. Bethe and E. E. Salpeter, Quantum Mechanics of One- and Two-Electron Atoms.

270
and the Laplacian operator is defined as
Equation (20) may be separated by defining

coordinate functions
4,,W = AfY(v)g,,(Oexpt? imq),
4,(r) as a product
v
of parabolic
+ (pe2hfi2),
( 24)
where A is a normalization constant and the functionsf, and g,. satisfy the
equations
At this point in the calculation, it is convenient to define dimensionless

variables so that the calculated eigenvalues will not be directly dependent
on the values of the electric field, reduced mass, and static dielectric constant,
but will be dependent only on two dimensionless parameters containing
these variables. The two dimensionless parameters of importance are a
dimensionless energy p and a dimensionless field 6/6,. The dimensionless
energy fl is
b'
= E,/hQ,
(26)
where h e is the electrooptical energy and is defined as
The separation constants, or eigenvalues, v and v may be made dimensionless

by defining new variables ti and ti which are given by
where bi is the ionization field for the ground state of the exciton, which is
given by
gi = R/ea
2.57 E; ' ( p / ~ n x) ~lo9 V/cm.
(29)
3.
ELECTROABSORPTION
271
Let us also define a dimensionless distance x such that

.Y
= (q/2a)(t"/4)l/3,
=
> 0,
< 0.
-(~/24(8/4)1/3,
With these substitutions Eqs. (25a) and (25b) become
Since from Eq. (16) we are only interested in calculating +,,(r) at r = 0, it

should be noted that the only nonzero values for +,,(r) at r = 0 come from
the m = 0 terms since
lim f ( x )K xlrnli2
x-0
and
lim g(x) K ( - x ) l m l i 2 .
-x+o
Thus only the m = 0 terms contribute to the exciton spectrum for direct
allowed transitions. For m = 0, Eqs. (31) reduce to
~ ) effective
~ ~ ~ .potential in Eq. (33)has singularities
where K' = ti + ~ ( C F JThe
at the origin and at plus and minus infinity. Thus the solutionsfand g for
x > 0 and .Y < 0, respectively, may be obtained by connecting the regular
solution at infinity to the regular solution at the origin by either numerical
integration or some other sort of interpolation scheme. The value of g(x) at
the origin may be determined by connecting the oscillatory asymptotic
solution, given by
gk.,p(x)
( -x
3/4
sin ( f (- .Y
+ 8)'i2 + K'( - x + p)'" + E ) ,
(34)
where 2 is an arbitrary phase angle, to a regular solution at the origin.

Since the phase angle E is arbitrary, g(0) is continuous function of K' and p.
The asymptotic solution for f ( x ) must fall off exponentially for x >> p.
Since only the exponentially decaying solution is allowed for large positive x,
then only certain values (eigenvalues) of ti will connect the regular solution
at the origin to the asymptotic solution. The asymptotic solution for f ( x ) is
272
given by
f,,s(x)
(x - 8)-3/4 exp{ -f(x -
8)32+ K(X - 8)-12} .
(35)
Connecting this solution to a regular solution at the origin determines a

set of eigenvalues K~ which are continuous functions of the dimensionless
energy fi.95A very good approximation to these eigenvalues K~ may be
obtained using the WKB approximation for calculating phase changes
between classical turning points. The WKB eigenvalues ~y~~ are defined
by the relationship
x2
dx[-(KyKB/x)
+ p - xI1l2 = (i - 1/2)n,
1 , 2 , 3 , 4 , . . . , (36)
JX,
where x 1 and x 2 are the classical turning points, i.e., the zeros of the
integrand. It is interesting to note that the percent difference between ~y~~
and the actual K~ was less than 1 % so that the ~y~~ serve as a good starting
point for a numerical integration to find the K ~ The
.
solution of Eq. (36) is
a hypergeometric function which may easily be calculated from various
approximate series.12 The K~ approach the asymptotic limit K~ = -(2i - 1)
(-8) for large negative 8. Since the eigenvalues are continuous functions
of energy, the normalization of the wave function is quite different from
normalization of wave functions which have discrete energy levels.
Since $,(r) has continuous eigenvalues with respect to energy, it is necessary
to normalize the integral of the wave function squared to a Dirac delta function
in energy instead ofa Kronecker delta. The normalization expression is given
by
dr $*E,v,m(r)$E,v,m(r)
&E - E ) ~
dmm
~
V
(37)
where E is the energy, v is the separation constant, and rn is the azimuthal

quantum number. The wave function is a product of functions of the parabolic
coordinates q, and cp :
c,
$E,v.m(r)
= AfE,v,rn(q)gE,v,m(O
~ X Pf
( imp).
(38)
The volume element dr and the Laplacian operator are given in Eqs. (22)
and (23) in terms of parabolic coordinates. The exp ( & irncp) part of the
wave function leads directly to the bmTm
normalization. The f ( q ) function is
bounded so that the integral of its modulus squared is calculated by machine.
The difficulty in evaluating the integral in Eq. (37) is that the g(c) function is
oscillatory and falls off slowly as is clear from its asymptotic solution in
Eq. (34). Calculating the integral of its modulus squared is not possible by
lZo
I. S. Gradshteyn and I. M. Ryzhik, Table of Integrals, Series, and Products, p. 1040ff.

Academic Press, New York and London, 1965.
3.
273
ELECTROABSORPTION
machine because this integral gives the Dirac delta function normalization
which blows up for E = E . Thus a different method from calculating the
integral in Eq. (37) must be used.
From Eq. (20),it is dear that
I d r [d)*V2$ -
4 V @*]
= (2p/h2)(E- E )
dr
$I*+,
(39)
where the primed function 4 has eigenvalues E, v, and m .Combining

Eqs. (20),(21), (37), and (39) gives the result
2P (E - E ) S(E
h2
E ) Svrv
The first term on the right side of Eq. (40) is zero sincef(r]) is zero at infinity
and q is, ofcourse,zero a t q = 0.Realizing also that the limit at ( = 0 of the
second term on the right side of Eq. (40) contributes nothing, we are left
with
2p(E
h2
- E ) 6(E - E ) Svrv= 2nA2
Since they,,, for a discrete set at a given energy E, then
is the normalization for f, and g is normalized as follows: For x << p, the

asymptotic solution for g is given by Eq. (34) which when used in Eq. (41)
gives
In the limit j? --* p, a
-+ tl
and we have
T(E - E ) 6 ( E - E ) .
(44)
274
Thus the normalization in terms of a Dirac delta function in energy is due

to the oscillatory part of the asymptotic solution. The normalization
constant A 2 can then be calculated to be
A2
(4nZa3R)-'
(45)
and from Eq. (19)we have
The normalization constant in Eq. (42) is defined such that
whereby
42(0)is dimensionless and
where K ~ '= K~ 2( 8i/)1'3,

f:(O) is a slowly varying function of fi, and
g:.(O) contributes resonances to @(O) for small fields and @(O) is related to
e2 through Eq. (18).
b. Nature of Solution
The function 42(0)is proportional to the absorption coefficient r and the
imaginary part of the dielectric constant e2 and is thus the theoretical expression for a physically measurable quantity. Thus 42(0)is given by Eq. (48)
and is a sum over the product ,f~,,(0)g2,,.,p(O).Calculating the bounded
function f ( x )determines the eigenvalues tii. These eigenvalues form a discrete
set of functions for any given energy but are continuous functions of energy.
The function g52(0) is calculable by machine because only the first few
eigenvalues make significant contributions to it near the direct edge. As an
example in which &/& = 1, Fig. 3 shows the contributions of the first
three eigenvalues toward the total 42(0).It is interesting to note that each
electric-field-induced oscillation is due to a different eigenvalue : thus, if
only the first eigenvalue is considered, the oscillations will not be seen.
None of the previous calculations have considered more than the first
eigenvalue.' 1 5 * 1 In general, f&(O) decreases with energy while giq..,.(0)
increases with energy until it reaches a maximum and then falls off very
'
3.
ELECTROABSORPTION
275
FIG.3. Contributions of different eigenvalue solutions to produce electric-field-induced oscillations using the equation @(O) = Zt=, d,(O). Example shown is for F = c F / ~=~1 . (After
Blo~sey.~~)
slowly with energy. The product f&(0)g~,,.8(O)then forms a peak for every
K~ which for large &/giare centered on the values j3 = [3n/2(i- 1/2)]23,
which are the points where K i ( / j ) = 0. For small b / b i ,gi,.,s(0)can exhibit
resonances which correspond to absorption by bound exciton levels. The
energy positions of the resonances of gi,,,s(0) correlate nicely with the
splittings and shifts of the hydrogenic atom as calculated from perturbation
theory for small &/i.The dramatic structure in @(O) is contained in g2(0),
whereasf(0) is always a slowly varying function of energy.
A few general features of the effect of an electric field can be seen by simply
examining the effect of a uniform electric field 8 on the coulomb potential.
The coulomb potential with and without electric field was shown in Fig. 2.
The major effect of the electric field is to lower the lip of the well and thereby
change discrete bound states into continuum states. When the lip of the
well moves below the energy of a bound level, then it takes no extra energy
to separate the electron and hole and that level is said to be ionized. A
secondary effect of the electric field is to slightly widen the well. This causes
the ground exciton state to shift to a lower energy because, from the WKB
point of view, a wave function with given quantum numbers must retain a
certain phase shift between classical turning points. Thus if the well widens.
the level must shift to a lower energy. These results will be seen in more detail
in the following section.
276
c. Results of Numerical Calculation
In the following, the function $(O), which is proportional to E (the

imaginary part of the dielectric constant) and a (the absorption coefficient)
will be plotted as a function of energy for several values of b/4.The energy
units will be effective Rydbergs and @(O) will be normalized such that it
approaches ( E - EJ1 for E >> E,. This is in accordance with Elliotts
continuum density of states for optical absorption by excitons. He calculated
that for zero-electric fieldlo4
4(0) = 211/[1 - exp( - 211E;
)I,
E > E*,
(49)
where Ed and E - E, and $~(0)-,( E - E,)l/ for E >> E , . Elliott also

calculated the zero-field intensity of the bound exciton lines ( E < E,) was
given by 41112 and
m
@(O) =
n= 1
(4n/n3)S(E- E,
+ R/n),
E < E,.
For n -, co,it may be shown that #(O) approaches the continuum value of
211. It will be shown in what way the electric field alters the zero-field spectrum
as described by Eqs. (49) and (50). Equations (49) and (50) do not include
the possibility of line broadening which must be included if a valid comparison between theory and experiment is to be made. Broadening will be
included in Section 4 so that experiment and theory may be compared.
n =1
n
120
/
80
40
-1.4
-1.2
-1.0
-08
-0.6
-04
-0.2
0.0
(E-E,)
FIG.4. Electric field effect on bound excitation levels for F

(After B l ~ s s e y . ~ )
&/&
= 0.005, 0.02.0.25, and 1.
3.
277
ELECTROABSORPTION
In Fig. 4, the exciton spectrum is shown for four different values of 8/4.
For 8/gi= 0.005, it is evident that the electric field has had little effect on
the 1s or 2s hydrogenic levels. The n = 3 and higher levels are however
greatly affected by this magnitude of electric field. The n = 3 level is split
into three parts by this field and all higher levels are smeared into a continuum. The three Stark-split branches of the n = 3 level correspond to
States with
mixtures of the 3s, 3p, and 3d hydrogenic states for small 8/4.
zero s character have been omitted. In terms of the R,[&,, hydrogenic wave
functions, the three branches correspond to
3-12R30Yoo
+ 2-12R31Ylo + 6-1/2R32Y20
(lower branch),
3-12R30Yoo - (2/3)-12R32 Y2o
(middle branch), (51)
3-12R30Y00 - 2-12R3, Y,,
(upper branch),
+ 6-2R32Y20
for $~(n= 3 , m = 0). One very interesting effect of this splitting is that the
lower branch which presumably lies deepest in the well is the one most
broadened by the electric field. This may be explained by the probability
distribution of the wave functions with respect to the lip of the well. In other
lo6
I0
--
I0
I0
-2
10
-4
10
-(
!O
I /
-016
I
- 0 I2
- 0 08
-004
(E-E,)
FIG.5. Electric field effect o n the 3s hydrogenic level for F = &/6i= 0.002S(a), 0.0040(b).
(After Blos~ey.~)
278
IANIEL F. BLOSSEY AND PAUL HANDLER

I 0"
I o4
I 0'
-8
I0
I o-2
-(
/I
-0 4
-0 2
-03
( E -E,
-0 I
FIG. 6 Electric field effect on the 2s hydrogenic level for F

0 025(c).(After B l ~ s s e y . ~ ~ )
8!8,= 0010fa). 0.016(bj.
words, if the wave function is more concentrated on the lip side of the well then
the chances of the electron escaping from the hole are improved and the probability +'(O) is reduced. This is exactly the case here. The 4'(0) for the lower
branch is broader because the wave function is concentrated on the lip side of
the well and that level is more susceptible to ionization. This effect has been
observed in the Stark effect on hydrogen."' Increasing 8/4from 0.005 to
0.02 smears the n = 3 levels into the continuum and splits the n = 2 level
into two parts. The two Stark-split branches of the n = 2 level correspond
to mixtures of 2s and 2p hydrogenic states for small 8/4.
In terms of the
R
the two branches are given by
",xm
2-1/2R20Y00 2 p 1 1 2 R Y
2,,
,
2-"2R20Y00 - 2 p ' / 2 R 2Y,,,
(lower branch),
(upper branch),
(52)
for 4(n = 2,m = 0). Again the lowest energy branch has been broadened
the most by the electric field which is due to the fact that its wave function
has a higher probability on the lip side of the well and thus a greater chance
to escape. Increasing 8/gi from 0.02 to 0.25 smears the n = 2 levels into the
continuum and broadens and shifts the n = 1 exciton level. The n = 1 level
3.
279
ELECTROABSORPTION
(E-E,)
FIG. 7. Electric field effect on the Is hydrogenic level for F

(After B l ~ s s e y . ~ ~ )
&/4 = O.IWa), 0.32(b), I.o(c).
corresponds to the Is hydrogenic state which is given by

+(n
1)
R,oYoo.
(53)
This ground state of the exciton shows the quadratic Stark shift to lower
energies for /L$ < 0.5 and at /L$ v 0.7 starts shifting back to higher
energies due to mixing with the continuum. For /42 1.0, no bound
exciton levels are distinguishable and the electric field has completely
ionized the exciton.
In Figs. 5-7, the effect of a uniform electric field on transitions to the
first three bound exciton levels is seen in more detail. Figure 5 omits the
n = 1 and n = 2 levels and shows the Stark splittings, shifts, and broadening
of the n = 3 level for 8/ =
, 0.0025 and 0.0040. Again it is interesting to
note that the lower branch is shifted and broadened more extensively than
the higher two branches of the n = 3 level. Figure 6 omits the n = 1 level
and shows the Stark splittings, shifts, and broadening of the n = 2 level
for &/L$ = 0.010,0.016, and 0.025. Figure 7 shows the Stark shift and broadening of the n = 1 level for /c$= 0.10, 0.32, and 1.0. These shifts agree quite
well with the energies as calculated from perturbation theory. To third order
280
in electric field &/4,the energies of the various Stark split states are given by
+ 1)
-(1/32)(b/&)2n4[17n2 - 3(n - 2i - m + 1)2 - 9m2 + 191
-(3/128)(~9/$)~n(n - 2i - m + 1)
x [23n2 - (n - 2i - m + 1)2 + l l m 2 + 391,
(54)
Enim = -(l/n2)
(3/2)(&/4)n(n - 2i - m
where in our case m = 0 and i refers to rci and in each level n, i = 1,2,. . . ,n.
For S/4 > 0.5, the perturbative result differs from the actual result as the
hydrogenic set of wave functions is not capable of describing the continuum
spectrum resulting from the application of the electric field.
For S / 4 > 1, $2(0)approaches the limit in which the electric field completely dominates the coulomb field. In fact, for b/& > 100 there is very
little difference between the (62(0)calculated with the coulomb potential
and $(O) calculated without the coulomb potential. For electric fields
b/$ > 1, absorption by the bound exciton states no longer dominates the
spectrum and the continuum exciton states become important. Since
Eq. (20)for &(r) does not specify whether the reduced mass p of the electronhole pair be positive or negative, it is possible to use Eq. (20) to calculate
the electric field plus coulomb field effects near both M o (positive p) and
M , (negative p) type critical points in the energy band structure. Critical
points in the energy band structure are points ink space where the conduction
and valence bands are parallel. At a critical point, V,(E, - Ev) = 0, which
causes a singularity in the interband density of states that may be expressed
as 12 1.122
where S is a surface of constant interband energy ECv(k).Equation (55)

does not include the electron-hole interaction or the electric field and is
thereby inadequate for our purposes, but it does show that single particle
theory connects singularities in the interband density of states with critical
points in the energy band structure. In the immediate vicinity of a critical
point ko in the Brillouin zone, the energy E(k) is a quadratic function of the
directional components of k - k,, or Aka = (k - k,). d, where B is a unit
vector in the coordinate direction a.
E(k) = E@,)
P2
L. Van Hove, Phys. Rev. 89, 1189 (1953).

J. C. Phillips, Phys. Rev. 104, 1263 (1956);Solid State Phys. 18 (1966).
3.
281
ELECTROABSORPTION
12
10
N 6
-0
-5
10
15
(E-E,)
FIG.8. Electric field effect near M o edge for F = Sj4
where the p, are defined as

pa-
l(a), lqb), lOo(c). (After Bl~ssey.'~)
' = m,$- ' + mza- '
There are four types of critical points M o , M

defined as
(57)
M , , and M , which may be
1239124
M , : pl , 1 1 2 , p3 all positive,
M' : p l , p, positive, p 3 negative,
M , : p , , p, negative, p 3 positive,
M , : p l , p 2 , p 3 all negative.
The number of critical points for transitions between two bands depends
on each individual band structure but the minimum number of critical
123
D. Brust, J. C. Phillips, and F. Bassani, fhys. Rev. Left.9,94 (1962).

D. Brust, fhys. Rev. 134, A1337 (1964).
282
points is fixed by the number of nondegenerate high-symmetry points in

the Brillouin zone.lZ2
In our case where both the coulomb potential and electric field are included,
it was necessary to assume an isotropic mass to make the problem soluble.
Thus we are limited to the case where p l , pzrand p 3 are all equal and have
the same sign. The M , (positive p) and M , (negative p) critical points are
referred to as being absorption edges; the M , edge is the fundamental edge
at the band gap and the M , edge corresponds to transitions from the bottom
of the valence band to the top of the conduction band.
Figure 8 shows @(O) near an M , type edge for &/4 = 1,10, and 100. For
&/4= 1, a small exciton peak below the edge is still in evidence. If a comparison were made between the calculated values of the amplitude of the
oscillations in 42(0)above the edge with and without the electron-hole
interaction, it would be quite evident that the coulomb potential enhances
the electric-field-induced oscillations above the edge as well as causing
absorption peaks below the edge. Thus, even if the electric field is strong
enough to ionize the bound exciton levels, the coulomb potential still
3.0
(E-E,
FIG.9. Electric field effect near M , edge for F
d?/4= I(a), lqb), IOO(c). (After Blo~sey. ~)
3.
283
ELECTROABSORPTION
contributes to the amplitude of the electric-field-induced oscillations above

= 10 and 100, the oscillations spread out approximately
the edge. For &/c$
as (&/c$)~/, and no resonances below the edge are observable.
Figure 9 shows Cp2(0)near an M, type edge for 8/&,
= 1, 10, and 100.
Having a negative mass and an attractive coulomb potential is the same thing
mathematically as having a positive mass and a repulsive coulomb potential.
Thus we would expect that inclusion of the electron-hole interaction would
decrease q52(0) near an M , type edge. This is to say that if 42(0)is the probability of an electron and hole being at the same point in the crystal then
inclusion of a repulsive electron-hole interaction should reduce +2(0).This is
exactly what happens. The repulsive coulomb potential not only reduces the
magnitude of qh2(0) but it also reduces the amplitude of the electric-fieldinduced oscillations near an M , type edge. This is perhaps one reason why M ,
edges have not been observed in electroreflectance, i.e., the optical density of
states is actually changing so slowly near an M , type edge that it is not altered
significantly by the electric field.
3. WEAKLYBOUNDEXCITON
LIMIT
In several semiconductors, the exciton binding energy is so small that any
small electric field or temperature will ionize the bound exciton levels. In this
case, it is quite reasonable to completely neglect the electron-hole interaction
and the equation for 4(r) for an electron and hole in an electric field may be
written as125p126
The solution to this equation is a product of Airy functions.

where
#,(d = C,C,C, Ai( - 5,) Ai( - ty)Ai( - 5,),
5,
= &/he,
+ r,h=
2/3(2p,* e&,)1/3
2
(59)
(60)
h e 8,~ p , ,
(61)
+ E , + E,,
(62)
and C,, C,, C , are normalization constants. The energy E, is that associated
with the solution for the coordinate r,; the energy E , is of course given by
En = E x
By manipulating integrals of Airy functions,

derive equations for the dielectric constants
26
D. E. Aspnes, Phys. Rev. 147, 554 (1966).

D. E. Aspnes, Phys. Rev. 153, 972 (1967).
+ ie,
was able to
near the four types of
284
critical points. The results of his calculations are shown in Fig. 10. For example, for an M , type edge, he calculated that $2(0)as defined in Eq. (19) is
given by
42(o)= n{(d Ai('I)ld'I)2- 'I(Ai('I))2}

9
(63)
where
'I = ( E g - E)/hO.
(64)
By comparison of the oscillations in @2(0)
from Eq. (63) and $2(0)as shown in
Figs. 8 and 9, it is evident that the electron-hole interaction enhances electricfield-induced oscillations near the M o edge and quenches electric-fieldinduced oscillations near the M , type edge.
Q.
Direct Transitions
In 1958, Franz6 and Keldysh' initiated the theory of optical absorption in

an electric field by predicting that photon-assisted tunneling from the
valence band to the conduction band was possible and that it would shift
the exponential tail in the absorption coefficient for the energy region immediately below the fundamental edge. There were two independent approaches to
electroabsorption theory that followed. C a l l a ~ a y , ' ~ ' *using
' ~ ~ the results of
Adams,' 29 Argyres,I3' Kane,I3' and Houston'32 calculated the wave function for the Bloch electron in an electric field. The electric field mixes Bloch
states along its direction in k space. Callaway then used this wave function to
calculate interband transition probabilities for an electron that interacts
with light. The second approach was put forward by Tha~-malingam'~~
using
the results of the calculations of D r e s ~ e l h a u s and
' ~ ~ Elliott 104,105 on excitons.
Tharmalingam calculated the effect of a uniform electric field on the probability of creating an electron-hole pair. In the process, he neglected the
electron-hole interaction with respect to the electric field. The solution that
he obtained is Eq. (63).Tharmalingam was the first to predict that there would
be electric-field-induced oscillations in the electroabsorption spectra above
the fundamental edge. A ~ p n e s ' ~ ~then
. ' ~ ~extended Tharmalingam's
result to include all four types of critical points. T o unify the electroabsorption theory, Aspnes et
then showed that both Tharmalingam's and
J. Callaway, Phys. Rev. 130, 549 (1963).
J. Callaway, Phys. Rev. 134, A998 (1964).

E. N. Adams, J . Chem. Phys. 21,2013 (1953).
I 3 O P. N. Argyres, Phys. Rev. 126, 1386 (1962).
1 3 ' E. 0. Kane, J . Phys. Chem. Solids 12, 181 (1959).
13' W. V. Houston, Phys. Rev. 57, 184(1940).
1 3 3 K. Tharmalingam, Phys. Rev. 130, 2204 (1963).
1 3 4 D. E. Aspnes, P. Handler, and D. F. Blossey, Phys. Rev. 166,921 (1968).
3.
285
ELECTROABSORPTION
A E ~ ( w , Ex) I0
-4L
aqf-pm
-4
L-4
FIG. 10. Effect of electric field on dielectric constant near critical points neglecting electronhole interaction. The line shapes of A E ~ ( wE,) and A E ~ ( wE,) are calculated at the condition:
hO = 10 meV, E, = 0.8 eV and B = 1. Here 9 = ( h a - E,)/hO, A = ( B . O'12)/w2. (After
Hamakawa e t a / . * ' )
286
Callaways approaches lead to the same result in the effective mass approximation. In their terminology, they showed that the imaginary part of the
dielectric constant E~ could be expressed as
k,c,v
where
and
The expression for c2 in the absence of an electric field is given by

~2 =
k.c.v
Ccv(k)4Ecv(k)- hw).
Thus, the effect of applying an electric field is to change the energy conserving
delta function in Eq. (69) with the properly normalized Airy function in Eq.
(65).The finite field .z2 is then just a convolution of the zero field e2 with an
Airy function.
b. Indirect Transitions
Electric field effects in indirect transitions were first calculated by Penchina,135F r i t ~ c h e , Chester
~~
and Frit~che,~
and Y a ~ o b y ~in* 1965. An
indirect transition is a phonon-assisted electronic transition between a
maximum in the valence band and a minimum in the conduction band not
occurring at the same point in k space. P e n ~ h i n a showed
~ ~ that the scattering by phonons could be calculated by starting with the direct transition
theory and making an additional sum over the center of mass wave vector.
This sum could then be approximated by an integral over the center of mass
energy
13
13
13
C. M. Penchina, Phys. Rev. 138, A924 (1965).

L. Fritsche, Phys. Status Solidi 11, 381 (1965).
M . Chester and L. Fritsche, Phys. Rev. 139, A518 (1965)
Y. Yacoby, Phys. Rev. 140, A263 (1965).
3.
287
ELECTROAHSORPTION
where
Mi
+ &.
AspneslZ6then used this result to calculate the electroabsorption theory for

indirect transitions. His analytical solution was that
c Z x Ai(y)
+ 7 Ai(y) + 7
Ai,(y),
(72)
where
where hK(,
is the phonon energy and
The electroabsorption due to indirect transition is only observable if the

indirect gap is less than the direct gap such as in germanium and silicon.
3
..
D..
0
2 34
2.44
2 54
2 64
2.74
2.84
Photon energy ( e V )
FIG. 1 1 . Theoretical absorption spectrum for lead iodide at 77K showing exciton line and
change with electric field. 0,
zero electric field; 0.
electric field equal to 2.85 x 10 V/cm;
A. electric field equal to 8 x lo4 V/cm.

I
W I 2 , Z .65Y t05V/cm
- Excitonic E A theory
--
2.34
Nonexcitonic EA theory
2 44
2.54
2.64
2.74
2.84
FIG. 12. Comparison of electroabsorption theory and experiment in lead iodide for
lo5 V/cm at 77K. 0 , experimental data. (Theory by B l o ~ s e y ,experiment
~~
by
Perov et
= 2.85 x
EXPERIMENT
To compare electroabsorption theory and experiment in which excitons
are involved requires that some sort of broadening be introduced into the
theory. The introduction of broadening into the theory is necessary because
electroabsorption measures the difference between the finite-field and zerofield absorption spectra. The theoretical zero-field exciton spectrum without
broadening is given by Eqs. (49) and (50). It is well known that for E < E,
the exciton absorption peaks have definite width and ate not delta functions
of energy. The question is not if broadening should be included but what type
of broadening should be employed. The two most common types of broadening that are used are Gaussian and Lorentzian. T o y ~ z a w a , in
' ~ discussing
~
the theory of exciton line shapes, showed that a weak exciton-lattice coupling
produced Lorentzian shaped exciton peaks and a strong exciton-lattice
coupling produced Gaussian shaped peaks. One of the authors (DFB) has
tried both types of broadening in comparing electroabsorption theory and
experiment and has found that the Lorentzian type broadening gives the best
results. The results of such a comparison are shown in Figs. 11-13 for PbI,.
Figure 11 shows the theoretical absorption spectra for lead iodide for electric
4.
COMPARISON OF THEORY
AND
13'
Y. Toyozawa, Progr. Theor.Phys. 20,53 (1958)
3.
0.8
0.0
2.34
P b 1 2 , 8 0 x ! 0 4 V/cm
- Excitonrc EA theory
n
--
Nonexcitonic EA theory
1
I
iY
- 1.6
289
ELECTROABSORPTION
2.44
E,
2.54
2.64
Photon energy ( e v )
2.74
2.84
FIG. 13. Comparison of electroabsorption theory and experiment in lead iodide lor
at 77K. 0 ,experimental data. (Theory by B10ssey:~ experiment by Perov
Q = 8 x lo4 V/cm
et a/.14o)
fields of 0, 8 x lo4, and 2.85 x 10' /cm. The 8,for lead iodide is given in
Table I as 4.6 x lo5 V/cm; thus the &/givalues are about 0.17 and 0.62,
respectively. A broadening of kT was used which in this case was the energy
equivalent of 77K. The field of 8 x lo4 V/cm caused the exciton line to be
shifted toward the red and diminishes its height. The field of 2.85 x lo5 V/cm
causes additional broadening of the line with very little shifting. In the
electroabsorption experiments performed by Perov et al. I4O on lead iodide,
the experimental data represented by the plus marks in Figs. 12 and 13 was
produced. The theoretical curves indicated are simply the difference between
the finite field a and the zero field a in Fig. 11.The parameters used to calculate
these theoretical curves were a dielectric constant of 6.25, a reduced mass of
0.21m0 for the electron-hole pair, where m,,is the actual electron mass, and
an energy gap of 2.577 eV. The broadening was kT at 77K.
There have been several attempts141-144
to include broadening effects,
such as collisions, into the single-particle electroabsorption theory, i.e., the
P. 1. Perov, L. A. Avdeeva, and M. 1. Elinson. Fiz. Tuerd. Tela 11,541 (1969) [English Trunsl.:
Soviet Phys.-Solid Stcite 11. 438 (196911.

14
144
R. Enderlein, Phys. S ~ u f uSolidi

s
20, 295 (1967).
R. Enderlein and R. Keiper, Phvs. Starus Solidi 23, I27 (1967).
H . D. Rees, J . Phys. Chem. Sotids 28, 353 (1967).
H. D. Rees. J . Phys. Chem. Solids 29. 143 (1968).
290
theory without the electron-hole interaction. Lorentzian type broadening

simply introduces an imaginary term into the argument of the Airy function
in Eq. (63).26 Enderlein and Keiper 142 tried this approach but erroneously
reported that the inclusion of collisions introduces a peak below the fundamental edge. Their mistake arises from the fact that they have used expressions
for the complex Airy function outside of their region of validity. The actual
effect of collisions is simply to damp the electric-field-induced oscillations.
111. Experimental Results
5. EXPERIMENTAL
METHODS
In order to determine the dependence of the optical properties of a material
on electric field, it is usually necessary to apply a large uniform field across
the region of interest. Electric fields on the order of lo4 to 106V/cm are
needed to cause appreciable changes in the optical spectrum: thus the earliest
work was done on insulator^.**^^'^^-'^^ F rova and Handler2*3 were the
first to use a method that made it possible to obtain fields of this magnitude in
semiconductors such as germanium, silicon, and gallium arsenide. Their
method entailed using a p n semiconductor junction to obtain high fields
over very short distances and thus avoided overheating of the sample which
would contribute to electrical b r e a k d ~ w n . ~Let
us first examine the more
straightforward technique of placing a dielectric between two transparent
conducting electrodes such as tin oxide.
a. Transpurent Electrodes
Figure 14 shows a parallel plate capacitor filled with an insulating dielectric. A monochromatic beam of light is normally incident on the plane of the
structure. The conducting electrodes are either transparent or semitransparent so that an appreciable fraction of the incident light may reach the
photo detector. Across the capacitor there is a dc voltage V,, and a small ac
modulating voltage i&. The light reaching the photodetector is related to the
absorption coefficient by
ln(I/Io)= -
s,
a ( x ) d x = -a(&)w,
(75)
where I , is the intensity of the incident light beam, a(&) is the absorption
coefficient as a function of electric field & and w is the width of the dielectric.
The change in light reaching the photocell upon introduction of the ac
145
146
14
K. W. Boer. H. J. Hanscho, and U. Kummel, 2.f h y s . 155, 170 (1959).

V. S. Vavilov and K. T. Britsyn, Fiz. Tuerd. Tela 2, 1937 (1960): 3,2497 (1961) LEnglish Transl. :
SOU fhyS.-SOlid StUte 2, 1746 ( I96 1 ) ; 3. 18 I6 ( I962)].
S. Damaskova and K. Patek, Z. Phys. 164.428 (1961).
3.
291
ELECTROABSORPTION
Transparent conducting
Dielectric
FIG. 14. Experimental arrangement using transparent electrodes for measuring electric field
effects on optical properties of materials. (After Handler.47)
modulating voltage is given by

(111)AllAV
= - Aaw/AV,
where
AV
2Ec
and
Aaw/AV
'v
da(l)/db
(77)
for small changes in total light due to the electric field. Using lock-in amplification signals AI/I as small as
have been observed using conventional
equipment. If the effect of the electric field on a(&) is very small, then
Aa
= a(&) - a(0)
(78)
which is the result for the p-n junction method as we shall see in the following.
b. p-n Junction Method

In a reverse biased pn junction where the p- and n-type regions are uniformly doped, the electric field is linear with distance across the depletion
region attaining its maximum value at the junction and falling to zero at the
292
'
rL+q
Incident
light
Modulotion
FIG.15. A schematic representation of the experimental technique for electric field modulation in a p-n junction: (a) light polarization perpendicular to electric field. (b)light polarization
parallel to electric field. (After Handler.47)
other side of the depletion region. Increasing the voltage simply widens the
depletion region and increases the maximum field in the junction. Figure 15
shows a schematic of an experiment for measuring the change in transmitted
light from a semiconductor due to an ac electric field to a back biased p n
junction. If the modulation voltage V,
is small compared with the bias
voltage V,,,, then the only changes that the light sees as it passes through the
depletion region are at the points of maximum field and at the edge of the
depletion region where the electric field is zero. If the modulation voltage
causes a change in the width of the depletion region of Aw, then
AI/I
= - [a(&,,,J
- a(O)] Aw.
(79)
Equation (79) is valid as long as the electric field is linear. The two techniques
mentioned here are the two most commonly used techniques in electroabsorption. In the remaining parts of this section, we will present experimental electroabsorption for Cu,O, Ge, GaAs, CdS, Si, TiO,, and PbI,.
3.
57 10
ELECTROABSORPTION
293
5740
(A1
FIG.16. Effect of electric field on yellow series of cuprous oxide. (After Grossmann ,149)
6. CUPROUS
OXIDE
The bound exciton spectrum is most evident in cuprous oxide since five or
more bound levels may be observed e ~ p e r i m e n t a l l y . ' '*
~ ~The
, ~ excitons in
Cu,O are of the forbidden variety, i.e., the interband matrix element at k = 0
is zero. Unfortunately, there can be no comparison made between the numerical calculation made for allowed transitions and the electroabsorption spectrum of Cu,O but there are still some interesting electric field effects to be
noted. Gross,'48 Nikitine et a/.,' I s and G r o ~ s m a n ' ~have
'
shown how the
electric field breaks the selection rules to allow forbidden transitions. Figure
16 shows the effect of electric fields on the yellow series of cuprous oxide.
According to Elliott's theory' O 4 for forbidden exciton transitions, only the
p-like hydrogenic states contribute to the optical spectra. This is a result that
may be derived from Eq. (17) of this chapter. For allowed exciton transitions,
148
149
E. F. Gross, Nuovo Cimento Suppl. 3,672 (1956).

M. Grossman in "Polarons and Excitons" (C. G . Kuper and G. D. Whitfield, eds.), pp.
374ff. Oliver and Boyd, Edinburgh and London, 1963.
294
-/
bResolution
9
H
-t
c)
-f
aI++
-L
-'
2 000
J
0
2 020
2 040
E (eV)
FIG. 17. Electroabsorption of cuprous oxide at 77K and 60 kV/cm. The I

the light polarization. (After Brahms and Card~na.'~')
IS
parallel to
only the s-like hydrogenic states will contribute, as is a direct result of Eq. (16).
Since the electric field breaks the selection rules to allow forbidden transitions
it is possible to watch the s-like peaks appear as the electric field increases.
As the field increases, these levels are also being ionized so that the peaks
appear and then disappear again as the field increases. From our calculations,
we do know that it takes a field of about 0.0058i to ionize the 3s exciton
level, so from Fig. 16 we can see that cTi is well in excess of 4 x lo6 V/cm and
probably on the order of lo7 V/cm for cuprous oxide. Thus for the fields
given in Fig. 16, 8/gi << 1. As calculated from the hydrogen series given in Eq.
(l),the exciton binding energy for the yellow series is about 96.5 meV, which
is a larger binding energy than any compound given in Table I, including lead
iodide.
Figures 17 and 18 show the electroabsorption measurements of Brahms
and Cardonal5O in the vicinity of the 1s exciton line in the yellow series of
Cu20. Electric dipole transitions to this state are forbidden in the absence
of the electric field.The dipole selection rule relaxes for finite electric fields,
and a line which increases quadratically with the electric field is seen. Brahms
and Cardona'" noted that the Is hydrogenic line at 2.0233eV had the
following characteristics in an electric field: (a) The strength of the line, as
measured by the peak height, is proportional to the square of the applied
'''
S. Brahms and M. Cardona, Solid State Commun. 6, 733 (1968).
3. ELECTROABSORPTION
-4
295
-3
-I
E (eV)
FIG. 18. Electroabsorption of cuprous oxide using polarized light in the region of the IS
exciton line of Cu,O at 77 K.The 8 = 35 kV/cm. (1) electric field and optical polarization
perpendicular, E IF ; (2) electric field and optical polarization parallel, EIIF. (After Brahms
and Cardona.)
field. No deviation from this dependence is seen for fields up to 80 kV/cm. (b)
The intensity of the line for I parallel to the light polarization is much larger
than for 8 perpendicular to the polarization. (c) The half width of the line is
about 3 x lop4eV. No change in broadening or frequency shift was observed
for fields up to 80 kV/cm. Since 8 must be on the order of 0.lgi to observe
any shift or broadening in the 1s hydrogenic line, this is a reasonable observation. Several phonon-induced peaks may also be seen in Fig. 17. The most
prominent pair occur at 2.0097 eV (phonon absorption) and at 2.0369 eV
(phonon emission). The energy of the corresponding phonons is 0.0136 eV.
This result shows that electroabsorption is also capable of giving information
about the phonon spectra as well as the band structure and exciton spectra.
7. DIRECT
EDGEOF GERMANIUM
In many semiconductors, even at low temperatures, it is difficult to observe
even one isolated exciton peak. From Table I it is easy to see that the binding
energies of the excitons in most semiconductors are so small that these
excitons should be thermally ionized at room temperature. Germanium
certainly falls into this category having a binding energy of only 1.4 meV. But,
strangely enough, the ground excitonic state is observable at low temperatures
296

T
- 400
-000
-1200
E,
-fiw
(rneV)
FIG. 19. Field-induced change in the absorption coefficient of germanium near its direct
edge for an electric field of 10 kV/cm taken at three different temperatures. (-) T 14"K,
E , = 0.889 eV; (-. - .) T 300"K, E , = 0.802 eV: ( . . . ) T 83"K, E , = 0.881 eV. (After
Hamakawa ef
and seems to be broadened by an amount less than kT This is presumably due to the fact that the acoustical phonons have very little electric
field associated with them in a covalently bonded crystal. In ionic crystals,
the thermal broadening is much higher with respect to kT. As was noted in
Part 11, the exciton peak does not have to be observable to have the Coulomb
interaction play a role in the electroabsorption spectrum. The Coulomb
interaction between the electron and hole enhances the electric-field-induced
oscillations near the edge and thereby cause deviations from the free electronhole pair electroabsorption t h e ~ r y . ~ ~ *lh
"~*'
The electroabsorption of germanium was performed most recently by
Hamakawa et u / . ~ * * ~ OThey used both the pn junction method and the
transparent electrode method and found identical results. The samples were
mounted in a liquid helium optical Dewar. A PbS detector was used to detect
the monochromatic light. Hamakawa et
measured the electroabsorption
spectrum near the direct edge as a function of electric field and temperature
and made a careful comparison between the experimental data and the
predictions of the free electron-hole pair electroabsorption theory. The
free electron-hole pair electroabsorption theory'25,126makes the following
predictions : (1) The energy gap should be very close to the first positive peak
3.
250
0
a
u
297
ELECTROABSORPTION
1000 1-
500
t-
0
500
1000
knc,
AC,d
I
086
088
090
092
094
Photon Energy t i w (eV)
FIG. 20. The change in the absorption coefficient at 14 K for three different fields near the
direct edge in germanium. (a) d = 3 x lo3 Vicrn: (b) d = 10 x lo3 V/cm: (c) & = 30 x lo
V i m . (After Hamakawa rt ul.)
observed as the light energy is being increased. (2) The amplitude of the peaks
in AMshould increase as &1 3. As long as the band edge is quadratic in k,the
peak height should never decrease with increasing electric field. (3) The relative amplitude of the various oscillations is fixed. (4) For light energies below
the gap, E < E , , the asymptotic form for Aa becomes
where K is a constant and h0 is the electrooptical energy defined in Table 11.

Knowing E,, 8,and AMas a function of E allows determination of the reduced
mass p of the electron-hole pair. (5) The amplitudes of the oscillations for
E > E , should decrease slowly with ( E - E,). ( 6 )The distance between the
peak heights and/or zeros should increase with field as &I3. The result of
checking these six predictions of the free electron-hole electroabsorption
theory showed that the predictions were only partially fulfilled as is shown in
Figs. 19-23.
Figure 19 shows the temperature dependence of Aa at three different temperatures but for the same electric field. The curves have been superimposed
298
*t
FIG. 21. The amplitude dependence (of germanium at T = 14K) of the first two positive
and first negative peaks as a function of the electric field. 0 : slope 3/4; 0 :
slope 5/4: x :
slope 3/4. (After Hamakawa et
on a common energy scale where the energy gap at each temperature

is taken to be zero. We note that the energy gap as determined by Macfarlane'" falls at the center of the negative peak rather than at the first zero. The
increase in amplitude of Act between 300 and 14 Kis a factor of 5. The 300K
result can be considered as thermal broadening of the low-temperature
results. The free electron-hole electroabsorption theory can fit either the low
energy tail or the last two half-oscillations but not both. In neither case is the
first negative peak ever matched.
Figure 20 shows the values of Aa for three different values of the electric
field. In Fig. 20 we see that the energy gap as determined by Macfarlane'"
lies above the first positive peak in all cases. Figure 21 shows the dependence
of the amplitude of the first three peaks on the applied electric field. Not only
do they increase faster than g1I3but the first negative peak does not follow
15
G. G. Macfarlane, T. P. McLean, T. E. Quarrington, and V. Roberts, Phys. Rev. Lerr. 2,252

( 1959).
299
I0
I T
80
60
A&, theoretical sum
40
20
I o3
rA
lo4
& (V/cm)
FIG. 22. Electric field dependence of the widths of the half-oscillations above the direct
edge of germanium at 14 K.For M,, theoretical sum with slope 2/3 ( p J m = 0.021, and
pH/m = 0.037). The experimental labels are shown in the accompanying tabulation. (After
Hamakawa er
AB,
A&2
66,
Measure by
p-n junction
Single crystal
the other two. This effect is presumably explained by including the electronhole interaction, which would cause the oscillations to have greater amplitudes with a special enhancement of the first negative oscillation. In Fig. 20(c)
the three quantities A&, ,Ag2, and A&3 have been denoted and are the widths
of the half-oscillations. According to the free electron-hole pair electroabsorption theory,126these energy differences should depend on the electric field as
g P z iFigure
3.
22 shows that A&2 and A& have the correct field dependence but
that AJ1 does not. Finally, Fig. 23 shows that Ag2 is relatively temperature
independent but that Ag1 is not. All these effects may be qualitatively explained as being excitonic in nature.I5*
15*
D. F. Blossey (unpublished).
300
14K
83K
R T
100
300
200
FIG.23. Temperature dependence of the widths A&, (solid line) and A&* (dashed line) of the
half-oscillations above the direct edge of germanium at various electric fields. (After Hamakawa
et
I47
1.48
--_L
I49
I
~~
1.50
hv (eV)
FIG.24. Absorption edge of GaAs for zero field (-) and electric fields of magnitude 6 ( - - ).
10 (-.-), and 30 ( . . . ) kV/cm. (After Paige and H. D. Rees.153)
301
1.5 -
Resolution
I
I
\
\
I
4700
4000
6,
FIG.25. The spectral dependences of the absorption of single crystal CdS films(1) for zeroelectric field at T = 77K and (2) for C = 4.84 x lo4 V/cm at T = 77K. (After Perov er a/.40)
Recently Handler et al. have shown in their electroreflectance experiments that, in addition. to the above effects, account must be taken of the
degeneracy of the light- and heavy-hole bands. Since each band has its own
effective mass, and since the period of the oscillations depends upon these
masses, it is expected that at energies above the gap the two signals would
begin to interfere. Handler et al. observe the destructive interference in the
neighborhood of the sixth half osciIIation in their electroreflectance data. In
addition, the beating of the two signals causes the envelope of the oscillations
to decrease faster, and this effect can be observed in electroabsorption
data.* In general this effect will not affect the line shapedirectly at the exciton
energy or one or two effective Rydbergs above or below. However, at
energies above the edge, interference effects from nearly degenerate valence
bands will occur in all cubic 111-V and 11-VI semiconductors and should be
considered.
302
8. GALLIUM
ARSENIDE
Figure 24 shows the data of Paige and Rees'53 for the electroabsorption of
gallium arsenide below the edge. This figure shows how the electric field
shifts the edge toward the red. They also observed an oscillatory electroabsorption spectrum above the edge but this spectrum was evaluated by
subtracting two curves in Fig. 24 and therefore had a quite large error. The
absence of a well-defined exciton peak in the zero-field absorption was
attributed to crystal defects. This was supported by the fact that their data
varied from sample to sample. Paige and R e e ~ noted
' ~ ~ that there were three
factors which prevented a direct comparison between their experiment and
the then existing t h e ~ r y . ' ~ ~(1)
~ Strong
' ~ ~ . effects
' ~ ~ of the Coulomb electronhole interaction pervade the regions of investigation.' 54 (2) Existing theories
do not take into account the degeneracy of the valence band edge at the center
of the Brillouin zone. (3) There is no provision for the strong specimen
dependence that they observed. They found that using the then existing
theory they needed a different reduced mass below the edge than above the
edge, 0.03rn0below the edge to fit the exponential tail and 0.06m0 above the
edge to fit the oscillations. Again these effects can be qualitatively explained
using excitonic electroabsorption theory and the contribution of both light
and heavy holes.'52*75
9.
CADMIUM SULFIDE
Cadmium sulfide is quite rich in exciton spectra as can be seen from Fig. 25.
The threeexcitonpeaks A, B, C'55*'5 6 areexcitons associated with transitions
from the three valence bands at k = 0. The width of peaks A and B is approximately kT The electric field effect on CdS has been investigated by several
people.8,67,68,'40,'57
As seen from Fig. 25, the electric field causes the exciton
lines to broaden and shift. Because of the close proximity of the exciton lines
A and B, the electric field effect on either line is not independent of the other
and the electric field can cause mixing of exciton states thus making it a very
complicated theoretical problem. In this light, the experimental data will be
presented without too extensive a theoretical interpretation.
Figure 26 shows the electroabsorption spectrum of CdS at electric fields
of 2.42 x lo4 and 1.45 x lo5V/cm at T = 77K. The position of each of three
negative electroabsorption peaks coincides with the position of the corresponding exciton absorption maximum (A, B, and C in Fig. 25). The positions
Is'
ls4
155
15
E. G. S. Paige and H. D. Rees, Phys. Reu. Lett. 16,444 (1966).

M. D. Sturge, Phys. Rev. 127,768 (1962).
D. G. Thomas and J. J. Hopfield, Phys. Reu. 116,573 (1959).
D. G. Thomas and J. J. Hopfield, Phys. Rev. 124,657 (1961).
H. Lange and E. Gutsche, Phys. Status Sofidi 32,293 (1 969).
3.
303
ELECTROABSORPTION
-10 -
1.45 x
10
/I
I l l
lo5
C (V-cm-)
FIG.27. The dependence of the magnitudes of the negative electroabsorption peaks on the
electric field strength for CdS. (After Perov er
304
2 -
FIG.28. The room temperature electroabsorption spectrum for CdS at 8 = 4.84 x lo4 V/cm
(broken line), d = 7.25 x lo4 V/cm (dotted line), and 8 = 9.7 x lo4 V/cm (solid line). (After
Perov rr a/.'40)
of these negative peaks are independent of the electric field strength. This
indicates that the Acx measured is simply the difference between the finite-field
curve and the zero-field curve with the peaks in CL corresponding to the negative peaks in Au. The effect of the electric field is to broaden the peaks in a
which would cause Aa to saturate at high electric fields, d N gi.
Figure 27 shows that indeed both the negative peak amplitudes A and B
saturate for high fields. From Table I, we see that eYi for CdS is about 1.4 x
lo5 V/cm for exciton A, and indeed its saturation occurs at about this field
with curve B saturating at about the same or maybe a little smaller electric
field. Figure 28 shows that at room temperature peaks A and B are smeared
into one negative peak in the electroabsorption spectrum. Perov et ~71.'~'
stated that they believed that the shift of the exponential absorption edge'58
of CdS at room temperature is connected with the effect of an electric field
on the exciton absorption edge and cannot be interpreted in terms of the
free electron-hole pair Franz-Keldysh effect.
*jg
B. Segall, Bull. Amer. Phys. SOC.11, 189 (1966).
3.
305
ELECTROABSORPTION
00 5
3 10
0 04
3 00
0 03
3 06
0 02
o a4
IU
0 Of
0 02
TO+O
- 0 01
w-I
-0 02
104
I08
1.12
I W
\
116
+IW
-a 02
I
20
124
-a 04
!8
(eV)
FIG. 29. Fine structure of fietd-induced absorption at the indirect edge of Si for three
different electric fields at T = 23C. TO IS the transverse optical phonon, TA is the transverse
acoustical phonon, and 0 is the optical phonon with zero momentum. (After Frova e / ~ 1 . ~ ' )
10.
INDIRECT
EDGEOF SILICON
Figure 29 shows the results of Frova et d3'for the field-modulated optical

absorption in a silicon pn-n' junction near the indirect gap. They noted that
the limiting factor in observing structure due to the various phonon-assisted
transitions was due to the overlapping of the various processes, which
becomes more and more significant as the electric field increases. From Fig.
29, it is apparent that a large electric field effect associated with the transverse
optical phonons (TO)and transverse acoustical phonons (TA)is present near
their thresholds for both phonon emission and absorption.
Figure 30 compares the curves associated with the TO emission and
absorption processes for the field E = 1.4 x lo4 V/cm by plotting the curves
versus photon energy as measured from their respective thresholds E , -t
ETo. The TO absorption curve was multiplied by a factor of 7.5 to bring the
amplitude of the main positive peaks into coincidence. As can be seen from
Fig. 30 the TO absorption and emission curves coincide quite nicely indicating that they are both single-phonon processes. An energy of 57.7 meV was
determined for the TO phonon by measuring the distance in energy between
306
FIG.30. The mapping of the two processes in Si at T = 23C associated with the emission (0)
and the absorption ( x ) of the transverse optical phonon for 8, = 1.4 x lo4 V/cm. The TO
absorption curve has been multiplied by 7.5 for coincidence at the main positive peak. The
theoretical curve (solid line) has been calculated from Penchinas theory. (After Frova
er ~ 1 . ~ )
equivalent points on the T O emission and absorption curves and dividing by

two. Similarly, the energy of the TA phonon was found to be 18.2 meV. Over
several runs, the error in observation was less than 0.1 meV. The solid curve
in Fig. 30 is a theoretical curve derived from Penchinas theory for indirect
transition^,'^^ using a reduced mass p = 0 . 1 8 for
~ ~the
~ electron-hole pair.
The deviation between theory and experiment is again presumably due to
exclusion of any electron-hole interaction and the assumption of a nondegenerate valence band.
1 1. INDIRECT EDGEOF GERMANIUM
The data of Frova et aL3* shown in Fig. 31 obtained for the germanium
indirect edge resemble those found for the silicon indirect edge. Small
electric fields were used to avoid effects from the nearby direct edge. The
various phonon-assisted thresholds lie much closer together than in silicon,
3.
307
ELECTROABSORPTION
0 20
0 16
0 i2
s
-6-
0 08
nI:
004
-16
- 0 04
- 0 08
- 0 12
- 0 16
062
064
066
068
fiw-E,
070
072
(eV)
FIG.31. Fine structure of field-induced absorption at T
23C at the indirect edge of Ge
for several different electric fields. The values for Rrn shown are: ( . . . ) 0.67 x 104V/crn:
(---)
0.95 x 104V/crn; (-)
1.55 x 104V/cm; ( - . - . ) 2.9 x 104V/cm. LA is the longitudinal acoustical phonon and TA is the transverse acoustical phonon. (After Frova et a / . 3 8 )
and small fields are needed to keep the various peaks separated. Following
the same procedure described for silicon, the following phonon energies
were obtained : LA, 27.7 meV ; TA, 7.3 meV where LA refers to the longitudinal acoustical phonon process and TA the transverse acoustical process.
These are in excellent agreement with previously reported data.' 5 9 The
theoretical fit was accomplished with a reduced mass ,u = 0.14m0,with a
result quite similar to Fig. 30 for silicon.
12. TITANIUM
OXIDE
Figure 32 shows the electroabsorption spectrum4' of polycrystalline
TiO,. The experiment was performed using 30&500A films grown on
L59
R. T. Payne, Phys. Rev. 139, A570 (1965).
308
3.0
4.0
3.5
+IW
(eV)
4.5
FIG. 32. Electroabsorption of polycrystalline TiO, for I = 5 x lo6 V/cm at room temperature. (After Frova et ~ 1 4 ' )
evaporated titanium. The field was applied between the metal substrate and
an electrolyte. Light at normal incidence passed through the T i 0 , film twice
after reflection from the titanium surface. Apparently electroreflection
effects were negligible in this case. The following features of the electroabsorption spectrum were stressed by Frova et d4
: (1) Light modulation at
3.75 eV for full 40-V peak-to-peak ac voltage (gmaX
_Y 5 x lo6 V/cm) was as
high as 20%. (2) The general shape of the electroabsorption curves for thin
polycrystalline films is somewhat similar to those of the single crystal.
13. LEADIODIDE
The work of Perov et ~ 1 . ' ~ ' on the absorption and electroabsorption
spectra of Pbl, crystals measured at 77K is shown in Figs. 33 and 34. The
absorption spectrum shown in Fig. 33 is in good agreement with other
data.1603161
The experimental study of the electric field effect on the absorption coefficient of PbI, near the absorption edge showed that, at room
temperature, the absorption edge was exponential and that it shifted to
lbo
S. Nikitine, J. Schmitt-Burckel, J. Biellman, and J. Ringeissen. J . Phys. Chem. Solids 25,951

( 1964).
V. V. Sobolev, Opt. i Spektroko. 20, 165 (1966)[English transl.: Opt. Spectry. ( U S S R ) 20.
87 (1966)l.
4700
4800
4900
309
5000
A (A)
FIG. 33. The spectral dependence of the absorption coefficient for Pbl, at 77K at R
(solid line) and 8 = 2.85 x lo5 V/cm (broken line). (After Perov et
lower energies with increasing electric fields. Perov er ~ 1 . ~ conducted
their
experiments at 77K and found that the free electron-hole electroabsorption
theory was inadequate. Section 4 of this chapter compares their data with the
~ ~ finds that this theory
excitonic electroabsorption theory of B l o ~ s e yand
gives a reasonable fit to the data for the reduced mass = 0.21m0,the energy
gap E , = 2.577 eV, the dielectric constant t o = 6.25, the electric field 8 =
8 x lo4 V/cm (broken line) and 2.85 x lo5 V/cm (dotted line), as was shown
in Fig. 11. The electroreflectance spectrum of Pb12 has been measuredI6
and has been put through a Kramers-Kronig transformation to produce Aa
with similar results.
14. DEFECTS,
IMPURITIES,AND MISCELLANEOUS
Although there are many examples of where electric field modulation has
been useful in the study of impurities and defects we shall only mention one
example of each. Figure 35 shows the change in absorption of F centers in
KCI as observed by Chiarotti rr u / . I b 3The effect of the electric field broadens
163
Ch. Gahwiller and G. Harbeke, Phys. Rrr. 185, 1141 (1969).

G. Chiarotti, U . M . Grassano, and R. Rosei, Phys. Rev. Leti. 17, 1043 (1966).
310
FIG.34. Electroabsorption of lead iodide at 77K for I = 8 x lo4 V/cm (broken line) and
I = 2.85 x lo5 V/cm. A comparison between the excitonic electroabsorption theory and these
data is shown in Figs. 12 and 13. (After Perov er
the F center line. The data show much more clearly than simple absorption
the F and K absorption lines.
Figure 36 shows the effect of an electric field on O H - ion in a substitutional
site in KBr as performed by Handler and A ~ p n e s . In
' ~ this
~ experiment the
electric field aligns the OH- dipoles along the field and therefore enchances
the absorption in the parallel direction and suppresses it in the normal direction.
Finally, Anastassakis et ~ 1 . ' ~have shown that in diamond, certain
Raman-active vibration modes can be made infrared active, giving rise to an
absorption proportional t o the first-order change in electronic polarizability
per unit cell with the relative displacement of the atoms. They have observed
such absorptions in the infrared in diamond and have been able to determine
the electric-field-induced effective ionic charge.
P. Handler and D. E. Aspnes, Phys. Rev. Lett. 17, 1095 (1966).
E. Anastassakis, S. Iwasa, and E. Burstein, Phys. Rev. Lett. 17, 1051 (1966)
lb5
3.
31 1
ELECTROABSORPTION
1
I
28
26
24
eV
22
20
FIG. 35. Relative change of the absorption coefficient in KCI in the region of the F and K
bands due to an applied electric field. 8 = 45 kV/cm, T = 77"K, N , = 9 x 10i6/cm3,F = 45
kV/cm. (After Chiarotti et a/.163)
IV. Summary
The preceding review has shown that electroabsorption may be used as a
tool to gain information about (1) the band structure of solids, (2) defect and
impurity states, and (3)phonon spectra in solids. By analysis of the electroabsorption spectrum, the band gaps and reduced masses of the electron-hole
pairs may be determined. Near indirect edges the electroabsorption spectrum
is rich with structure due to either phonon emission or absorption, which
allows direct determination of phonon energies. Defect and impurity states
within the forbidden gap may also be observed using electroabsorption
techniques.
Electroabsorption does have the advantage over eiectroreflectance in
that its spectrum may be directly correlated with theory whereas electroreflectance requires a Kramers-Kronig transformation. Both the electric field
312

Polarization.
FIG.36. The absorption and electric-field-induced change of absorption of the OH- vibrational mode of O H - in KBr for parallel and perpendicular polarizations of incident light
specified by propagation vector k for applied electric fields E along the [lOO], [110], and [ I 1 I ]
crystal directions. The abscissa K denotes the wave number of the radiation. (After Handler
and Aspnes. '")
and the strain may be oriented t o observe any anisotropy in the band structure. Thermoreflectance has the advantage that no electrical or mechanical
contacts need be made to the sample but has the disadvantage that the
results are difficult to interpret because of the changing phonon populations
as well as anharmonic effects.
and the understanding
The excitonic electroabsorption theory of B10ssey~~
of how the degeneracy of the valence band contributes seems to have removed
most of the discrepancies between theory and experiment. A comparison
between the excitonic electroabsorption theory and experimental data was
given in Section 4 of this chapter. In terms of the excitonic electroabsorption
theory there are five major points to be made: (1) The excitonic peak need not
be observable in the absorption spectra for the Coulombic electron-hole
interaction to affect the electric-field-induced oscillations near an M , type
edge, ( 2 ) The electron-hole interaction enhances the electric-field-induced
oscillations near an M , type edge and quenches these oscillations near an M ,
3.
ELECTROABSORPTION
313
type edge. ( 3 ) If the exciton peak is observable in the absorption spectra, then
the first negative oscillation in the electroabsorption spectrum is located at
the peak energy. (4)The theory is limited to isotropic bands with constant
curvature over the region of interest. ( 5 )An artificial broadening parameter
on the order of kT is needed to obtain agreement between theory and experiment. Lorentzian type broadening worked best compared to Gaussian type
broadening.
Electroabsorption and other modulation spectroscopy experiments have
enhanced our understanding of electronic states in solids but there are still
several problems that need to be resolved : (1) an electroabsorption theory for
forbidden transitions such as in Cu,O, (2) anisotropic effects in the excitonic
electroabsorption theory, and (3) a better treatment of broadening effects.
These are just a few of the unresolved problems and, undoubtedly, by solving
these problems, new problems will be created. All in all, electroabsorption
has made a significant contribution toward the understanding of the electronic states in solids.
Appendix
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P. Handler, Phys. Rev. 137, A1862 (1965).
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55. B. 0. Seraphin and N. Bottka, Phys. Rev. Lett. 15, 104 (1965).
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58. B. 0. Seraphin and N. Bottka, Phys. Rev. 145,628 (1966).
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79.
J. Stuke and G. Weiser, Phys. Status Solidi. 17, 343 (1966).

A. G. Thompson, M. Cardona, K. L. Shaklee,and J. C. Woolley, Phys. Rev. 146,601 (1966).
A. G. Thompson and J. C. Woolley, Can. J. Phys. 45,2597 (1967).
S. Torniyama and Y. Ito, Jap. J. Appl. Phys. 5, 1132 (1966).
R. A. Forman, D. E. Aspnes, and M. Cardona, J. Phys. Chem. Solids 31, 227 (1970).
P. H. Wendland and M. Chester, Phys. Rev. 140, A1384 (1965).
P. Handler, S. Jasperson, and S. Koeppen, Phys. Rev. Lett. 23, 1387 (1969).
Y. Yacoby, Phys. Rev. 142,445 (1965).
I. Balslev, Phys. Lett. MA, 1 13 (1967).
I. Balslev, SolidStute Commun. 5, 315 (1967).
W. E. Engeler, H. Fritzsche, M. Garfinkel, and J. J. Tiemann, Phys. Rev. Lett. 14, 1069
(1965).
80. W. E. Engeler, M. Garfinkel, and J. J. Tiemann, Phys. Rev. Lett. 16,239 (1966).
81. W. E. Engeler, M. Garfinkel, and J. J. Tiemann, Phys. Rev. 155, 693 (1967).
82. M. Garfinkel, J. J. Tiemann, and W. E. Engeler, Phys. Rev. 148,695 (1966).
83. R. Ludeke and W. Paul, Phys. Rev. 167,736 (1968).
84. F. H. Pollak, M. Cardona, and K. L. Shaklee, Phys. Rev. Lett. 16,942 (1966).
85. A. Balzarotti and M. Grandolfo, Phys. Rev. Left.20, 9 (1968).
86. B. Batz, Solid State Commun. 5, 985 (1967).
87. C. N. Berglund, J. Appl. Phys. 37, 3019 (1966).
88. J. Nanns, J. Feinleib, and W. J. Scouler, Phys. Rev. Lett. 19, 16 (1967).
89. E. Matatagui and M. Cardona, Solid State Commun.6, 313 (1968).
90. E. Matatagui, A. G. Thompson, and M. Cardona, Phys. Rev. 176, 950 (1968).
91. W. J. Scouler, Phys. Rev. Lett. 18,445 (1967).
92. B. Batz, Solid State Commun.4, 241 (1966).
93. A. Feldman, Phys. Lett. 23,627 (1966).
94. I. Filinski, Phys. Rev. 107, 1193 (1957).
CHAPTER 4
Thermal and Wavelength Modulation

Spectroscopy
Bruno Batz
1.
11.
INTRODUCTION .
316
EXPERIMENTAL
PROCEDURES .
1. Instrumentation .
.
.
2. Sample Preparation and Mounting
320
320
3 24
PHENOMENOLOGICAL
BASIS.
.
.
.
.
3. The Optical Constants .
.
.
.
.
.
.
.
.
4. Formulas for Modulated Reflectance and Transmittance
.
5. Phenomenological Theory of Thermal Reflectance
6. Dispersion Relations
.
.
.
.
.
.
.
.
I. Thermal Reflectance and Trunsmittance at the Fundamental
Absorption Edge .
.
.
.
.
.
IV. ELEMENTARY
THEORY. ,
.
.
.
.
8. The Absorption Coefficient ,
.
.
9. Matrix Elements and Selection Rule
.
10. Joint Density-ofstates and Critical Points
.
.
.
.
1 I . Thermal und Waiielength Modulation of the Dielectric Constanr
at Critical Points .
,
.
.
.
.
.
.
111.
V. THE ELECTRON-PHONON
INTERACTION.
.
12. Perturbation Theory and the Scattering Matrix
13. Indirect Transitions and Thermoabsorption
14. Band Shift and Broadening with Temperature
Element
.
.
.
VI . THEELECTRON-HOLE
INTERACTION .
15. Exciton Effects ut the Fundamental Absorption Edge .
16. Exciton Effects above the Fundumenral Absorption Edge
VII.
VIII.
EXPERIMENTAL
RESULTS .
11. Transmittance Data
.
18. Refectance Data .
.
19. Measurements on Merals
.
.
335
338
338
34 1
343
341
352
352
354
358
365
365
368
NOTEADDEDIN PROOF .
.
.
.
.
.
20. Thermoreflectance ( T R )
.
.
.
2 I . Wavelength Modulated Reflectance ( W M R ) and Absorption
(WMA)
.
.
.
.
.
.
315
326
326
321
330
333
374
374
380
393
396
396
399
316
BRUNO BATZ
I. Introduction
The usefulness of optical studies to investigate the band structure of solids
has been demonstrated, for instance, in the analysis of the absorption spectra
of insulators near the fundamental edge. which has provided information
about the electronic states in the vicinity of the band extrema. The details
of the spectra have been interpreted in terms of electronic interband transitions, and even some fine structures observed under high resolution and
not implied by the one-electron approximation have been successfully
explained as arising from electron-phonon or electron-hole or other
interactions.
Above the fundamental edge, the absorption coefficient K is difficult or
impossible to measure because of the opacity of the sample at these higher
photon energies. The reflectivity R is then the attainable optical parameter.
When it is measured in a wide enough spectral range it can be converted to
another quantity ofmore direct physical significance such as E ~ the
, imaginary
dielectric constant, by a Kramers-Kronig transf~rmation.~
But whereas the
fundamental absorption edge itself, which originates from the first interband
transitions that take place for increasing photon energies, is clearly observed
against the preceding transparent region, any structure above this threshold
is superimposed on a background with the possible consequence of being
lost, or poorly revealed.
At any rate, some structural features are observed in the spectra of the
.
have been correlated
optical constants, and in particular in those of E ~ They
to the band structure of the solid4sS through the joint density-of-states
function. This function gives the density, with respect to interband energy,
of the pairs of states connected by the electronic transitions, and it has
analytic singularities a t the energies of the critical points6v7 of the pair
band structure, usually symmetry points in the Brillouin zone. It now
appears, however, that the broad peaks and edges in the E~ curve should
not be attributed exclusively to optical transitions taking place near critical
points. The contribution of transitions occurring in extended regions of
the Brillouin zone are liable to produce these coarse structures and the
T. P. McLean, Progr. Srmirond. 5 , 53 (1960).
E. J. Johnson, in Semiconductors and Semimetals, (R. K. Willardson and A. C. Beer, eds.).

Vol. 3. p. 153. Academic Press, New York, 1967.
H. R. Philipp and E. A. Taft, Ph-ys. Ret.. 113. 1002 (1959).
J . C. Phillips, Solid Sfate Phys. 18, 55 (1966).
J . Tauc, Progr. Srmicond. 9. 87 (1965).
L. Van Hove, Phys. Ret.. 89, 1189 (1953).
J . C . Phillips, Phys. Rrt:. 104, 1263 (1956).
F. Herman, R. L. Kortum, C. D. Kuglin. and J. L. Shay, in II-VI Semiconducting Compounds (Proc. 1967 Int. Conf., Providence) (D. G . Thomas, ed.), p. 503.Benjamin, New York.
1967.
4.
THERMAL AND WAVELENGTH MODULATION SPECTROSCOPY
317
specific spectral features brought in by the critical points may come out as
finer structures distinguishable with difficulty.
In the optical modulation techniques, the response of the optical constants
of a solid to a change impressed periodically on a parameter such as electric
field, pressure, temperature, or wavelength of the incident radiation, is
measured. The resulting spectra show well-resolved lines with spectral
widths far smaller than those of the structures obtained by conventional
methods. It has generally been assumed that these lines originate from the
critical points which would thus be isolated and separated from the background, less sensitive to the modulation. The theoretical calculations made
on this basis to fit the experimental line shapes must still be considered to be
in an early stage, but are, at least qualitatively, encouraging.
It will be apparent to the reader of this book that the family of the optical
modulation techniques has grown to a fair size since Seraphin, only a few
years ago, demonstrated the potentiality of electroreflectance t o elucidate
the electronic structure of solids.1 Two of the youngest members of the
family with temperature . I 2 and wavelength, respectively, as modulation
parameters are presented in this chapter. l 4 These two techniques may seem
to be quite unlike. Wavelength modulation is in fact different from the
other modulation methods in that it leaves the sample unaffected, whereas
in the other methods the band structure o r some other properties of the solid,
depending on the modulation parameter, are varied periodically leading to
a corresponding speci6c change in the optical constants. A wavelength
modulation spectrum is the derivative of an ordinary spectrum, a fact that
simplifies its interpretation. It contains no new information, but it has the
advantage of enhancing some structures, in particular those connected
with critical points.
The two methods are reviewed together because they are expected to
yield in some instances, according t o simple theory (see Parts I11 and IV),
essentially similar spectra in the vicinity of critical points. This conclusion
is supported by the available experimental data for which a comparison
can be made. A reason among others for this similarity is that temperature
B. 0. Seraphin, in Physics of Semiconductors (Proc. 7th Int. Conf.), p. 165. Dunod, Paris
and Academic Press. New York, 1964.

B. 0. Seraphin and R . B. Hess, Phy.r. R w . Lett. 14, I38 ( I 965).
I B. Batz, Solid State Commun. 4, 241 (1966).
l 2 C. N . Berglund, J. Appl. Phys. 37, 3019 (1966).
1. Balslev, Solid State Commun. 3, 2 I3 ( 1965).
l 4 Derivative spectroscopy by wavelength modulation has actually been introduced some I5
years ago in another context.4a
14=C.S. French, A. B. Church, and R. W. Eppley, Carnegir lnst. Washington, Year Book 53, 182
( 1954).
15
E. Matatagui, A. G . Thompson. and M . Cardona, Phys. Reu. 176,950 (1968).
In
318
BRUNO BATZ
is a scalar quantity while the other modulation parameters such as electric

field or uniaxial stress have a vectorial character. A wealth of information
can be obtained by varying the orientation of these vectors with respect to
the sample or to the polarization vector of the incident light, but at the
expense of simplicity. If thermal or wavelength modulation methods do not
share these possibilities, they are nevertheless attractive precisely in that
they seem to be related to simple processes, enabling a straightforward
interpretation.
The experimental procedures concerning both methods are described in
Part 11. It will be seen that the experimental realjzation is somewhat more
complex in the case of wavelength modulation. Both methods have otherwise
the widest potentialities with regard to the spectral or temperature ranges
in which the experiments can be performed, or to the diversity of materials
that are liable to be studied.
Part 111 deals with the phenomenological basis necessary to handle the
experimental data and t o convert them into forms more convenient for their
interpretation. All this analysis is based on the interrelations existing between
the optical constants.16 In this as in the other parts of the chapter, the useful
formulas (as the Kramers-Kronig dispersion relations, of fundamental
importance in modulated reflectance studies) have been derived from first
principles for the sake of continuity in the development when that could
be done briefly. The spectral behavior to be expected in the vicinity of
critical points for the changes As, and AcZ in the real and imaginary components ofthe dielectric constant, C = c l + icZ,due to thermal or wavelength
modulation, are computed from a simple model of 2 near the critical points.
In another example based on a step function model of the fundamental
absorption edge, the modulated transmittance and reflectance spectra are
also computed.
The models mentioned above are discussed in Parts IV, V, and VI. In
Part IV, the basic theory of light absorption in insulating crystals is summarized. e2 is found to be proportional t o the joint density-of-states function,
whose behavior is computed near the four types of critical points. The line
shapes of Ae, and As, are then calculated, lifetime broadening effects being
included, by assuming that the action of the change in temperature is to
shift the energy bands rigidly and to modify the broadening parameter. The
corresponding line shapes resulting from wavelength modulation are
directly obtained by differentiating c l and s2 with respect to the photon
energy h a .
Part V is devoted to the effects arising from electron-phonon interactions.
These are of concern to thermal modulation mainly as the phonons' concen-
''
F. Stern, Solid Stare Phys. 15, 299 (1963).
4.
319
tration is a quantity which is sensitive to temperature. The effects of the

interactions on thermally modulated transmission at the fundamental
absorption edge of indirect semiconductors are examined in Section 13.
The way according to which electron-phonon interactions affect the lifetime
broadening and the temperature shift of an electronic energy level in a band
is investigated in Section 14. It is found that near the band extrema the
temperature coefficients of the broadening and of the shift are equal when
the electrons are scattered by optical phonons, but that the temperature
coefficient of the shift is by far the larger for acoustic phonon scattering.
The situation is not as clear for levels deeper in the bands and one should
then rely on some experimental evidence to decide about the relative magnitude of the coefficients, an information of importance to carry out the analysis
of thermoreflectance spectra. Although the sample is not affected by wavelength modulation, it could nevertheless be required t o take into account
the possible energy dependence of the levels broadening to interpret the
experimental spectral structures.
The consequences of the electron-hole interaction are considered in
Part VI. Following the Wannier-Elliott treatment of the exciton problem,
the modifications arising from the interaction at the fundamental absorption
edge are examined in Section 15. Section 16 deals with the more obscure
case of the higher energy edges where the exciton effects are difficult to handle.
Toyozawas approach to the question is outlined to give an idea of the
kind of line shape that a critical point may be expected to produce. O n
account of their basic simplicity, thermal and wavelength modulated
reflectance experiments should prove helpful in shedding some light on this
problem.
Energy band calculations by semiempirical methods rely on the knowledge
of a few parameters such as interband energies at symmetry points in the
Brillouin zone. In this connection the ability of the optical modulation
techniques to bring out well-localized structural features supposedly related
to critical points of the pair band, and to yield the corresponding energies
accurately, is invaluable. The identification of these structures however often
remains a problem, but the interplay between band calculations and experimental analysis has led to a clear general picture of the energy band structure
of many solids. The thermal o r wavelength modulated transmittance and
reflectance data available t o this date are not very numerous, and they have
come too late to provide any really new and conclusive results. The value
of the methods is yet of a potential character and the comments about the
R. J . Elliott, in Polarons and Excitons (C. G. Kuper and G . D. Whitfield, eds.), p. 269.
Y. Toyozawa, M. Inoue, T. Inui, M. Okazaki, and E. Hanamura, J . Phys. Sor. Japun 22,1337
(1967).
320
BRUNO BATZ
experimental results which are presented in Part VII are thus mainly intended
to illustrate the theoretical conclusions of the preceding sections rather than
to discuss the band structures of the crystals that are considered. Transmittance data are reviewed in Section 17 and reflectance data in Section 18.
Our interest in this chapter is focused on semiconductors but the field of
applications of both techniques is much wider. If this is obvious for wavelength modulated spectroscopy, it is also true for thermoreflectance, which
has been tried on metals and which could even for instance be used to study
liquids. The experiments made on metals are mentioned in Section 19 for
the sake of completeness.
11. Experimental Procedures
1. INSTRUMENTATION
The several experimental arrangements that have been used in the optical
modulation studies are quite similar. The methods are usually based on
phase sensitive detection of the periodic component of the light reflected or
transmitted by the sample which is studied, and they are devised to measure
directly, as a function of photon energy, the relative change in reflectance
ARIR, or in transmittance ATr/Tr due to the modulation of a physical
parameter. One possible instrumental setup, a block diagram of which is
given in Fig. 1, is described below as an example. Equivalent experimental
configurations can be found elsewhere.20-22 The wavelength modulation
method is examined separately as its experimental realization is inherently
more complicated.
The optical path is represented in Fig. 1 by a broken line. The light from
a high pressure xenon arc (or a tungsten filament lamp or any other adequate
source) is focused on the entrance slit of the monochromator. The resulting
monochromatic beam is focused on the sample, from which it is reflected at
near-normal incidence and directed on a photomultiplier (or a PbS cell,
or another suitable detector depending upon the wavelength region). It is
advantageous to make use of a high-intensity radiation source to increase
the signal-to-noise ratio (proportionalto the square root of the light intensity).
Since the temperature of the sample is modulated, thermal radiation
emitted at the modulation frequency may be detected if the detector is
sensitive in the infrared, giving rise to a constant response. This spurious
signal can be substracted from the final spectra but it is often possible to
l9
2o
22
B. Batz, ThermorCflectivite du Germanium, thesis. Free University of Brussels, 1967 (unpublished).

B. 0. Seraphin, Phys. Rev. 140, A1716 (1965).
A. Frova, P. Handler, F. A. Germdno, and D. E. Aspnes, Phys. Rev. 145, 575 (1966).
M . Cardona, K . L. Shaklee, and F. H. Pollak, Phys. Reo. 154,696 (1967).
4. THERMAL AND
WAVELENGTH MODULATION SPECTROSCOPY
321
FIG. 1. Experimental setup for temperature modulated reflectance measurements. (See text
for further details.) (After Batz.'')
eliminate it by interposing an adequate optical filter between the sample and

the detector.
The angle of incidence on the sample's surface is taken to be as close as
possible to the normal, usually less than lo" off, thus allowing the use of
Fresnel's formula giving the reflectivity at normal incidence [Eq. (20)] to
analyze the results. But experiments have been performed that take advantage
of the effects arising at oblique i n c i d e r ~ c ewith
~ ~ . polarized
~~
light.
The procedures used to heat the sample periodically are described in the
next section. The power amplifier shown in Fig. 1 is intended to supply the
power required for this purpose a t a frequency fixed by the wave generator.
The signal developed by the photomultiplier is proportional, at each
wavelength, to the intensity of the intercepted radiation. It consists of a
dc part s and a small ac component As resulting from the change AR =
(dR/dT)AT in the reflectivity of the sample caused by the temperature
modification AT. The dc component s is proportional to the reflected
'' J . E. Fischer and B. 0.Seraphin. Solid Strirr Comntcn 5,973 (1967).
A . Balzarotti and M . Grandolfo, Solid Srrrtr Commun. 6, 815 (1968).
322
BRUNO BAT2
intensity I , = R I , which is the product of the average reflectivity R by the

intensity of the incident beam I i , Thus
s
yRIi,
where y is the spectral sensitivity of the photomultiplier. The amplitude of

theacportionofthesignal, As,isequal to(y A R Ii) = y AI,.Itisapparent that
Asls = AIJI, = A R / R .
(2)
The continuousoutput s is maintained constant throughout the experiment

by a servomechanism which controls the light intensity by varying the
width of the monochromators slits. The ac signal is detected by a lock-in
amplifier, the reference of which is supplied by the same wave generator that
settles the modulation frequency. A recorder receives the phase corrected
output of the lock-in amplifier and simultaneously marker pulses from the
monochromator for wavelength calibration.
It can be noticed that this procedure yields directly the recorded spectrum
of A R / R since the dc signal appearing at the photomultiplier remains
constant during the experiment so that As a ARIR. The result is independent
of the incident intensity and it is not affected by the possible fluctuations of
the source which are automatically compensated by modifications of the
slits width. Another way to maintain s constant is to act with the servomechanism on a voltage divider, varying the high voltage applied to the
photomultiplier. But still other convenient methods have been devised
that allow the ratio ARIR to be measured d i r e ~ t l y . ~ ~ I n~ *modulated
~~~~
transmission experiments it is obviously the light transmitted through the
sample that should be collected and directed on the radiation detector.
I t is then the spectrum of ATr/Tr that is recorded. If I , = f , T r is the transmitted intensity, we have
As/s = AlJl,
ATr/Tr
13)
Let us now briefly turn our attention to the wavelength modulation

technique. The general layout represented in Fig. 1 could be essentially
maintained in the simplest case, as discussed below, with a modified monochromator however. The modulation of the wavelength of the incident light
has been accomplished either by vibration of one of the slits of the monochromator, 3 , 1
or by rotational oscillation of a beam deflecting mirror
4a*28729
W. E. Engeler, H. Fntzsche, M. Garfinkel, and J . J. Tiemann, Phys. Rrc. Lerr. 14, 1069
( 1965).
26
A. Frova and P. J . Boddy, Phys. Rev. 153,606 (1967).

D. E. Aspnes, Rev. Sci.Instr. 38, 1663 (1967).
C. S. French and A. B. Church, Curnegie Inst. Wushingron, Year Book 54, 162 (1955).
I. Balslev, Phys. Rev. 143, 636 (1966).
4.
323
placed inside the monochromator30-34 or of a transparent plate placed in

the dispersed beam.30*35The last procedure allows a minimum of interference with an existing instrument. In their modulated reflectance experiments, Shaklee et
have placed a vibrating quartz plate in the entrance
beam of the monochromator.
The wavelength modulated incident light is then reflected from the sample
into the photomultiplier whose signal is filtered as before through phasesensitive detection. The slit, mirror, or plate is vibrated with a loudspeaker
membrane, or with another device driven by the same wave generator that
provides the reference frequency to the lock-in amplifier.
By differentiation of Eq. (1) it follows that
AsJs = AyJy f A l i / l i iARJR.
(4)
A similar relation applies for transmission experiments

AsJs = Ay/y
+ Ali/li + ATr/Tr.
(5)
The ratio AsJs of the ac to the dc component of the signal produced by

the radiation detector is no longer equal to the relative modifications A R / R
or ATrJTr, in reflectivity or transmission, respectively, resulting from the
wavelength modulation. This is due to the fact that the incident intensity li
and the detectors sensitivity y are wavelength dependent. If the functions
Z,(hw)and y ( h o ) of the photon energy ho are relatively flat in the spectral
region of interest, the two first terms in Eqs. (4) and (5) may be neglected
with regard to the third and the situation is similar to the one prevailing in
the other techniques. The validity of the approximation may be checked by
performing a run without the sample (but with a reference) to separate those
two terms. If they are small, they can be subtracted from the spectrum
obtained with the sample. A more satisfactory but much more complicated
procedure is to use a double beam optical system.28,33*34*36
We shall not
deal with this question here, nor with other interesting problems, as how to
obtain higher derivatives of the optical spectra o r how t o find the optimum
modulation amplitude. A general discussion of wavelength modulated
optical derivative spectroscopy has been given by Bonfiglioli et a1.32*33
1. G. McWilliam, J . Sci. Insrr. 36, 51 (1959).
G. Bonfiglioli and P. Broveto, Phys. Lett. 5, 248 (1963).
3 2 G. Bonfiglioli and P. Broveto, Appl. Opt. 3, 1417 (1964).
3 3 G. Bonfiglioli, P. Brotevo, G. Buscd, S. Levialdi, G. Palmieri, and E. Wanke, Appl. Opt. 6,447
( 1967).
3 4 R. Braunstein, P. Schreiber, and M. Welkowsky, Solid Stare Commun. 6,627 (1968).
3 5 R. E. Drews, Bull. Amer. Phys. Sac. 12, 384 (1967).
K . L. Shaklee, J . E. Rowe, and M . Cardona, Phvs. Rer. 174, 828 (1968).
31
324
BRUNO BATZ
Let us however say a word about another correction required in the

method and depending on the monochromators dispersion law. There is a
correspondence between photon energy in the spectrum displayed in the
exit slit plane and the abscissa x across the plane : ho = hw(x).If the spectrum
near the slit is periodically displaced by an amplitude Ax, assumed to be
maintained constant throughout the experiment, AR in Eq. (4)is given by
AR = [dR/d(hto)][ d ( h o ) / d x ]A X .
(6)
The measurement yields the derivative with respect to x. This result must be
divided by d(hw)/dxto produce the desired derivative with respect to photon
energy. A similar conclusion applies for ATr.
2. SAMPLE PREPARATION AND MOUNTING
No specific treatment is required for the samples intended to be studied

by the modulated wavelength method. They can be prepared as for conventional measurements, with the advantage that very flat surfaces are not
necessary as in absolute reflectivity measurements where scattered light
must be avoided. Cleaved surfaces, surfaces of growth or etched surfaces,
which are known to give sharp spectra, are adequate.
Such surfaces are also suitable for thermoreflectance experiments on
semiconductors. In this case the samples are advantageously cut in the form
of small thin slabs to reduce their heat capacity. They are mounted on an
electrically insulated heat sink to which a good thermal contact should be
maintained, with silicone grease for instance. A heat sink made of sapphire
is convenient, s , 3 7 , 3 8 as sapphire is an electrical insulator, but a good thermal
conductor.
Conducting samples can be periodically heated by current pulses passing
directly through them
or by a strip heater placed between the slab and
the heat sink. 9,39 This last procedure is useful for nonconducting samples.40
If silver paint is used to bond the crystal to the heat sink, it can also serve
as an indirect heater. The similarity of the spectra obtained by direct and
indirect heating in the case of Ge,9-39 as for other semiconductors,
suggests that in the direct heating mode the optical response has indeed a
thermal origin and that other possible effects such as carrier injection are not
important. It has, however, been found that ohmic contacts are required in
order to avoid light emission resulting sometimes from the injection of
carriers, especially at high current levels.24The dependence of the response
on the modulation frequency gives another support to the thermal origin
37
3M
39
40
E. Matatagui and M. Cardona, Bull. Amer. Phys. SOC.12, 1033 (1967).

E. Matatagui and M. Cardona, Solid State Commun. 6 , 313 (1968).
B. Batz, Solid State Commun. 5, 985 (1967).
H. Lange and W . Henrion, Phys. Status Solidi 23, K67 (1967).
4.
325
of the effect. Modulating frequencies ranging from 1.5 to 1500 Hz have been
tried, yielding a decreasing response,' 9 . 3 9 but useful results are usually
obtained at frequencies below 100 Hz.
The heat sink is necessary to remove the power fed into the sample and to
maintain the average temperature of its surface a t a stationary value which is
somewhat higher than the temperatureofthecooling system. The temperature
on the sample's surface can be measured with a thermocouple placed away
from the incident light beam. A t very low modulation frequencies this
arrangement may also give an idea of the magnitude of the temperature
modulation which is typically of the order of 1C. A better estimate of AT
should result from the measurement of A R / R below the fundamental
absorption edge. If the temperature coefficient of the refractive index is
known in this region, A T = An/(dn/dT) is calculable from Eq. (23)'' One
should be cautious when interpreting thermoreflectance spectra near and
below the fundamental absorption edge. A large peak may arise at the edge
due to the temperature modulated absorption of the light transmitted through
the sample and reflected at its back surface or by the sample mount.39q40
These interfaces may also produce interference fringes in the transparent
region, A roughened back surface is advisable for the sample if one wants to
reduce or to suppress these effects.
The overall simplicity of the assembly allows the experiments to be
conducted easily at low t e m p e r a t ~ r e ' ~ . b~y~mounting
. ~ ' ~ ~ ~ the heat sink
on the cold finger of a cryostat. The wide range of application of the method
and the possibility to perform the experiments without special inherent
difficulty in a wide spectral range was first demonstrated by the measurements
of S c o ~ l e r on
~ 'gold
~ ~ which
~
have been carried a t photon energies out to
10 eV. In these experiments a metal film is evaporated onto a glass or another
substrate such as mylar or silicon, and the temperature of the sample is
modulated by passing a current through it. Indirect heating has been used
by Matatagui and C a r d ~ n a ~ ' in
* ~the
* study of low melting point sample
films. This was accomplished with a sandwich assembly of films deposited on
a sapphire substrate, the first evaporated film, a gold heater, being separated
from the sample by an insulating LiF film. Modulation frequencies as high
as 400 Hz are possible with this arrangement without producing a significant
decrease in the thermoreflectance signal.
In his pioneer work on thermoabsorption, which has so far remained
almost isolated, Berglund modulated the samples' temperature by pulsing
current through them at 4 Hz. A difficulty of this technique, especially when
thick samples are needed, is that the temperature may not be homogeneous
'
41
42
W. J . Scouler, Bull. Amer. Phys. Sor. 11,828 (1466).

W. J. Scouler, Phys. Rev. Letr. 18, 445 (1967).
326
BRUNO BATZ
through the bulk of the crystal. The reported experiments based on

combination techniques are not numerous either, and they will not be
described here. The interested reader is referred to Balslevs work 3.29
which deals with wavelength modulated absorption in strained Ge and Si
about current modulated
crystals, and t o a short note by Feinleib er
magnetoreflectivity in InSb.
111. Phenomenological Basis
3 . THEOPTICAL
CONSTANTS
The propagation of a plane electromagnetic wave through a material
can be described at each frequency w by a set of two optical constants which
tell at what speed the wave progresses and to what extent it is attenuated as
it proceeds. The frequency dependence of these constants reflects of course
some properties of the material. Their relation to the electronic structure of
the crystal is basic for the interpretation of optical spectra. This important
question will be investigated in Parts IV-VI. We shall now be concerned
primarily with the general properties of some equivalent sets of optical
constant^'^.^^ without reference to the microscopic structure of the material,
and of their use in expressing experimental results. Only nonmagnetic,
homogeneous and isotropic media will be considered ; the optical constants
can then be treated as scalars.
Indicating complex quantities by a caret, the electric field for instance,
in the electromagnetic wave, is represented by
E
where
A
gE + E*),
E, exp(ik r
A
iwt),
and li = K~ + i~~ is the complex wave vector. It is clear that

the decay of the wave amplitude. The relations
1 ~ =~ nw/c,
1
1 ~ =~ kw/c,
1
K~
describes
(9)
can be used to introduce the complex index of refraction

Ti
+ ik.
(9a)
In the above, n is the index of refraction and k the extinction coefficient;

c is the velocity of light.
The electromagnetic field vectors E, H, D, and B are interconnected by
Maxwells equations. T o these one must add the material equations (mks
4J
44
J. Feinleib, C. R. Pidgeon, and S. H . Groves, Bull. Amer. Phys. SOC.11,828 (1966).

E. E. Bell, in Handbuch der Physik (S. Fliigge, ed.), Vol. XXV/2a, p. 1. Springer-Verlag.
Berlin, 1967.
4.
327
units) : B = pok (for nonmagnetic material, fi = p o is the magnetic permeability of vacuum) and
D = EOE
+ P = Eo&,
+ ie,,
(10)
where q, is the permittivity of free space (q,pO= c-). A phase shift can occur
between the polarization P and the electric field E.The resulting phase shift
between E and the displacement D has been taken into account in Eq. (10)
by introducing the complex dielectric constant
= E~
(11)
where E~ and e 2 are, respectively, the real and the imaginary parts of &.
For plane waves having an exp(iii. r - iot) space and time dependence,
Maxwells equations yield the relation 8 = ti2, from which it follows that
c1 =
nz
k2,
( 124
( 1 2b)
e2 = 2nk.
Resolving these equations in n and k , we obtain
n
= [%E,~
= [3E12
+ E,)/~ +
+
E22)12
(13a)
(13b)
+&1]12.
I t can be shown that the average, over a full cycle of the power dissipated
by the electromagnetic field is given by
=
E*. Thus, c 2 describes
energy dissipation ; the real part c 1 describes dispersion.
The Poynting vector S = E x H gives the power flow per unit area. It
measures the intensity of the electromagnetic wave. Its average over a
period can be written
w $2~,~,e
S = a(nce0/2)E E* = a(ncc,,2)Eo&,* exp( - 2~~ . r),
(14)
where a is a unit vector in the direction of propagation. The intensity of the

wave decreases exponentially with r in the direction of propagation so that
the quantity 2 1 ~can
~ ) be identified with the absorption coefficient K ( o )
I<
2~~ = 2kwIr
mZ/nc.
(15)
The absorption coefficient may also be expressed as the ratio of the energy
loss per unit volume and unit time to the energy flux
W/lsl
=O E ~ / ~ C .
(16)
4. FORMULAS
FOR MODULATED
REFLECTANCE
AND TRANSMITTANCE
The reflectivity R of a material is a quantity which can be measured in a
straightforward manner. It is indeed the relative modification of reflectivity
328
BRUNO BAT2
(ARIR), resulting from the modulation of a physical parameter, that is

measured against photon energy in the modulated reflectance experiments.
I t will be useful to know, for the interpretation of the experimental spectra,
how R is related to the other optical constants.
We are mainly concerned here with the simple case of normal incidence.
The incident wave Ei, which is propagating in vacuum, is reflected by a
semi-infinite medium bounded by a plane. For normal incidence, the complex
amplitudes of the incident and reflected waves Roi and @,,, respectively,
are connected by
kOr=
117)
where ?(a),
which is a complex number when the waves are not in phase.
is given by
i = (li - 1)/(A
+ 1) = (i(etQ.
(18)
The phase angle cp(w) may therefore be written

tancp
2k/(nz + k Z - 1 ) .
The reflectivity R ( w ) is the ratio

incident energy fluxes. We have
R(w) =
fir. E,*fii. Ei* of
( n - 1)
( n + I)
i19)
the reflected to the
+ k2
+ k
The contribution of n and k to the modulated reflectance are separable

by differentiating this equation. We obtain
-AR
_ - 4(n2 - k2 - 1)An + 8nkAk
R
[(n + 1)
+ k 2 ] [ ( n- 1)2 + k]
where An and Ak are the changes in n and k resulting from the modulation.
The ratio
(22)
2nk/(n2 - k 2 - 1) = c ~ / ( E ,- 1)
is a measure of the relative weight taken by n and k through the spectrum to

modify the reflectivity. Particularly, when k << n (this case can occur in
semiconductors near and below the fundamental absorption edge), ARIR,
which remains dependent upon the index of refraction only, is reduced to
AR/R
[4/(n2 - 1)]An
[2/(n2- l ) n ] A ~ , ,
k << n .
(23)
The reflectivity can also be expressed as a function of the real and imaginary
components and c2 of the dielectric constant by substitution of Eqs. (13)
4.
329
into Eq. (20).This gives
The effect on reflectivity of the changes Acl and

in E , and c2 induced by
the modulation is made explicit by differentiating Eq. (24). The result has
the form
ARJR = M ( E ~ ~, 2 A) E ~ / 3 ( ~ 1 , ~ At2.
2)
(25)
The coefficients a and weight, respectively, the contributions of A E and

~
to the modulated reflectance. They are functions of E , and E~ : they have
been derived by Seraphin and Bottka in connection with electroreflectance
a n a l y ~ i s , ~and
their spectral dependence has been computed for several
semiconductors (Ge,22.45Si,45G ~ A Sfrom
~ ~the
) experimental values of the
optical constants. The theoretical modulated reflectance spectrum results
from the substitution into Eq. (25) of the values of A E and
~ Ac2 calculated
according tosome suitable hypothesis. If the theoretically computed spectrum
fits the experimental one, an interpretation is possible.
Fischer and Seraphinz3have calculated the coefficients a and fl at oblique
incidence for light polarized parallel to and normal to the plane of incidence.
The coefficients are then (complicated) functions of the angle of incidence 4+
as well as of the optical constants. For the case of germanium, the normal
components c1, and 8, are found to decrease monotonically with increasing 4.
But the parallel components xP and 11, exhibit extrema in a small angular
region near the Brewster angle + B . An enhancement of the modulation of
the reflected light can thus be obtained. More interesting is the possibility
of separating the contributions of Ael and A E by
~ choosing properly the
angle of incidence in regions where a p >> /3, or where /3, >> zprrespectively,
as the extrema of a,, and /3, d o not fall exactly o n the same angle. Thermal
reflectance measurements at oblique incidence, have been performed by
Balzarotti and GrandolfoZ4o n silicon.
and A E ~
A more straightforward procedure is perhaps to compute
from the experimental data in view of direct comparison with the theoretical
line shape^.'^'^^ I t is indeed the interpretation of
and At2 that allows a
correlation to be established between band structure and modulated reflectance.
By separating the real and imaginary parts of Eq. (1 8) after differentiation,
we obtain
2 A k = kn(AR/R) + (n2 - k2 - l ) A q ,
(26a)
2An
45
i(n2 - k 2 -
l)(AR/R) - 2kw A q .
B 0. Seraphin and N. Bottka. Phys. R w . 145, 618 (1966).
(26b)
330
BRUNO BATZ
Differentiating now Eqs. (1 2), we find

AE,
2n An
2k A&,
(274
2kAn 2nAk,
and the substitution of Eqs. (26) into Eqs. (27) leads to the result
=
AE,
= $n(nz -
3k3 - l ) ( A R / R )- k(3n2 - k Z - 1)Aq,
$c(3n2 - k Z - l ) ( A R / R )+ n(n2 - 3k2 - l ) A q ,
(27b)
(28a)
(28b)
where A q is calculable from the experimental spectrum of A R / R by a
Kramers-Kronig analysis as explained in Section 6 [see Eq. (50)],so that
A E ~and A E are
~ computable from the modulated reflectance data if the
optical constants nand k are known.
Let us consider for the moment light transmission through a slab of
thickness d of a material with absorption coefficient K . It is assumed that
interference phenomena are negligible in the experiment. This condition
occurs when the sample is thick with respect to the wavelength if its faces
are not parallel enough for the fringes to be resolved. If we can furthermore
assume that k << n in the spectral domain of interest (this generally applies
in the region where transmission measurements are possible), the ratio of
the average transmitted energy flux to the incident flux is given by
=
T r ( o ) = ( 1 - R)/(eKd- R Z e - K d ) ,
k << n .
(29)
Multiple reflections in the slab have been taken into account in this formula.
But it often happens that eZKd>> R 2 .Then the average transmission is simply
for
Tr
(1 - R)ePKd,
n,
e Z K d>> R 2 .
For the modulated transmission we find
ATrlTr
- 2 A R / ( 1 - R ) - K Ad - dAK
(32)
by differentiation of Eq. (30).Because of thermal expansion, the second term

on the right side should give a contribution when the modulating parameter
is temperature. But in the spectral interval where transmission experiments
are workable, K is small and this term may be neglected. The third is usually
the leading term so that ATr/Tr is proportional to the variation AK of the
absorption coefficient related to the temperature change.
5. PHENOMENOLOGICAL
THEORY
OF THERMAL
REFLECTANCE
Anticipating the results of Part 111, we are now going to indicate, although
without much rigor, how the line shapes for A E , and Ac2 associated with
4.
331
critical point softhe pair band structurecan becomputed when themodulating

parameter is temperature or wavelength. The identification of a critical
point in an experimental spectrum should then be possible by comparison
with the theoretical line shape.
The behavior of the dielectric constant versus photon energy hw is known
from simple theory to be of the form15 h ( h o - E,)2 (see Section lo),
where h = i for a critical point of type M, and where E , is the interband
energy at the critical point. Lifetime broadening can be accounted for
phenomenologically by replacing in this formula the energy hw by hw ir,
where r is the (positive) Lorentz broadening parameter. This substitution
yields for 2 the expression
6 a h(htu
+ ir
(33)
E,).
Introducing the reduced variable

=
(ho
- E,)/r
(34)
we obtain
6
GC
hr1/2(.u
+ i)/2.
(35)
The separation of the real and imaginary parts leads to the result
with
&x) = [x
+ (x2 + 1)
l / 2 112
(37)
The temperature modulates 2 through E , and r. A small temperature

variation AT leads to a corresponding change At of the complex dielectric
constant, given by
Ai: cc i b r - ([F( - x )
+ iF(x)](dT/dT)
[F(x)- iF( -x)](dE,/dT)J AT,

(38)
where the function F ( x ) = 2(d4/d.x) has the following explicit form

F(.x) =
[(XZ
1)2
(x2 +
+
1)12
x]12
(39)
This is the important function of wavelength and thermal reflectance theory.

It is plotted in Fig. 2. The line shapes of A t , and Az2 associated to any type
of critical point can, in principle, be built from it. This question is discussed
further in Section 11 (see there Fig. 7 and Table 11). The experimental line
shapes o f A E l and Ac2 computed with Eq. (28) may then be directly compared
332
BRUNO BATZ
FIG.2. The function F ( x ) given by Eq. (39)from which wavelength and temperature modulated
reflectance spectra are computed. (After bat^.",^^)
to the theoretical ones in view of critical point identification ;or the theoretical
and A E may
~ be substituted in Eq. (25), if a and are known,
values of
to try to fit the theoretical and experimental spectra of ARIR.
Besides the functions a(hw) and P(hw) [or n(hw) and k(hw) when using
Eqs. (28)],which must, as a preliminary step, be inferred from experimental
data, the temperature coefficients of r and E , should also be determined ;
at least their ratio should be known. The coefficient dE,/dT is negative in
most cases with which we have t o deal; a typical value is - 4 x lo- eV/
C.5 * 4 6 The sensitivity to temperature of the Lorentz parameter has generally
been neglected in the analysis of thermoreflectance spectra. 5 - 3 9 Equation (38)
then reduces to
A g a -&r-1/2[ F ( x )- iF( -x)](dE,/dT) AT.
(40)
Assuming this simplification t o be valid, it turns out that the wavelength
modulation technique should yield the same spectra near critical points
as those obtained by temperature modulation. Indeed, as 2 depends on the
difference ( E , - Am), it is equivalent to modifying E , (by changing the
temperature) or Aw. A variation A(hw)in the radiation frequency changes 2 by
A2 cc
46
ibr- 1 / 2 [ F ( ~-) iF(x)]A(Aw)
(41)
M. Cardona, in Semiconductors and Semimetals (R. K. Willardson and A. C. Beer. eds.),

Vol. 3, p. 125. Academic Press, New York, 1967.
4. THERMAL AND WAVELENGTH MODULATION SPECTROSCOPY
333
to be compared to Eq. (40). Matatagui et af. have pointed out the similarity
of the spectra obtained by the two methods in the case of InSb for which
wavelength modulation results are available.36 (The spectra are shown in
Section 18.) This fact justifies the approximation made in writing Eq. (40).
Nevertheless, the approximation cannot be expected to be valid in all
cases. Balzarotti and Grandolfo4 have interpreted a line shape in their
thermoreflectance spectrum of graphite by taking into account the temperature dependence of the broadening parameter only. But I is not necessarily
independent of hw either and Eq. (41) could have to be replaced in some
instances by the more complete form, similar t o Eq. (38), given by Eq. ( 1 33).
These matters are discussed in greater detail in Section 14.
6. DISPERSION
RELATIONS
The functions E ~ ( wand
) E ~ ( Q ) are not independent, since the dispersion
and dissipation, which they describe respectively, are two sides of one
phenomenon. In fact, the knowledge of one of these functions at all frequencies implies the knowledge of the other. This interdependence is made
explicit in the dispersion relations (47), often called the Kramers-Kronig
relations. These relations are of prime importance for the analysis of modulated reflectance spectra.
The polarization P(t) at time t can be evaluated as resulting from the
values taken by the field E a t all previous moments. For a linear relationship
between field and polarization, we may write48
P(t) =
SI
q(t - t)E(t)dt.
(42)
If the field E(t) has been applied only during the time interval ( t , t + dt),
its effect will persist at times r > 1 + dt as a result of the inertia of polarization. The function q(r - t) describes the decrease of P and it has the property
v(t - t) -+ 0
as
t + 00.
(43)
For harmonic fields, in particular for plane waves of the form given by
Eq. (8), Eq. (42) becomes, if t - t = u,
E Jox
q(u)eiod u .
(44)
Comparing this relation with Eq. (10): P = ~ ~ -( l)e,

8 we find
E,,(&
47
- 1) =
s,
q(u)eioud u .
A. Balzarotti and M. Grandolfo, Phys. Reu. Left.20,9 (1968).
(45)
H. Frohlich, Theory of Dielectrics.Oxford Univ. Press (Clarendon), London and New

York. 1958.
334
BRUNO BAT2
FIG.3. Integration contour for the deduction of dispersion relations.
We now let w have complex values.49 The above integral, as well as its
derivative with respect to w , converges for I m w > 0 as a consequence of
condition (43) on q. Thus &(o)
- 1 is analytic in the upper half-o plane and
it goes to zero when 10) + 00 : Cauchys formula can be applied with the
contour of integration shown in Fig. 3. This leads to the equation
C ( 0 ) - 1 = 79
do
because the contribution to the integral of the large circle is zero ;Ydenotes
the Cauchy principal value of the integral.
It follows from Eq. (45) that (?i - w ) = 8*(w). This relation shows that the
real part of 8 is an even function of o and that the imaginary part is an odd
function of w : c l ( - w ) = ~ ~ (and
0 E
) ~ ( - w=
) - E ~ ( w )Making
.
use of these
properties when separating the real and imaginary parts of Eq. (46), we
obtain
dw,
(474
The temperature-induced change in E~ causes a related change in

which, according to Eq. (47a), is given by
AE~(o=
J ) -9
dw
Although the whole frequency range is implied in the above integrals,

it can be shown that the spectral structures occurring in E ~ ( wand
) E~(UI),
49
J. Tauc, in The Optical Properties of Solids (Proc. Int. School Phys. Enrico Fermi.
Varenna, Italy) (J. Tauc, ed.), p. 63. Academic Press, New York and London, 1966.
4.
335
or in Ae,(w)and Ac2(w),are correlated. An isolated line around one frequency

in the spectrum of Ac2 (resulting, for example, from a critical point in the
band structure), can be considered alone, independently of other features of
the spectrum, to determine the behavior of Acl at neighboring frequencies.
One can thus hope to be able to match an experimental sharp structure in
the modulated reflectance with the line shape computed by Eqs. (25) and (48)
from the calculated contribution to Ae2 of only one critical point in the band
structure.
It can also be shown that the phase angle cp is connected to the reflectivity
by the very useful dispersion relation16
This formula makes possible the calculation of the optical constants, through
the use of Eqs. (19) and (20), when the reflectivity has been measured in a
wide enough frequency interval. Of more direct interest to us is the fact
that it allows the change Acp in phase angle to be computed from the related
relative change in reflectivity AR/R. We find
dw
It is with the help of this expression that the values of Azl and A&,, as given
by Eqs. (28), are computed for comparison with theory. Kramers-Kronig
analysis thus appears as a fundamental tool in the attempt to correlate
modulated reflectance spectra with some features of the solids band structure.
7 . THERMAL
REFLECTANCE
AND TRANSMITTANCE
AT THE FUNDAMENTAL
ABSORPTION
EDGE
The behavior of the absorption coefficient in the neighborhood of the
fundamental absorption edge of a semiconductor is discussed in Section 15
and is represented there in Fig. 9 for a direct allowed edge. It is seen that the
main features of the spectrum are a high absorption peak corresponding to
the formation by the absorption process of bound excitons in the ground
state, followed on the high energy side by a continuum corresponding to
the formation of ionized pair states. The continuum starts abruptly and it
may well be represented by a step function.
Let us assume that these spectral structures are broadened by finite
lifetime effects. The complex dielectric constant associated with a discrete line
at energy E , is derived from Eq. (45) by assigning to the function q(u) the form
2 exp( - h / h ) sin(E,u/h), fi exp[ - (r + iE,)u/h] - i exp[ - (r - iE,)u/h],
336
BRUNO BATZ
where I-, the Lorentz broadening parameter, is assumed to be much

smaller than E,. This function satisfies condition (43) and it is real as
required. As r << E,, the contribution to 2 - 1 of the second term, which is
proportional to [(E, + hw) + iT]-, can be neglected near ho = E , . The
main contribution then comes from the first term. If T = u/A, we obtain
iL- 1 cc
lom
i exp[i(ho - E&] exp(-rT) d.r = [ ( E , - ho)-
irl- 1 .
(51)
Separating the real and imaginary parts, we have approximately

q L- 1 a
EL
- ( h a - E,) - 1 - x
( h a - E,) + rz r 2 + 1
-~
x ( h o - E , ) ~+ rz- r x2 + 1
where the reduced variable x is defined by Eq. (34).These are the standard
Lorentzian line shapes. The functions (x
1)- and -x(x + I ) - are
represented in Fig. 4. It is seen that is the half width of the E~~ peak at
half maximum and that the E~~ dispersive curve has extrema at ho = E , k r.
When the peak is positive, E~~ has a maximum on the low energy side with
respect to E, and a minimum on the high energy side; the inverse is true
for a negative peak.
Differentiating Eq. (51) or Eqs. (52) we find for the temperature-induced
change of E ~ and
L
cZL
2~
(x
z)
dT
_ - X - 1 dEo
1) dT (x2 + I)
AT
2x
(53a)
(53b)
The functions (x2 - l)(x + 1)- and 2x(x2 + 1)- are also plotted in
Fig. 4. The line shapes given by Eqs. (52) and (53) describe adequately the
contribution of a bound exciton level to E and AE, respectively. [A more
accurate result is however given by Eq. (145).]
If the absorption constant rises abruptly at the absorption edge, E will
have a similar behavior. Representing this energy dependence at the edge
by a step function at the energy E , broadened by lifetime effects, we may
write
4. THERMAL AND
337
I
I
09
08
\
2\....
(x2+02
____c------
-8
-6
..-
--_
4
.-.
\\
-2
\
10.
'
6fibJ-E,
x=
'
'?
\
\
II
I
\ I
\-0
5
I
I
I
I
I
FIG.4. Lorentzian c2 peak and dispersive E , line shape (solid line) and the corresponding line
shapes of A E , and Ac2 in response to the modulation of the peak energy or of the broadening
parameter (broken line).
where x = (hw - En)/T, x = (ho- E,')/T. and y = ( h o - E)/T. In this

simple model, En' stands for the upper limit of the absorption band, and it
is assumed that E,' - En >> T. A temperature modification produces changes
in &, x, and x', which are related by A2 cc (x' i)-'Ax' - (x i ) - ' Ax, as
can be seen by differentiating Eq. (54).Calculating the explicit dependence of
338
BRUNO B A T 2
Ax and Ax' upon AT, we find, approximately, near the absorption edge
When the broadening parameter is assumed to be constant (dT/dT = 0).

the results expressed by Eqs. (53) and ( 5 5 )are equivalent to those that would
have been obtained from wavelength modulation with AEo = ( d E , / d T )AT
replaced by - A(hw) in the formulas.
Near the absorption edge, ARIR cc A E , [Eq. (2311 and ATr/Tr ,x- A E ~ .
This last result is a consequence of Eq. (32) in which only the third term on the
right side is taken into account, if one assumes that AK cc Ac2 in the narrow
energy range considered. Modulated reflectance line shapes are thus given by
Eqs. (53a) and (55a) and modulated transmittance line shapes by Eqs. (53b)
and (55b). In particular, when dT/dT is zero, a dispersive type curve and a
Lorentzian peak are expected in the spectra of ARIR and ATrlTr, respectively
[Eqs. (5211, on the basis of this simple model, at the absorption edge. Such a
behavior actually takes place in some instances as will be seen in Part VII.
IV. Elementary Theory

8. THEABSORPTION
COEFFICIENT
The detailed knowledge ofthe band configuration ofa solid is a guide to the
understanding of some of its optical properties. Conversely, the analysis of
its optical behavior is an essential method to investigate the electronic
structure. Optical modulation techniques are interesting precisely in that
they are more sensitive than conventional measurements to some features of
the band structure. They yield spectra with sharper lines, which, to be interpreted, must be correlated with the peculiarities of the energy bands. We
develop here and in Parts V and VI the basis for such an interpretation.
Under the action of the electromagnetic field, an electron belonging to a
full valence band of a crystal may be excited into a state of a higher (conduction) band, an electron-hole pair being created in the process at the same time
that a photon is absorbed. The modifications expected to be brought to the
theory by including the electron-hole interaction (exciton effect) are discussed in Part VI. A wholly satisfactory theory of the exciton problem is
however not yet completed. The comparison of the experimental data with the
results which follow from the theory without electron-hole interaction is thus
4.
339
enlightening. We derive in this section the absorption coefficient K(hto), or

more exactly the equivalent parameter ~ ~ ( h ( ofor
) . this simple case, applying
standard semiclassical radiation theory.
Let u s introduce the vector potential A in the same way that was done for
the other field vectors [Eqs. (7) and (811.
A
&Ao exp[i(r - r
+ c.c.),
156)
(nt)]
where C.C.denotes the complex conjugate. In this expression, the wave vector
is taken to be real : K = r l .The electromagnetic field is assumed to propagate
in a transparent medium apart from the effect of the valence absorbing
electrons which are being studied. The Hamiltonian for these electrons can
be written as
where pj and rj are the momentum and position vectors of the jth electron,
and where rn and e are the electrons mass and charge (in absolute value),
respectively ; Xe is the unperturbed Hamiltonian Xjpj2/2rn V ( r l , . . . ,r N )
and Xeris the perturbation brought in by the interaction with the radiation
field. Neglecting second order terms in A, the interaction becomes simply
(V A = 0 for transverse fields)
As this operator does not operate on spin coordinates we shall not introduce
them explicitly.
The antisymmetrical wave function Yo, which describes the ground statc
of the insulating crystal (full valence band, empty conduction band), can be
written as a Slater determinant of one-electron Bloch functions $vk(ri).
suitably n o r m a l i ~ e d ~ . ~
51
L 1. Shim. Quantum Mechanics. McGraw-Hill. New York, 1949

N e w York. 1940
F. Seitz, The Modern Theory of Solids McGraw-Hill,
340
BRUNO BATZ
An excited-state wave function can be described by a similar determinant.
describes the crystal with an empty valence state of wave vector k and energy
Ev(k), and an electron raised in the conduction band state k at energy
Ec(k).This wave function is adequate for treating problems in the one-electron
approximation. A more general form of wave function, required, for instance,
when electron-hole interaction is taken into account, can be contructed by
making a linear combination of such determinants for all possible pairs of
k and k'. If only one valence band and one conduction band are taken
into consideration, the excited-state wave function is thus given by
@
kk'
Cck',vkyck',vkr
where k and k run over allowed values in the Brillouin zone. The values of
the coefficients C c k ' , v k must be determined by the interactions not included
in the one-electron approximation.
As the perturbation Zer
is a sum of one-electron operators, it has nonvanishing matrix elements between Slater determinants which differ by only
one Bloch function. If the initial state is the ground state Yo,the field induces
only one-electron transitions to final states of the type y c k , , v k . The probability
per unit time for this transition to take place is
according to time-dependent perturbation theory. The delta function

expresses energy conservation when a photon is absorbed. We are disregarding the effect of the second term on the right side of Eq. (56) which leads to
photon emission. Using Eqs. (58H60),Eq. (62) becomes
Pck',vk(hW)
rcez2h mz
= - --AoAo*l(ck'lei"'a
- pluk)12 6[Ec(k') - Ev(k)
hw],
(63)
where luk) and ( c k ) represent Bloch states : a is a unit vector parallel to A.
4.
341
The rate of energy absorption at photon energy hw due to all possible

transitions between the energy bands v and c is given by W(hw)=
AwC,, &k, P,k',,k(hw), the sums on k and k' being extended to all allowed
values in the Brillouin zone and those on v and c to all the valence and
conduction bands. We shall however assume that only on$ pair of bands
contributes to W(hw)at energy hw. Using the relation E = A = -iwAand
Eq. (14),the Poynting vector may be written = ~ ~ c E ~ w ~ Substituting
A ^ ~ ~ ~ * .
these values of
and Winto Eq. (16), one readily obtains the absorption
coefficient K(hw),or the imaginary dielectric constant. It is found that
Is1
1st
E2(hO) =
27~ he
- -
&O
1
~
kk'
I(ck'lr'"''a. plvkk)126[E,(k') - E,(k) - Rn,].
(64)
The factor 2 accounts for the two spin possibilities of the electron in each
orbital state.
9. MATRIXELEMENTS
AND SELECTION RLJLE
The Bloch functions have the form

$b*(r)
exp(ik r) uhk(r)
(63
where the functions Ubk(r) have the periodicity of the lattice. If they are
normalized for the unit volume, the matrix element in Eq. (64) has the
explicit form52
1
Jcrys
+&'(r)exp(iK' r) a ' p $vk(r) dr
=
X
1exp[i(u + k - k') -Re]

a (p +
dr ,
1
VP
*
hk)U,k
I,,,
exp[i(r + k - k') r]
where R, is a lattice vector. The sum vanishes unless

K
+ k - k'=
K,
167)
where K is a vector of the reciprocal lattice. There is completely constructive

interference in this case and the sum's value is N , the number of cells in
the crystal. At the scale of the zone's extension K is a very small vector and it
can be neglected. The umklapp processes for which K # 0 may affect the
value of the matrix element, particularly when the wave vectors of the
electrons end near the zone's b ~ u n d a r y .But
~ the normal processes for
'*
R. A. Smith, "Wave Mechanics of Crystalline Solids." Chapman & Hall, London. 1963
342
BRUNO B A T 2
which K = 0 are usually appropriate and the condition of conservation of

wave vector is simply
k.
(68)
The transition is said to be direct, or vertical when referring to its

representation on the band scheme. The matrix element (66)becomes
(ckla plllk)
n-
cell
uzka
PUvk
dr ,
(69)
where i2 is the volume o f a unit cell. The part of the last integral which contains
hk, in Eq. (66), vanishes because of the orthogonality of the Bloch wave
functions for different bands.
We shall be concerned with limited domains in the Brillouin zone, often
centered about symmetry points, which are responsible for some singular
properties of the optical constants near the corresponding interband energies.
It is of interest to be aware of the behavior of the matrix element around a
point k,, the center of such a domain. Expanding the matrix element in
powers of (k - k,), we obtain
(ckla * pluk)
(ck,la
- p)uko) + (k - ko)
{Vk(ckla. pl&)}k=k,,
+ ... .
(70)
The matrix element is not expected to vary very much near k, and it may
be taken equal to the first term in the expansion (symmetry allowed transitions). It is however possible that this term vanishes as a consequence of
the symmetry properties of the functions uvk(r)and uCk(r)at the symmetry
point k, (symmetry forbidden transitions). But the second term in the expansion still allows absorption to take place at finite k - k,.
Disregarding some special cases (the occurrence of umklapp processes,
of symmetry forbidden transitions,. . .), the matrix element can be assumed to
vary slowly through the Brillouin zone, or, more restrictively, in a limited
domain of the zone of particular interest. By choosing a suitable average,
(cia p(v), Eq. (64) can be written as
where
343
and G ( E ) is the combined density of states for the pair band (tt, c). I t is the
density with respect to energy of the pairs of states which are connected by
the selection rule (68) and separated in energy by E. This function, which
essentially determines the energy dependence of the optical constants, is
called the joint density-of-states.
AND CRITICAL
10. JOINT DENSITY-OF-STATES
POINTS
It is seen from Eq. (71) that the decoding of an optical spectrum of a solid
in terms of its electronic structure is based on the manner according to
which the joint density-of-states function is related to the band configuration.
The interpretation is made easier by some general properties of this function.
Indeed, G ( E )possesses singularities of well-defined types at critical points
of the reciprocal space as a result of the relation which exists between G ( E )
and E(k).5-7353
The function G ( E )has the form
G ( E )=
(73)
as a consequence of its definition. The factor ( 2 ~gives

) ~the~ density of
states for each spin direction in reciprocal space (per unit volume of crystal) ;
the integral is to be taken over the volume, in the Brillouin zone, bounded
by the surface S ( E ) of constant energy E = E , ( k ) - E,(k). The distance
between two surfaces S ( E ) and S ( E + d E ) is dk, = dE/IVkEI, and the volume
between these surfaces is JscE, (dE/IVkEI)dS, if dS is a surface element on
S(E). It follows that Eq. (73) can be written as
(74)
This representation of G ( E ) shows that the function is bounded except
eventually if V k E = 0. That circumstance suggests that singularities are
likely to appear in a spectrum only if the gradient of E ( k ) is zero at one or
more points in the Brillouin zone. These points for which
V , E ( k ) = VkE,(k) - VkE,(k) = 0
(75)
are called critical points.

An analytic critical point k , is defined as being a point at which the following conditions are satisfieds3 :
A. A. Maradudin, E. W. Montroll, and G. H . Weiss, Solid Stare Phys. Suppl. 3 (1963).
344
BRUNO BAT2
(1) Equation (75) is fulfilled.

(2) There is a neighborhood D of k, in which E(k) can be expanded in a
Taylor series
E(k) = Efko) +
1bi,(ki - ko,)(kj - koj) + ... .

ij
(3) The determinant Id2E/dki dkjl does not vanish in D.
Keeping only second order terms, the Taylor expansion can be written as
E(k) = Eo
+ C aiui(kf - kio),,
(76)
where, by virtue of the third condition, a change of coordinates has been

made, bringing the ki on the principal axis. Here E , is the interband energy
at the critical point. The ai are positive quantities related to the reduced
pair band effective mass mi (ai = h2/21rnil). The type of the singularity is
settled by the numbers uiwhich can take the values 1 or - 1.
A further simplification results from the transformation si = a!I2(ki - koi).
It leads to the expressions
E = Eo + u 1 s I 2+ u
+ us
~~
s~
(77)
and
(78)
where s = (s12 sZ2+ s3,)ll2. Let us calculate G(E) for the four types of
critical points M , , M , , M,, and M,, the index indicating the number of
negative uis in Eq. (77).
Minimum M ,
E - Eo
s12
+ s , ~+
s2.
The surfaces of constant energy around the critical point are spheres in
s space. The integration in Eq. (78) is straightforward and it yields
G(E) = 0,
G(E) =
E < Eo,
1
(E 47c2(a1a2a3)~2
Eo)2,
E > Eo
Saddle point M ,
E - Eo
s12f s2, - s3,
r2 - s 3 , ,
r2 = s12
+ s22.
(794
345
The constant energy surfaces in s-space are hyperboloids of revolution of

one or two sheets according to whether E > E , or E < E,. When E = E,,.
the surface is a cone passing by the critical point and r, as defined above, is
the radius of a section of the hyperboloid perpendicular to the axis s j .
The integration in Eq. (78) must be limited to some distance from the critical
point to give useful results. A convenient way to express this restriction is to
choose s2 = r2 + s32 < 0 2 .On the other hand, since r2 = s32 - ( E ( , - E),
the values taken by s3 are restricted to the interval - C < s3 6 C, where
The integral in Eq. (78) can be written as
where dl is an element of arc on the hyperbola E - E , = r2 - s32 in the

(r, s3)plane. We have
and the third form of the above integral arises from the second form by
substitution of this value of di.
The cases E < E , and E > E o are to be considered separately as the ranges
of integration of s3 are different. For the two-sheeted hyperboloid ( E < E n )
one must not integrate between the vertices situated at + _ ( E , - E)!* on the
sj axis. We thus obtain
= (47t2)-1(~l~2~3)-1 2 ([ EC, -
and
s,
E)2], E < E,,
(834
G(E)= ( ~ Z ~ ) - ( U ~ ~ , U ~ ) - ds3
~ =(4~2)-(~l~2~3)-i~
E 2>CEn.
,
(83b)
The behavior of G ( E ) at a saddle point M 2 or at a maximum M 3 can be

inferred from its behavior at the M , or M , critical points, respectively, by
346
BRUNO BATZ
TABLE I
BEHAVIOR
OF THE JOINT
FUNCTIONS
G(E) IN
CRITICAL
POINTS
DENSITY-OF-STATES
OF THE
THE VICINITY
4n(a,u,a3)2G(~)
Type
Minimum M ,
Saddle point M ,
Saddle point M ,
Maximum M,
Id1
I
1
-1
-1
-I
-1
E < E,
u.3
1
1
1
-1
0
( E , - E)
C
(E, - E ) *
E > E,
(E
(E
E,)
C
-
E,)
permutation of E and E,. (All the results are summarized in Table 1 and
Fig. 5.)
In the case of a saddle point, the function C appears both when E < E ,
and when E > E,. This function, as well as its derivative, is continuous at
E = E,. It thus contributes only to a continuous background, whereas the
terms ( E , - E) and ( E - E o ) l i 2 , although equal to zero at E = E,, have
infinite discontinuities in the derivatives. These terms are responsible for
the rapid variation of G ( E ) at the critical point. The area of the constant
energy surfaces decreases very rapidly when the one-sheet hyperboloid is
transformed into a two-sheet hyperboloid E passing through E,. This sudden
decrease in area is the cause of the IE, - El - I 2 discontinuity in the derivative
of G ( E ) which is turned to advantage in the spectroscopic analysis of solids
using thermal or wavelength modulation techniques.
FIG.5. The joint density-of-states function G(E) near the four types of critical points according
to Table I .
4.
347
As the functions E,(k) and E,(k) have the periodicity of the reciprocal
lattice, the function E(k) = E,(k) - E,(k) has the same periodicity. This
circumstance which implies for E(k) (assumed to be continuous) the existence
of at least one minimum and one maximum in each cell of reciprocal space,
also implies the existence of at least three saddle points of each kind. It can
be shown that the number of critical points of the different types are not
independent. As a matter of fact, one has the relations : N o 2 1, N - N o 2 2,
N , - N , + N o 2 1, and N , - N ,
N , - N o = 0, where N ispecifies the
number of critical points of type Mi.
Symmetry considerations are useful to localize critical points which are
often found on high symmetry elements. Equation (75)is satisfied particularly
when
These conditions are generally fulfilled at points of high symmetry. For

instance the center of the zone k = 0 (rpoint) is always a critical point. But
critical points can occur anywhere in the Brillouin zone (repeated of course
by the symmetry operations corresponding to the crystal), and usually for
these
Van Hove6 and Phillips' have studied the singularities introduced by

nonanalytic critical points. We shall only mention the "fluted" critical points.
They arise from contacts between branches of E(k) at symmetry points
and give rise to singularities of the same character as those due to the
analytic critical points, with which they make up the class of ordinary critical
points.
11. THERMAL
AND WAVELENGTH
MODULATION
OF THE DIELECTRIC
CONSTANT
AT
CRITICAL
POINTS
It is now a simple matter to calculate the contribution of a critical point

to the modulation of the dielectric constant." For instance, the change in
c2 resulting from a change AE, in the edge energy of a M , critical point is,
using Eq. (71) and Table I,
B (hw - E , ) 2
(hw),
AEZ = --
AE,,
hw > E,,
348
BRUNO BAT2
where
The corresponding change in the real part of the dielectric constant is

obtained from A E ~by performing a Kramers-Kronig transformation
[Eq. (48)]. We find for A E the
~ following approximate behavior near the
critical energy
AE=
~
B ( E , - hw)-I2
AEO,
2
(hay
--
h w < E,,
It can be seen that the derivatives of E~ and .c2 with respect to E , are one
anothers reflection on the critical energy, where they each have an infinite
discontinuity. The methods of measurement which are sensitive to these
derivatives will have a far better resolution than the usual methods, the
continuous background being moreover not detected. The approximate
E ,shown in Fig. 6 for the four types of
behavior of de,/dE, and d ~ ~ / d is
critical points. They have the same general structure as that given by Eqs. (86)
and (88) except for the sign or for a reflection on E,.
We shall not pursue the analysis on these lines because we need a more
elaborate theory to interpret the experimental results. We have implicitly
considered the ideal case of infinite lifetime for the excited states of the
crystal, but the more realistic hypothesis of a finite lifetime T brings important
modifications to the spectra. An energy broadening of the order of h/s is to
be expected from the uncertainty principle. The mechanism of this broadening
is discussed in Section 14.
It is convenient to assume that finite lifetime effects can be described with
the help of a constant Lorentz broadening parameter r, independent of k,
near a critical point. The optical constants are then calculable from Eq. (71),
with the S function replaced by a normalized Lorentzian peak
The contribution of the critical point t o the imaginary part of the dielectric
constant is thus given by
4.
349
FIG.6. Line shapes of A E , (solid line) and Ac2 (broken line) in response to the modulation of
the interband energies near the four types of critical points. Broadening effects are neglected.
(After Batz.")
The real part of the dielectric constant results from a Kramers-Kronig

transformation of this equation. In fact, for a narrow Lorentzian line (r<< Eo),
E~ is obtained by replacing the Lorentzian peak by the dispersive line given
by Eq. (52a). We can write
&,(ha)
=
~
M 2 1 s ' ' ( E - ho)G(E)

dE
7~
(ho- E ) +
~ rz
For an M , critical point we have
where y
( E - E,)/T. The reduced variable x has already been introduced
350
BRUNO BATZ
in Section 5 [Eq. (34)], as well as the function 4(x) which is defined by

Eq. (37).
If the contribution of the function C is disregarded (it is expected to have
little effect on the derivatives of e l and E , which we want to evaluate), we
find for an M critical point
where z = ( E , - E)/T. The last equality holds if E,/T is large so that the
integration can be extended to infinity without much error, and it applies
to the values of hw of interest which are close to the critical energy E,.
The results for M , and M, critical points turn out to be the same as those
for M , and M points, respectively, except for a change of sign. The derivatives
of E , with respect to hw, E,, and r are easily expressed in term of the function
F ( x ) defined by Eq. (39). They are given in Table 11. When calculating the
and E , with respect to hw it has been assumed that
derivatives of
de,,,/d(hw) = ( r t r ~ ) - d~ [ ( h ~ ) ~ ~ ~ , , ] / dnear
( h w ) the critical point. Then
ds,,,/dE, = -ds,,,/d(hw), since ( h w ) 2 ~ , are
. , functions only of x.
The values of computed with Eq. (90b) diverge if one uses throughout
the whole energy range the expressions for G(E)given in Table I. Actually,
G(E)should vanish at small and large energies. We can, however, avoid
this difficulty by calculating directly the derivatives of interest. For an M ,
TABLE I1
THEBEHAVIOR
OF THE DERIVATIVES
OF E~ AND c2 WITH RESPECTTO THE PHOTON
ENERGYhw.
INTERBAND ENERGYE o , AND THE LORENTZIAN
BROADENING
PARAMETER
r NEAR THE
CRITICAL
POINTS"
THE
MO
M2
F(-X)
-F(+x)
-F(-X)
M3
F(+x)
Ml
-F(-X)
F(+x)
F( - x)
-F(+x)
-F(+x)
-F(-x)
F(+x)
F(-x)
F(+x)
F(-X)
-F(+x)
-F(-x)
-F(+x)
-F(-X)
F(-x)
-F(+x)
F(+x)
F(-x)
-F(-x)
F( x)
The function F( + x) which is given by Eq. (39) is represented in Fig. 2, and c = 2(ho)2(2r)1'2/iB
4.
351
critical point, we can write
de,
d(ho)
de,
dEo
dY
and for an M , critical point we find approximately
dE1
d(R4
--=--
dE1
dEo
B
1 1 Eojr(Z + x)z-l2
dz
(hw) 2r1I2
I
I
~( z
x)
1
The same results with a change of sign are found, respectively, for M , and
M, critical points. It is also immediately apparent by inspection of Eqs. (90a)
and (90b) that we have
dE,/dT = - d ~ , / d ( h w ) .
(95)
The results are summarized in Table 11. As they are equivalent to those
expressed by Eqs. (38) and (41), the phenomenological treatment of Section 5
is justified. The line shapes of d c , , , / d ( h o ) = -dsl,,/dEo and dE1,,/dr are
represented with the help of only one function F ( x ) for the four types of
critical points [Eq. (39) and Fig. 21. These line shapes are shown in Fig. 7.
FIG.7. The derivative of
(solid line) and
E*
hw and the Lorentzian broadening parameter

from Table 11. (After Matatagui et
(broken line) with respect to the photon energy

r for the four types of critical points, derived
352
BRUNO BATZ
They should allow the identification ofthe experimental line shapes computed
with the use of Eq. (28) as it has already been explained in Part 111.
The previous treatment could be extended to more complicated models
ofthe band structure. Shaklee et ~ 1have
. calculated
~ ~ da,/d(ho) and da2/d(ho)
from the k p band structure to discuss their wavelength modulation data
on InSb.
V. The Electron-Phonon Interaction

12. PERTURBATION
THEORY
AND THE SCATTERING
MATRIXELEMENT
The temperature modulated optical properties of a solid depend strongly
on electron-phonon interaction. As discussed in Section 14, this interaction
takes a large part in the broadening and the shift of an electronic energy
level in a band. It is also responsible for the indirect optical transitions, as
explained in the next section. These processes are sensitive to temperature
through the variation of the number of phonons with temperature.
Let us consider the crystal Hamiltonian
Xc = Xe
+ X, +
(96)
Xed,
where Xe,which has already been introduced in Section 8, involves only

the electron coordinates; Xl = C,ho,a,+a, is the lattice Hamiltonian
expressed in terms of the phonon creation and destruction operators a,,+
and a,. We shall need to take into account only one phonon branch (pertaining to the longitudinal acoustic or optical modes) at a time, and only
the terms concerning this branch appear in Xt. The sum over the phonon
wave vector q is extended to the allowed values in the Brillouin zone. The
electron-lattice interaction potential is assumed to depend linearly on the
(small) nuclear displacements. It is then linear in a,+ and a, :
%, =
1[A,u, exp(iq
qj
rj)
+ A,*a,+
exp( - iq rj)],
(97)
where rj is the coordinate of the jth electron.

According to simple deformation potential theory, we have54
where El, is the deformation potential attached to band b, p is the density

of the crystal, and oq= c,q (where cd is the longitudinal sound velocity),
is the frequency associated to the longitudinal acoustic mode q. This formula
is useful particularly for nonpolar crystals.
54
C. Kittel, Quantum Theory of Solids. Wiley, New York, 1963.
4.
353
In polar crystals, the electron-phonon interaction results mainly from the

polarization of the lattice produced by the longitudinal optical modes.
It is known from polarm theory that we have in that case54.5s
if the screening of the interaction by the free carriers is not taken into account.
Here ~ ( 0is)the static dielectric constant and it differs by the lattice polarizwhich includes only the contribution of the electronic
ability from &(a)
polarizability. The longitudinal optical phonon energy hwOpis assumed to
be independent of the wave vector.
If the electron-lattice coupling is small, the effect of Xetcan be derived
by using perturbation theory. Let Is) and E(s) [or li) and E(i)] denote an
eigenstate and the corresponding eigenvalue of the unperturbed Hamiltonian
He + He. The perturbed wave function Is) may be written as
It follows that the optical matrix element between states Is) and Is)is given
by
The sums are to be taken over all possible intermediate states for the electrons
and the lattice.
But Ze,
does not affect the lattice and it has finite matrix elements between
unperturbed states which are different in their electronic part only, by a
one electron function (see Section 8). Equation (68) applies : Radiation
induced transitions are vertical, and the specification of the intermediate
states in the sums of Eq. (101) can be restricted to the band index b.
The only nonvanishing matrix elements of Xetare those connecting lattice
states differing by one phonon in a mode, and electronic states which differ
55
H . Frohlich, in Polarons and Excitons (C. G . Kuper and G. D. Whitfield, eds.), p. 1.

354
BRUNO BATZ
by a one-electron wave function. These matrix elements have the form

($%&Is)
= (bk;n, f l[Zetlbk;nq) =
Aq*(nq
+ 1)12 6(k - k + q),
A,n:/26(k - k - q),
( 1 02)
where the 6 functions express the conservation of crystal momentum
(umklappprocesses are disregarded). The two expressions are approximations
which should be quite good for small q, (k k), when b = b. They correspond, respectively, to the emission and the absorption of one phonon in
mode q. The equilibrium value of n,, the number of phonons initially in that
mode, is given by
n,
(103)
[exp(hw,/k,T) - I]-,
where k , is Boltzmanns constant.

A more explicit form of Eq. (101) can now be given. If we consider an
optical transition from a valence state Juk)to a conduction state (ck),we
obtain for the matrix element
(ckIXerI uk)*
=
(ck ;n,lZe,luk ; n,) 6(k - k)
+ c E(ck nq 1) E(bk; n,) 6(k - k f 9)

( c k ; n , k llZerlbk;nq l ) ( b k ; n , f 1(&&k;nq)
+c
E(ok; n,)
E(bk; n, f 1)
(ck ;n,
f lIxeAbk ; a), (bk; n,I*,luk;

;
x 6(k
n )
k f q).
(104)
13. INDIRECT
TRANSITIONS
AND THERMOABSORPTION
The so-called indirect transitions arise from the second and third terms
of Eq. ( l a ) , as the first term, which is identical to the matrix element considered in the treatment without electron-phonon interaction, is related to
vertical transitions only.
The selection rule expressed by Eq. (68) is relaxed for the indirect transitions: the momentum of the absorbed or the emitted phonon provides the
needed change in the electrons momentum. These indirect transitions affect
optical spectra when they do not compete with the more probable direct
transitions. This situation occurs, for instance, at the fundamental absorption
edge of some indirect gap semiconductors such as germanium and silicon
in which the minimum E,, of the conduction band situated at k, in reciprocal
space does not fall on the same point that the maximum E,, of the valence
band which is located at k,. A term with a small denominator in the sums
4.
355
FIG.8. Schematic energy diagram indicating an indirect transition from a valence band state
of wave vector k to a conduction band state of wave vector k with an intermediate state of
wave vector k in band b. A phonon of wave vector q is absorbed or emitted in the process.
of Eq. (104)will usually predominate. It is thus the vertical optical transition

of energy closest to the band gap which is determining, although energy is
not required to be conserved in the intermediate state.
Let us consider the case illustrated in Fig. 8. The state Ibk) is the important
intermediate state. The maximum of the valence band lies at the center of
the zone, and k k, = 0. We also have k' k,
-tq. The matrix elements
for optical transitions between states in the neighborhood of the band
extrema are approximately constant and equal to
- -
where E,, - Eb, in the denominator is an approximation for Ec(k') - EJk)
-t hwkc, the phonon energy hwkcbeing assumed t o be small with respect to
E,, - Eb0.If the transitions to the intermediate states at k = 0 are allowed,

( c I ~ ~ , ~isv independent
)
of the particular transition, from the valence to the
conduction band, which is considered. The probability for such a transition
to take place in the unit of time, a photon of energy hw being absorbed in
the process, is given by
356
BRUNO BAT2
where the 6 function expresses energy conservation. The absorption coefficient

can be deduced by a procedure similar to the one followed in Section 8 in
connection with Eq. (64). We have
K*(ho)
1 6[Ec(k)- E,(k) - hw f hwkc].
(l/hw)I(cIKrIu)*12
tt
(107)
The densities of states in the bands, for each spin, are given by
[Ec(k)- Eco]1/2=
2mc)3/26112, (108a)
4n2 h2
(108b)
for parabolic bands. These are similar to the results given by Table I for
M , and M, critical points. The rn, and rn, are the effective masses in the
conduction and valence bands, respectively, and
is the electron energy in the conduction band, measured from the bottom
of the band.
In Eq. (107), the sum is taken over all possible pairs of states separated
in energy by E,(k) - Ev(k) = ho f hoke, and its dependence upon photon
energy is readily obtained. We find
n
h%c - E,),
8
where E, = E,, - E,, is the energy gap.
According to Eqs. (102),(105), (107), and (1 lo), we finally obtain52*56-58
= -(Am f
K(hw) = 0,
Aw
< E,
hok,
(1 1 la)
J. Bardeen, F. J. Blatt, and L. H. Hall, in Photoconductivity Conference (Proc. Atlantic City

Conf.) (R. G . Breckenridge, B. R. Russell, and E. E. Hahn, eds.) p. 146. Wiley, New York and
Chapman & Hall, London, 1956.
57 H. Y . Fan, Rep. Progr. Phys. 19, 107 (1956).
5 8 H. Y. Fan, in Handbuch der Physik (S. Flugge, ed.), Vol. XXV/2a, p. 157. Springer-Verlag,
Berlin. 1967.
56
4.
357
+hqc-
C
K(ho) = -(ho
ho
Eg)2nk,,
E, - h q c < h o < E,
+
(Illb)
where C is a constant. Equation (Illb) applies in the photon energy range

in which transitions are possible only when a phonon is absorbed. At higher
photon energies a phonon can also be emitted and the absorption coefficient
becomes
C
K ( h o ) = -[(ho
ho
hmk,
E,)nkc
+ (ho - hot, -
+ I)],
E,)(nk=
ho > E,
+ AmkE.
(lllc)
Here K ( h o ) is mainly sensitive to temperature through nk,, the number of

phonons of wave vector k,, which has a temperature dependence given by
Eq. (103). The change AK in K arising from a temperature change AT is
given by
AKlAT
AKIAT
= K(nkc
(112a)
h o < E, - hWkF,
0,
E, + 1)(hokc/kBT2),
hakc
< hw < E,
+bkF.
(112b)
If the two first terms in Eq. (32) are neglected, it is seen that the modulated
transmission experiments yield AK directly. It is however of greater significance to compute A(ln K). Indeed, according to Berglund, we have :
(113a)
A(ln K)
-AT
(nk,
( h o - hWk, - Eg)
+ I)[ + 2[(hw - E,)Z + (hok,)21nk,

h a > E,
+ hWkc.
(11 3 ~ )
These equations show that the measured value ofA(1n K)/AT versus photon
energy ho should increase abruptly at ho = E, - hwkc from zero at lower
energies to a constant between E, - h o k c and E, h w k , where Eq. (113b)
holds. At higher energies, this function should decrease as described by
Eq. (113c). The energy gap E,, as well as the energy of the phonons implied
358
BRUNO BAT2
in the transitions, should then be easily deduced from the position and
extension in energy of the flat part of the experimental curve.
Phonons of more than one type could take a part in the optical absorption
process and they could be included in the treatment with the consequence
of introducing corresponding thresholds at the adequate energies. However,
the experimental results discussed in Section 17 are in quite good agreement
with the simpler theory.
Phonon-assisted transitions can also take place in direct-gap semiconductors. Only optical phonons must be considered because the energies of
the acoustic phonons are negligible at the small wave vectors implied in this
case. Equations (113a) and (113b) still apply at photon energies lower than
the band gap energy. When the photons energy is increased to a value equal
to, or higher than that of the gap, the direct transitions become the most
important mechanism of optical absorption, and they also have a determining
effect on the temperature modulated transmittance through the temperature
modulation of the band gap as discussed in the preceding sections.
One may hope to observe some effects involving phonons in transitions
to higher bands by making thermoreflectance experiments. Although this
is not impossible as the phonons concentrations are sensitive to temperature,
the spectral structures arising from such effects should be small compared
with those resulting from the singular character of the joint density-of-states
function at critical points.
14. BANDSHIFTAND BROADENING
WITH TEMPERATURE
It appears from Eq. (38) that one should be aware of the parts taken,
respectively, by dE,/dT and dT/dT in the temperature modulated reflectance
in view of the interpretation of the spectra. Electron-phonon scattering
probably brings the most important contributions to both quantities, but
there is no general rule which settles their relative magnitude.
Several scattering processes are responsible for the lifetime broadening
of the bands energy levels by producing transitions among the states.
Electron interaction with the impurities or lattice defects may be important
at low temperature. But even then, they can be disregarded if very pure and
perfect samples are used. Recombination by spontaneous emission of photons
usually leads to comparatively long lifetimes. Impact ionization (the transfer
of the energy of an excited electron-hole pair to another electron in the
valence band) may be an efficient process at high energy leading to short
lifetime. We shall nevertheless focus our attention on electron-phonon
interaction because it often has the decisive effect in determining the lifetime,
and also because we are concerned not only with the absolute broadening,
but mainly with its temperature dependence which is presumably important
in the case of phonon scattering.
4.
359
The half-width Ts of a state Is) is related to the electron transition rate P,

from this state to all possible states li) by the relation Ts = i h P s . We thus
have
and
rs= z C I(ii;llu,cls)12 d[E(s) - E(i)].
(115)
If the initial and the final states in an optical transition have half widths
and r c k , the broadening parameter which we introduced previously is
equal to58*58a = ITvk- Tck,J.
In what follows, we shall only consider
the broadening of a level in a conduction band as the treatment is similar
for a valence band. Neglecting transitions between bands, we can write,
according to Eqs. (115) and (102)
rvk
r k =
+ l)d(&k
- f&, +
lAk-kr12{(nk-k
k
+nk-kfd(&k
- &k
hwk-k,)
( 1 16)
hok-k.)},
where we have dropped the band index and 4,the energy with respect to
the band minimum, has already been defined by Eq. (109).
The temperature shift of an electronic energy band in a crystal is also
a consequence of lattice vibrations. Part of the shift results from thermal
expansion, but of usually more significance is the part due to the self-energy
of the electron interacting with the phonon field. The state of things is
similar t o that of the interaction of an electron with the electromagnetic
field, which is known to modify the electrons energy by an imaginary
damping term and a self-energy term.59
Using Eq. (100) we can find how the electrons energy is modified by the
scattering. We have
The shift in energy is brought in by the last term, the electron self-energy
dE,. It can be seen that 6 E , and Tsare related by
6 ~ +, ir, = lim
o-+o
59
R. Brout, Phys. Rev. 107,664 (1957).
I(iIxeeIs>12
C E(s)
E(i)
-
ia
W. Heitler. The Quantum Theory of Radiation. Oxford Univ. Press, London and New
York, 1954.
360
BRUNO BATZ
as a consequence of the &function representation
With the help of Eq. (102), the self-energy term takes the more explicit form
Unfortunately, the band shift and broadening have been studied in

connection with phenomena where only the levels near the top of the valence
band and near the bottom of the conduction band are implied. Little is
known about the state of things at the levels deeper in the bands, which are
generally involved in the optical modulation studies.
The absorption limit in many insulating crystals is displaced to longer
wavelengths with increasing temperature. The corresponding narrowing of
the band gap cannot be accounted for by the too small effect of thermal
expansion. Radkowski6' has attempted to explain the phenomenon by the
reduction of the gap which would result from the broadening of the levels
near the band extrema due to electron-phonon scattering. His calculations
lead to a correct order of magnitude in the case of polar crystals, but to very
small effects for nonpolar crystals. Fan57*58*61
ha s demonstrated that the
electron-lattice interaction energy in both polar and nonpolar crystals implies
a shift of the band extrema of the proper magnitude and temperature dependence. He pointed out that the broadening should affect the shape rather
than the position of the absorption edge. A similar treatment has been
carried out by Muto and Oyama62and Cohen62ahas considered the case of
many-valley semiconductors.
The temperature coefficient of the energy gap can be written asz
at constant pressure, where f? is the coefficient of thermal expansion. The

last term, which depends on the difference of the deformation potentials of
the bands, gives the contribution of lattice dilatation.
In the case of electron scattering by longitudinal acoustic phonons rck
and 6Eck may be computed quite easily at the minimum of the conduction
'"A. Radkowski, Phys. Rev. 73, 749 (1 948).

'' H. Y.Fan, Phys. Rev. 82, 900 (1951).
'*
T. Muto and S. Oyama. Progr. Theor. Phys. 5 . 833 (1950).

6ZsM.L. Cohen, Phys. Rev. 128,131 (1962).
4.
361
band at temperatures for which k,T>> hw,. Equation (103) takes the
approximate form
n,
- k,T/hw,
kBT/hC,q >> 1
(122)
if the dispersion law wq = c,q is assumed, and nk-k, can be substituted without much error for ( n k - k , + 1) in Eqs. ( 1 16)and (120).It appears from Eq. (98)
that the product JA,I2n, = E:,k,T/2clZp is then independent of the phonon
wave vector q. At the bottom of the band 8 k = 0, and we must retain only
the term of Eq. ( 1 16) corresponding to phonon absorption. It follows that
where g , ( 2 r n , ~ , ~is) the density of states in the band at energy 2rncc;. It is in

a state of this energy that an electron initially in the lowest state of the
conduction band is scattered if it absorbs a phonon ; that is
It follows from Eq. (108a) that g , ( 2 r n , ~ , ~=

) rnc2c,/n2h3,and we finally obtain
r,, = E~,rnczk,T/2nk3c,p.
(125)
An electronic transition can take place with the absorption or the emission
of a phonon from a state of energy d larger than 2rn,csZ. The phonon wave
vectors involved in the transitions are small, and so are the phonon energies,
which become negligible with respect to the electron energies when
6 >> 2rn,c;. This restriction is not too compelling since 2m,ccZis a very small
energy. The two terms in Eq. (1 16) give almost equal contributions so that
rck =
2n
(Ak-kr(Znk-r
6(dk - 8 k )
Ifthephononenergyis also disregarded in Eq. (120),the following dispersion

relation connecting 6 E to applies.
~ ~ (=8( I1/ ~ ) Pr(gy(8- 8)d b .
(1 27)
362
BRUNO BATZ
At the bottom of the band, the shift is given by
where q,, which is the maximum magnitude of the phonon wave vector, is
also the maximum value that k can take. This expression is equivalent to
the temperature-dependent part of Fans r e s ~ l t . ~ The
~ * conduction
~ * ~ ~ ~
band is seen to be shifted downward and a similar treatment shows that
the top of the valence band is shifted upward. The energy gap thus decreases
with increasing temperature.
The ratio of the temperature coefficients of T o and hE,, is
where Aw, is the maximum phonon energy. This ratio is a rather small
quantity, much smaller than one. The formulas are somewhat different
at temperatures lower than the Debye temperature, but a general conclusion
is that in nonpolar crystals temperature modulated optical effects near the
absorption edge which do not involve indirect transitions should be explicable on the basis of the temperature shift of the energy gap only.
The broadening arising from the scattering of electrons by the optical
phonons may be computed with the use of Eqs. (99) and (116). Transitions
from the bottom of the conduction band involve only processes in which
phonons are absorbed. We can write
where no, is the concentration of the optical phonons in each mode. As
c,,k-
6(hWop - 8kk.) = (ii/2m,W0,)g,(hC00,)
(1/47L2)(2m,/h2)2(hC00p)-12
one obtains6
2mc
Tco= - e2(hwo,)2
2
A similar expression with m, replacing rn, applies at the top of the valence
band. The calculation of the energy shift is somewhat longer but it leads
essentially to the same formula with (nop 1) in place of n0p57958.61
(with a
change of sign when a conduction band is considered), and the temperature
coefficients of Tcoand -6E,, (or of r,, and 6Evo)are equal. The quantities
dT/dT = IdTvJdT - dT,JdT( and -dE,/dT = IdEvJdTI IdE,JdT(,which
4.
363
appear in Eq. (38), may thus be expected to be comparable in the case of

optical phonon scattering. In polar crystals these temperature coefficients
may be relatively large, of the order of
eVPK. But even in compound
semiconductors the effects of polar modes may be important and should not
be overlooked.
As noted by Fan,58 an important difference between the calculations of
rband 6 E , is that the former involves real transitions in which wave vector
as well as energy are conserved, while the second deals with virtual transitions
for which only wave vector conservation is required. The wave vectors of
the phonons concerned by real transitions taking place near the bottom of
the band are restricted to small values because of the conservation of both
wave vector and energy. This is not true for virtual transitions, and since the
matrix element for acoustic phonon scattering is precisely proportional to
the phonon wave vector, one may indeed expect the shift to be much larger
than the broadening in this case. The matrix element in the case of polar
mode interaction is inversely proportional to the phonon wave vector : the
scattering by optical phonons of large wave vectors is less effective and r b
and 6 E , are thus found to have very close values.
The state of things at an internal band edge is much more intricate. McLean
and Paige63r64have already pointed out that the deeper a level lies within
a band, the broader it is at all temperatures simply from the availability of
final states. Real transitions involving acoustic modes are no longer restricted
to small values of momentum transfer because electronic states may be
present at the required energies and momenta, and these states are likely
to occur in greater number in the depths of the band. Near a saddle point
of the band structure for instance, the transitions are not assigned to take
place in a small region of reciprocal space. If the phonon energy is neglected,
the third form in Eq. (126) holds, that is, the broadening of a level is proportional t o the density of states g a t the energy of the level. The forms taken
by the functions g at the singularities of the band are similar to those given
in Table I, and the associated shifts could be deduced with Eq. (127). But it
is the density of states for the whole zone that should be used rather than
the local density of states related to the singularity.
Langreth,65 using Green's function methods, has investigated the effects
of phonons on optical transitions near critical points in the band structure
of insulators or semiconductors, in view of checking whether or not the
phonons introduce a structure of their own. Assuming an electron-phonon
coupling parameter independent of wave vector, he finds that, except when
b3
64
65
T. P. McLean and E. G. S. Paige, J . Phys. Chem. Solids 23,822 (1962).

T. P. McLean and E. G .S. Paige, Proc. I n f . Con$ Phys. Semicond., Exeter, 1962, p. 450. Inst. of
Phys. and Phys. SOC., London, 1962.
D. C . Langreth, Phys. Rev. 148, 712 (1966).
364
BRUNO BAT2
the critical point is near threshold, the phonons only give rise to Lorentzian
broadening, a conclusion which justifies the substitution (89) and the
treatment of Section 11.
Although the problem of evaluating the relative importance of r and
6 E has not yet received a clear theoretical answer for critical points above
threshold, it is known experimentally that the temperature coefficients of
the interband energies at critical points of most semiconductors are of the
order of -4.10-3 eV/K.5346The temperature coefficients ofthe broadening
parameters likewise could probably be deduced from (modulated optical)
experiments performed at several temperatures, thus placing the interpretation of thermoreflectance spectra on firmer grounds.
In Parts 111 and IV, the interband broadening parameter has been assumed
to be independent of energy. A look at Eq. (126) shows however that Tck
depends strongly on energy. We find for instance from Eqs. (125) and (126)
that
( 1 32)
rcJrco= UJCG
where uk is the velocity of the electron with wave vector k near the bottom
of the conduction band. This ratio is large for values of k at which Eq. (126)
applies. The broadening of the states in the neighborhood of an internal
band singularity may be expected to vary in a relatively slow manner with
respect to the electrons energy, and it should not be a bad approximation
in that case to assume r independent of energy when studying thermal
reflectance effects.
In the case ofwavelength modulation the neglect of the energy dependence
of the broadening may be of greater significance. Actually, the modulation
of the dielectric constant as it is expressed by Eq. (41) is an approximation
for
9
At
= $bT-{[F(-x)
+ iF(x)]dr/d(hw)+ [ F ( x ) - i F ( - x ) ] } A(hw)
(133)
in whichdT/d(ho) has been taken equal to zero :This procedureis questionable

because the derivative with respect to energy of the broadening may possibly
be very large near a band singularity. We have already noted that for acoustic
phonon scattering, the broadening of a level is proportional to the density
of states g at the levels energy, for vanishing phonon energy [Eq. (126)], and
we know that the derivative ofg, and therefore the derivative of the broadening
also, has an infinite discontinuity at a band singularity. This kind of treatment
is of course oversimplified : at a saddle point in the band structure especially
where the electronic transitions may involve phonons of large wave vector
and energy, the neglect of the phonon energy may be of consequence. Even
at the minimum of the band it would lead, for instance, to an infinite ratio
rc,Jrco
in Eq. (132). But the argument suggests nevertheless that should
not necessarily be assumed independent of hw.
4.
365
VI. The Electron-Hole Interaction

15. EXCITONEFFECTSAT
THE
FUNDAMENTAL
ABSORPTION
EDGE
The optical absorption near the fundamental absorption edge of insulating

or semiconducting crystals, as modified by the Coulomb attraction between
the electron and the hole created in the process, has been carefully studied
by E l l i ~ t t . On
~ . ~account
~
of the interaction, the electron-hole pair may
be formed in a bound hydrogen-like state with smaller energy than that of
a free pair. Although the term exciton is generally used to designate such
a bound pair, exciton effects refer in a less restrictive manner to all the
implications of the interaction.
Weakly bound excitons, which were first discussed by Wannier? are
conveniently studied within the effective mass approximation. In order to
lend some support to the phenomenological treatment of Section 7, we shall
examine here the simple case of direct excitons, confining ourself to standard
energy bands. More elaborate accounts on the exciton problem will be
found in several very good review a r t i ~ l e s . ~ * ~ ~ , ~ ~ - ~ ~
An excited state 1 of the crystal should be adequately described by a
wave function Ql of the form given by Eq. (61). The coefficients Cck,vk are
determined by the interactions not included in the one-electron approximation. The optical matrix element
is thus a linear combination of matrix elements involving determinant wave

functions, identical to those introduced in Sections 8 and 9. Using the results
and the notations of these sections, without forgetting the selection rule
k = k (direct transitions), the matrix element becomes
and the imaginary dielectric constant is given by [see Eq. (71)]
66
R.J. Elliott,
Phys. Rev. 108, 1384 (1957).
G. Wannier, Phys. Rev. 52, 191 (1937).

6 8 S. Nikitine.Progr. Semicond. 6, 233 (1962).
R. S. Knox, SolidState Phys. Suppl. 5 (1963).
O J. 0. Dimmock, in Semiconductors and Semimetals (R.K. Willardson and A. C. Beer,
eds.), Vol. 3, p. 259. Academic Press, New York, 1967.
366
BRUNO BATZ
where El is the energy of the excited state 1. The wave function corresponding
to this state can be written
@I =
ci@)yck,vk
k
11 Fj(R,) exp( - ik
N-
R,)
yck,vk
( 136)
where
F,(R,) = N -
cC,(k) exp(ik R,)

k
(137)
is the Fourier transform of C,(k).

Let us consider the weakly bound exciton in the case of simple energy
bands with effective masses mvand m,. In the effective mass approximation,
the envelope function F(R),with R,the electron-hole separation, regarded
as a continuous variable, is a solution of the hydrogen-like Schrodinger
equation,
h2
2m,
e 2 R)F(R) = EF(R).
4xs(O)
--V2--
The electron-hole interaction potential - e2/4m(0)Ris a Coulomb potential

) the solid; E , is the direct
screened by the static dielectric constant ~ ( 0of
energy gap and rn, is the redwed mass: rnr- = rn;
m,- .
The eigenvalues of Eq. (138) yield the exciton levels which form a hydrogenic series
E , = - R,,/n2
(139)
where the exciton rydberg Rex,the energy needed to separate the electron
from the hole in the ground state n = 1, is related to the hydrogen rydberg
by: Rex = R,(mr/m)e(0)-2,rn being the free electron mass.
We have seen in Section 9 that when the transitions are allowed in the
range of k of interest, the matrix element (ckla * p(vk) is approximately a
constant: (c(a plv). It follows that
A =
1C*(k)(ck(a - plvk)
k
- N/2(cla - plv)F*(O)
( 1 40)
according to Eq. (137). But F(0) is nonzero only for s states; then
I F ( O ) I=~ i/na*3n3,
(141)
where a* is the effective Bohr radius. A series of absorption lines are therefore
to be expected at energies hw = E , - R,Jn2 with intensities decreasing as
n-3. These lines will overlap and form a quasi-continuum at the upper values
of n. Because the density of states increases as n3 in this model, the resulting
absorption coefficient is independent of energy. In the true continuum, at
energies higher than E,, it results from Eqs. (135)and (140) that the absorp-
4.
367
tion coefficient K(hw) = EZw/ncis equal to its valuesK,(ho) without electronhole interaction multiplied by IF(O)l*. More explicitly, it is found that66
K(hw) = Ko(hw)lF(0)12= K,(hw)nae""/sinh(m),
where
L7 =
[R,,/(ho -
E0)]1'2.
(143)
The behavior of K in the case of allowed transitions is shown in Fig. 9(a).

The continuous absorption comes in abruptly, as it was assumed in the simple
model of the absorption edge introduced in Section 7, and the finite value
at which K starts at ho = E , can be shown to be equal to the constant
absorption coefficient arising from the quasi-continuum just below the
band edge.
Equation (140) is not applicable if the transition is forbidden at the band
extrema. It is found in this case that the nonzero optical matrix elements
correspond to p-like envelope functions. The exciton lines occur again at
energies hw = E , - R,,/n2 but the first line n = 1 is now missing and the
intensities are proportional to (n' - l)/n5. In the continuum, the absorption
coefficient has the form66
K(hw) = K,(ho)ncr( 1 c?)e""/sinh(lccr).
(144)
These results are represented in Fig. 9(b).
The consequences of exciton-phonon interaction on the optical properties
are similar to those described in Sections 13 and 14 where the electron-hole
attraction was not taken into account : indirect transitions become possible
and the spectral structures may be broadened and shifted, all these effects
being temperature dependent.
A perturbation calculation of the indirect exciton absorption COcan be performed by generalizing the argument of Section 13.
The computation is complicated, however, and the reader is referred to the
original articles for the details. As the selection rule k' = k, which leads to
discrete lines in the case of direct transitions, is relaxed, and as no specific
value is assigned to k' - k, bound exciton bands result which give rise to
continuous absorption. But the contribution to the absorption coefficient of
each bound exciton band is made up of several components, two for each
phonon branch, with thresholds corresponding, respectively, to phonon
emission and absorption. The functional energy dependence of the components is modified when dissociated excitons are created in the absorption
process, but the general behavior is otherwise essentially the same. Steps
in the absorption curve may be expected to occur at the threshold energies.
It is interesting to note that all the components associated with phonon
emission on the one hand and with phonon absorption on the other hand
have, respectively, the same form of temperature dependence [see Eqs. (1 1 1 I]
368
BRUNO BATZ
-R
2R
3R
4R
FIG. 9. Direct absorption near the fundamental edge in the one-electron approximation
(broken line) and with electron-hole Coulomb interaction (solid line). (a) The transitions are
allowed; only the lines n = 1 and 2 are shown. (b) The transitions are forbidden; only the lines
n = 2 and 3 are shown. (After Elliott.)
whether the electron-hole interaction is neglected or not. The treatment of

Section 13 can therefore easily be generalized to analyze the contribution
of each exciton band to a thermoabsorption spectrum.
The broadening and shift of exciton absorption lines has been investigated
by T o y ~ z a w a ~who
~ - has
~ ~ given a general theory of the line shapes in
which the exciton-phonon coupling is exactly taken into account. When
the mutual influence of the other absorption peaks (interband effect) is
neglected, the line shape of a peak is Lorentzian in the case of weak coupling,
and the spectral line shapes obtained by thermal modulation are given by
Eqs. (53). The interband effect modifies the shape into an asymmetric Lorentzian line such that
B a (1 - A)/[@, - ho)- ir]
(145)
instead of Eq. (51).The asymmetry parameter A in this expression is temperature dependent as are E , and ; this should be remembered when analyzing
the results of temperature-modulated optical experiments.
16. EXCITON
EFFECTS
ABOVE THE FUNDAMENTAL
ABSORPTION
EDGE
A look at Fig. 9 shows that the optical properties of a semiconductor are
deeply affected near the fundamental edge by the electron-hole Coulomb
attraction, and it can be inferred that the one-electron approximation will
probably be unsatisfactory in accounting for the state of things at the higher
edges. But the inclusion of the interaction is much more difficult to handle
theoretically in this case, owing to the specific character of the saddle point
singularities and to the interference between the discrete and the continuous
Y. Toyozawa, Progr. Theor. Phys. 20, 53 (1958).
73
Y. Toyozawa, J . Phys. Chem. Solids 25, 59 (1964).
Y. Toyozawa, Progr. Theor. Phys. 27,89 (1962).
4. THERMAL
AND WAVELENGTH MODULATION SPECTROSCOPY
369
states, the first being embedded in the second. Phillips4774has assumed the
existence of metastable excitons at the saddle-point edges, an opinion which
has beencontroverted.75~76T~y~zawaet
u1.18977-81
h ave derived a line-shape
expression in which the local and band characters coexist, that is, the metastable exciton and the Van Hove singularities. Velicky and Sak82 have
obtained similar results.
As a consequence of their basic simplicity, which allows a straightforward
interpretation, thermal and wavelength reflectance modulation techniques
should become an efficient tool for the experimental investigation of these
problem^.'^.^^ It may thus be useful to give here a view of the modifications
arising from the electron-hole interaction to be expected in the optical
spectra. We shall follow very closely, for this purpose, the enlightening
article by Toyozawa et a1.*
A Bloch function is related to the Wannier functions67by the transformationS2
Ybk(r) = N ub(r - R,) exp(ik R,),
( 146)
where ub(r - R,) is the Wannier function localized at the lattice point R,.
Inserting this expansion in the expression of the optical matrix element
given by Eq. (134), we obtain successively
Al = N -
=
k jm
C,*(k)exp[ - ik(Rj - R,)]
1c C,*(k)exp( - ik - R,)
k
= N
= NI2
c (Iln)(rtlp)
uc*(r - R,)a pu,(r - R,) dr
u,*(r - R,)a pu,(r) dr
1F,*(R,) juc*(r - R,)a

n
pa,(r) dr
= N2(/l~),
(147)
fl
J. C. Phillips, in The Optical Properties of Solids (Proc. Int. School Phys. Enrico Fermi,
Varenna, Italy) (J. Tauc, ed.), p. 155. Academic Press, New York and London, 1966.
7 5 C. B. Duke and B. Segall, Phys. Reu. Lett. 17, 19 (1966).
7 6 J. Hermanson, Phys. Rec. Lett. 18,170 (1967).
Y. Toyozawa, M. Inoue, T. Inui, M. Okasaki, and E. Hanamura. J . Phys. Soc. Jupun 21,208
(1966).
E. Hanamura, M. Okazaki, T. Inui, M . Inoue, and Y . Toyozawa, J . Phys. Soc. Jupan 21.209
( 1966).
7 9 M. Inoue, M. Okasaki, Y. Toyozawa, T. Inui, and E. Hanamura.J. Phys. So(. Jupun 21, 1850
( 1966).
8o Y. Toyozawa, M. Inoue, T . Inui, M. Okazaki, and E. Hanamura, Proc. Int. Cuqf: Phy.r.
Seniicond. Kyoto, 1966 (J. Phys. Soc. Jupun. Suppl.. 21). p. 133. Phys. SUC.Japan, Tokyo,
1966.
M. Okazaki, M. Inoue, Y. Toyozawa, T. 1nui.and E. Hanamura,J. Phys. Soc. Jupun22,1349
(1967).
8 2 B. Velicky and J. Sak, Phys. S/afus So&& 16, 147 ( 1966).
74
BRUNO BAT2
370
where use has been made of Eq. (137) to introduce the envelope function
F,(R,). This function and the last form of the integral appearing in Eq. (147),
which we denote by p,,,are regarded as the nth components of the ket vectors
( I ) and Ip), respectively: F,(R,,)= (nll) and p,, = ( n l p ) , where p,,is a rapidly
decreasing function of R,.
Keeping only the significant terms which determine the line shape, we
obtain, according to Eq. (135), for the imaginary part of the dielectric
constant
( z = hw
where the 6 function representation given by Eq. (119) has been used;
S,
the Hamiltonian for the relative motion of the electron-hole pair (with
k = k'), has eigenvectors I/) and eigenvalues E , . If the electron-hole interaction can be neglected, Eq. (71)applies and E ~ ( A w ) ,which is then proportional
to the joint density-of-states function G(hw), has Van Hove singularities
corresponding to the critical points, as given in Table I.
In view of formulating mathematically the problem of the coexistence of
local and band aspects of the absorption spectra, Toyozawa ef a/. separate
the lattice points into internal points (i) located symmetrically around R, = 0,
and external points (e). The Hamiltonian is likewise decomposed into three
parts :
2
= x(i)
+
x ( e )
+ X'
so
+ S,
(149)
where A"(i)has matrix elements with internal points (n,n') only, S(e)
with
external points only while %'just connects the internal and external points.
The complete orthonormal set of eigenvectors of Xo = Zfi)
+ yPe)are
classified into two categories according as they have amplitude only on the
internal or external points
2ol.)
= #(i)lCt)
Rolk)
= 3yice)lk)=
Emla),
(150a)
E,(k).
( 150b)
The (a)'s represent local solutions while the (k)'s consist of the continuous
pair band modified by the presence of the cavity and possibly by a long
range (Coulomb) potential.
4.
371
lntroducing the identity
and the quantity
we can write (remembering that 2' only connects internal and external
states)
and obtain the simultaneous equations
Because X" only connects internal to external states, we have
Aaaz(hco) iraa,(hco)
(15 5 )
by using Eq. (119); 92 is the shift-broadening matrix of the internal states

resulting from their contact with external states, with Hermitian and antiHermitian parts A and r, respectively given by,
2;k=%?La,n6(hO - Ek).
raa.(hCO)=
(156b)
As $(z) is non-Hermitian, the modified energy matrix for the internal states
are diagonalized by a nonunitary matrix T(z) :
372
BRUNO BATZ
[See the Appendix of Toyozawa for a proof of the nonnegativity of the renormalized broadening T,(hw).] Inserting into Eq. (154), we find
The function pn may be assumed to vanish on the external points as it

decreases rapidly with R,; using Eqs. (153) and (158) we can thus write
where
Inserting Eq. (159) into Eq. (148), the final expression for the line shape is
A number of qualitative inferences can be drawn from the form of this

formula. A term Iz represents an asymmetric Lorentzian peak at energy E,
with intensity Fa,broadening Fa,and asymmetry A,, if the energy dependence
of the renormalized quantities Ed, Fa, Fa, and 2, is neglected, and In) =
Xala)Tu, may in this case be considered as a quasi-local state if Fais sufficiently small. When hw falls outside the pair band continuum Fa and A, vanish,
and the solutions ofhw - E,(ho) = 0 then give the line spectra corresponding
to true bound states.
As for the band character, it is introduced through the broadening function
Taa,(hw)
which, according to Eq. (156b),is proportional to the joint density-ofstates function G(hw).The Van Hove singularities, modified by the transformation (157), will thus appear in the renormalized quantities and also in Eq.
(161), which therefore incorporates the local as well as the band aspect.
The metastable exciton and the Van Hove singularities do not however
coexist independently, but they interfere in an intricate way, affecting the
absorption spectra. As a result of appreciable mixing of internal states
4. THERMAL
373
FIG. 10. Metamorphism of Van Hove singularities. As the electron-hole attractive potential
is applied and increased, the shape of the singularity at a critical point changes clockwise,
starting from its original Van Hove singularity, which is denoted by M,, M I , M , , or M , in
the figure. (After Toyozawa ef a [ . )
through external states, it can happen that FA < 0 near Ro = EAfor certain A
with sufficiently small FA. Then, there is a dip (an antiresonance) instead of
a peak (a resonance) associated t o the quasi-local state. As the line shape is
there are in fact four types of resonances
also affected by the sign of AA,
depending on the combination of signs of and JAFA.
If the interplay of local and band aspects has an influence on the local
states located in the band continuum, the Van Hove singularities likewise
are in a reciprocal manner modified by the local perturbation. The broadening function T,,.(hw) being proportional to G(hw) possesses singularities of
the forms given in Table I, corresponding to the critical points. The shift
function A,,.fRw) defined by Eq. ( I 56a) is connected to T,,,(hw)by a dispersion
on
relation similar t o Eq. (127); as a consequence, a singularity of Aam,(Rw)
one side of Eo corresponds to a singularity of l-,,.(hw) on the other side of the
energy E o of a critical point. The transformation T mixes the shift and broadening parts so that the renormalized quantities, and also the line shape of E~
given by Eq. (161), have singularities on both sides of E o which have the
general form
b-,(Eo - E)2,
E < E,,
b + , ( E - EO),
E > 150, (162)
irrespective of the type of critical point, except at the lowest M o and highest
M 3 points, where the behavior is as given in Table I. There are four types of
374
BRUNO BAT2
singularities according t o the combinations of the signs of b- and b , as

shown in Fig. 10.The special cases b- = 0 and b+ = 0 yield the Van Hove
singularities. As the attractive potential is applied and increased, the metamorphism of the singularity at any critical point proceedsclockwise in Fig. 10,
starting from its original position ; calculations based on simple models of
electron-hole interaction potential^'^.^ 1 * 8 2 show that thecontributionsof M ,
and M I points t o E , are enhanced, giving sharp structures, while the spectral
features associated with M , and M , points are reduced or smeared out. As
can be seen in Fig. 10, an M , point produces a peak and an M , point an
inverted S-like curve when the interaction is switched on.
The metamorphism of the Van Hove singularities should clearly come
out in the modulated reflectance data. The appearance of the line shape in the
neighborhood of the critical point Mi may be expected to be composed of an
admixture of M iand M i + (with M , = M , ) one-electron lifetime broadened
line shapes as they are given in Table I1 and Fig. 7. Such exciton effects have
been invoked by Shaklee et
to interpret experimental spectra in the case
of wavelength-modulated reflectance and by Matatagui et a/. in the case of
temperature-modulated reflectance. The results obtained by both methods
give strong support to the existence of excitons at M , and M , critical points
(see Section 18).
VII. Experimental Results

17. TRANSMITTANCE
DATA
Wavelength modulated transmission experiments on semiconductors
were first performed by B a l ~ l e v to
~study
~ ~ ~the fine structure of the indirect
absorption edge of Ge and Si. These measurements were made at liquid
nitrogen temperature on samples subjected to uniaxial stress in order to
observe the resulting shift and splitting of the band extrema and to determine
the deformation potential of the bands. Our survey is however restricted to
results obtained with unstrained crystals. Other measurements on Si in the
indirect absorption region have been made by Braunstein et
Temperature modulated absorption experiments were first reported by
Berglund* who carefully studied the fundamental edge of Si, GaAs,CdS, and
KTaO, . Similar measurements on Ge made by Batz are also described
below.
a. Germanium
The absorption coefficient corresponding t o the formation of indirect
excitons is made up of several components, two for each type of interacting
phonon (see the end of Section 15). Such a component has an energy depen-

a)
C)
b)
:I
375
d)
fl
1 0 - 1 - 2 3
fiw- E
: r i d * ev)
1 0 - 1 3
1 0 - 1
1 0 - 1
FIG. 1 1 . Wavelength modulated transmission spectra of Ge at 80K with E , + = 0.761 eV.

Stress is parallel to the [ l l 11 direction and sample thickness d = 2 mm. (a) 0 kgm/cm2. (b)
681 kgm/cm2. (c) 925 kgm/cmz. (d) 1540 kgm/cmz. (After B a l ~ l e v . ~ ~ )
dence of the form*66
above the threshold ET = E , - (ReX/n2)F ho,,in the allowed case and for
the production of bound excitons, whereas a 312 power law and a threshold at
E , ho, apply for unbound excitons. The wavelength modulated transmission spectra shown in Fig. 11 were obtained by B a l ~ l e with
v ~ ~a vibrating
slit technique at 80K. The derivative of the intensity ofthe light falling on the
detector is plotted versus photon energy; it is in this case essentially proportional to e-ICdd K / d l , if d is the samples thickness and I the wavelength.
The spectra were recorded near the 0.761-eV threshold from emission of a
L A phonon. In the first spectrum of Fig. 1 1 which corresponds to an unstrained crystal, the high peak is due to the broadened - 1/2 power function
[the derivative of Eq. (163)]. The additional structures on the high energy side
ofthe main peak indicates allowed transitions with thresholds associated with
the emission of TA and TO phonons. The other spectra shown in Fig. 1 1 are
related t o strained crystals ;the splitting of the peak is interpreted in terms of
the changes in the band structure with strain.
376
BRUNO BATZ
FIG. 12. Temperature-modulated absorption spectrum of Ge at 300K in the vicinity of the

indirect absorption edge for A(ln K)/AT. (After Batz.)
Thermoabsorption in Ge has been studied in regions of the direct and

indirect absorption edges at room temperature. A sharp negative peak
appears in the spectrum of AKlAT at the direct gap energy (0.80 eV), as is
expected for a steep broadened absorption edge displaced rigidly with
temperature (see Section 7). Measurements on thin samples (20p) have
revealed a small additional peak near 1 eV which is believed to be due to the
onset of transitions from the lower valence band, but shifted in energy as a
consequence of instrumental inadequacy in this region of very high absorption constant ;the use of still thinner samples, of the order of a few microns,
should be advantageous.
Because the values of AK/AT and those of K (which were obtained from
McLean), used to compute A(ln K)/AT near the indirect energy gap, were
measured neither simultaneously nor at the same temperature, the results
given in Fig. 12 should not be taken too literally. Nevertheless, a flat
portion appears in the curve, extending from 0.632 to 0.690 eV. According to
Berglunds analysis [see Section 13 and Eqs. (11311 it should cover an energy
interval (centered on E , = 0.661)corresponding to the absorption and emission of phonons. The LA phonons involved here should thus have an energy
of 29 meV, in fair agreement with other estimates.
b. Silicon
The wavelength modulated transmission spectrum for unstrained Si

obtained by BalslevZ9is shown in Fig. 13. It was recorded around the energy
threshold at 1.210 eV specified by the emission of a TO phonon. The interpretation of the sharp peak is similar to that given in the case of Ge. For
higher photon energies the 312 power absorption shows up in d l / d l as a
4. THERMAL AND
377
- 1 - 2 - 3
h w - E L * 1 1 0 - 2 eV)
FIG. 13. Wavelength-modulated transmission spectrum of unstrained Si at 80 K with E , + =

1.210eV and d = 1.5 mm. (After Balslev.2y)
square root curve reduced by the factor exp( - K d ) , with a threshold about
10 meV above the exciton ground state level, in accordance with McLean.'
Braunstein et
have also used wavelength modulation to investigate
phonon-assisted indirect transitions in Si. They identified the bumps in their
spectrum of (AI/Av)/I, shown in Fig. 14, as arising from transitions assisted
by TO, TA, and TO 0 phonons.
The spectrum of dK/dTobtained at room temperature by thermal modulation by Berglund*2near the indirect absorption edge is shown in Fig. 15 with
the d(ln K ) / d T curve. The behavior of d(ln K)/dT is as expected from Eqs.
(113). It is verified that the transitions involve optical phonons of approximately 60 meV, and the room temperature gap is 1.11 eV wide. The peak
appearing at 1.17 eV is attributed to another temperature-dependent contribution to K.
c. Gallium Arsenide
The spectra of d K / d T and of d(ln K ) / d T have been determined by Berglund

at room temperature near the band edge. Both curves appear as asymmetrical
peaks with maxima between 1.370 and 1.375 eV. The general behavior is as
378
BRUNO BATZ
Energy (eV)
FIG. 14. Wavelength-modulated transmission spectrum of Si near the indirect absorption

edge. (After Braunstein er
-.
I
I
I
Photon Energy (eV)
FIG. 15. The spectrum of d K / d T and d(ln K ) / d T for Si near the band edge at 300K. (After
Berglund.)
4. THERMAL
379
Photon Energy (eV)

(a)
0 228
230
232
234
236
238
240
Photon Energy (eV)
(b)
FIG. 16. (a) d K / d T and d(ln K)/dT for CdS near the band edge at 300"K, light polarized
perpendicular to the c-axis. (b) d K / d T and d(ln K ) / d T for CdS near the band edge at 300"K,
light polarized parallel to the c-axis. (After Berglund.")
expected from a direct gap semiconductor but the involved temperaturedependent effects determining the details of the line shapes are probably
complex.
d. Cadmium Sulfide
Figure 16 shows the spectra ofdK/dTand d(ln K)/dTobserved by Berglund
for light polarized perpendicular and parallel to the c-axis. The results are
interpreted in terms of phonon-assisted transitions to direct excitons states,
using Eq. (113b).
380
BRUNO BAT2
For light polarized perpendicular to the c-axis, the only important exciton
is associated with the upper valence band and the extension and location of
the flat part of the d(ln K)/dTcurve is assumed to correspond to the energy of
a LO phonon (35meV as measured here) under the exciton band energy. The
light polarized parallel to the c-axis couples strongly with the exciton associated with the second valence band. A spectrum similar to that obtained with
the perpendicular polarization, but shifted in energy by the separation of the
two upper valence bands (16 meV) results. An additional structure due to
interband scattering between exciton bands appears at the low energy
threshold observed for perpendicular polarization.
e. Potassium Tantalate
Berglund has measured dKfdT and d(ln K)/dT at room temperature near
the absorption edge. The d(ln K)/dT curve seems to be flat on its low energy
side although it was not possible to complete it to the threshold because the
very small absorption coefficient of KTaO, prevented the measurements
from being made at lower energies. Nevertheless, the available data suggest
that KTaO, has an indirect energy gap of 3.45eV at room temperature if an
energy of 0.1 1 eV is assumed for the interacting phonon.
18. REFLECTANCE
DATA
Thermoreflectance measurements on nonmetallic solids have been made by
Batz 1.19.39 on Ge at several temperatures, by Lange and Henrion4 on CdS
and Seat room temperature, by Balzarotti and Grandolfo on graphite4 and
Si,24also at room temperature, and more recently on 17 semiconductors by
Matatagui eta[. In this important work the thermoreflectance spectra of Si,
AISb, Gap, GaAs, GaSb, InP, InAs, InSb, ZnO, ZnS, ZnSe,ZnTe,CdS, CdSe,
CdTe, HgSe, and HgTe obtained at both liquid nitrogen and room temperatures are reported. Current modulated magnetoreflectance experiments have
been performed by Feinleib et al.?, and have been reviewed in Chapter 2 of
this volume by Aggarwal.
Our aim is not to discuss the details of the band structures of the semiconductors mentioned above, but rather to demonstrate the power of thermoreflectance as a tool for energy-band studies and to indicate the kind of
information that it is able to give. We shall thus focus our attention particularly on the data that have been analyzed in view of their comparison with
theoretical line shapes. These concern Ge, Si, InSb, CdTe, and graphite. The
spectra ofInPand CdS aregiven as additional examples. The reader interested
in the other thermoreflectance data and in a more comprehensive discussion
is referred to the original articles. The locations of the spectral features in the
thermoreflectance spectra are in general agreement with those occurring in
electroreflectance spectra.22
4.
381
FIG. 17. Thermoreflectance spectra of Ge at 120K (dashed line) and 400K (solid line).
(After bat^.^')
Available wavelength-modulated reflectance data are less numerous.

Experiments on several semiconductors (CdS, ZnS,35and Ge, GaAs, InSb,
HgTe36)have been performed, but only the results concerning InSb, obtained
by Shaklee et ~ 1at liquid
. ~ nitrogen
~
temperature, or quoted from Shaklees
thesis, have been published.
a. Germanium
Thermoreflectance spectra of G e obtained at approximately 120K and

400 K are shown in Fig. 17.39 The El and El + A 1 doublet near 2.2eV
appears clearly ;the corresponding theoretical line shapes shown in Fig. 18

have been computed, using Eq. (25) with constant and equal fractional
382
BRUNO BAT2
n,
U
a
I
1
I/
2.5
(a)
(C)
FIG. 18. Thermoreflectance line shapes for the A3-A, transitions in G e calculated on the
hasis ofa thermal modulation of the gap for three values of the Lorentzian broadening parameter:
(a) r = 0.025 e V ; (b) r = 0.033 eV; (c) = 0.050 eV. (After bat^.^^)
coefficients CI and 8,45in an attempt to reproduce the experimental structure.

It was also assumed that the effects arise mainly from the variation with
temperature of the interband energies at the critical points, although, as
can be seen in Fig. 17, the broadening of the structures is also temperature
dependent. The contributions of two M critical points, weighed in a 2: 1
ratio, a t 2.1 and 2.3eV, respectively, have been added to take care of the
spin-orbit splitting of the A 3 level. The curves of Fig. 18 correspond, respectively, to three values of the Lorentzian broadening parameter, r = 0.025,
0.033, and 0.05 eV, and a negative interband temperature coefficient dE,/dT
has been assumed to calculate them. It is seen that the agreement with the
experimental data is satisfactory.
4.
383
-2
-4
Energy ( e V )
FIG. 19. Thermoreflectance spectra of Si at (a) liquid nitrogen temperature and (b) room
temperature. (After Matatagui et a1.I5)
This kind of analysis is not as conclusive in the case of the E , peak occurring
near 4.4eV because, as a result of the rapid variation of the coefficients
a and jl in that spectral region, the computed line shape is sensitive to the
assumed location of the critical point. A single M , edge2*could however be
sufficient to account for the observed shape. A more direct procedure to
interpret the data, which avoids unnecessary assumptions and the guesses
about the energies at which the critical points occur, would be to compare
the experimental A E , and A E , curves to the theoretical line shapes of Fig. 7.
The Kramers-Kronig transform required to obtain Ae, and Ae2 from the
spectra of Fig. 17 has, however, not been performed.
The thermoreflectance spectrum in the vicinity of the direct fundamental
absorption edge has been found to be close to a Lorentzian dispersion
shapeI9 as is expected for a steep edge displaced with temperature if A R / R
is dominated by A E [see
~ Eqs. (23) and (55a)l.
BRUNO BAT2
01
0.1
a
W
a
V
-0.1
-0
-0 2
-0.2
Energy (eV)
FIG.20. The values of AE, (solid line) and A E (dashed

~
line)for Si at liquid nitrogen temperature
as obtained from the Kramers-Kronig analysis of the data of Fig. 19(a). (After Matatagui er ~ 1 . ~ )
b. Silicon
The thermoreflectance spectra of Si obtained by Matatagui et u1. at liquid
nitrogen and room temperatures are shown in Fig. 19. The dominant
structures are the Eo and E 2 peaks which are located at 3.43 and 4.55 eV
in the low temperature spectrum. The 3.43-eV peak and the shoulder seen
at 3.32 eV are supposed to correspond to the peaks observed at neighboring
energies in the low-temperature electroreflectance spectra. The KramersKronig analysis of the low-temperature data is shown in Fig. 20; similar
results obtained from room temperature measurements by Balzarotti and
~ ~also
) shown, in Figs. 21 and 22,
G r a n d ~ l f oand
, ~ ~by Batz ( ~ n p u b l i s h e dare
respectively. It is interesting to note that these spectra differ in some details,
although the important structures are essentially the same ; one should
83
I should like to thank Dr. Grandolfo, who has performed the Kramers-Kronig analysisofmy
thermoreflectance data on Si, for his kind assistance.
4.
385
-*I
-20
-30
I t
I?
FIG.21. The values of A E , (dashed line) and Ac2 (solid line) for Si at room temperature. The
main singularities of the band structure at zeros of the AeZ curve: (1) 3.40eV; (2) 4.24eV;
(3) 5.18 eV. (After Balzarotti and Grandolfo.24)
thus be cautious about the interpretation of the smaller features of the

spectra.
If the effects arising from the temperature dependence of the broadening
can be neglected, the dominant structure a t 3.4 eV is seen to be intermediate
between those produced by the thermal shift of the bands at critical points
of types M and M as given by the simple theory (see Table I1 and Fig. 7).
According to the discussion of Section 16, this behavior is explained by
exciton effects a t an M I critical point and the lower energy part of the
structure is possibly due t o an M , critical point, also with exciton interaction.
Matatagui et al. interpret the structure above 4 eV in their low-temperature
resultsas being due to M , and M,critical pointsat 4.3 and 4.5eV,respectively,
with exciton interaction.
Balzarotti and Grandolfo locate the main singularities of the band
structure a t zeros of the Az2 curve (marked by the arrows in Fig. 21 and
falling at 3.40, 4.24 and 5.18 eV) but this analysis seems over-simplified.
386
BRUNO BATZ
100
x
80
60
40
20
0
-20
-40
- 60
- 80
-100
FIG.22. The values of A E , (filled circles) and A E (open

~
circles) for Si at room temperature
(After Batz, u n p ~ h l i s h e d . ~ ~ )
These authors have also made experiments at oblique incidence, choosing

an angle of incidence of 55", with light polarized parallel and normal to the
plane of incidence. The reflectance modulation is considerably amplified
in the case of parallel incidence.
c. Indium Phosphide
An example of well-resolved structures is given by those due to the E ,

and E , + A, transitions in InP, which appears near 1.4 eV in the low- and
room-temperature thermoreflectance spectra" shown in Fig. 23. A value of
O.lOeV is found for the splitting A, and a small peak, probably caused by
an impurity level, is seen at about 0.02eV below the main E , peak. The
assumed origin of the other spectral features is indicated in the figure.
4.
387
- I0
- 5
-0
- -5
-
-10
-5 -
Energy (eV1
FIG. 23. Thermoreflectance spectra of InP at (a) liquid nitrogen temperature and (b) room
temperature. (After Matatagui er ~ 1 . ~ )
d. Indium Antimonide
The thermoreflectance spectra of InSb observed by Matatagui et al. at
nitrogen and room temperatures are shown in Fig. 24. The strong peaks are
due to E , and E l + A 1 transitions near 2 eV (similar asymmetrical El peaks
6
appear in the spectra of AlSb, GaSb, InAs, and HgTe), and to E , and E ,
3
-I
-2
-3
Energy feVl
I
5
FIG.24. Thermoreflectance spectra of lnSb at (a) liquid nitrogen temperature and (b) room
temperature. (After Matatagui et ~ 1 . ~ )
388
BRUNO BATZ
f
FIG.25. Wavelength modulated reflectance spectrum of lnSb at T = 110K. (After the thesis
of Shaklee as quoted by Matatagui et
L
I
Energy ( e V )
FIG. 26. The values of Ael (solid line) and Ae2 (dashed line) for InSb at liquid nitrogen temperature as obtained from the Kramers-Kronig analysis of the data of Fig. 24(a).(After Matatagui
er a/.)
4.
389
CdTe
3
Energy Lev)
FIG.27. Thermoreflectance spectra of CdTe at (a) liquid nitrogen temperature and (b) room
temperature. (After Matatagui et d L 5 )
transitions at 4.2 and 4.8 eV in the low-temperature spectrum. The splitting

A1 = 0.51 is in accordance with electroreflectance results.
Figure 25 shows the wavelength modulation spectrum obtained by
Shaklee (quoted by Matatagui et a1.15)at low temperature and containing
the E and E + A 1 structures. The similarity ofthe corresponding line shapes
in Figs. 24 and 25 suggests that the thermoreflectance data have their origin
mainly in the temperature shift of the bands, the contribution of the broadening being small. This demonstration is not entirely convincing because the
appearance of the wavelength modulation spectra may be affected by the
energy dependence of the broadening (see Section 14); but it is on this basis,
as in the case of Si, that the Kramers-Kronig transform of the low-temperature thermoreflectance data, shown in Fig. 26, is discussed by Matatagui
et al.I5
According to Table I1 and Fig. 7, the El and El + A 1 line shapes in the
A E , and Ac2 curves (Fig. 26) could be explained as being produced at an M I
390
BRUNO BATZ
0 01
2i
0 01-
Energy ( e V )
FIG.28. The values of AE](solid line) and A E (dashed

~
line) for CdTe at liquid nitrogen ternperature as obtained from the Krarners-Kronig analysis of the data of Fig. 27(a). (After
Matatagui et ul.)
critical point by roughly equal contributions of band shift and broadening.

The effects of broadening being discarded, the structures are seen to result
from a mixing of M , and M , line shapes corresponding to band-shift
modulation, as is expected for exciton interaction at M , critical points.
The strong E, peak can be interpreted with either shift and broadening
modulation at M 2one-electron critical points, or more probably with only
shift modulation at M , critical points with exciton interaction. These
possibilities are of course not exclusive.
e. Cadmium Telluride
Figures 27 and 28 show, respectively, the low- and room-temperature
thermoreflectance spectra of CdTe, and the Kramers-Kronig analysis of
the low-temperature data obtained by Matatagui ef al. The peaks between
3 and 4 eV correspond to the El and El + A1 doublet which has a splitting,
A 1 , of 0.56 eV, and the structure occurring at 1.5 eV is due to the Eo edge.
The Elstructures in Fig. 28 are similar to those in InSb, although less well
defined, and they can be interpreted in the same manner. The line shapes
related to the E , edge may be produced either by the gap shift and broadening
4.
391
Energy ( e V )
FIG.29. Thermoreflectance spectra of hexagonal CdS at (a) Iiquid nitrogen temperature,

T 80K. (b) Acetone and dry-ice temperature, T 200K and (c) room temperature, T
280K. (For further detatls, see text.) (After Matatagui et al.'5)
modulations or by the gap-shift modulation and exciton effects at an M ,

critical point. As for Si and InSb, the second possibility is preferred.
f. Cadmium Suljide
The thermoreflectance spectra of CdS measured at approximately 80,200,
and 280K are shown in Fig. 29.15 The lines A and B correspond to the two
upper valence bands which are split by the crystal field. Transitions from
both bands are allowed for light polarized parallel to the c-axis while only
the higher energy component B is allowed for light polarized perpendicular
392
BRUNO BATZ
to the c-axis. These lines are well resolved at 80"K, the peaks being located
at 2.544 and 2.560 eV. The splitting keeps the value of 0.016 eV at 200"K,
but the peaks are no longer separated at room temperature. We may recall
here that Berglund also finds a splitting of 0.016eV at room temperature
from his temperature-modulated absorption data.
The third component C, allowed for both polarizations, arises from the
valence band split off by spin-orbit interaction ; an A-C splitting of 0.075 eV
is obtained at 80K. Matatagui et al. suggest that the small peak seen below
the A line could be due t o a bound exciton or back surface reflection. In fact,
the larger negative peaks occurring below the edge at the higher temperatures
are caused by back surface reflection since small interference fringes were
observed on their low-energy side.
Lange and Henrion4' have obtained a thermoreflectance spectrum of CdS
that looks somewhat different from that of Fig. 29(c). If one attempts to
correlate their results to those of Fig. 29, it appears that the spectrum was
probably taken at a temperature considerably higher than 280K as the
spectral features seem to be shifted to lower energies. Structures that could be
recognized as the negative A, B peaks and the C peak are no more well
resolved and separated in the (E Ic)and (E 11 c)curves. In this work, however,
the authors identity the A and B transitions to the positive peak (separated
in fact by 0.015 eV) just following the large negative back reflection peak in
each curve.
g. Graphite
Balzarotti and Grandolfo4' have measured the thermoreflectance of

graphite, whose strong anisotropy has interesting consequences on the
optical properties, from 4 to 6.5 eV. In the two-dimensional model, which
neglects the cohesion between the carbon layer planes, there are critical
points of types M , and M I only, which produce, respectively, step and
logarithmic singularities in the joint density-of-states function.6 If broadening
effects are included, the behavior of the optical constants may be approximated at an M , point by the Lorentzian lines described by Eqs. (52), and
it follows that AE, and Ac2 resulting from the modulation are given by
Eqs. (53); at an M , critical point, 2 is given by Eq. (54) and A E and
~ A E ~
by Eqs. (55).
Balzarotti and Grandolfo have interpreted their data on the basis of two
critical points of types M, and M , located, respectively, at 5.1 1 and 5.96 eV
(this last structure has not been resolved before). They assume that the
effect of temperature is to modulate the broadening parameter only at the
M , point and the interband energy only at the M , point. The computed
line shapes, similar to those shown in Fig. 4, are fitted in Fig. 30 to the
4.
393
FIG. 30. Experimental (solid line) and theoretical (dashed line) A E for
~ graphite due to an
MI saddle point at 5.1 1 eV and an M o threshold at 5.96 eV. (After Balzarotti and G r a n d ~ l f o . ~ )
experimental A E curve
~
taking r = 0.185 eV near 5 eV and
near 6 eV. The agreement is seen to be very good.
0.172 eV
19. MEASUREMENTS
ON METALS
A detailed discussion of the data concerning metals is beyond the scope
of this article. We shall however mention the works that have been done
in this field for the sake of completeness, and also because thermal and
wavelength derivative spectroscopy turn out to be important methods of
investigation for metals as electroreflectance is less useful in this case.
Scouler started these investigations by measuring the low-temperature
thermoreflectance of Au from 2 to 10eV.41*42His results for A R / R are
shown in Fig. 31, together with the conventional reflectance spectrum of
the same sample, which is in contrast rather featureless. The dominant
BRUNO BAT2
394
(-
FIG. 31. Thermoreflectance and reflectance spectra of a gold film.

- -) R
77K. (After S c o ~ l e r . ~ )
(-)
AR/R
- 120K:
16 12
I l6
8-3
41.
OL1
IT
-5
-4 -8 -
1 0.3 0 4 0.5
Photon Energy ( e V )
FIG.32. Thermoreflectance (a) and reflectance (b)spectra of a nickel film. (a) A R / R

(solid line); R 77K (dashed line). (b) A R / R (solid line). (After Hanus er
-12
- 120K
4.
395
-10
03
0.4
Microns
05
06
FIG. 33. Thermoreflectance spectra of two potassium films at T

I W K showing Interference fringes (thin film. dashed line) and a peak at the plasma frequency (thick film, open circle)
to which a theoretical curve (solid line) has been fitted. (After Matatagui and C a r d ~ n a . ~ ?
structure is a sharp dispersion-like line at 2.5eV. Scouler points out the

similarity of the AR/R curve to the piezoreflectance data. In fact, since the
sample is bonded to a substrate having another coefficient of thermal
expansion, a strain is induced due to the effect ofdilatation,which is estimated
to be of a magnitude comparable to the stress modulation in piezoreflectance
experiments.
A similar work has been done on Ni by Hanus et aLS4 Figure 32 shows
the low-temperature spectra that they obtain in a spectral range extending
from the infrared up to the vacuum ultraviolet. The authors restrict the
discussion to the structures in the low-energy region, which favors a reordering of the bands at the L point of the Brillouin zone.
The alkali metals K, Rb, and Cs have been investigated by Matatagui
and C a r d ~ n a . ~ . ~
Peaks
in the thermoreflectance spectra are associated

with the plasma frequency up.The line shapes computed on this basis
84
J. Hanus. J. Feinleib, and W. J. Scouler. Phys. Rev. Lett. 19, 16 (1967).
396
BRUNO BAT2
30
20
N
'0
x
2.0
30
40
Energy (eV)
FIG.34. Wavelength-modulated reflectance spectrum of evaporated silver in the neighborhood

of the plasma edge. (After Braunstein er
have been fitted to the experimental data in a satisfying manner with the
following values for h o p : 3.82 eV for K, 3.40 eV for Rb, and 2.85 eV for Cs.
These results in the case of K are shown in Fig. 33. Another peak seen at
higher energies is attributed to interband transitions. The oscillations in the
thin film spectrum are interpreted as interference fringes in the region of
transparency.
Figure 34 shows the wavelength modulation spectra of Ag obtained by
Braunstein et a1.34The large peak occurs at the plasma edge at 3.88 eV.
VIII. Note Added in Proof

In this note are mentioned some publications that have appeared since
this chapter was initially completed.
20. THERMOREFLECTANCE
(TR)
New methods to modulate the temperature of the sample have been used
in some TR studies. A direct heating of the reflecting surface has been achieved
by pressing against it a film of SnO, evaporated on a quartz plate, a periodic
4.
397
current passing through the film.85986A l o p Mylar spacer was used to

insulate the sample from the SnO, film and all the air gaps were filled with
silicone oil. The attainable spectral range is limited by the transparency of
the SnO, film as in the sandwich arrangement in electroreflectance measurements. Temperature modulation has also been performed with a pulsed CO,
l a ~ e r , ' ~ *or,
' ~ as reported in another context,88 by illuminating the sample
with the chopped and adequately filtered radiations from a high power
tungsten lamp. In his book on modulation spectroscopy, Cardona' discusses the factors that affect the efficiency of thermal modulation.
A periodically gated electron beam was used independently by McCoy and
Wittry90*91and by Broser et aL9' to modulate the reflectance of some
semiconductors (Ge90-91s92
and Si, GaAs, GaP91). The dominant effect is
claimed to arise from thermal modulation, at least at high beam intensities
and low freq~encies.~'
McCoy and W h y 9 , obtain spectra similar to former
TR result^,'^*^^ but with greater amplitude of modulation and more details.
"
500K
In the TR spectrum ofGaAs observed by Dzhioeva et ~ l . * ~ *near
and covering an energy range from the E o edge up to 3.5 eV, the structures
A,, E l , and E , + A 1 transitions appear as in
associated with the E , , E ,
a former work,' but additional peaks are found at 2.08 and 2.32 eV which
are not visible in other modulated reflectance spectra. It is worth noting
that this spectrum was taken at the Brewster incidence (- 74").
Georgobiani and Fridrikh93 have measured the TR of (cubic) ZnS near
the fundamental edge at 325K. They find structures due to the E o and
Eo A, transitions around 3.68 and 3.75eV. The spectra are analyzed
according to the theory of Section 5 and very accurate values are proposed
for the energies of the critical points. The splitting A, is found to be 71 meV,
in agreement with the result obtained at 80K by Matatagui et
who
however, attribute the observed peaks to discrete exciton states.
Discrete exciton lines at the fundamental edge should come out when the
exciton binding energy is greater than the broadening parameter. Investiga-
V. S. Vavilov, V. S. Ivanov. D. B. (B. D.) Kopylovskii, and V. B. Stopachinskii. Fiz. Tuerd.

Tela 12, 1678 (1970) [English Transl. : Souief Phys.-Solid Sfate 12, 1329 (197011.
sb A. A. Balashov, V. S. Ivanov, B. D. Kopylovskii, and V. B. Stopachinskii, Fiz. Tekhn. Poluprou.
4, 869 (1970) [English Transl.:Soviet Phys.-Semicon. 4, 736 (1970)l.
8 7 S. G. Dzhioeva, V. S. Ivanov, and V. B. Stopachinskii, Fiz. Tekhn. Poluprou. 3. 1316 (1969)
[English Transl.: Soviet Phys.-Semirond. 3, 1096 (1970)l.
G. Feher, R. A. Isaacson, and J. D. McElroy, Rev. Sci. Instr. 40. 1640 (1969).
M. Cardona, Solid State Phys., Suppl. 11 (1969).
90 J. H. McCoy and D. B. Wittry, Appl. Phys. Lett. 13,272 (1968).
9 1 J. H. McCoy and D. B. Wittry, J . Appl. Phys. 42, 1174 (1971).
9 2 1. Broser, R.-A. Hoffmann, and H.-J. Schulz, Solid State Commun. 8. 587 (1970).
93
A. N. Georgobiani. and Kh. Fridrikh, Fiz. Tuerd. Tela 12, I086 (1970) [English Transl.: Souiet
Phys.-Solid State 12, 849 (1970)].
85
398
BRUNO BATZ
tions on CdTea53x6(at 80K), on CdS94,95(from 108 to 315K) and on

GaSe96(from 77 to 243K) have revealed negative peaks in the TR spectra,
which are interpreted as arising from the rigid shift with temperature, of
exciton Lorentzian lines. Using Eq. (23)and Eq. (53a) with dT/dT = 0, the expected spectral line shape of a peak in AR/R is that of the (x2 - l)(x2 + 1)curve in Fig. 4. The experimental results concerning CdS94*95and the
interpretation are quite similar t o those of Matatagui et al. (see Fig. 29).
O n the contrary, in the CdTe spectrum obtained by Balashov er al.,* the E
structure is different from that observed by Matatagui et a/. (Fig. 27), which
was also interpreted differently (see Section 18). In a recent work, Antoci
and S a m ~ g g i ahave
~ ~ studied, at several temperatures, the TR associated to
the El edge in CdTe and they are able to find a close theoretical fit by assuming
an asymmetric Lorentzian structure fort [Eq. (145)],a result that is in accordance with Eq. (161) if one A term is dominant. An attempt to fit the data
using the metamorphism hypothesis, as in the case of InAs described below,
was unsuccessful.
Exciton effects are invoked by Antoci et
in a careful investigation of
the El - (El + A l ) spin-orbit-split doublet in InAs to explain their TR
spectra taken at ten temperatures ranging from 74 to 397K.The temperature
dependence of the line shapes is interpreted on the basis of Toyozawas
theory (see Section 16) predicting the mixing, due to Coulomb interaction,
of critical points (MI and M , points in this case). The authors show, using
a curve fitting method, that the M , contribution increases on going to lower
temperatures (from 30% near 400K to 80% near 100K for the El edge),
while that of M , correspondingly decreases. They also determine the temperature coefficients ofthe shifts ( - 5.5 x
eV/K)and of the broadening
(+0.9 x 10-4eV/K). A similar work done in connection with the
E , - (El A J doublet in Ge,97 leads to conclusions of the same type.
. reconsidered
~ ~
the thermal reflectance of graphite in
Anderegg et ~ 1have
the 4.4 t o 5.5 eV energy range. Their results, which differ markedly from a
preceding m e a ~ u r e r n e n t(see
~ ~ Section 18 and Fig. 30) were obtained at
80K under a 45 angle ofincidence. A synthesis of the experimental spectrum
has been attempted through the use of Eqs. (25) and (38). A good fit is
obtained by superposing three singularities at 4.52 eV (assumed to be at L
points in the Brillouin zone) and at 4.76 and 4.82 eV (at Q points in the zone),
M. Iliev, I. Assenov, and S. Stoyanov, Phys. Status Solidi 40,K51 (1970).

M. Iliev and I . Assenov, Phys. Status Solidi 42, 383 (1970).
96 A. Balzarotti, M. Grandolfo, F. Somma, and P. Vecchia. Phys. Sfafus Solidi (b) 44. 713
( 197 1 ).
9 7 S. Antoci and G. Samoggia, private communication (1970).
98 S. Antoci. E. Reguzzoni, and G. Samoggia. Phys. Rea. Lett. 24, 1304 (1970).
99 M. Anderegg, B. Feuerbacher, and B. Fitton, Phys. Rev. Letf. 26, 760 (1971).
94
95
4.
399
with a main contribution of gap energy shift, the broadening giving a minor
contribution.
In order to supplement reflectance and electroreflectance data in a study
of some II-IV-As, compounds (in the zinc blende and the chalcopyrite
structures), Kwan and Woolley o o * l o l have performed room temperature TR
measurements on ZnGeAs, (from 1.5 to 5.5 eV) and ZnSnAs, (from 0.5 to
5.5 eV). A better resolution is obtained by electroreflectance than by thermoreflectance, but both sets of spectra show closely correlated features.
A n interesting form of thermal reflectance spectroscopy has been reported
by Otmezguine et d l o 2 in a study of narrow variable bandgap materials
(Cd,Hg, -,Te alloys). The method was used to determine the gap of HgTe.
The sample, submitted to a slight temperature modulation, was illuminated
by a CO, laser while its energy bands were continuously shifted by a slow
temperature variation (from 230 to 320"K), the reflected beam being synchronously detected. The resulting spectrum, recorded as a function of T,
shows an S shaped curve attributed to the r6--t T8 transitions, and the value
of the gap is found to be equal to the photon energy of the CO, laser (1 17.04
meV) at 286 2K.
Following the work of Matatagui and C a r d ~ n aon
~ alkali
~ . ~ ~
metals, TR
measurements have been conducted in the plasma regions of Sb,Te3 -$3eX
corn pound^,'^^ for which accurate values are determined for the hole
plasma frequency, and of Ag.lo4
Beside its use in the studies of the electronic properties of solids, Aymerich
and Mula'05 have shown that thermoreflectance can also be useful as a way
of measuring thermal conductivities.
'
MODULATED
REFLECTANCE
(W MR)
2 1. WAVELENGTH
AND ABSORPTION
(WMA)
Because of the experimental difficulties inherent to wavelength modulation
spectroscopy, this technique has not been, until recently, as popular as the
other modulation methods in spite of the obvious advantage that a direct
comparison with theory is possible; the interpretation of the spectra is not
obscured, as it is in the other methods, by the effect of a perturbation on the
optical properties. Early calculations of the modulated reflectance (of
C. C. Y. Kwan and J. C. Woolley. C m . J . Phys. 48. 208s (1970).
C. C. Y. Kwan and J. C. Woolley. Phys. S r a m Solidi (b) 44, K93 (1971).
I n * S. Otmezguine, F. Raymond, G. Weill, and C. Verie, Proc. 10th Intern. Cmf. Phys. Semicond.
Cumbridge, Mussuchuserts 1970, p. 537. USAEC Div. Tech. Information, Oak Ridge, 1970
(available as CONF-700801 from Nat. Tech. Information Serv.. Springfield, Virginia 221 51).
Z. Hurych and C. Wood, Solid S t a t e Commun. 9, 181 (1971).
I o 4 G. Baldini and M.Nobile, Solid Szatt Cnmmun. 8,7 (1970).
lo'F. Aymerich and G . Mula, Phys. Stutus Solidi (b) 43, K17 (1971).
loo
lo'
400
BRUNO BATZ
graphite,Io6 or of GaAs, Gap, and ZnSe'") had to be compared to TR

spectra because WMR data were not available. However, very remarkable
results have now been obtained with carefully constructed double beam
wavelength modulation spectrometer^.^^*^^*'^*- ' ' '
Zucca and Shen' '' have measured the WMR of Si, Ge, GaAs, GaSb,
InAs, and InSb from 1.75 to 6eV at 5, 80, and 300K. They were able to
determine the origin of the observed peaks with the help of the existing band
structures of the crystals. In the case of Si and GaAs, a direct comparison
has been made between the experimental and the calculated WMR spectra
The room
obtained by using the empirical pseudopotential method.'
temperature WMR and TR'5*39spectra look much alike. But at low temperature, WMR shows a real improvement, yielding more details, with a
resolution even better than in electroreflectance spectra. The reflectivity
peaks are found to shift to higher energies and to become sharper as the
temperature is lowered. The sharpening, which is most evident in the case
of the El - (El+ A') doublets, is thought to be due to a reduction oflifetime
broadening of the hyperbolic excitons. The temperature dependence of the
band structures has been investigated more closely in the case of GaAs' ' '
for which the positions of the El - ( E l + A') doublet and the E , major
peak have been measured at 5, 80, 150, 225, and 300K. By incorporating
Debye-Waller and lattice expansion effects in a pseudopotential calculation,
a correct theoretical determination of the temperature shift of the reflectivity
peaks is obtained.'14
Braunstein and Welkowsky have, in another important work,' l 6 measured
the WMR of Ge, Si, GaAs, Gap, GaSb, InAs, InP, InSb, and AlSb at 80
and 300K in the spectral range from 1.6 to 5.0 eV. The general conclusions
are consistent with those of Zucca and Shen.' A Kramers-Kronig analysis
''
' 9 '
lo'
'08
A. Imatake and Y. Uemura, J . Phys. Sac. Japan 28,410 ( 1 970).

J. P. Walter and M. L. Cohen, Phys. Rev. 183,763 (1969).
M. Cardona, Proc. IX Intern. Conf. Phys. Semicond., Moscow, 1968, p. 365. Nauka, Lenin-
grad, 1968.
T. 0.Tuomi, Phys. Status Solidi 38,623 (1970).
' l o K. L. Shaklee and J. E. Rowe, Appl. Opt. 9,627 (1970).
1 1 1 R. R. L. Zucca and Y. R. Shen, Phys. Rev. B1, 2668 (1970).
I2 R. R. L. Zucca, J. P. Walter, Y. R. Shen, and M. L. Cohen, SolidState Commun. 8,627 (1970).
' I 3 J. P. Walter, R. R. L. Zucca, M. L. Cohen, and Y. R. Shen, Phys. Rev. Lett. 24, 102 (1970).
A similar calculation has been made by Keffer et
in connection with the positive temperature coefficient of the fundamental gap of PbTe, which according to Fan's theory (see
Section 14) should be negative. Such determinations of the temperature dependence of the
bands should prove helpful in TR studies.
C. Keffer, T. M. Hayes, and A. Bienenstock. Phys. Rev. B2, 1966 (1970).
R. Braunstein and M. Welkowsky, Proc. 10th Intern. Conf. Phys. Semicond. Cambridge.
Massachusetts, 1970, p. 439. USAEC Div. Tech. Information, Oak Ridge, 1970 (available
as CONF-700801 from Nat. Tech. Information Serv., Springfield, Virginia 221 51).
log
4.
401
of the spectrum of GaAs has been performed in order to produce the

derivatives of and e 2 . The resulting line shapes associated with the E l and
E , + A 1 structures can be interpreted, according to the metamorphism
hypothesis (see Section 16), as arising from transitions at an.M, critical point
with exciton effects.
Wavelength modulated reflectance measurements have been performed
' GaAs submitted to compressive uniaxial stress along
by Rowe et ~ 1 . ' ~on
[loo]. The results strongly support the existence of hyperbolic excitons. A
splitting, dependent on the polarization direction relative to the stress axis,
is observed in the structures associated with the E l - (El + A t ) doublet.
This splitting can be accounted for by the electron-hole exchange interaction,
and a range of 10 A is estimated for the electron-hole interaction.
~
presented the WMR spectrum of Cu obtained at 7K
Fong et ~ 1 . ' 'have
in the 2 to 6 eV energy range, together with a calculated spectrum. The good
agreement between theory and experiment allows the identification of many
structures.
A careful investigation of Se has been made by T ~ o m i . ' ' ~The WMR
spectra with the light polarized perpendicular and parallel t o the [OOOl]
direction, obtained at 77K between 1.7 and 3.7 eV, and stress modulated
reflectance spectra, were presented and discussed. The effect of compressive
uniaxial stress along [OOOl] on the energies of the spectral structures was
studied. Wavelength modulated transmission spectra were also given.
Wavelength modulated absorption has been used essentially to study the
exciton absorption at the fundamental edge of indirect semiconductors.
The reason is that the absorption coefficient [which is given by Eqs. (1 11)
without Coulomb interaction] takes the form given by Eq. (163) when it is
associated with the formation of an indirect exciton in its nth energy level,
a phonon being emitted or absorbed in the process. The derivative measurement yields a [hw - E , (R,,/n2) f hwq]-"2 dependence, and hence it
produces a singularity. Taking broadening into account, the spectral shape
becomes that given by Eq. (39) and Fig. 2. Cardona" has fitted this curve
very nicely to the WMA spectrum of Si obtained by Balslev (Fig. 13) with a
broadening parameter equal to 1.2 meV.
Shaklee and Rowe' l o have analyzed their WMA spectra of G a P obtained
at 240 and 65K in this way. They are able to distinguish the peaks due to the
formation of indirect excitons aided by TA, LA, and T O phonons. The results
are in general agreement with those of a former work"' in which WMA
measurements on strained crystals were also reported. The case of AlSb
I7
I8
I9
J. E. Rowe, F. H. Pollak, and M. Cardona, Phys. Rev. Letr. 22,933 (1969).

C. Y. Fong, M. L. Cohen, R. R. L. Zucca, J . Stokes, and Y. R. Shen. Phys. Rev. Lett. 25.
1486 (1970).
I. Balslev, Proc. Intern. Conf. Phys. Semicond. Kyoto, 1966 ( J . Phys. SOC. Japan Suppl. 21),
p. 101, Phys. SOC.Japan, Tokyo, 1966.
402
BRUNO BATZ
has been examined by Rowe et al., at 77K, and the spectral features
corresponding to the emission and absorption of TA, LA, and LO phonons
were identified. A study of the same material under uniaxial stress has likewise been made.
A quite impressive work has been conducted on Si by Shaklee and
Nahory
using a sensitive wavelength modulation spectrometer. They
obtained a low temperature (13K) WMA spectrum containing many
structures of the broadened inverse square root shape (Fig. 2). These
structures were identified as arising from the phonon assisted formation
of indirect excitons, not only in the ground state [ n = 1 in Eq. (163)] but
also in excited states [n = 2 and even n 2 31. The energies of the emitted TA,
LO, and T O phonons were found to be 18.2 f 0.2, 55.3 i-0.4, and
57.3 f 0.4meV respectively, and the exciton Rydberg was found to be
14.7 f 0.4 meV. The effect of uniaxial stress on the indirect exciton spectrum
has been investigated by WMA in the case of Si also.23
The action of charged impurities on the indirect exciton absorption in
highly compensated Ge has been investigated at 77 and 4.2K by Safarov
et
The exciton structure in the WMA spectra taken at 4.2K gradually
disappears as the concentration of charged impurities is increased, and it
~ agreement with
vanishes at a critical concentration of 2 x l O ~ m - in
theoretical estimates.
ACKNOWLEDGMENT
I should like to thank Professor S. Amelinckx for his kind interest in this work and for continuous support.
lZ3
J. E. Rowe, K. L. Shaklee, and M. Cardona, Solid Stufe Commun. 7,441 (1Y6Y).

L. D. Laude, M. Cardona, and F. H. Pollak. Phys. Rev. Bl, 1436 (1970).
K. L. Shaklee and R. E. Nahory, Phys. Rev. L e f t .24,942 (1970).
L. D. Laude, F. H. Pollak, and M. Cardona, Phys. Rev. B3.2623 (1971).
V. I. Safarov, 1. S. Shlimak, and A. N. Titkov, Phys. Status Solidi 41,439 (1970).
CHAPTER 5
Piezooptical Effects
Ivar Balslev
1.
11.
111.
INTRODUCTION
MACROSCOPIC
THEORY
A N D NOTATION
I . Stress, Strain, Stizness, and Compliance
2. Optical Anisotropy.
.
.
.
.
STRAINPERTURBATION .
.
.
.
3. Splitting of Energy Leoels and Po1ari:ed Transitions
4. Second Order Effects
.
.
.
.
.
.
.
.
1V. ELECTRONICINTERBAND AND INTRABAND TRANSITIONS.

5. Influence of Strain on Band E-ytrema.
.
.
.
6. Piezooptical Eflects near Fundamental Absorption Edge
I . Shifts oj'Exciron Binding Energies .
.
.
8. Transitions at Higher Enrrgic,s.
.
.
9. Free-Carrier Dispersion and Absorption
.
10. Suroey ofBand Edge Dejbrmation Potentials
.
.
V.
VI.
VII.
ELECTRONICIMPURITY STATES
1 I . Shallow Letlels
.
.
12. Deep Levels .
.
LATTICEVIBRATIONS.
13. Phonons
.
.
14. Local Modes.
.
.
.
EXPERIMENTAL
CONSIDERATIONS
.
.
.
15. Compensation Methods .
.
16. The Differential Technique.c. .
I I . Arrangements,for Static Stress.
.
18. Methods,for Application of'Oscillatory Stress
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
403
405
405
409
411
411
414
415
415
419
428
430
433
439
.
.
441
441
443
.
.
441
447
448
.
.
.
.
.
.
449
449
451
453
455
1. Introduction
Piezooptical studies concern changes in the optical properties, e.g., the

complex dielectric function E(w),luminescence, photoconductive response,
etc. of a solid as it is subjected to elastic deformation. All configurations of
homogeneous strain can be divided into two contributions : the isotropic
or hydrostatic components which gives rise to a volume change without
403
404
IVAR BALSLEV
disturbing the crystal symmetry, and the anisotropic component which,

in general, reduces the symmetry present in the strain-free lattice.
Reviews on the influence ofisotropic deformation, particularly on electronic
energy levels, have been reported previously. A large number of workers
have demonstrated that a variety of fruitful conclusions can be derived from
studies of spectral structures and transport properties in the presence of
hydrostatic pressure. In contrast, we shall concentrate here on the effects
of anisotropic strain configurations, especially in cubic crystals.la
The basic macroscopic phenomena with which we shall be dealing are
splitting of spectral structures and optical anisotropy. These effects arise
from strain-induced lifting of degeneracies which are present in the eigenvalue
equations for the motion of electrons and ions and for the light propagation,
respectively. In transparent regions of a solid the most important observable
effect is piezobirefringence, i.e., polarization-dependent changes of the
refractive index. The interference phenomenon associated with such changes
has been an indispensable tool in the technological investigations of stress
distributions.2 In basic solid state physics, however, the birefringence
experiments are generally more indirect than piezooptical studies of reflectance, transmission, and luminescence, which give less ambiguous information about stress-induced changes of levels, oscillator strengths, and lifetimes
of excited states.
The interpretation of piezooptical investigations of broad spectral
structures, for which the attainable energy shifts are smaller than the line
widths, is rather complicated since elaborate line-shape analysis and essential
assumptions regarding strain induced changes of matrix elements are
involved. In dealing with sharp structures, however, the experiments provide
immediate information on splitting of energy levels, selection rules, etc.
Here the dependence of the induced fine structure on polarization direction
and strain configuration relative to crystal orientation is important in the
speculations on symmetry properties of the states involved. Moreover, the
magnitude and functional dependence on stress of the energy splittings are
interesting in the detailed comparison with theory. The first accurate studies
of this kind were reported as late as 1960-1961 by Thomas3 (excitons in
W . Paul and D . M. Warschauer, eds. Solids Under Pressure. McGraw-Hill. New York,
1963.
A review article on a similar theme was published by F. H. Pollak, Proc. lOrh Intern. Cot$
Phys. Semicond., Cambridge, Mussuchusefts, 1970. p. 408. USAEC Div. Tech. Information,
Oak Ridge, 1970 (available as CONF-700801 from Nat. Tech. Information Serv.. Springfield. Virginia 22151).
H. T. Jessop and F. C. Harris, Photoelasticity. Cleaver-Hume Press, London, 1949 or
Dover, New York, 1960.
D. G. Thomas, J . Appl. Phys. Suppl. 32,2298 (1961).
5.
PIEZOOPTICAL EFFECTS
405
CdTe), Gross and Kaplyanskii4 (excitons in Cu,O) and Schawlow et uL5

(electronic levels ofCr in MgO). Fundamentals of the theory on level splitting
and selection rules in strained crystals have been developed in a very general
form by Kaplyanskii6 (localized electronic states and k = 0 Bloch-type states,
Sections 3 and 4). Independently, Kleiner and Roth7 and Pikus and Bir
considered specifically the valence band edge in semiconductors, whereas
Herring and Vogt, Brooks, and Keyes analyzed the piezoeffect associated
with many valley band structures (Section 5).
The late start of piezospectroscopy compared t o related fields is probably
caused by the fact that the application of anisotropic stress has no analog
outside solid state physics. Thus there was no old tradition inherited from
atomic physics and the physics of gaseous plasmas, as was the case for
magnetooptic and electrooptic effects. However, in recent years the piezooptical technique has become a standard tool in solid state spectroscopy for
revealing multiplicities due to spatial symmetry (except inversion), just as
a magnetic field is used for investigating degeneracies caused by time reversal
invariance.
A survey of piezooptical experiments is presented in Sections 6-14 according to their microscopic origin. These works have made use ofa large number
of different experimental techniques (Sections 15-1 8) for applying external
forces to the specimens and for revealing changes in the optical behavior.
Special attention will be devoted to the differential methods in spectroscopy,
since these greatly enhance the sensitivity when analyzing stress-induced
fine structures that are superimposed on a large background signal.
11. Macroscopic Theory and Notation
1 . STRESS,
STRAIN,
STIFFNESS,
AND COMPLIANCE
A homogeneous stress in a solid may be described by a second rank

tensor X with elements Xijdefined as the ith component of the force transferred perpendicular to the jth coordinate direction. The sign convention
E. F. Gross and A . A . Kaplyanskii. Fiz. Tverd. Tela 2, 1676, 2668 (1960) [English Transl.:
SOU.Phys.-Solid State 2, 2637, 1518 (1961)].
A . L. Schawlow, A . H . Piksis, and S. Sugano, Phys. Rev. 122. 1469 (1961).
A. A. Kaplyanskii, Opt. Spektrosk. 16, 103 I (1963) [English Transl.: Opt. Specrr. ( U S S R )
16, 556 (196411.

W. H. Kleiner and L. M. Roth, Phys. Reu. Lett. 2,334 (1959).
* G . E. Pikus and G . L. Bir, Fiz. Tuerd. Tela 1, 1642 (1959) [English Transl.: Sou. Phys.~-Solid
lo
Sfale 1, 1502 (195911.

C. Herring and E. Vogt, Phys. Rev. 101, 944 (1955).
H. Brooks, in Advances in Electronics and Electron Physics (L. Marton, ed.), Vol. 7,
p. 85. Academic Press, New York, 1955.
R . W. Keyes, Solidstate Phys. 11, 149 (1960).
406
IVAR BALSLEV
prescribes positive diagonal elements for tensile stress. l a Newtons third law
implies symmetric stress tensors.
A homogeneous deformation is characterized by a displacement field u(r)
which is linear in the space coordinates r. Zero-order terms of u correspond
to trivial uniform translations, and rotations of the entire medium lead to
antisymmetric forms of the first order term Vu. Without losing generality
we therefore define the symmetric strain tensor e by the elements
Note that the relative change of volume is1=

AV/V
e:l = zeii.
i
The fourth rank stiffness tensor C is given by
and similarly, the compliance tensor S is defined by

kl
both relations being valid only for elastic deformation. The 81 elements of
C or S are mutually dependent because of the symmetric forms of e and X.
Hence, the fourth rank tensor notation for stiffness and compliance is too
complicated and is usually replaced by the more compact matrix notation.
According to this the tensors e and X are transformed into 6 x 1 matrices
(el and { X ) in the following wayI3
11
e12
e13
e21
e22
e23
e31
e32
e33
and
Frequently used units for stress and pressure: I kbar = 10dyn/cm2 = 987atm = I020
kg/cm2 (or kgf/cm2 where kgf stands for kilogram force).
l 2 J. F. Nye. Physical Properties of Crystals. Oxford Univ. Press, London and New York.
1957.
I Z JThroughout this chapter, the symbol 1 stands for the unit second rank tensor. A colon denotes the inner product of two second rank tensors.
l 3 C. Kittel, Introduction t o Solid State Physics. Wiley, New York. 1956.
,I
5 . PIEZOOPTICAL EFFECTS
407
Note the factors of 2 in the off-diagonal strain elements. These arise from
the unfortunate fact that the matrix notation has been derived from "conventional" strain with the off-diagonal elements equal to'
corresponding to the shift in angle between the cubic axes. The stiffness and
compliance are then 6 x 6 matrices defined by
where simple matrix multiplication is used.

Energy conservation and the elastic approximation require that { Cj and
{ S ) be symmetric matrices.' Thus, the total number of independent elements
describing stiffness and compliance is 21. In cubic crystals this number is
reduced to 3, and the compliance matrix has the form
where the cubic axes of the crystal form the basis. In case of elastic isotropy
we have S , , - S , , =
The homogeneous strain configurations of interest in practice are first of
all those induced by uniaxial stress or hydrostatic pressure. In the latter
case the stress X is
where p is the pressure (positive for compression). For cubic crystals we have
and
408
IVAR BALSLEV
TABLE I
ELEMENTS
OF TENSORS
DESCRIBING
THE STRAM
e OR THE SHIFT
A t OF THE DIELECTRIC
CONSTANT
IN CASEOF UNIAXIAL
STRESS ALONG HIGHSYMMETRY
DIRECTIONS
IN CUBIC
CRYSTALS"
Stress 11 [OOI]
fp - fq
0
0
fp - f q
fp
Stress 11 [I101
Stress 11 [1llIb
+ fq
fp f r f r
f r j-p f r
+r +r + p
fp
+ iq
+r
fp
f-r
+ bq
0
Stress // [I121
0
j-p - i q
kr
+r
0
$r
fp - +q
fr
+ p - fq
j-r
j-r
f p + fq
" For e the quantities p , q, and r are given by : p = ( S ,

2SI2)X; q = ( S , I - S , z ) X : r =
+S,,X. For A t these parameters are: p = ( S l , 2SlZ)(Wl1 2WI2)X; q = ( S l l - S12)
x (Wl1 - W , , ) X ; r = +S44W44X.
where X is the magnitude of the uniaxial stress, and the
coefficients S and Ware discussed in the text.

Principal values: f p + fr and f p - fr, parallel and perpendicular to the stress. respectively.
For uniaxial stress we shall denote the magnitude by X, positive and

negative for tensile and compressive stress, respectively ; 2 will stand for a
unit vector parallel to the uniaxial stress. Then the stress tensor X is given by
x = {r22}X,
where throughout this chapter the symbol { } denotes the dyadic product.
The elements of the strain tensor e for cubic crystals stressed uniaxially
along certain high symmetry directions are given in Table I. In this crystal
symmetry the trace of the strain is X ( S , , + 2S,,), independent of the stress
direction. The same volume change is obtained for a hydrostatic pressure
of - X / 3 .
In a thin specimen rigidly mounted on a thick substrate, it is possible to
apply stresses different from the above types. If the z axis is perpendicular
to the surface ofthe specimen, then the strain configuration may be calculated
from
x =x = x =o
zz
YZ
XZ
and from the fact that exx, eyvrand exv are equal to the corresponding strain
elements of the substrate.
In reflectance measurements a useful strain configuration is obtained by
crystal bending.14 The surface strain can easily be calculated from the
curvature of the bent sample and its thickness.
H. R. Philipp, W. C. Dash, and H. Ehrenreich, Phys. Rev. 127,762 (1962).
5. PIEZOOPTICAL
409
EFFECTS
2. OPTICAL
ANISOTROPY
For a linear local relation between the electric field E and the induced
polarization P the general form of the dielectric function is12
P = [c(w)- 11 . E
= [cl(a) -
ic2(o)] . E
where L, c l , and c2 are second rank tensors. In case of cubic crystals or

amorphous or polycrystalline solids there is optical isotropy, implying that
the dielectric function can be represented by scalars e l and e 2 . For lower
symmetries of single crystals the tensor character must be retained, but
Onsagers reciprocal theorem (see, for example, de Groot 5 , simplifies the
structure of c1 and c 2 to be symmetric in the absence of a magnetic field.
The general solutions to Maxwells equations in optically anisotropic
media are not transverse waves and only selected polarization directions
are decoupled. The analytical expressions for electric and magnetic fields
associated with waves propagating in an arbitrary direction are rather
complicated.2 Only the case of common principal axes of c and c2 and light
propagation along any of these axes has simple transverse solutions. Then
the decoupled modes represent polarization directions along the remaining
principal axes. These modes are characterized by scalar optical constants
and c2 as in isotropic media.
Anisotropy in transparent media (c2 = 0) appears as double refraction
or birefringence arising from ellipsoidal structure of c 1 . The word
dichroism is used for absorption anisotropy. Natural optical anisotropy
is present in uniaxial and biaxial single crystals with, respectively, one and
zero axes of more than twofold symmetry. Artificial anisotropy occurs
generally in the presence of a magnetic, electric, or strain field in otherwise
isotropic substances ofcrystalline as well as amorphous nature. For magnetic
fields, however, the first order optical anisotropy is characterized by antisymmetric tensors giving rise to, e.g., Faraday rotation,16 the analog to
birefringence.
The functional dependence on strain of the complex dielectric tensor
may be expressed as
c(e) = r(0)
+ Ar(e).
(9)
Since Ar and e are symmetric, Eq. (9) implies that the piezooptical behavior
is described by six complex functions Acij of seven real variables ( r i jand the
I
l6
S. R. deGroot, Thermodynamics of Irreversible Processes. North-Holland Publ., Amsterdam, 1951.

T. S. Moss, Optical Properties of Semiconductors. Butterworths, London and Washington,
D.C.. 1961.
410
IVAR BALSLEV
frequency). This formalism is far too complicated to treat in general, and

in this section we shall present notations for some simplified cases.
For changes of c that are linear in strain, Gobeli and Kane have introduced the elastooptical fourth rank tensor W defined by
or, when using the matrix form,
(AE) = [ W }{ e )
where the 6 x 1 {AE}matrix is given by
CAE
1 1 7 A622
AE3 3 ? AE2 3 9
13 7 A E I 2
1.
For cubic crystals, { W ) has the same structure as shown in Eq. ( 5 ) for { S } .
Thus the strain-linear phenomena in cubic structures are described by three
complex functions of frequency, namely
For arbitrary stress and strain configurations the trace of c is given by

r : l = (Wll
+ 2W,,)1 :e = ( W l l + 2W,,)(SI, + 2S1,)1 :X.
(12)
Elements of Ac for selected directions of uniaxial stress are given in Table 1.

As the highest possible elastic deformation in the materials concerned is
of the order of only
one would expect that considerable nonlinear
changes of c with stress occur only in rare cases. Several optical studies,
however, concern sharp spectral structures with line widths comparable to
the stress-induced shifts. Then, for a fixed frequency one observes drastic
nonlinear variation of c (although the frequency shifts and splittings are
linear in strain). In such cases there is no sense in expanding t in a power
series in e. We therefore introduce a notation for arbitrary functional
strain dependence of c, but we limit ourselves to uniaxial stress in cubic
crystals along high-symmetry direcfions. For the stress directions (001) and
( 1 1 1 ) there is optical isotropy perpendicular to the stress axis, and we may
write
G . W . Gobeli and E. 0.Kane, Phys. Rezl. Letr. 15, 142 (1965).
5.
411
where ~ ( 0w, ) is the zero stress dielectric constant (isotropic) and X , denotes
the stress X along the direction 1 being [Ool] or [ 1111. The symbols 11 and I
refer to polarization direction with respect to the stress axis. Such notation
is frequently used also for other optical quantities, e.g., reflectivity, transmission, etc. For [110] stress, the principal axes will be [110], [lTO], and [Ool]
along which A&in general will have three different values.
Usually, all relevant information on cubic structures is gained by investigating the four complex functions E ~ , ( a),
X ~E ~~ ~
( X, ~w, ),, ~E l, I ( X l l 1w),
,
zI(X1 1, o)of the scalar variables X and w , whereas studies of the behavior
for [110] stress may be used as a check of the data and interpretation.
111. Strain Perturbation

3. SPLITTING
OF ENERGY
LEVELS
AND POLARIZED
TRANSITIONS
A fundamental piezooptical effect is the splitting of spectral structures
such as absorption edges and lines originating from transitions in which
degenerate states are involved. Unless a degeneracy is due to time reversal
invariance or spatial inversion symmetry it can be lifted by an appropriately
chosen strain field. If the configuration of the strain and the symmetry of
the degenerate state are known, then a group theoretical analysis will yield
the number of split levels and selection rules for specified types of transitions.
Using perturbation theory it is possible t o calculate relative magnitudes of
transition matrix elements. A very general and complete presentation of
this procedure and calculated results for a large number of specific situations
are given by Kaplyanskk6 His analysis covers electronic eigenstates in
cubic symmetric fields, but his results can easily be extended to vibrational
states. Here, we shall briefly present the principal lines of his treatment and
apply his results to a particular transition.
In the first step of the analysis it is important to determine the symmetry
properties of the strained lattice. For a cubic lattice having the symmetry
operations of the 0, group* the principal stress directions [ l l l ] , [OOl], and
[110] lead to the groups D3,, D,,, and D,,, respectively. Similarly, the
D,,, and CZv,respectively. The splitting of
cubic group T, converts into c3,
energy levels can be established from the compatibility relations between
strained and unstrained representations. A subsequent analysis of the transformation properties of the operator for the electromagnetic radiation
generates those transitions that are forbidden for a selected polarization
direction (totally polarized transitions).
G . F. Koster, Solid Stare Phys. 51 (1957).
412
IVAR BALSLEV
TABLE I1
COMPATIBILITY
RELATIONS
FOR REPRESENTATIONS
OF THE GROUP
Oh AND ITS SUBGROUP D,,, AND RELATIVE
INTENSITIES OF ELECTRIC
DIPOLE
TRANSITIONS
FROM A STRAIN-SPLIT
VALENCEBAND
Point group D,,
Point group 0,
(degeneracy)
(4)
(2)
(2)
Transition
Representations:
rs++
iM1*
M6+
M,'
+ M ~ *
rl*
rh*
Valence band
sublevel
Polarization
11 stress
(degeneracy)
(2)
(2)
(2)
(2)
Polarization
I stress
A more quantitative study of the polarization dependence is possible by

perturbation theory. T o first order in the strain e the perturbation H(e)may
be written as
H ( e ) = H,:e ,
(14)
where the operator He is a second rank tensor. If H(e)acts on an i-fold
degenerate state, the zeroth order wave functions are given by
where qnis the unperturbed basis, the eigenvectors a,,,,, diagonalize the matrix
($,,,IH(e)l$,,), and the energy shift of the mth state is
AEm =
<$mlH(e)l$m).
(16)
It is appropriate here to mention a general relation for first order strain

perturbation. We make the average
where the quantity in parentheses is independent of the strain and the basis
chosen. Thus the mean shift of a strain split level (and the shift of an unsplit
level) depends only on the trace of e, i.e., the volume change. A similar law
5.
413
holds for Bloch-type states with k # 0 if the shifts are averaged over equivalent k vectors. The relations provide a simple means for comparing energy
shifts from uniaxial and hydrostatic strain configurations in cubic crystals.
For a transition from a strain-split sublevel i into another (possibly
strain split) state f the square of the matrix element of the radiation operator
H p is
IMfit2 =
I<$:IHpI$:)12
(17)
r,s
where $: and $si are diagonalized bases of final and initial states, and the
summation r, s runs over degenerate states of the sublevels, i.e., the states
which remain degenerate in the strained crystal. Since the operator H , for
the electromagnetic radiation depends on the direction of the electric field,
the sum of Eq. (17)yields the relative intensities and the polarization dependence for transitions between sublevels of the states i and f.
Using this procedure and the results of Kaplyanskii,, we shall calculate,
as an example, the splitting and polarization dependence associated with
electric dipole transitions between the k = 0 valence and conduction band in
germanium. The crystal structure of Ge belongs to the point group Oh, and
we will consider a uniaxial stress parallel to [OOI] yielding D4,, symmetry.
Since spin is included we use the double group representations and obtain the
compatibility relations listed in Table 11. Here and throughout this chapter,
Koster's group theoretical notation" is adopted. It is seen that the valence
band in Ge at k = 0 transforms as the ,I representation splits up into two
doubly degenerate sublevels (M, and M, +), whereas the conduction band
with representation r, - remains unsplit. According to the results of Kaplyanskii6 the electric dipole transition
+
M,'
M,-
is allowed only for stress-parallel polarization, and
is allowed for any polarization direction. Instead of denoting the split levels
of the valence band by group representations we shall use the J M j notation as
traditionally preferred in this case.'' Then a basis for the Tsi state may be
eigenstates specified by the magnetic quantum number M , equal to *$ and
+$. For [Ool] and [ l l l ] stress, M , is a good quantum number if quantized
along the stress direction whereas a general stress causes mixing." In our
case ([Ool] stress) the basis in which the 4 x 4 strain perturbation matrix is
l9
H. Hasegawa, Phys. Rev. 129, 1029 (1963).
414
IVAR BALSLEV
diagonal is therefore
I,b - with representation M 7 + and I,b + 3 1 2 , I,b - 312
with M 6 + symmetry. The matrix elements appearing in the sum of Eq. (17)
for optical transitions from these states t o the unsplit M,- conduction band
are given in Table 5 of Kaplyansk? for different polarization directions.
Using Eq. (17) the summation over Kramers degeneracies will yield transition probabilities as given in Table 11. This polarization dependence turns out
to be valid also for [l 1 11 stress.20
The above example is typical for cubic symmetry in the sense that the
relative intensities for [lll] and [OOl] uniaxial stress are independent of the
parameters which determine the splitting. General strain configurations
yield intensities which depend on the ratio between the splitting parameters
for [1 111 and [Ool] stress.
4. SECONDORDEREFFECTS
In addition to the results of Section 3 on level splitting and intensities of

the split components we shall present some of Kaplyanskii's considerations6
on strain dependence of matrix elements.
Let the unperturbed states cpf and 'pi remain unsplit under action of the
strain perturbation H(e)= He :e.To first order the perturbed wave functions
are
and
indicating a strain proportional admixture of other states (cp, and cp,) of the
system. Acting with the radiation operator Hp the transition matrix element
to first order in H(e) is
Mfi = (IC/flHplI,bi) = ((PflHplVi)
If (cpflHplqi) # 0, then the transition is allowed in the strain-free crystal and

a first order shift of JMfi/'is induced. Such effects are rarely observable since
the fractional change of IMfi12is typically of the order of the strain (lop3-
*'
E. Adler and E. Erlbach, Phys. Rev. Lett. 16, 87 (1966), Erratum, Phys. Rev. Lett. 16, 927
( I 966).
5.
415
10- 2 ) . More interesting cases are transitions forbidden in the unperturbed

crystal (<cpf(H,(qoi)= 0). Then the intensity lMfi12 of the transition is proportional to the square of the strain. It is seen that the strain may break
selection rules and thus enable an investigation of otherwise inaccessible
transitions. These will appear as spectral structures with intensities having a
square dependence on the applied stress.
The mixing effects of a second order treatment will also influence the strain
dependence of energy levels. Using the wave function $f Eq. (18) we obtain to
second order in H(e)
Still assuming H ( e ) to be linear in strain [H(e)= H,:e], we find that the

second term gives a quadratic dependence on strain of the energy. If, for
simplicity, we consider a single secondary level Emand assume (cp,(H,\cpf)
and (cpf(H,lcpm) to be of the same order of magnitude, then the quadratic
- EmI.Thus, as the shift of the
shift will be of the order of ((cpflH(e)lcpf))2/1Ef
primary level Ef becomes comparable to the distance to the secondary
levels, the quadratic term becomes important.
If a higher order treatment is necessary, it is useful to extend the unperturbed basis to include the closely lying states. This type of perturbation
theory is described by Lowdin,*' who divides the unperturbed states into two
classes A and B-the class A being considered as the basis, the class B
bands being remote. Such treatment of the effect of strain has been developed
for the valence band in Si by Hasegawa.'
IV. Electronic Interband and Intraband Transitions
5. INFLUENCE
OF STRAIN
ON BANDEXTREMA
In dealing with electronic Bloch states, it is important to analyze qualitatively the strain-induced shifts as a function of the wave vector, particularly
near a band edge. Furthermore, it is of interest to derive expressions for a
perturbation operator for calculating energy shifts from unperturbed wave
functions.
Consider a state Ink) with a Bloch type wave function t+hnk(r)= eik"unk(r),
$Jr) is eigenfunction to the Hamiltonian
2'
P.Lowdin, J . Cbem. Pbys. 19, 1396 (1951).
416
IVAR BALSLEV
where the single electron potential Vo(r) is invariant for the symmetry
operations leaving the unstrained lattice unchanged. For a homogeneous
strain e we denote the perturbed potential by V(r, e) where
V(r, 0 ) = Vo(r).
We notice that shape and size of the elementary cell for V(r, e ) is altered. The
difference
W ,e ) - W ,0)
cannot be treated directly as a small perturbation since the two terms have
different periodicity intervals. This difficulty is solved in the method developed by Pikus and Bir. Here, a variable r = r - e r is introduced. Then
to first order in e,
r
and the potential
= r + e s r ,
V(r, e) = V(r
(22)
+ e - r, e )
(23)
is taken as a function of r and e. The functional dependence on r is characterized by an elementary cell in the r space identical to that of Vo(r)in the r
space. Then, after further transformations the elements of the tensor He[Eq.
(14)] are found to have the form
Lo.
a2 + a v ( r + e - r , e )
m axiaxj
aeij
h2
..=--e.11
where the derivative d/deij is evaluated for constant r. Pikus and Bir point
out that the deformable ion model yields
V(r,e)
Vo(r)
and simply
For a nondegenerate21a edge state I n k ) , the deformation potential tensor

is defined as
%o
= (nk~l
Helnko)
and the energy shift is then
E,,(ko,e) = &(ko,0) +
21a
:e.
(25)
Here we consider a Kramers doublet as nondegenerate since spin degeneracies are not
removed by strain.
5.
417
For cubic symmetry of the lattice, and band extrema with ko along [OOI] or
Enko may be expressed as
[ 1111, simple symmetry arguments yield that

I
= Edl
or
Snko= El1
+ Eu{koko}
, . A
(26)
(27)
E,({CoC,} - + I ) ,
where the notations using Ed,

zuand E , ,E , were introduced by Herring and
Vogt and by Brooks, respectively. The structure of the latter expression
has the advantage that the deformation potentials E , and E, describe
separately the effects of, respectively, pure dilatational strain (e = e : l ) and
pure shear (e:l = 0). Nondegenerate states at k, = 0 have E, = E2 = 0
and do not shift with pure shear. In Herring and Vogts notation the mean
shift of the valleys is Z, + ZJ3 times the volume change. There is no splitting
for strain configurations in which the valleys remain equivalent. For a
uniaxial stress X along a valley direction the splitting between the stress
valley(s) and the remaining equivalent valleys is E,X(S,, - S12)in case of
k, 11 (100). The similar splitting for ( 1 11) valleys is 9E,XS4,/4.
Still to first order in e, the behavior of E(k,e )near k = k, may be expressed
as4
E(k,e) = E(k,,O)
=ko:e
+ w : { ( k - k,)(k
- k,)},
(28)
where w is the reciprocal mass tensor, and terms of orders higher than
(k - k,) and e(k - k,) are ignored. Hence the important piezo-effect on
nondegenerate band extrema off the zone center is characterized by unequal
shifts of valleys that are differently oriented relative to the strain configuration. The wave vector of the extremum and the shape of the energy surfaces
are unchanged.
The effect of strain on degenerate band edges has been extensively studied
by Pikus and Bir. In Section 3 we already discussed the splitting at k = 0
ofthe r, type valence band in Ge. Applying in addition the k p perturbation,, these authors find for Ge and Si the following energy dependence
to first order in e and secnd order in k.
where
E(k,e ) = E(0,O) + Alkl
+ a1 : e f (E, + Ee2 + E;,J,,
+ ( D 2 - 3B2)(kxky2+ kx2kz2 + k:kz2),
Ek2= B2(kI4
Ee2 = (b2/2)Mex*- eyJ2 + @ y y - ezA2 + (ezz -
+ d2[eZy+ eiz + e,2,],
C. Kittel, Quantum Theory of Solids. Wiley, New York, 1963.
(29)
418
IVAR BALSLEV
and
where A, B, and D are effective mass parameters, and a, b, and dare deformation potential constants.22aThe sign convention for B, D,b, and d is related
to the symmetry ofthe split bands as discussed in Hasegawa and Hensel and
Feher.23 The complicated structure of the above energy dependence can be
summarized as follows: A strain proportional splitting of 2E, is induced at
k = 0. Near k = 0, the energy surfaces are ellipsoids with principal axes
and masses that depend on strain configuration, not on strain magnitude.
For uniaxial stress along [loo], the k = 0 surfaces are ellipsoids of revolution
with reciprocal masses A B and A f $B for wave vectors parallel and
perpendicular to the stress, respectively. The corresponding mass parameters
for [lll] stress are A +_ D/312and A T D/2(3)I2.For large wave vectors the
surfaces are warped and subject to strain-proportional energy shifts which
depend on orientations of stress and wave vector, but not on the magnitude of
k (see Fig. 1).
FIG.1. Illustration of stress induced changes of the valence band structure in G e as calculated
from Pikus and Birs theory. Here a compressive uniaxial stress is applied in the [Ool] direction.
The quantities A, B, D, and E , are discussed in the text [Eq. (29)]. At left, the constant energy
surfaces are shown for the heavy holes at zero stress and for the upper valence band in the high
stress limit. The expressions in the parentheses are inverse masses along various high-symmetry
directions. At right the energy verus kZ dependence is shown for wave vectors along the cubic
axesandthe(lll)directions.(-)E,
= I meV;(---)Ee = 0 ; N = 3 2 D ; B / A = 0.65;NI3A =
0.85. Note the pronounced nonparabolicity for k 11 (1 1 I ) .
22a
z3
Kleiner and Roth use the deformation potentials: 0. = - 36/2, D,, =

D, = -3a/2.
J. C. Hensel and G. Feher, Phys. Rev. 129, 1041 (1963).
- 32
d/2. and
5.
419
In zinc-blende type semiconductors there is no inversion symmetry which

implies that their valence band structure contains a small k linear term
yielding band extrema slightly off the zone center. A discussion of strain
induced changes of such band edges is given by Bir and P i k ~ s . ~
Another situation which is different from that in Si and Ge is encountered
in gray tin and HgTe. In these semimetals the r, state and the s-like r,state are reversed. Cardona analyzed theoretically the influence of stress
and concluded that stresses of the order 5 x lo3 kg/cm2 in gray tin would
produce semiconducting characteristics of the band structure.
6. PIEZOOPTICAL
EFFECTSNEAR FUNDAMENTAL
ABSORPTION
EDGE
a. Indirect Transitions
In the semiconductors Si, Ge, and Gap, the indirect transitions from the
k = 0 valence band to a set of conduction band valleys off the zone center
can be studied since these take place for photon energies below the threshold
of the direct transitions. The indirect absorption edges in these material^'^*^^
are built up of a number of components, each corresponding to a particular
type of phonon interaction and having energy thresholds E, given by
G(e)= E&o
- Ev(O,e)
+_
E,b(ko, e) - Eex(k0, el,
( 30)
where Ec(ko,e) and Ev(O, e )are extremum energies of valence and conduction
band, Epb(k0,e ) is the energy of a branch b phonon, and Ee,(ko, e) is the
ground state binding energy of the indirect exciton. Apart from small
corrections discussed in later sections, the strain dependence E,(e)is solely
determined by the behavior of the band extrema Ec(ko,e) [see Eq. (25)] and
E,(O, e) [see Eq. (29)]. Each threshold will thus split up in the presence of uniaxial stress as observed in the piezotransmission spectra ( B a l ~ l e v ~ - ~Due
~).
to the monotonic character of the indirect absorptionz6 the fine structure
is resolved accurately by applying wavelength or stress modulation. In these
differential spectra (see Fig. 2) the square root rise of each absorption component above its threshold produces an asymmetric line with convenient
24
25
26
27
28
29
O
G. L. Bir and G. E. Pikus. Fiz. Tverd. Tela 3. 2332 (1963) [English Transl.: Sor. Phys.-Solid
Stare 3, 2221 (1962)l.
M. Cardona, Solid State Commun. 5, 233 (1967).
T. P. McLean, in Progress in Semiconductors (A. F. Gibson, ed.), Vol. 5, p. 55. Heywood,
London, 1960.
P. J. Dean and D. G. Thomas, Phys. Rev. 150, 690 (1966).
1. Balslev, Phys. Rev. 143, 636 (1966).
1. Balslev, Phys. Letr. MA, 113 (1967).
1. Balslev, Proc. Int. Con$ Phys. Semicond. Kyoto 1966 (J. Phys. Soc. Japan Suppl. 21),
p. 101. Phys. SOC.Japan, Tokyo.
420
IVAR BALSLEV
1 0 - 1 - 2 3
1 0 - 1
hv-E,(O) (10.' eV)
FIG.2. Piezotransmission spectra of 2-mm thick germanium at 80K recorded with wavelength modulation. The uniaxial stress X is parallel to [I 111 and unpolarized light is used.
The dominant peak corresponding to creation of indirect excitons and LA phonons [threshold
energy E,(O) = 0.761 eV] is split into four components for X # 0. This splitting E , ( X ) is shown
in Fig. 5. The components a , and a3 are due to transitions from the upper valence band, and
a, and a2 are due to transitions to the lower [l 111 valley. The weak structure for X = 0 is
assigned to transitions with emission of TO and LO phonons. (a) Stress X = 0, d = 2 mm.
(b) Stress X 11 [I 1I] = 925 kgf/cm2. (After B a l ~ l e v . ~ ~ )
indication of E l . The dependence of the absorption coefficient a, given by

yields
a(w, X ) a [ho- E , ( X ) ] ' / 2 ,
da/al cc - aa/(hw)a - [hw - E,(x)]

- 'I2
for wavelength modulation and
a a l a x a [ - as,(x)/ax]
[ho- E,(x)]'I2
for stress modulation. It is seen that the peaks in aa/aX may be positive or
negative according to the sign of the stress coefficient - 8 E J d X .
421
and A1Sb3'" has

The qualitative splitting behavior in Ge, Si,28
verified the accepted symmetry properties of valence and conduction band
extrema, i.e., multiplicity and location in the Brillouin zone. Consistency
requirements for results from three stress directions led to an unambiguous
assignment of the split components. It was thus possible to derive the values
of E, + EJ3 - u, Eu,b, and d [Eqs. (26) and (29)] from the observed dependence of the peaks on static stress.
The polarization dependence of the fine structure should be compared
with theoretically calculated matrix elements. These can be derived if a
single intermediate state of the indirect process is dominant.26 In case of Ge
and G a P the measured polarization dependence of the piezoabsorption
established the lowest k = 0 conduction band to be the most important
intermediate state. The spectra agreed with the selection rule of Table 11,
and the resulting M, classification of the valence band sublevels indicated
negative signs of the deformation potentials b and d. In Si, however, Erlbach3'
concludes that several intermediate states contribute comparably to the
second order matrix element. So far, the relative strengths of the indirect,
strain split components have not been interpreted with certainty.
Piezotransmission measurements near the indirect edge of diamond are
reported by Dean and C r 0 ~ t h e r . jNeither
~
splitting of thresholds nor
polarization-dependent absorption were found, but an interesting absorption
tail, present only for [ 1101 or lower symmetry stress directions, suggests a
phonon-free exciton production which might be possible through coupling
to strain-induced lattice defects with exchange of negligible energy.
The band extrema of Cu20, assumed to lie in the zone center, have the
same parity which implies that the dipole matrix element for direct transitions is zero for k = 0. Ground state excitons can, however, be created
through phonon-assisted processes which form a continuous absorption
similar to the indirect edges in Si and Ge. Shifts and splittings with stress as
well as polarization dependence of the split components have been observed
~ ~ data and the piezooptical behavior of
by Gross and c o - w o r k e r ~ .These
exciton lines (see Section 6c) have been important in the speculations on the
very complex bandstructure of C U , O . ~ ~
""L. D. Lucien, M. Cardona, and F. H . Pollak, Phys. Rev. 51, 1436 (1970).
3 1 E. Erlbach, Pbys. Rev. 150, 767 (1966).
P. J. Dean and P. A. Crowther, in "Radiative Recombination in Semiconductors" (7th Int.
Conf.). p. 103. Dunod, Paris and Academic Press, New York, 1964.
3 3 E. F. Gross, A. A. Kaplyanskii, and V. T. Agekyan, Fiz. Tverd. Tela 4, 1009 (1962) [Engfish
Transl.: Sou. Phys.-Solid State 4, 744 (1962)l.
'' E. F. Gross, B. P. Zakhartshenya, and A. A. Kaplyanskii, Proc. Int. Con. Phys. Semicond.,
Exeter 1962, p. 409, Inst. Phys. Phys. SOC.,London (1962); R. J. Elliott, Phys. Rev. 124,
340 (1961).
''
422
IVAR BALSLEV
A recent work by A ~ c a r e l l concerned

i~~
the stress linear changes of the
indirect absorption in AgBr. The modulated piezooptic technique was
employed, and the spectra provided new information on the location in the
Brillouin zone of the valence band maxima.
b. Direct Transitions in Ge and I l l - V Compounds

In a large number of the best known semiconductors (Ge, InSb, GaAs, etc.)
the conduction band at k = 0 is a simple minimum with symmetry r7which
does not split in the presence of strain. Several piezooptical investigations
have concerned direct transitions from the strain-split valence band to this
band. The spectral shape is here characterized by an exciton peak at the
energyz6
- E m - E,,,
E,, being the ground state binding energy of the direct exciton, and by an
almost constant absorption level of the order of lo4 cm- on the high energy
side of the exciton peak. This relatively high magnitude of the absorption
prevents the application of controlled stress on crystals with thicknesses of
the order of the skin depth without use of a substrate. It has therefore been less
simple to measure quantitatively the splitting with stress of the exciton peak.
Piezotransmission studies on Ge near the direct edge (hw z 0.8 eV) have
~
been reported by Kleiner and Roth,' by Glass,36 and by 0 s i p 0 v . ~These
authors used a technique based on cooling of a sandwich made of a thin Ge
crystal (5-lop in thickness) mounted on a transparent substrate with a
different thermal expansion coefficient. The uniform strain in the plane of the
crystal surface was of the other of
and the observed splitting yielded
values of Ibl, Jdl,and a' - a, where a' is the dilatational deformation potential
of the conduction band.
The reflectance structure near the direct edge of Ge is sharp but represents
very small fractional changes (less than 1 %). In the modulated piezoreflectance measurements by Engeler et aL3' (Fig. 3) the piezooptical response of
this structure was recorded. The reflectance modulation is mainly due to
changes in the refractive index n in the spectral range considered. Hence the
stress derivative dR/dX of the reflectivity R is proportional to anlax. A
Kramers-Kronig transformation yields
where c is the free space light velocity and a is the absorption coefficient.
G . Ascarelli, Phys. Rev. Lett. 20,44 (1968).
A. M. Glass. Can. J. Phys. 43, 12 (1965).
37 Yu. V. Osipov, Fiz. Tuerd. Tela 8, 2280 (1966) [English Transl.: Sou. Phys.-Solid Stare 8.
1820 (1967)l.
3 8 W. E. Engeler, H . Fritzsche, M. Garfinkel,and J. J . Tiemann, Phys. Rev. Letr. 14,1069(1965).
35
3b
423
2x10-4-
0
W
J
LL
I -
J r
0.810 0.820
&
Y2
-I
0
F
-2 -
LL
-3
d
z
Y
a
The spectral shape of the stress derivative of the absorption a E / a X is,

neglecting valence-band splitting, determined by a rigid shift of the direct
band gap with stress. Then, for a step-like absorption edge, du/aX has the
shape of an appropriately broadened line. This leads to a spectral structure of
the Kramers-Kronig transform anlax similar to that of A E for
~ a single
oscillator. The spectrum in Fig. 3 agrees qualitatively with these simple
arguments.
Combined static and dynamic piezoreflectance measurements yield
further information ( B a l ~ l e von~ ~
Ge and GaAs). The structure present for
zero-static stress was observed to split up into two additive components due
to the valence-band splitting. The amplitude of the components appearing
in the differential spectra can be shown to be proportional to the intensities
of Table I1 multiplied by the stress coefficients dE,,/dX, where Egapis the
direct band gap associated with the valence-band sublevels. By variation of
the static stress the appropriate deformation potentials for Ge and GaAs
were determined (Section lo), and the assignment that the M, = - - moves
up for compessive stress (h < 0, d < 0) yielded a detailed agreement for the
observed relative strength of the components. A recent analysis based on
piezoreflectivity revealed by wavelength modulation has been performed on
the direct absorption edge of AISb.30a
The stress-induced splitting of direct excitons has been revealed by other
techniques. First, piezoemission experiments on InSb, GaSb, and GaAs
J9
I . Balslev, Solid S f a f eCornrnun. 5 , 3 I5 (1967)
424
IVAR BALSLEV
have been reported by Guillaume and L a ~ a l l a r d ~and

~ . ~by
~ "Bhargava
and Nathan:'
respectively. The latter authors achieved very high magnitudes
of stress and were able to see nonlinear strain dependence of one of the
strain-split components (M, = ki)due to mixing with the deeply lying
J = $ split-off band. Second, Pollak et
combined the electroreflectance
technique with uniaxial stress in experiments on Ge and GaAs. Third,
Riskaer and Balslev4j interpreted the dispersive part of the piezobirefringence
s ~ the
~ absorption edge as arising a strain-split
in Ge43 and G ~ A near
exciton absorption. Thus, in Ge the magnitude and spectral nature of the
deviations from the low frequency piezobirefringence are consistent with
results from a Kramers-Kronig analysis of the direct edge dichroism calculated from the valence-band splitting and the degree of polarization of the
split levels (Table 11). Later this type of analysis has been interpreted in more
detail 44a and extended to A1Sb.44b
c. II-VI Compounds and Cu,O
The electron-hole interaction in semiconductors which are more ionic

than the I l l - V compounds is so strong that the binding energies of direct
excitons are of the order 1CL200 meV. This implies that the spectrum near the
fundamental absorption edge is characterized by resolvable exciton lines.
The influence of elastic deformation on such intrinsic lines has been studied
~~
Some of the
by Thomas3 (CdTe) and by Gross and c o - ~ o r k e r s(Cu,O).
features of these measurements and interpretation will be presented in this
section.
The ground state exciton in CdTe (zinc blende structure) produces an
absorption line at 1.6 eV which is strong enough to appear in reflection as a
pronounced narrow structure. In the presence of uniaxial stress Thomas
observed a splitting into two polarized components, indicating that the
exciton is derived from J = $ components of a p-like valence band an s-like
conduction band (both at k = 0) as in Ge and the 111-V compounds (see
Fig. 4). The valence-band splitting was found to be almost stress-isotropic
with the stress coefficient of 14 x 10-6eV-cm2/kgf which corresponds to
C. Benoit a la Guillaume and P. Lavallard, Proc. Int. Con$ Phys. Sernicond., Kyoto. 1966
( J . Phys. Soc. Japan Suppl., 21).p. 288. Phys. SOC.Japan. Tokyo 1966.
40sC.Benoit a la Guillaume and P. Lavallard, J . Phys. Chem. Solids 31,411(1970).
41 R. N. Bhargava and M. I. Nathan, Phys. Reo. 161,695 (1967).
4 2 F. H. Pollak, M. Cardona, and K. L. Shaklee. Phys. Rev. Lett. 16,942(1966); A. P. Smith,
M. Cardona, and F. H. Pollak, Bull. Amer. Phys. SOC.12, 101 (1967).
43 S. Riskaer and I. Balslev, Phys. Lett. 21, 16 (1966).
44 V. I. Nikitenko and G. P. Martynenko, Fiz. Tverd. Tela 7,622 (1965) [English Transl.: Sot!.
Phys.-Solid State 7,464(1965)l.
44aF.H. Pollak. M. Cardona, and C. W. Higginbotham, Phys. Rev. B2. 352 (1970).
44bA.Yu. Shileika, M. Cardona, and F. H. Pollak, Solid State Comrnun. 7 , 1 I13 (1969).
40
5.
425
kg/cm2
1220
617
411
ELSTRAIN-
51.58
I-
1.60
1.62
E l l STRAIN1.58
1.60
1.62 1.58
1.60
1.62
PHOTON ENERGY
IF!
1.58
1.60
1.62
FIG.4. Reflectivity spectra of uniaxially stressed CdTe near the direct exciton peak. Note the
absence of the B component for polarization E parallel to the stress (cf.Table 11). (After Thomas.3)
b = -1.2eV and d = -5.OeV. The negative signs for b and d (positive

values of D, and flu)were established from the polarization dependence of
the split lines since the M, = -ti valence band, being absent for stress
paralfel polarization (see Table II), moves down in energy for compressive
stress. From the stress linear splitting behavior it was concluded that no shift
in the exciton binding energy is induced by strain.
In Cu,O the ground state (n = 1) exciton can be formed only by phononassisted dipole transitions and by quadrupole transition^.^^ The latter
process gives rise to a sharp absorption line with strength appropriate for
simple piezotransmission measurements on crystals of millimeter dimensions.
The splitting of this line and the step-like indirect absorption was studied by
Gross and Kaplyan~kii.~
The numbers 2, 2, and 3 for the split components
were observed for, respectively, [ 1111, [Ool], and [110] uniaxial stress, which
with
supports the assumption that the valence band is a p-like state (rZ5)
negligible spin-orbit coupling and that the conduction band is s-like (rl).
This assignment yields a detailed agreement in the comparison between
theoretically calculated relative intensities and the polarization dependence
found for the quadrupole line and the phonon-assisted absorption. i t should
be mentioned that the matrix elements for the two types of transitions are
426
IVAR BALSLEV
significantly different ; for example, for fully polarized components the

Gross group also studied the excited
selection rules are
states n 2 2 of the same series. Here no splitting was resolved but as the
stress was applied the lines became strongly polarized.
In contrast to the above-mentioned cubic materials the Wurtzite-type
crystals CdS, ZnO, etc., have k = 0 Bloch states which, in general, are only
Kramers degenerate. Therefore, from a symmetry point of view the piezooptical studies on electronic excitations would seem less interesting. It
turned out, however, that the stress behavior of the exciton lines in this family
of materials is extremely helpful in the identification of the valence-band
sublevels. The valence-band structure in hexagonal crystals is explained by
Hopfields quasi-cubic
Here a p-like state is perturbed by spin-orbit
interaction and by a small, uniaxial deviation from a cubic one-electron
potential. This leads to a splitting into three Kramers doublets of the sixfold
p-state. The signs and magnitudes of these perturbations are well established
for CdS and CdSe. The assignment of the exciton lines is beyond doubt since
the relative oscillator strengths as a function of polarization and the energy
separations agree with the quasi-cubic
Also the behavior of the
exciton lines for stress along the c-axis (Rowe et
Grynberg, Chadderton ef ~ 1 . ~ is )consistent with the accepted band ordering. Interestingly, the
observed nonlinear shifts can be explained by stress-proportional changes in
the crystalline field pert~rbation.~
This overall consistency is not present for ZnO. There is still doubt about
the ordering of the valence band levels and the strength of the spin-orbit
coupling since various experiments are inconsistent with any of two proposed
structure^.^^*^^ Recent piezooptical experiments are new attempts to settle
the problem. Unfortunately, the nonlinear energy shifts with stress parallel
to the c-axis (Rowe et dS4)
in ZnO are too small to be conclusive. Most
E. F. Gross, A. A. Kaplyanskii, V. T. Agekyan. and D. S. Bulyanitsa, FIZ.Tverd. Telu 4,
I660 ( 1962) [English Transl.: SOC.Phys.-Solid State 4, I2 19 ( I962)].
46 V. I. Cherepanov, Fiz. Tverd. Tela 3, 1493 (1961) [English Transl.: SOC.
Phys.-Solid State 3.
1082(1961)]; S . A. Moskalenko and A. I. Borysheva, Fiz. Tverd. Tela 4, 1994 (1962)
[English Transl. Sou. Phys.-Solid State 4. 1462 (1962)l.
4 7 J. J . Hopfield, J . Phys. Chem. Solids 15,97 (1960).
4L( D. G. Thomas and J. J. Hopfield, Phys. Rev. 116, 573 (1959).
49 J. E. Rowe, M. Cardona, and F. H . Pollak, in 11-VI Semiconducting Compounds (Proc.
Int. Conf.). p. 112. Benjamin, New York and Amsterdam. 1967.
5 M. Grynberg, in Physics of Semiconductors (Proc. 7th Int. Conf.), p. 135. Dunod, Paris
5 L. D. Chadderton, R. B. Parsons, W. Wardzynski, and A . D . Yoffe, J . Phys. Chem. Solrds
23,416 (1962).
5 2 D. G. Thomas, J . Phys. Chem. Solids 15. 86 (1960).
53 Y. S. Park, C. W. Litton, T. C. Collins. and D. C. Reynolds, Phys. Rev. 143, 143 (1966).
5 4 J . E. Rowe, M . Cardona, and F. H. Pollak, Solid Srare Commun. 6 , 239 (1968).
45
5.
421
interesting is the work by Koda and Langer,55 who observe a splitting of

the exciton lines for uniaxial stress perpendicular to the c-axis and light
propagation parallel to the c-axis. Each of the two exciton lines present in
this geometry (Thomas A and B excitons) decompose into two fully polarized
lines. This behavior is inconsistent with the conventional Wannier-Mott
exciton concept since the one-electron band extrema remain unsplit. The
phenomenon emphasizes the two particle nature of the exciton, and is
explained by exciton exchange interaction. The short note by Akimoto and
H a ~ e g a w aand
~ ~ extended investigation^^^*^'" are based on perturbation
theory incorporating exchange interaction and uniaxial stress. In the most
recent work by Skettrup and B a l ~ l e v a~ total
~ of 12 exciton states is considered, namely excitons derived from three different valence bands, with two
different electron spins, and with two different hole spins. Four types of
perturbations : spin-rbit interactions, crystal field, external stress, and
exchange interaction are applied to these exciton states and the comparison
with experiments favors Thomas assignment52 of the ZnO spectrum.
d. Alkali Halides
The excitons in alkali halides give rise to lines in the ultraviolet reflectivity
spectra. These are rather broad (0.1-0.2 eV) because of strong coupling
between electronic excitations and polar modes of the lattice. Gerhardt
and Moehler applied to KBr and KI a dynamic strain of 5 x
in the
bending mode and investigated the reflectance modulation ARIR near such
exciton lines. Assuming strain-independent matrix elements and exciton
binding energies, these authors derived dilatational and shear deformation
potentials for two lines in KBr (6.8 eV and 7.3eV) and one lines in KI
(5.9 eV). However, the quantitative results of Gerhardt and M ~ h l e are
r~~
inconsistent with a recent work by Gavini and C a r d ~ n aThese
. ~ ~ authors
measured the piezobirefringence in six alkali halides near the fundamental
absorption edge. Applying the interpretation procedure similar to that
developed for direct edge piezobirefringence in Ge43 (splitting of valence
band extrema and oscillator strengths as given in Table II), it was possible
to derive shear deformation potentials. The quantities b and d have opposite
signs in all cases and each deformation potential changes sign when going
from NaCl to CsCl structure. A tight binding analysis accounts for this
behavior.
T.Koda and D. W. Langer, Phys. Rev. Lett. 20, 50 (1968).
0.Akimoto and H. Hasegawa, Phys. Rev. Lett. 20,916 (1968).
5 7 T. Koda, D. W. Langer, and R. N . Euwema, Proc. Int. Con$ Phys. Semicond., 9rh, Moscow,
1968, Vol. 1 , p. 242. Publishing House Nauka, Leningrad, 1968.
57aT.
Skettrup and I . Balslev, Phys. Status Solidi40 (1970).
5 8 U. Gerhardt and E. Mohler, Phys. Status Solidi 18, K45 (1966).
A. Gavini and M . Cardona, Phys. Reo. 177, 135 1 (1969).
55
56
428
IVAR BALSLEV
7. SHIFTSOF EXCITONBINDINGENERGIES
As mentioned previously the shifts and splitting phenomena of absorption
edges and exciton lines are generally determined only by the behavior of
the band extrema (and, for indirect transitions, the phonon energies) rather
than shifts of exciton binding energies. The work by Koda and Langer55
represents an exception from this. Another possibility of considerable stressinduced changes in exciton binding is due to the piezoeffects on energy
surfaces near k = 0 for a p 3 / 2 valence band state [see Eq. (29)].
In the limit of infinite stress (decoupled and ellipsoidal bands) the effective
mass equation for the relative motion attains the form
where E,,(n) is the binding energy of the nth hydrogenic state, E is the dielectric
constant (for simplicity assumed to be isotropic), and m; I, my- and mi
are principal values of the inverse reduced mass tensor for the electron-hole
pair.
In the case of indirect excitons in Si and Ge this is a sum of tensors for
the valence band sublevel and the conduction band valley in question.
The resulting principal values depend not only on the ellipticity of the band
extrema but also on the mutual orientation of the ellipsoids. For both
materials stressed along [11 11 and [Ool] directions the binding energy E,,
of the s-like ground state has been calculated (Balslev2') by means ofa method
developed by Kohn and Luttinger6' in connection with the donor problem.
The values of E,, fall in the regions 12.CL12.5 meV in Si and 2.5-2.7 meV in
Ge with the exception that the combination of a [ l l l ] valley and a prolate
valence band in [l 111 stressed Ge yields 3.4 meV. These values should be
compared with the calculated zero-stress results of 12.7 meV (Si)and 3.0 meV
(Ge).6' Experimentally, most observed shifts of E,, and mutual differences
for the split components were comparable to the spectral resolution, but a
satisfactory overall agreement was found in the comparison with the results
from the effective mass approximation.28 Particularly interesting is the
observation for [l 111 stress in Ge where, as expected, one of the four component exhibited an exceptional splitting behavior (Fig. 5). A surprising
result from the study in Ge of the intermediate stress range, where E,,
varies between values for zero and infinite stress, is that the valence bands
to the excitons are decoupled for splittings as small as 1 meV. This indicates
6o
''
W. Kohn and J . M. Luttinger, Phys. Rev. 98,915 (1955).

T. P. McLean and R. Loudon, J . Phys. Chem. Solids 13, 1 (1960).
Uniaxial stress x
429
lo3 (kgflcrn)
FIG.5. Splitting into four components of the LA emission threshold E, = 0.761 eV in the
indirect absorption spectrum of Ge at 80K (see Fig. 1). The strain-induced shifts in exciton
binding energies can be derived from extrapolation to zero stress of the splitting lines. Thus
the component a2 exhibits a larger exciton energy than do a l , a 3 , and a4, which is in agreement with calculations and the assignment that ct2 is derived from the lower [l 1I] valley
(stress X // [lll]) and the prolate valence band. (After Balslev.*)
that the valence band states appearing in the expansion of the exciton state
correspond to hole energies somewhat less than the binding energy of 3 meV.
Theoretical studies on direct excitons in strained Ge based on the same
principles as discussed above have been reported by 0sip0v.~Due to the
small conduction-band m a d 2 (0.03 m0),in this case the exciton binding
energy is less dependent on the valence band anisotropy. The values 1.4 and
1.33 meV were calculated for, respectively,
and infinite4* stress.
Osipovs calculations in the intermediate stress range lead to values of E,,
for [OOl] stress which are approximately 30% higher than the results in the
two limits. Such deviations are hard to understand intuitively and have not
been verified experimentally.
62
B. Lax and S. Zwerdling, in Progress in Semiconductors (A. F. Gibson, ed.), Vol. 5 ,

p. 221. Heywood, London, 1960.
430
IVAR BALSLEV
8. TRANSITIONS
AT HIGHER
ENERGIES
The optical constants of semiconductors for energies above the fundamental edge will exhibit structures due to transitions near critical points of
the interband density of states. The spectral shape of the contribution to E~
from a particular band pair is identical to that of the joint density-of-states
if lifetime broadening, electron-hole interactions, and variation in the
Brillouin zone of the matrix elements are neglected. The interpretation of
the observed spectra is, however, complicated by simultaneous contributions
of several active band pairs and by a breakdown of the above simplifications.
The results from theoretical band calculations have therefore been essential
in identifying the observed critical points with respect to type (minimum,
maximum, or saddle point) and location in the reduced zone. An experimental
complication is due to the strength 104-106cm- of the absorption which
prevents reliable transmission measurements.
The purpose of piezooptical studies on higher energy interband transitions
is primarily to establish the location in the Brillouin zone of the critical
points by investigating the orientation dependence of the piezoreflectance
~ p e c t r a . Secondly,
~
the quantitative analyses of the piezooptic response
provide valuable information on interband deformation potentials.
Unfortunately, in such studies elaborate analyseP are necessary in order to
distinguish effects of level splitting from those of strain-induced shifts of
matrix elements, since the attainable magnitudes of splitting are generally
much smaller than the broadening of the structures. As pointed out by
Gerhardt,64 a particularly complicated situation appears if the critical point
is not fixed to a symmetry point in the zone and is thus able to move (e.g.,
along a symmetry line) as the stress is applied. In spite of these difficulties,
the conclusions of Gerhardt from his piezoreflectance measurements on Si
and Ge have indeed yielded new relevant information on the character of
the critical points investigated. Thus, the structure at 2.2 eV in Ge (see Fig. 6 )
was assigned to transitions along the { 111) k-directions, and the reflection
peak at 3.4eV in Si was identified as being due to transitions along the
(001) directions rather than at the center of the zone as previously assumed.
An increased sensitivity of the high energy piezoreflectance spectra has
been obtained by strain m o d u l a t i ~ n . ~ Th
. ~us,
~ ~Gobeli
~ ~ - ~and
~ Kane17
verified Gerhardts results and established the 3.4 eV critical points in Si
to be of the M , type. Recent studies by Sell and Kane6 on the 2.2-eV
structure in Ge have established that changes of matrix elements produce
E. 0. Kane, Phys. Rev. 178, 1368 (1969).
Gerhardt, Phys. Reu. Lett. 15,401 (1965).
M. Garfinkel, J. J. Tiemann, and W. E. Engeler, Phys. Rev. 148,696 (1966).
U. Gerhardt, D. Beaglehole, and R. Sandrock, Phys. Rev. Lett. 19,309 (1967).
D. D. Sell and E. 0. Kane. Phys. Rev. 185. 1103 (1969).
b3
U.
WAVELENGTH
560
I
520
2.3
2.2
2.1
PHOTON ENERGY eV
600
1
nm
2.0
Light polarized to the stress axis

Parallel
Extension
Compression
Without stress
v v
Perpendicular
v v
A A
0 0
FIG.6. High-accuracy reflectivity spectra of the 2.2-eV structure in G e tat 300 K)strained
by bending. The arrows show reproducibility and resolution. and curves obtained with stress
are shifted arbitrarily along the reflectivity scale. The stress axis is parallel to [ 11 I J, and the strain
is approximately 0.40/0.The polarization dependence indicates that the interband transitions
responsible for this structure take place along the ( I 1 I ) wave vector directions. (After Gerhardt ")
432
IVAR BALSLEV
considerable piezoreflectance response. Extensive studies on GaAs have

been reported by Sell and Stokow~ki.~'"
The very complete work on Cu by
Gerhardt et a1.66has unambiguously verified the band calculations on this
material. The spectra revealed critical points in the interband joint densityof-states as well as in that of Fermi surface-to-band transitions. A similar
analysis has been carried out by Nilsson and Sandel167bon Ag and AgAu
alloys.
The differential piezoreflectance spectra and a subsequent KramersKronig a n a l y ~ i s ~ yield
' . ~ ~ real and imaginary parts of the elastooptical
matrix { W } [Eq. (lo)]. Neglecting stress-dependent lifetimes and matrix
elements, the spectral structure of { W 2 }can be assigned to shifts and splittings
of energy levels. Then transitions along k 11 (001) in cubic crystals will
appear as singularities for the quantity (W2)1 - (W2)12, whereas (W2)44
exhibits structure for transitions along (1 11). Transitions at k = 0 produce
no changes with shear strain (W, - W12 = W4, = 0) unless a degenerate
initial or final state is split by shear strain (r,states in cubic crystals). Some
difficulties are encountered in the above procedure. First, it is important to
establish the true zero of the ARIR spectra since experiments with a zero
offset due to geometrical effects (see Section 18) will lead to an incorrect
Kramers-Kronig transform if directly analyzed. Secondly, the changes with
strain of transition matrix elements require a complex interpretation procedure ( Kane63).
Critical point structures have been studied extensively in the presence of
a static stress and a modulated electric field (Pollak and Cardona6'). Gerh a r d t ' ~assignments
~~
for Ge were confirmed and were extended to the
similar 3.1-eV structure in GaAs. Some features of the spectra for Si have
not yet been understood in detail. F e l d m a ~used
~ ~ a~rotation technique for
a sensitive direction of stress-induced reflectivity anisotropy in Si and SrTiO, .
In recent years also the wavelength modulation technique has been
successfully used for revealing singularities in the reflectivity above the
fundamental absorption edge?'-'''
An extremely interesting effect revealed
67sD,D. Sell and S. E. Stokowski, Proc. 10th Inr. ConJ Phys. Semicond., Cambridge. Mussachusetts, 1970, p. 417. USAEC Div. Tech. Information, Oak Ridge, 1970. (Available as
CONF-700801 from Nat. Tech. Information Serv., Springfield, Virginia 2215 I ) .
676
P. 0. Nilsson and B. Sandell, Solid State Commun. 8, 721 (1970).
6 8 F. H . Pollak and M. Cardona, fhys. Rev. 172, 816 (1968).
69 A. Feldman, Phys. Lett. 23, 627 (1966).
O K. L. Shaklee, J. E. Rowe, and M. Cardona. fhys. Reu. 174,828 (1968).
"5. E. Rowe, F. H . Pollak, and M. Cardona, Phys. Rev. Lett. 22, 933 (1969).
'"R. R. L. Zucca and Y. R. Shen, fhys. Rev. B1, 2668 (1970).
70cR. Braunstein and M. Welkowsky. Proc. 10th Int. Con$ Semicond., Cambridge, Massachusetts, 1970. p. 439. USAEC Div. Tech. Information, Oak Ridge 1970 (available as CONF700801 from Nat. Tech. Information Serv.. Springfield. Virginia 22151).
5.
433
in this way is reported by Rowe et aL70aThe spectra of stressed GaAs near

3.3 eV exhibits a splitting and polarization behavior which cannot be
explained by transitions between one-electron states. For the first time the
concept of hyperbolic excitons is demonstrated in an experiment, and the
exciton exchange-stress theory 5 - 5 7 * 5 7a applied to the data indicates an
exciton radius of 10 A.70a
Finally, it should be noted that the nondispersive part of the piezobirefringence below the fundamental absorption edge provides valuable
information on piezodichroism at high energies. The very anisotropic
behavior of the piezobirefringence in Ge7 [( W,),, >> ( Wl)l I - ( WJ1 2 , Eqs.
(1 l)]agrees with G e r h a r d t result
~ ~ ~ that the polarization dependence of the
prominent reflectance peak at 2.2 eV is stronger for [ 1111 stress than for [ 1001
stress. As demonstrated by Higginbotham et
a slight dispersion of the
piezobirefringence in G e and GaAs below the absorption edge is induced
by high-energy transitions. Also the piezobirefringence of the alkali halides
has been subject to extensive s t ~ d i e s . ~ ~ . ~ ~
9. FREE-CARRIER
DISPERSION
AND ABSORPTION
a. Intraband Transitions
In the classical limit the electronic intraband transitions can be treated in
the Drude forrnali~m.~
According to this, the contribution to the optical
constants of free charge carriers corresponds to a single oscillator with
resonance frequency equal to zero and a strength derived from the effective
massapproximationand ciassical electrodynamics. For carriers in a spherical,
parabolic band the contribution E to the effective dielectric constant is
Ne2
m*E0 - w 2
&S =-.
+ iwwcol,
(33)
or
and
where n is the conductivity, e is the unit charge, N is the carrier density,

and m* is the effective mass. For less simple band extrema, e.g., a degenerate
edge or a set of anisotropic valleys, an appropriate mean value should be
K . J . Schmidt-Tiedemann, J. Appl. Phys. 32,2058 (1961).
K . G. Bansigir and K . S. Iyengar, Acla. Crysfall.7, 14, 670, 727 (1961)
P. Dtude, Phys. Z . I , 161 (1900).
72
434
IVAR BALSLEV
inserted for m*.74 The collision frequency wco,,accounts for relaxation into
thermal equilibrium, i.e., T = l/mco,, is the time constant appearing in
Boltzmanns transport equation.
At low frequencies and for dc, the piezoeffects of the conductivity [Eq. (35)]
have been investigated for a long
In fact, piezoresistance in n-type
Si and G e was a major contribution in establishing the many valley structure
of the conduction band of these materials. In this case, the conductivity
tensor u may be expressed as
~ ( e=) e
subject to
1Ni(e)pi
N , ( e )=
i
(36)
N,(O) = N ,
I
where N , ( e )and pi are, respectively, the carrier density and mobility tensor
of the ith valley. Thus pi describes the combined anisotropy of relaxation
and effective mass, both contributions and the total carrier density N being
assumed to be strain independent ;and N,(e)may be calculated from FermiDirac statistics applied to a system ofvalleys with different extremum energies
as indicated in Eqs. (25)-(27). The above description is thus based on repopulation, which implies that the anisotropic nature of the individual valleys
becomes apparent.
S~hrnidt-Tiedemann~~
applied these arguments to the real part L , of the
dielectric tensor and developed the theory for optical frequencies (w << w,,,,),
thus avoiding the influence of scattering anisotropy. In the case of n-type Ge,
uniaxial stress X 11 [lo01 will yield zero piezobirefringence and X I( [l 1 13
induces a splitting AE = $Z,XS,, between the [ill] valley, No. 1, and the
remaining three valleys, Nos. 2, 3, and 4. For E, > 0 the [ 1111 valley moves
down for compressive stress. Denoting the corresponding densities by N ,
and N2,3,4one obtains
where mll and m , are, respectively, longitudinal and transverse mass of the
valley. Figure 7 shows the dependence of the quantity ( N , - N2,3,4)/Nas
a function of the stress. The curves are calculated assuming the Fermi level
several times kT below (curve A ) and above (curve B) the lowest valley,
corresponding t o Maxwell-Boltzmann and degenerate Fermi-Dirac statist74
W . G. Spitzer and H. Y. Fan, Phys. Rev. 106,882 (1957).

(R. Loudon, ed.), p. 515. Academic Press, New York.
S. H. Koenig, in Semiconductors
1963.
7h
K. J . Schmidt-Tiedemann, Z . Narurforsch. 16a, 639 (1961); Phys. Rev. Left. 7 , 372 (1961).
5.
1-N2,3,4
1.0
435
-0.4 -
COMPRESSION FOR I,>O
FIG.7. Normalized repopulation versus valley separation AE for [ 1 111 stressed germanium.
where N , - N 2 , 3 , Ais the excess density of the [ I I 1 3 valley and N is the total carrier density.
Curve A is calculated for Maxwell-Boltzmann statistics ( -EF >> k T ) , and curve B is calculated
for Fermi statistics with the Fermi level for zero stress EF(0)much farther than ( k 7 ) above the
band edge. The scale of the abscissa applies to the stress-proportional quantities AEikT and
AEIEAO) for curves A and B, respectively. The sign convention for Ewis such that the curves
to the right should be used for compressive stress and Eu > 0 (as the case for Ge). Note that the
maximum slope of curve A at the black dot is somewhat higher (33 7;)than the zero stress slope.
ics, respectively. The saturation for high magnitudes of stress indicate that
all the carriers are transferred to the lower valley(s). A curve for [Oollstressed silicon, slightly different from curve A in Fig. 7, is given by Aubrey
et al.77 in connection with the analyses of the high-stress piezoresistance in
silicon.
Schmidt-Tiedemanns free carrier piezobirefringence measurements on
n-type Si and Ge7*were performed with low-tensile stress (up to 300 kgf/cm2)
and exhibited no signs of saturation. A satisfactory agreement was found
between measured and expected dependence on temperature and carrier
density of the birefringence. Later, Riskaer determined the discrete stress
values up to lo4 kgf/cm2 which gave half-integer phase shifts in n-type Si
and Ge at 77K. The saturation shown in Fig. 7 and observed for highcompressive stress yielded a determination of Zuwithout a Hall measurement
of the carrier density.
Unlike the above works on materials with relatively small Fermi corrections, the measurements of Feldman8 concerned degenerate n-type Ge at
J. E. Aubrey. W. Gubler, T. Henningsen. and S . H . Koenig, fhys. Reo. 130, 1667 (1963).
K. J. Schmidt-Tiedemann. Pruc. h r r . Cur$ Phyx Semicond., Ererer. 1962. p. 191. Inst. Phys.
and Phys. SOC.,London, 1962.
lY
S. Riskaer, fhys. Rev. 152, 845 (1966).
no A . Feldman. fhys. Rer. 150. 748 (1966).
11
436
IVAR BALSLEV
1.2K. The birefringence exhibited a behavior as shown in Fig. 7 (curve B)

and the value E, = 18 eV was found by fitting the data to the theoretical
stress dependence.
The birefringence due to free carriers in a degenerate band extremum
(holes in Si and Ge) is caused by changes of effective masses [see Eq. (29)]
and by repopulation effects. Schmidt-Tiedemann estimated the low-stress
birefringence with valence-band splitting much less than (kT),and R i ~ k a e r ~
extended the analyses to stress values giving decoupled and ellipsoidal bands.
These theories do not take into account the intervalence-band transitions
which, in Ge, were ~ b s e r v e d t ~o contribute to the birefringence in the near
infrared. In Si the data agree qualitatively with the theory based on intraband
transitions. Thus, signs and approximate magnitudes of the deformation
potentials b and d could be determined.
Returning t o dissipative effects, Eq. (35)indicates that the piezodichroism
in the optical region is qualitatively similar to the dc piezoconductive effects.
A single work has been reported on this phenomenon. Walton and Everett
measured the absorption component a, in the infrared region for [ l l l ]
stressed n-type Ge. It was established that the scattering anisotropy derived
is significantly different from the results at dc. This is not surprising since
the absorption behavior in the infrared deviates from that of a Drude theory.
It should be noted that even if the Drude model were appropriate, then the
optical piezoeffects would be basically different from those for dc. For
o >> ~ c o l the
l
piezoabsorption is determined by anisotropy of the product
z - m- whereas the conductivity tensor for dc depends on the product rrn- .
6. Interband Transitions
In semiconductors, the free electrons and holes thermalized at band
extrema closest to the forbidden gap can be excited optically to other bands
or secondary minima. Best known is the momentum conserving transitions
in Ges3ss4and GaAs8 between three valence-band sublevels. The transitions
are parity forbidden at k = 0, but the k p induced mixing with conduction
band states leads t o optical absorption in p-type material. Hobson and
Paigee6 found a strong stress induced dichroism associated with these
transitions and explained the basic mechanisms involved. As an illustration
we shall discuss a simplified model.
K. J. Schmidt-Tiedemann, Philips Zentrallab., Rept. 47. 1963.

A. K . Walton and C. R. Everett, Solid State Commun. 5, 275 (1967).
H3 R. Newman and W. W. Tyler, Phys. Rev. 105, 885 (1957).
H4 A. H. Kahn, Phys. Rev. 97, 1647 (1955).
R. Braunstein, J. Phys. Chem. Solid.? 8. 280 (1959).
G. S. Hobson and E. G. S. Paige. in Physics of Semiconductors (Proc. 7th Int. Conf.).
p. 143. Dunod, Paris and Academic Press, New York, 1964.
437
I
0.3
0 4
0.5
FIG. 8 . Calculated zero-stress absorption and first-order piezodichroism due lo direct

transitions between the heavy-hole band and the spin-orbit split-off band. The model involves
spherical, parabolic bands [Eqs. (38-39)] with band parameters A , B, and A comparable to those
of Ge and GaAs. The values used are: - A = 13.3h/2m: - B = 10.0h/2m; kT = 0.01 eV;
E, = 0.01 eV; A = 0.30eV. (After Balslev.8)
Consider a p3,2 - p 1 1 2 valence band manifold with spherical, parabolic

bands. These are the heavy hole band (No. l), the light hole band (No. 2),
and the spin-orbit split-off band (No. 3) (see Fig. 8). For photon energies
ho larger than the spin-orbit coupling A, only 1 + 3 transitions take place.
Kahn84finds for this model (zero stress) the spectral shape of the absorption
expressed as
a13
ho
where A and B are valence band parameters [cf. Eq. (29) with D = 31/2B].
In the presence of stress, the energies E , and E 3 and the 1 + 3 transition
probability depend differently on the wave vector k. There are three effects
producing an anisotropic absorption. Firstly, the induced changes of E l
lead to a preferential population in k space. Secondly, for a fixed vector k
the transition probability has a first-order shift with stress. This shift depends
on the angle between k and the stress axis. Finally, the previously spherical
438
WAR BALSLEV
surfaces with constant El - E 3 become more or less ellipsoidal. These

three types of change and the zero-stress dependence of the transition
probability on Ikl and the angle between k and the light polarization direction
lead to considerable dichroism. For spherical, parabolic bands one can
derive an analytical expression for the first order absorption anisotropy.
The result is (Balslev8')
(39)
where E , is the strain perturbation energy of Eq. (29). The first term arises
from repopulation effects. In Ge, for example, a compressive stress induces
a preferential population of holes into states with k perpendicular to the
stress axis (see Fig. 1). The second term is due to changes in transition matrix
elements and in surfaces with constant E1-E3 separation. Spectra of
and aV3 - .i3 are shown in Fig. 8 for values of A , B, A, E,, and kT which are
appropriate for a rough comparison with the case of compressive uniaxial
stress in Ge.
Nonparabolicity and nonsphericity in Ge and GaAs cannot be neglected
in the analysis of experimental results. In a numerical treatment Hobson
and Paige86include these features of the band structure but their comparison
with piezotransmission measurements on p-type G e suggested an insufficient
accuracy in the computation or a breakdown of Pikus and Bir's deformation
potential theory.8 However, a recent reexamination (Balslev8'") brought
agreement between the experiments on Ge and a different k . p treatment
which included the lowest conduction band in the class A basis2 As in Ge,
the spectra for G ~ A s "exhibit
~
different spectral behavior of a I 3 - ai3, in
the cases of [ 1001and [ 11 11stress. This is a consequence of the strong warping
of the heavy-hole surfaces. In fact, it is possible to deduce valence-band
mass parameters from the piezooptical effect associated with these interband
transitions.
In n-type semiconductors, the existence of higher lying conduction bands
often gives rise to absorption structures that cannot be accounted for by
intraminimum transitions.88 Piezotransmission measurements in n-type
GaAs supported the assignment that the near infrared structure of the freecarrier a b ~ o r p t i o n 'is
~ due to indirect transitions from the lowest (0oO)
minimum to a set of secondary (001) valleys.
87
1. Balslev, Thesis, Techn. Univ. Denmark. Phys. Lab. 111, Lyngby. Denmark (Polyteknisk
Forlag). 1969.
8 7 a I . Balslev, Phvs. Reu. 177. 1173 (1969).
W. G. Spitzer and J . M. Whelan, Phys. Rev. 114, 59 (1959).
*' 1. Balslev, Phys. Rev. 173, 762 (1968).
5.
10.
SURVEY OF
439
BAND EDGEDEFORMATION
POTENTIALS
The values of deformation potential constants for band extrema and

interband critical points obtained from various piezoexperiments have great
interest for several fields connected with both fundamental physics and
technical applications.
First of all, it is interesting t o establish consistency between results from
different piezoeffects derived from the same band extremum. An agreement
with respect to character and magnitude of shifts and splitting supports the
interpretation. Secondly, a comparison with first principle calculations of
deformation potentials is an important check of the validity of the theoretical
model. Thirdly, for charge carrier transport in semiconductors, the
predominant scattering due to long wave acoustic phonons can be calculated
from the knowledge of the band structure of macroscopically strained
crystals since the carriers feel these phonons as an almost static deformation with a long wave variation in space. This model applied to many-valley
structures was first investigated by Herring and V ~ g t Later,
.~
the theory
was successfully extended to warm electron^.^'.^^ For p-type Si and Ge the
acoustic mobility is harder to express by deformation potentials since the
warped energy surfaces and the two-band character of the valence band edge
complicate Boltzmanns transport equation. More or less simplified models
have been treated by Ehrenreich and Overhau~er,~
and by Lax and Mavroides.g4 Recently, a very complete, numerical treatment has been reported
by L a ~ a e t z . ~
In connection with sensitive strain gauges, the explanation of the pronounced piezoresistance effect in extrinsic Si and Ge is directly related to
the splitting of band extrema. 1 * 7 5 , 7 7 * 9 6It has further been observed that
very anisotropic point stress on p-n junctions has drastic, though reversible
influence on the voltagexurrent character is ti^.^' In fact this effect has been
proposed to be applicable in electromechanical transducers, e.g., micro1. Goroff and L. Kleinman, Phys. Reo. 132, 1080 (1963).
H . G. Reik and H. Risken, Phys. Rev. 124,777 (1961); 126, 1737 (1962).
9 2 M. H. Jergensen, Phys. Rev. 156,834 (1967).
y 3 H . Ehrenreich and A. W. Overhauser, Phys. Rev. 104, 331,649 (1956).
94 B. Lax and J . G . Mavroides, Phys. Reti. 100, 1650 (1955).
9 5 P. Lawaetz, Thesis, Phys. Lab. 111, Tech. Univ. of Denmark, Lyngby, Denmark, 1967;
Phvs. Rev. 174, 867 (1968).
96 G. L. Bir, A. I. Bloom, and U. V. Ilisavsky, in Physics of Semiconductors (Proc. 7th Int.
Conf.), p. 529. Dunod, Paris and Academic Press, New York, 1964.
Various works o n the effect of point stress on p n junctions: K . Bultius, J . Appl. Phvs. 37,
2066 (1966); W. Rindner, J . Appl. Phys. 36, 2513 (1965); Appl. Phjs. Let?. 6 225 (1965);
Y. Matukura, Jup. J . Appl. Phys. 3, 516 (1964); J . J . Wortman, J. R. Hansen, and R. M.
Burger, J . Appl. Phys. 35.2122 (1964); 37, 3527, 3884 (1966).
90
440
IVAR BALSLEV
TABLE 111
SHEAR
DEFORMATION
POTENTIALCONSTANTS
b AND d
ZINCBLENDE-TYPE
CRYSTALS
Shear deformation potentials of k
Material
Ge
Si
GaAs
GaP
lnSb
CdTe
GaSb
AlSb
b (eV)
d (eV)
0 valence bands
Indirect piezoabsorption'
Direct piezoreflection*
Direct piezoabsorption'
Direct piezoelectroreflectanced
Piezoresistance'
Intervalence band transitions'
Cyclotron resonanceg
Indirect piezoabsorptionh
Cyclotron resonance'
Band calculations'
Direct piezoreflectanceb
Direct piezoelectroreflectanced
Piezoemission'
Intervalence band transitions'
Indirect piezoabsorption"
Piezoemission"
Direct piezoreflectance"
Piezoemissionp
Indirect piezoabsorptionq
'
DIAMONDAND
Method and reference
-2.4 f 0.4
-3.5 f 0.4
-4.1 f 0.4
-2.4 f 0.2
(f)2.7 f 0.3 ( f ) 4 . 7 f 0.5
-4.7 f 0.4
-2.6 f 0.3
(*)2.l f 0.2 (+)7.0 f 1.5
-4.1 f 0.3
-2.3 f 0.2
-4.4 f 0.2
-2.2 f 0.2
-5.3 f 0.4
-2.4 f 0.2
-5.1 f 0.9
-2.3 f 0.4
- 2.5
- 5.7
-4.4 f 0.5
- 1.7
0.2
-6.5 f 0.3
-2.1 f 0.1
-5.4 f 0.3
- 2.0 f 0. I
-2.0 f 0.2
-5.3 f 0.4
-4.4 f 0.5
- 1.4 f 0.2
- 5.0 f 0.5
-2.0 f 0.2
- 1.2
- 5.0
-4.6
- 2.0
- 1.35
0.1
-4.3 f 0.4
Bal~lev.*~
Bal~lev.~~
Glass.36
Pollak and Cardona.68
and Koening and
Hall.'07b
Bal~lev.~~
g Hensel."*
Balslev.28
'Hensel and FeherZ3 with the
reinterpretation of Balslev and
Lawaetz.'07'
FOR
Goroff and Kleinman.90

Bharpava and Nathan.41
I B a l ~ l e v . ~ ~ ~
B a l s l e ~with
~ ~elastic constants
of Weil and Groves.'"
" Guillaume and L a ~ a l l a r d . ~ ~
" Thomas3
Guillaume and La~allard.~"'
q Lucien et
j
phones.'* Finally, in the possible application of stress for laser tuning99 and
for the recently discovered Gunn effect in stressed Ge,'oo.'o' it is important
98
W. Rindner, G. Doering, and R. Wonson, Solid State Electron. 8, 227 (1965).
'' P. R. Emtage, J . Appl. Phys. 36, 1408 (1 965).

loo
A. A. Kastal'skii and S. M. Ryvkin, Fiz. Tekh. Poluprou. 1, 622 (1967) [English Tmnsl.:
Sou. Phw-Semicond. 1. 523 (1967)l.
J. E. Smith, Jr., Appl. Phys. Lett. 12,233 (1968).
5.
441
to know the magnitudes of the deformation potentials of the band extrema

involved.
Tables I11 and IV102-'07dsurvey the shear deformation potentials obtained
from electric and optical measurements on externally strained crystals.
Also given are values derived from band calculations and from acoustic
mobility (of strain-free crystals). Minor adjustments of the originally quoted
results have been included. For the shear deformation potential Zu,
an error
was introduced in some free-carrier experiments based on repopulation.
The calculated zero-stress slope for the change with stress of the observable
quantity (piezoresistance and piezobirefringence) was equated with an
apparently stress-linear behavior for valley splittings up to 1 to 2 kT. In the
worst case of [ l l l ] stressed n-type Ge, this procedure leads to errors of the
order 20-25 % (cf. Fig. 7). Other corrections are commented on in the tables.
There is a good overall agreement in Tables I11 and IV where different
experimental and theoretical determinations concern the same band extrema.
A similar consistency exists in most cases for dilatational stress coefficients'
found from uniaxial and hydrostatic stress configurations. An exception is
an unexplained discrepancy concerning the indirect energy gap in Si and
Gap. The uniaxial experiments28v30
exhibit 2 to 3 times larger shifts than do
the measurements with hydrostatic pressure.'
V. Electronic Impurity States
11. SHALLOW
LEVELS
The best source of information on shallow electronic levels in semiconductors is the far infrared absorption spectrum, as first observed by
Burstein et u1.'08 In such experiments, the low temperature absorption is
due to excitation of ground state acceptors or donors to higher localized or
free states. The theoretical studies by Kohn and Luttinger6' and by
J . C. Hensel, Solid State Commun. 4,231 (1966) with revised stress calibration and extended
experiments (private communication).
lo'
F. J . Morin, T. H. Geballe, and C. Herring, Phys. Rev. 105,525 (1957).
l o 4 G. Weinreich, T. M. Sander, and H. G . White, Phys. Rev. 114, 33 (1959).
' 0 5 1. V. Dakhovskii. Fiz. Twrd. Tela 5. 2332 (1964) [English Trand.: Sou. Phys.-Solid State 5,
lo'
1695 (196411.
R. Weil and W. 0. Groves, Bull. Amer. Phys. SOC.5,764 (1966).

I"' W. E. Krag, W. H.Kleiner, H. J. Zeiger, and S. Fischler, Proc. Int. Conf. Phys. Semicond.,
( J . Phys. SOC.Japan 21, Suppl.), p. 230. Phys. SOC.Japan, Tokyo, 1966.
107aJ.J . Hall, Phys. Rev. Lefr. 5 , 550 (1960).
' o'bS.H. Koenig and J. J. Hall, Phys. Rev. 128,68 (1962).
1 0 7 c I ,Balslev and P. Lawaetz, Phys. Leu. 19, 6 (1965).
'07dH.Fritzsche, Phys. Rev. 115, 336 (1959).
'"' E. Burstein, J . J . Oberly, J . W. Davisson, and B. W. Henvis, Phys. Rev.82, 764 (1951).
'06
442
IVAR BALSLEV
TABLE IV
SHEAR
DEFORMATION
POTENTIAL
E, FOR CONDUCTION
BANDVALLEYSI N
SEMICONDUCTORS
WITH INDIRECTBANDGAPS"
Material and
valley location
Ge ( L )
Si (A)
G a P (X)
AlSb (X)
16.3 f 0.2
15.9 & 0.3 (300K)
17.3 & 1.5'
15.8 f 0.5h
18.0
(4K)
17.3
17.0 f 1.0'
16.0 f 1.6 (300K)
16.5
19.2 k 0.4
(4K)
Interband piezoabsorption'
Piezobirefringenced
Piezobirefringence'
Piezo birefringencef
Piezoresistance"
Piezoresistance*
Acoustoelectric effect'
Zero-stress mobility'
Studies of donor binding energies
(piez0resistance)l
8.6 f 0.2
9.2 f 0.3 (300K) Interband piezoabsorption'
8.1 f 0.4'
Piezobirefringence'
Piezoresistance"
8.3 f 0.3
Warm electrons"
8.4
7.9 & 0.2
Piezospectroscopic effect of
neutral donors"
9.57
Band calculationsP
Interband piezoabsorptionq
7.0 f 0.5
5.4 k 0.3
The experimental results were obtained for temperatures near 100K

unless otherwise indicated.
Values corrected according t o text.
Bal~lev.~~
S~hmidt-Tiedemann.~'
Ri~kaer.~~
Feldman.80
Morin e l U I . ' ~ ~
K~enig.~~
'
Method of determination
and reference
Shear deformation
potential 5"(eV)
' Weinreich et
Dakh~vskii.'~'
Fritz~che.'~'~
' Balslev.z8
Aubrey Y I a/."
Jorgensen.''
" Krag et ~ 1 . ' ~ '
p Goroff and K l e i n ~ n a n . ~ ~
4 Bal~lev
with
~ ~ elastic constants of
Weil and Groves."'
'Lucien et a/.""
j
Schechter"' have demonstrated that the effective mass approximation

applied with a screened Coulomb attraction is a useful basis for the understanding of the excitation spectra. However, the lowest state is usually too
localized to agree in detail with the effective mass theory, and in the oftenencountered case of anisotropy and/or degenerate band extrema, the
effective mass treatment becomes very complicated. Thus the conclusions
'09
D. Schechter, J . Phys. Chem. Solids 23, 237 (1962).
5.
443
from the comparison between calculated and observed spectra have often
been rather ambiguous.
An extremely helpful tool for the further studies of donors and acceptors
has been the application of uniaxial stress. The piezooptic behavior of the
far infrared spectra have been explored extensively for several types of centers.
The shallow impurities which have been studied are group 111and V elements
in Si and Ge, donorlike dislocations in Si, and Se and Te in 111-V compounds."O Deeper centers such as lithium and sulfur in Si and zinc in Ge
l 2 The
have also been subject to piezospectroscopic investigation^.'^^^'
works in this field were all carried out after 1963 and the principal contributions are due to Aggarwal, Jones, Fisher, Onton, Ramdas, Skoczylas, and
White.' l o In the interpretation of these experiments, the basic ingredient has
been Kaplyanskii's6 theory on level splitting and polarized transitions in
stressed cubic crystals.
The complexity of the spectra even for zero stress and the elaborate
computations necessary for a detailed assignment prevent a general discussion of this fruitful branch of piezospectroscopy. We shall only present
some features of a specific center, namely boron acceptors in silicon. Figure 9
shows the splitting and polarization behavior as observed by Onton et a/.' l o
The principal conclusions drawn from these data concern the degeneracies
of ground state and excited states. For example, the splittings confirm the
r, symmetry of ground state since an equal splitting into a t least two components is observed for all lines. The splitting into four components is seen
to occur for the lines 1,2, and 3. This indicates that the three lowest excited
levels have r, symmetry as the ground state. The excited states responsible
for the 4-4A complex are concluded to be three nearly degenerate levels with
symmetry r,, I-, ,and r, . Higher excited states of the p3,2 series (lines 5-10,
not shown) are similarly identified. A splitting into two components of the
2p' line confirms the assumption that the excited state is the lowest level
derived from the pli2 split-off band. Note that the states are denoted by
representations of the group Tdsince the inversion symmetry of the diamond
lattice is absent near a substitutional impurity.
" 7 '
12. DEEPLEVELS
In several insulators the localized defects (impurities, vacancies, etc.) act as
centers for strong emission and absorption below the fundamental absorption
edge. In some cases, e.g., in diamond and ZnO, the origin and nature of such
centers appearing without intentional doping are not fully established.
'lo
'"
Iz
A. Onton, P. Fisher, and A. K . Ramdas. Phys. Rev. 163, 686 (1967); and cited works.
R. L. Aggarwal, P. Fisher, V . Mourzine, and A. K . Ramdas, Phys. Rer. 138, A 882 (1965).
P. Fisher, R. L. Jones, A. Onton, and A. K . Ramdas, Proc. Int. Con$ Phys. Semicond.,
Kyoto. 1966, ( J . Phys. Soc. Japan, Suppl., 21), p. 224. Phys. SOC. Japan, Tokyo, 1966.
444
IVAR BALSLEV
Photon energy (meV1
FIG.9. Piezospectroscopic data for boron doped silicon [Si(B) 51 at 4.2K. The encircled
numbers refer to zero stress absorption peaks while the two figure indications denote split components. E and F are, respectively, polarization and stress directions, E 11 F(---): E IF(-);
and F 11 [111]. (After Onton ef a[.)
Other materials such as alkali halides and alkaline earth fluorides are
suitable host lattices for the studies of specific impurity ions.
In the complicated situation for diamond the piezooptical work by
Crowther and Dean1I3 has great importance. Figure 10 shows the splitting
pattern of the N.9 center in natural diamond for stress parallel to [110].
Several fundamental piezospectroscopic effects are demonstrated in this
example. Nonlinear shifts (level repulsion) and stress-enhanced intensity of
forbidden transitions are obvious from the spectra.
Considerable interest has been devoted to substitutional impurities of
rare earths and transition metals in cubic insulators. Here the excitation
spectra of the impurity ions as observed in absorption and fluorescence are
disturbed by the crystal field of the surrounding lattice. The crystal field
splitting is small or negligible for the electronic ground state, but is easily
resolvable for the excited states with orbitals less shielded from the cubic
potential. In cases of divalent rare earths (Sm2+and Eu) in alkaline-earth
fluorides (CaF,, SrF, , and BaF,) most of the lines observed in the visible
P. A. Crowther and P. J. Dean, J . Phys. Chem. Solids 7 , 115 ( 1967).
5.
445
5.254 ev
5.263 ev
0.1
I
5
10
I
15
I
20
Uniaxial stress (kbar)
FIG. 10. Splitting behavior with uniaxial [ I 101 stress of the N.9 doublet at 5.26 eV in natural
diamond. The E and X are, respectively, polarization and stress directions, and the emission
spectra are taken at 90K. Note the level repulsion and the stress enhanced intensity of forbidden
transitions (B.7 and B.8). A-E I X : 0 - E )I X : X 11 (110) (18 khar). (After Crowther and
Dean. ")
446
IVAR BALSLEV
range correspond t o electric dipole transitions from the incomplete 4f shell

to 5d
The d state splits up due to the cubic field into three levels
and r;, . As for the r;, level, the spin-rbit
with representations rl,rI2,
interaction splits off a Ts+component into which dipole transitions from
the f ground state are forbidden. The remaining Ts+component (a pair of
Kramers doublets) has been extensively studied in the presence of external
strain by Runciman and Stager' 5 , 1 and by Kaplyanskii and co-workers.
A few lines of the Sm2+ spectrum" and all lines observed for activation by
trivalent rare earths' l 8 are due to magnetic dipole transitions inside
the incomplete f shell. This assignment has been confirmed through
piezospectroscopic studies by Kaplyanskii's group. We shall further mention
the very early investigations by Schawlow et uL5 and by Sturge"' on
transitions metal ions (Cr3+and V2+) in MgO. Again, the first excited state
of the ions is affected by strain (a splitting into two components), and a
surprisingly good agreement was found between the observed magnitude of
the splitting and results derived from Hartree-Fock wave functions. A
recent work by Burke and Pressley'"" on the fluorescence of SrTiO, :Cr3+
is an excellent example of informative nonlinear stress effects.
In the above examples, the field near the impurity has the same transformation properties as a lattice site in the host lattice. O n the contrary,
for "oriented impurities" or "anisotropic centers" the potential is noncubic
even though the host lattice may be cubic (for a review, see Clark et ~ 1 . ' ~ ~ ) .
Basic experimental and theoretical studies on piezospectroscopic effects of
these centers are reported by Kaplyanskii'2' and by Crowther and Dean.' l 3
In conclusion, it should be stressed that this brief presentation of works
on strain-induced splitting and polarization of impurity lines in insulators
only gives a vague impression of the complexity of the spectra and the
fundamental character of the phenomena observed in this field. Many
interesting details that are not discussed above can be found in the cited
works.
' '
''
A. A. Kaplyanskii and P. P. Feotilov, Opt. Spektrosk. 13, 253 (1962) [English Transl.:
Opt. Spectr. ( U S S R ) 13, 129 (1962)].
l 5 W. A. Runciman and C. V. Stager, J . Chem. Phys. 37, 196 (1962).
W. A. Runciman and C. V. Stager, J . Chem. Phys. 38,279 (1963).
' I ' A. A. Kaplyanskii and A. K . Przhevuskii, Opt. Spektrosk. 19, 597 (1965); 20, 1014 (1966)
[English Trans/.: Opt. Specrr. (USSR) 19, 331 (1965);20, 577 (1966).
' I 8 A. A. Kaplyanskii and V. N. Medveder, Opt. Spektrosk. 18, 451 (1965) [English Transl.:
Opt. Speclr. ( USSR) 18.45 I (1965)l.
' I 9 M. D. Sturge, Phys. Rev. 131, 1456 (1963).
'I'
lZo
J. Burke and R. J. Pressley, SolidState Commun. 7, 1187 (1969).

C. D. Clark, G . W. Maycraft, and E. W . J . Mitchell, J . Appl. Phys. 33,378 (1962).
A. A. Kaplyanskii, Opt. Spektrosk. 7, 677, 683 (1959); 10, 165 (1961); 16, 602 (1963)
[English Trans/.:Opt. Spectr. ( U S S R ) 7,406,409 (1959); 10, 83 (1961); 16. 329 (1963)J.
5.
447
VI. Lattice Vibrations

13. PHONONS
Little is known about the strain dependence of vibrational frequencies,
particularly the splitting in cubic crystals induced by shear strain. Obviously,
the degeneracies present for equivalent wave vectors are lifted with anisotropic
strain as in the case of electronic Bloch states (Section 5). Such splittings for
phonons are discussed by Hobson and Paige.lz2 However, there is not a
detailed analogy between Bloch states and free vibrational eigenstates.
First, the degeneracies for transverse phonons with wave vectors along high
symmetry directions are not present for free electronic states. In general,
these degeneracies are removed by shear strain unless the transverse polarization directions remain equivalent. Second, the singular behavior of the
optical branches near k = 0 in polar crystals requires that the stress dependence of these modes be discussed separately. Here, much qualitative insight
can be obtained from the phonon spectrum of uniaxial crystals.
Experimentally, Paynelz3 determined the shear deformation potentials
for phonons at L in G e by phonon-assisted tunneling experiments. All
splittings per unit shear were found to be less than three times the phonon
energies. Hobson and Paige used the two-phonon infrared absorption
in stressed Si t o learn more about changes of the frequencies and of the
photon-two-phonon coupling coefficients. Little quantitative information
was gained on degeneracy removals since no splitting phenomena were
revealed. From the polarization dependence of the spectra, the coupling
coefficients were concluded to change fractionally as much as 1 M times
the strain.
A recent attempt to analyze further the piezoabsorption spectrum of Si
in the multiphonon range is reported by Liith.lz4 Here the infrared piezoabsorption was revealed by modulated stress along the [ 1001 direction, but
the experiments did not yield unquestionable results on the symmetry
properties of the spectral singularities.
In a recent work by Anastassakis er ~ 1 . ~the stress-induced
~ ~
splitting
of the k x 0 optical vibration frequency in Si was investigated by Raman
scattering. Since Si is a homopolar cubic crystal, the k x 0 vibration is triply
degenerate. Stress along high-symmetry directions ([loo] or [l 1 11) induces
a splitting into a singlet level and a doublet level corresponding to
ionic displacements parallel and perpendicular to the stress, respectively.
G. S. Hobson and E. G. S. Paige, Proc. Phys. SOC.88,437 (1966).
R. T. Payne, Phys. Reo. Leu. 13,53(1964).
H . Luth. Phys. Sfatus Solidi 39, 131 (1970).
L24aE.Anastassakis, A. Pinczuk, E. Burstein. F. H. Pollak, and M . Cardona, Solid Srate
Commun. 8, 133 (1970).
448
IVAR BALSLEV
The splitting between these levels was found to be 1.4 cm- or 0.26% for
a shear of 1 % produced by uniaxial stress in the above-mentioned directions.
Interestingly, the doublet level has the lowest frequency for [ l l l ] stress,
but the highest frequency for [ 1001 stress.
14. LOCALMODES
In recent years much work has been devoted to the vibronic modes
associated with substitutional impurity atoms. For sufficiently small concentrations, the crystal is still almost perfect in the sense that spheres with
radius of the mean free path of phonons around each defect represent a
small fractional volume. In such cases the mutual interaction between the
vibrating impurity atoms is negligible, and the intensity of the local mode
absorption will be proportional to the impurity concentration. Such spectra
are qualitatively understood from one- or three-dimensional models involving
a defect atom with mass and force constants to neighbors that are different
from the parameters of the perfect lattice. Most theoretical work has been
done on one-dimensional configurations, and it has been possible to derive
eigenfrequencies and eigenstates for the combined motion of the defect and
the atoms of the host lattice.
Here we shall be concerned only with a simple situation particularly
Hydrogen
related to an interesting piezooptical study by Hayes et
(and deuterium) ions in alkaline earth fluorides dissolve substitutionally on
the fluorine sites. Due to the light mass of H - (and D-) there exist vibrational
states characterized by local excitations of the defect and negligible displacement of the rest of the lattice, which is composed of much heavier ions. The
hydrogen ion then moves in a potential well that may be expanded in a
power series in the displacement from the equilibrium site. Elliott et
estimate that the predominant term is a spherical potential giving rise to
harmonic oscillator levels E = (n $)/ho,and that weaker cubic terms,
all having the transformation properties of the lattice site (point group &),
induce small splittings of the spherical levels. The crystal symmetry implies
that some levels remain degenerate, but full splitting can be obtained by an
appropriate anisotropic strain. The piezospectroscopic studies by Hayes
et ~ 1 .concern
l ~ ~ transitions from the nondegenerate ground state [r,(n = O)]
and the r15levels of the excited states with n = 1 and 2. A very detailed
agreement is found between the infrared spectra and the expected splitting
behavior and selection rules. An interesting piezoeffect is the observation of
transitions that are forbidden in the unstrained crystal [r, ( n = 0 )-,
rl (n = 2) and rl(n = 0)+ rlz(n = 2 ) ] .These become apparent for stresses
greater than 2 x lo3 kgf/cm2 (see Section 4).
125
W. Hayes, H. F. Macdonald, and R. J. Elliott, Phys. Rev. Leu. 15, 961 (1965).
R. J. Elliott, W. Hayes, G . D. Jones, H. F. Macdonald, Proc. Roy. Sac. 289, 1 (1965).
5.
449
VII. Experimental Considerations

15. COMPENSATION
METHODS
The determination of changes in dispersive and absorptive properties
withelasticdeformation involves the application of acontrolled homogeneous
stress to the specimen and simultaneous measurement of the optical properties. If the effects studied exhibit large changes of the optical constants, then
these experiments may be carried out with static deformation and conventional optical methods. In such cases it is important to ensure that c1 and c2
have common principal axes if both tensors are involved in the observation
and that the polarization direction is parallel to one of these axes. Otherwise,
unwanted coupling of modes and double refraction will appear. An appropriate geometry for the investigation of cubic crystals is characterized by
normal incidence (reflection or transmission) with propagation perpendicular
to a uniaxial stress along [OOl] o r [ l l 13. Then the quantities TI, TL, R 11,
and R,, defined in the same way as and E~ [Eq. (13)], may be determined
as function of stress and frequency.
In some cases the fractional shifts of the optical constants are very small
for obtainable magnitudes of strain. Then special techniques for revealing
small piezooptic effects should be employed. These are the differential
methods discussed in Section 16 and also some compensation arrangement
that will be mentioned in this section.
First, the use of a double-beam setup reduces the influence of fluctuations
in light source intensity and detector efficiency. For example a double-beam
arrangement may be operated with a strained and a strain-free sample in
the two beams, provided that the samples are otherwise identical. Second,
in normal-incidence reflectance measurements, one can use the fact that the
coupling between a polarization mode and its orthogonal mode is sensitive
to optical anisotropy. For orthogonal setting of polarizer and analyzer
(e.g., 45" to the stress axis) there is no response for isotropic reflection. The
information gained in such arrangements concerns R I , - R , as well as the
difference ell - 3!, between phase shifts during the reflection.
Third, piezobirefringence in transparent crystals can be determined by an
interference method well known from photoelastic studies.2 Here, the
ellipticity of the light transmitted by a slab is analyzed when the incident
beam is linearly polarized at 45" to the principal axes. The angular retardation
cp between the uncoupled modes having refractive indices nil and n, is
given by
where d is the thickness and ;1is the wavelength in free space. For stress-linear
450
IVAR BALSLEV
Dark conditions;
.2)
I
I
'
'p
FIG. 11. Schematic diagrams of optical arrangements for measuring the birefringence
retardation cp of a stressed sample with principal axes along the stress and the light propagation.
The S, P, A, and D are, respectively, monochromatic source, polarizer, analyzer, and detector.
Without a quarter wave plate (Method 2) only discrete values of cp can be detected and the sign
of cp is not revealed. Method 1 is useful for sign determination of cp and for experiments with
IcpI < IT. However, quarter wave plates have the required retardation of n/4 + PIT only for
discrete values of wavelength. (After Jessop and Harris.')
changes in cubic crystals we may write for [OOI] uniaxial stress

where n is the isotropic value of (el)'''. Similarly, for [ l l 13 stress
This gives the connection between the real part of { W} [see Eq. (lo)] and
the piezobirefringence matrix {Q) used in photoelastic investigations.'
Experimentally, the retardation is usually determined either by detecting
conditions where cp = pn or ( p + i)n ( p integer) or by using a quarter wave
plate which changes the polarization from elliptic to linear character (see
Fig. 11). In contrast to birefringence, the uncoupled modes in Faraday
rotation16 are left- and right-circularly polarized light. Otherwise these two
types of experiments are based on similar interference phenomena. Combined
5.
451
measurement^'^' with uniaxial stress and magnetic field, respectively,

perpendicular and parallel to the light propagation produce very complicated
data, but yield no further information compared to separate measurements
of piezobirefringence and Faraday rotation.
16. THE DIFFERENTIAL
TECHNIQUES
7a
Measurements based on differential techniques are characterized by an
applied oscillatory variation in time of a variable, the influence of which on
an observable quantity is studied. The induced modulation of this quantity
is then detected in phase with the applied variation. By using this method in
contrast to the corresponding static experiment the requirements on the
long term stability of the experimental setup are reduced. The advantages of
the differential techniques are generally limited to situations where the
fundamental noise is considerably smaller than the long-term drift, i.e.,
a low frequency noise due to insufficient stabilization of the experimental
setup. Such situations are often encountered in optical investigations in the
visible, near infrared, and near ultraviolet regions where the dark noise of
the detector may be, for example,
times the signal even for relatively
good spectral resolution. In static measurements a maximum amount
of information would then be gained by a stability better than
Obviously, the reduction to such limits of fluctuations of light source,
optical alignment, detector efficiency, and electronic amplification is rarely
possible. Some of the above mentioned contributions to long term drift
may be eliminated in double-beam arrangements where the light path is
alternating between sample and a reference. However, the convenience of
single-beam operation and problems with optical alignment have led to a
very extensive use of differential methods.
It seems appropriate in this section to discuss in general the differential
optical methods developed during the last decade. Consider an observable
quantity R (reflected o r transmitted light intensity, photoconductivity,
luminescence, etc.). We may express this quantity as a function
Q(A, 0, E, H, e, T ) ,
where 1 is the free-space wavelength of the light, the angle 6 characterizes

the polarization direction, E, H, and e are, respectively, electric, magnetic,
and strain field, and T is the sample temperature. To any of the parameters
in the parentheses of Eq. (41), it is possible to apply an oscillatory time
variation. Subsequently, using phase sensitive detection (first or higher
C. R. Pidgeon, C. J . Summers, T. Arai, and S. D. Smith, in Physics of Semiconductors
(Proc. 7th Int. Conf.), p. 289. Dunod, Paris and Academic Press, New York, 1964.
The recently published monograph by M. Cardona, Modulation Spectroscopy, Solid Slate
Phys. Suppl. 1 1 (1969). covers all aspects of the optical differential techniques.
127
452
IVAR BALSLEV
TABLE V
NATURE
OF REPORTED
DIFFERENTIAL OPTICAL EXPERIMENTS
AND
APPROPRIATE REFERENCES
_ _ _ _ _ _ ~
Modulated variable
Static parameters
(other than A,@, and T )varied in
the experiments
none
ep
E
noneg
Hh
ed
H
The quantities 1.0,T, H, E, and e are defined

in the text.
Modulation by rotation of sample or
polarizer.
Works cited by Braunstein127band others.
70-7Oc
Balslev.2*
Fe1dma1-1.~~
f Cardona et a1.127c
8 Batz127d
and Berglund.lz7
n
H
none
E,eX
E.H
Groves et aI.127f
Iwasa and J a ~ a n . (Detection
~~
also of
second harmonics.)
j Seraphin.127h
Pollak and Cardom6
Feinleib et
Gobeli and Kane17 and Engeler et
Bal~lev.~
Aggarwal.128
harmonics), one can measure the appropriate partial derivative (see Table
v 12 7b-128 ). It is often convenient to provide a direct recording of the
logarithmic derivative since this quantity is independent of multiplicative
factors that are irrelevant and are not modulated (e.g., source intensity,
Ior 8
misalignment attenuation, and detector efficiency). Modulation of ,
may be called passive methods where the oscillatory variation concerns
the optics rather than the solid. In the remaining active differential
techniques an applied modulation of a field or the temperature induces
oscillatory changes of the optical behavior. In both cases, we are dealing
with techniques rather than new effects in the sense that the information
gained concerns the parametric dependence in Eq. (41). Fundamental
127bR.Braunstein, P. Schreiber, and M. Welkowsky, Solid State Commun. 6 , 627 (1968).
127cM.Cardona, F. H. Pollak, and K. L. Shaklee, Proc. Int. Con$ Phys. Semicond., Kyoto,
1966, p. 89. Phys. SOC.Japan, Tokyo, 1966.
27dB.Batz, Solid State Commun. 4, 241 (1966).
lZ7C.N. Berglund, J . Appl. Phys. 37,3019 (1966).
H. Groves, C. R. Pidgeon, and J. Feinleib, Phys. Rev. Lett. 17,643 (1966).
127gS.Iwasa and A. Javan, Proc. Int. Conf. Phys. Semicond., Moscow, 1968 (to be published).
127hB.0. Seraphin, Proc. Int. Conf. Phys. Semicond., Paris, 1964, p. 165. Dunod, Paris and
1 2 7 i J . Feinleib, C. R.Pidgeon, and S. H. Groves, Bull. Amer. Phys. Soc. 11, 828 (1966).
12 R. L. Aggarwal, Chapter 2, this volume; R. L. Aggarwal and C. R. Pidgeon, Proc. 10th h i .
Conf: Phys. Semicond., Cambridge, Massachusetts, 1970, p. 531. USAEC Div. Tech. Information, Oak Ridge, 1970 (available as CONF-700801 from Nat. Tech. Information
Serv., Springfield, Virginia 221 51).
5.
453
mechanisms producing a dependence on the modulation frequency of the

spectra are ignored in all differential optical experiments.
The derivative signals are usually recorded as a function of parameters
that are also found in the parentheses of Eq. (41) (see Table V). For example,
Mavroides et al.28amodulate the strain and record aR/ae as a function of
1 and H.Here the piezooptical effect is of secondary interest whereas the
magnetooscillatory effect revealed in the A, H dependence of dQ/de is
important. The strain is used only for obtaining a meaningful signal with
little uninteresting background. In other words, the enhanced sensitivity of
a specific differential method can be used in the studies of the dependencies
on a large variety of static variables. In fact, measurements of the most
versatile derivative aQ/aL replace all other differential methods provided
that the uncertainty of the spectra is determined exclusively by fundamental
noise. This is demonstrated in the piezooptical investigations of the indirect
absorption in G e reported with modulation of
and wavelength.2*
It seems possible also t o study in full detail the electroreflectance behavior
by recording a R / a l as a function of I and of a static electric field since a
wavelength-independent contribution to aR/aE is of minor interest.
We shall finally point out a fundamental limitation of the passive
methods. Usually nonideal optics produce spurious signals. For example,
with wavelength modulation, the spectral dependence of light source
radiation, atmospheric absorption, detector efficiency, etc., may induce
considerable contributions to dCl/al. Correction for such effects must be
carried out by subtracting the response without the sample or by using
double-beam compensation.30*3 0 Fo r very large spurious signals, e.g.,
from sharp atmospheric absorption structures, the advantages of wavelength
moduIation are doubtful even in double beam arrangements.
17. ARRANGEMENTS
FOR STATICSTRESS
Numerous methods have been developed for application of a well-defined
static stress t o solids. The basic principles and design of the mechanical
arrangements are determined by several factors, such as the strength and
dimensions of the samples, operating temperature, desirable magnitude and
homogeneity of the stress, type of optical or electrical access, etc. For optical
transmission measurements the most versatile geometry is characterized by
uniaxial stress perpendicular to the light propagation. Then, for high
symmetry stress directions, the polarization can be chosen to be along any
128aJ. G. Mavroides, M. S. Dresselhaus, R. L. Aggarwal, and G. F. Dresselhaus, Phys. Reu.
lZ9
13
Lett. 17, 8 (1966).

W. E. Engeler, M. Garfinkel, and J . J. Tiemann, Phys. Rev. 155, 693 (1967).
K. L. Shaklee and J. E. Rowe, Appl. Opt. 9,627 (1970).
454
WAR BALSLEV
of the principal axes of the dielectric tensor. This method and the bending
geometry are suitable for reflection and luminescence studies. 14764
There are few experimental difficulties in measurements performed at
room temperature on samples of millimeter dimensions and with strain
magnitudes far from the yield strength of sample and mechanical parts.
Also, there is an option between tensile and compressive uniaxial stress, and
homogeneity is assured by using slim samples. If it is desired to operate near
the yield strength, then special attention must be paid to the stress distribution
near the externally applied forces. In this case a compressive stress (or
bending) is preferred and two carefully guided forces are applied to the ends
of the specimen. A uniform stress at the sample surface can be provided by
epoxy cement, by spacers of lead or tin, or by accurately polished surfaces
of the sample and the steel pistons. The influence of differing elasticities of
sample and pistons may be reduced by choosing the stress-parallel dimensions
much larger than the perpendicular ones. In the opposite limit, i.e., stress
perpendicular t o the surfaces of a thin disk, one also obtains a good homogeneity, but the strain configuration is then determined by the elastic properties of both sample and piston. (The transverse extension is independent of
the sample elasticity.)
At low temperatures several problems need to be solved unless the wavelength region permits experiments with the sample immersed in a liquid
coolant (transparent coolant and cold seal windows). Otherwise a stress
frame must be built on a cold finger, and complicated rod systems need to be
operated through the vacuum jacket of the cryostat. For operation in
vacuum as well as with immersed samples, there are some difficulties in
constructing a mechanical arrangement sufficiently rigid that the sample
moves little with respect to the optics as the forces are applied.
Advanced constructions for low-temperature piezooptical experiments
have been reported by tho ma^,^ Dean and C r ~ w t h e r Dickey
, ~ ~ and Dimmock,131 Schawlow et a!.,' and Shatas et ~ 1 . l The
~ ' ~
last mentioned group
developed a principle similar t o that shown in Fig. 12.132
Here the supporttube-pulling-rod arrangement gives a rigid support with negligible thermal
drain. In situations with modest requirements on variation and measurement
of the stress, it is convenient to induce the strain by cooling an arrangement
with different thermal expansions of sample and sample holder, as described
by R o ~ e - I n n e s . 'For
~ ~ thin samples (less than 0.1 mm) the use of a substrate
may introduce wanted or unwanted strain at low temperature^.^^.^' Further
1 3 ' D. H. Dickey and J. 0. Dimmock, J . Phys. Chem. Solids 28, 529 (1967).
I3laR.A. Shatas, G . A. Tanton, and J. E. Williams, Rev. Sci.Insfr.39, 1380 (1968).
13' M. Cuevas and H . Fritzsche, Phys. Rev. 137, 1847 (1965).
1 3 3 A. C. Rose-Innes, Proc. Phys. SOC.
72, 5 I4 ( I 958).
5.
455
PULLING ROD
SUPPORT TUBE
g-UPPER
&
PISTON
PIN HOLE
PIN FIXING
UPPER PISTON
ACCESS TO
SPECIMEN
FIG. 12. Stress apparatus suitable for piezooptical experiments at low temperatures and
with compressive forces up to 300 kgf. The principles shown here were first reported by Cuevas
and Fritzsche.' 3 2 (After Balslev.z8)
strain in thin samples supported by a substrate can be induced by applying

stress to the substrate.
18. METHODSFOR APPLICATION
OF OSCILLATORY
STRESS
In piezoelectric crystals a sinusoidal variation in time of the strain can be
induced by application of an ac voltage across appropriate electrodes. The
maximum amplitudes obtained are of the order of
A mechanical
to
coupling between a piezoelectric driving crystal and a solid being studied
optically is possible in two fundamentally different ways. Gobeli and Kane's l 7
technique is based on acoustic resonance of a rod with one end mounted
onto a piezoelectric transducer. The length of the rod was tuned to maximum
456
IVAR BALSLEV
amplitude of a longitudinal standing wave. The frequency of the strain

modulation was 130kHz. Engeler et aL3 used a transducer operated at
1 kHz as a substrate for a thin crystal or an evaporated layer. This technique
is therefore restricted to reflection measurements. Also suitable for dynamic
piezoreflectance spectra is the technique developed by Gerhardt.58T66Here
was obtained by low-frequency
a well-defined strain of the order of 5 x
bending(200 Hz)ofa bulk crystal. Another method for inducingan oscillatory
stress was developed134on the basis of the strain apparatus shown in Fig. 12.
A modulated force superposed on a static force was applied to the pulling rod.
However, since friction in the sliding guide of the lower piston depends on
the static force transferred, the design in Fig. 12 did not provide a reproducible
amplitudeofthedynamicstresscomponent for high magnitudeofstaticstress.
This problem is avoided in a modified design.34
The external force modulation applied in the bending or uniaxial modes
has been generated m a g n e t i ~ a l l y ~34~ .or pne~matically.~
These methods
are slow (5&200 Hz) compared to techniques based on piezoelectric transducers. However, at low temperatures and for combined static and dynamic
operation, the mechanical methods are superior.
A common experimental difficulty encountered in any modulated piezooptical technique is the influence of an oscillatory motion of the sample with
respect to the optics. This gives rise to a spurious signal that cannot be
separated from the purely piezooptical response. An unknown offset of the
instrumental zero may be estimated by measuring the signal in spectral
regions in which the piezooptic effect is known to be absent.65 However,
Gerhardt 3 5 has pointed out that photomultiplier tubes may introduce a
spurious modulation which depends on the wavelength. The light passing
through the semitransparent photocathode is scattered inside the tube and
detected from the back side of the cathode coating. A modulation of the light
pathaffects this scatteringwhich implies that the spectral absorption structure
of the cathode produces a considerable wavelength dependence of the zero
offset.
34
135
I. Balslev, Reu. Sci. Instr. 38, 1528 (1967).

U. Gerhardt, private communications.
CHAPTER 6
Electric-Field Effects on the Dielectric Function

of Semiconductors and Insulators
D.E. Aspnes und N . Bottka
I.
11.
INTRODUCTION
. . . . . . . . . . . . . . . .
1. Notation, Units, and Consentions . . . . . . . . . .
. . . . . . . . . . . . . .
2. Historical Survey
INTERACTION OF LIGHTW I T H MATTER. . . . . . . . . .
3. The Dielectric Function . . . . . . . . . .
. .
4. General Properties ofthe Dielectric Function . . . . . . .
ELECTRIC
FIELDEFFECTS
IN THE ONE-ELECTRON
APPROXIMATION
. .
5. General Physical Considerations . . . . . . . . . .
6. The Dielectric Function in the Effective Mass Approximation . .
. . . . .
7. One-Electron Wave Functions in an Electric Field
8. The Field-Dependent Dielectric Function . . . . . . . .
9. Special Topics in the One-Electron Approximation . . . . .
GENERALIZATIONS
OF THE ONE-ELECTRON
THEQRY. . . . . .
10. The Generalized Convolution Formalism . . . . . . . .
1 I . The Electric Field as a Vector Potential . . . . . . . .
ANALYSIS
. . . . . . . . . .
12. ARIR Expression in the E M A . . . . . . . . . . .
13. Symmetry Character of ARJR . . . . . . . . . . .
CONCLUSION
. . . . . . . . . . . . . . . . .
I
111.
Iv.
V.
VI.
457
460
462
465
465
469
475
415
476
492
503
51 1
520
522
526
533
534
538
542
I. Introduction
Since the early days of quantum mechanics, the problem of the effect of
an electric field on crystalline solids has been a challenge to many physicists.
Because it is mathematically the simplest nontrivial perturbation which can
be added to the crystal Hamiltonian (a potential linear in position), it has
been extensively investigated. The first investigation concentrated mainly
on transport phenomena in conducting solids; in 1928 an approximate
quantum mechanical treatment was given by Bloch.' Except for Zener
t~nneling,',~the importance of conduction overshadowed other possible
' F. Bloch, 2. Phys. 52, 555 (1928).
H. Jones and C. Zener, Proc. Roy. SOC.144, 101 (1934).

C. Zener, Proc. Roy. SOC.145, 523 (1934).
457
458
D . E. ASPNES AND N . BOTTKA
electric field effects. In 1940, Houston4 took the first step toward our present
understanding of electric field effects upon insulating solids by obtaining the
first accurate approximation to the wave functions describing crystal
electrons in an electric field. But it was not until 1958 that a calculation of
the effect of an electric field upon the oprical properties of solids was accomplished, a lag caused in part because the extremely small influence of the
field upon optical properties had escaped experimental detection. In 1958,
Keldysh and Franz6 published, independently, the first calculations of the
electric field effect on the optical properties of insulators concerning the
transparent region or forbidden gap. These calculations, together with the
experimental observations of their predicted effect by Williams, Moss,
Boer et ~ l .and
, ~ Vavilov and Britsyn, opened up a new branch of physics
which has since grown enormously.
The stimulus for this growth is due to several factors, the primary ones
being the development of the experimental method of phase-sensitive
detection,Oa and the simultaneous development of methods for calculating
the energy band structure of solids. l 1 Phase-sensitive detection techniques
allowed experimentalists to observe small changes in the optical properties
of crystals induced by electric fields and other perturbations. Band structure
calculations indicated the possibility of associating these small changes
with perturbation-induced effects at specific points in the Brillouin zone.
As a result, it was thought that modulation experiments could be used to
probe the energy band structure of crystals. Possible applications of electric
field modulation to obtain information about higher lying energy band
structure were soon recognized, and the initial electroreflectance experiments of Seraphin and co-workers demonstrated this as an experimental
fact. Since that time, much mutually complementary work has been done in
band structure theory and optical modulation experiments, the latter
W. V. Houston, Phys. Rev. 57, 184 (1940).
* L. V. Keldysh, Z h . Eksp. Teor. Fzz. 34, 1138 (1958) [English Transl.: Sou. Phys.-JETP
7, 788
(1958)l.
W. Franz, Z . Naturforsch. 13,484 (1958).
R. Williams, Phys. Rev. 117, 1487 (1960);126,442 (1962).
T. S. Moss, J . Appl. Phys. 32, 2136 (1961).
K. W. Boer, H. J. Hansche, and U. Kiimmel, Z . Phys. 155, 170 (1959).
l o V. S. Vavilov and K. I. Britsyn, Fiz. Tverd. Telu 2, 1937 (1960) [English Trunsl.: SOL..Phys.Solid State 2, 1746 ( 196 1 )].
See, for example, Chapter 1 on electroretlectance by Seraphin in this volume.
See, for example, J. Callaway, Energy Band Theory. Academic Press, New York, 1964,
and references therein.
B. 0. Seraphin. in Physics of Semiconductors (Proc. 7th Int. Conf.). p. 165. Dunod.
Paris and Academic Press, New York, 1964: B. 0. Seraphin and R. B. Hess. Phys. Rev. Lett.
14, 138 (1965).
6.
ELECTRIC-FIELD EFFECTS
459
involving not only electric field modulation, but stress,12a,bthermal,'2ce and

wavelength' 2 f * g modulations as well. Due to the abundant experimental
information obtained from these measurements and the necessity of interpreting these data, a renewed interest developed in the theoretical description
of the effect of the electric field on insulating or semiconducting solids. The
result has been a great increase in our knowledge of electric field effects
in the past five years, extending the old boundaries of wave function behavior
and Zener tunneling into new areas such as electrooptical effects, collision
broadening, exciton effects, crystal anisotropies, and symmetry determination of optical and band structure features. It is the purpose of this review
to bring into focus these advances and to emphasize some of the problems
which still lie ahead.
The plan of the article will be as follows : Notation, units, and conventions
will be defined, and a historical introduction to electric field theory will be
given. The interaction of light with matter and the definition and general
properties of the dielectric function will be treated next. Useful band structure
concepts such as critical points, joint density-of-states, etc., will be discussed.
The theoretical treatment of the electric field effect on the dielectric function
will be introduced through the simplest theory, the effective mass approximation (EMA).The detailed effect of the electric field upon the electronic wave
functions in the one-electron approximation, described by the Houston
functions for the crystal momentum representation (CMR) treatment, based
on Bloch functions, will be discussed next. The wave functions so obtained
will be used to derive the convolution integral describing the general electric
field effect on the dielectric function in the one-electron approximation.
This will be followed by a series of applications of the one-electron theory
which will consider the weak field approximation, Stark steps, crystals
without inversion symmetry, forbidden transitions, collision broadening, etc.
Extensions of the theory, including more general interactions, will be treated
in the extended one-electron approximation of Rees,' and the recent
formalism of Enderlein. l 4 Finally, an application to symmetry determination
in crystals will be given.
We will focus our attention principally on the theoretical description of
the electric field effect upon the dielectric function arising from direct optical
lzaW.E. Engeler, H. Fritzsche, M.Garfinkel,and J . J . Tiemann, Phys. Reg. Leu. 14,1069(1965).
lZbG.W. Gobeli and E. 0. Kane, Phys. Rev. h i t . 15, 142 (1965).
"'C. N. Berglund, J . Appl. Phys. 37, 3019 (1966).

l Z d A .Balzarotti and M . Grandolfo, P h w . R w . Lett. 20. 9 (1968).
I z e E . Matatagui. A. G . Thompson, and M. Cardona, Phys. Rea. 176.950 (1968).
I ZfG. Bonfiglioli and P. Brovetto, A p p l . Opt. 3. 1417 (1964).
l Z a K .L. Shaklee. J . E. Rowe, and M. Cardona, Phys. Reo. 174, 828 (1968).
l 3 H. D. Rees, J . Phys. Chem. Solids 29. 143 (1968).
l 4 R. Enderlein. Phys. Status Solidi 26, 509 (1968).
460
D . E. ASPNES AND N. BOTTKA
transitions in the one-electron approximation. Many-body methods have

been applied recently by EnderleinI4 and Porsch, and it appears that the
theory will develop in this direction in the future. For completeness, we
extend as far as possible all derivations beyond their original presentations
(which usually concern only the M , or fundamental threshold, as for
example, the works by Reed3 and Et~derlein~)
where only a more general
mathematical treatment is required. The experimental treatment of the
electric-field effect in reflectance is contained in the chapter by Seraphin.
Throughout the chapter, we will adhere to contemporary nomenclature.
1.
NOTATION, U N I T S , AND
CONVENTIONS
The one-electron Hamiltonian of an electron in a crystal
%,(r) = -(h2/2rn) Vr2 + V(r),
(1)
where if Ri is a lattice vector, then

V(r
+ Ri) = V(r).
(2)
In general, let % be the Hamiltonian consisting of %, plus a perturbation.

We will work with the time-dependent Schrbdinger equation
&$(r, t ) = ih d/& $(r, t ) .
(3)
If X is independent of time, the solutions of Eq. (3) are stationary (constantenergy) states where the time dependence of $ can be separated from the
spatial part as
$(r, t ) = $(r)e-iur
(4)
For the unperturbed lattice, 2 = Sois independent of time and the

Schrbdinger equation can be written as
&oVn(k, r) = hOn(k)Vn(ktr) = En(k)Vn(k, r)
(5)
where the spatial functions cp,(k, r) are of Bloch form, and are described by
the wave number k and band index n. We assume k belongs to the first
Brillouin zone in the reciprocal lattice generated by the reciprocal lattice
vectors Ki, and n is the band index in the reduced zone scheme. The energy
E,(k) and the Bloch functions cp,(k, r) are periodic in the reciprocal lattice
vectors K i; the Bloch functions have the form
q,(k, r) = eiku,(k, r) ,
M. Porsch, Phys. Status Solidi 27,359 (1968).
E. 1. Blount, Solid State Phys. 13, 306 (1962).
C. Kittel, Quantum Theory of Solids. Wiley, New York. 1963.
lb
(6)
6.
461
where the functions un(k,r Ri) = un(k,r) have the periodicity of the lattice.
If the volume of the crystal is Vand the unit cell volume is a, then the number
of cells N = V / Q , and we normalize the Bloch functions according to the
convention
Since the unit cells are equivalent, Eqs. (6) and (7) lead to an orthogonality
and normalization condition on the un(k,r)
[
a d3r u:(k, r)un(k,r) = S,.,/N,
where k is in the first Brillouin zone. Equation (7) leads to the completeness
relation
C Vn*(k, r)V,,(k,r) = W - r),
n.k
(9)
where r. r E V . We will also make use of the Wannier functions : l
and can be used to express the Bloch functions as
4nn(k,r) = (1/*)
- -
exp(ik RJ an@- Ri)

R,
(12)
r, r E V. The dielectric function will be expressed in terms of the momentum

matrix element between Bloch states, defined by
d3rq,3k, r)pcp,(k, r) = &,kpn,n(k)j
(13)
where p = (h/i)V.The &,k arises from the explicit use of the periodicity of
the un(k,r), and PnSn(k)
can also be written as
Pn.,(k) = N
s,
d3r u:(k, r)pu,(k, r).
(14)
It should also be noted that the terminology one-electron approximation

will be used in the broader sense of the random phase approximation,
462
D. E. ASPNES A N D N . BOTTKA
implying not only an approximation in which many-body wave functions

are assumed to be separable into products of one-electron wave functions,
but also assuming that each electron moves in an effective average potential
which is produced by all other electrons.
2. HISTORICAL
SURVEY
The effect of a uniform field on the electron-dependent properties of a

crystalline solid is described in the one-electron approximation by the
solution to the time-dependent Schrodinger equation
+ -
[So e b r]$(r, t ) = ih a$@, r ) / d t .
(15)
where J?~is the unperturbed Hamiltonian defined in Eq. (l), t+b(r,t) is the
one-electron wave function of the system, and 8 is the constant electric field.
The solution of Eq. (15) is the foundation of all calculations of the properties
of the solid, and we will outline the historical development of various
approximations and applications.
Until 10 years ago, the only interest in the solutions of Eq. (15) concerned
the electrical properties of crystals. Several approximate solutions to Eq. (15)
were proposed, and some general characteristics of these solutions were
obtained. In his investigation of the properties of conduction in solids,
Bloch' showed that a Gaussian wave packet of Bloch functions from a single
band moved as though the wave vector changed at a uniform rate under
the influence of the electric field. Bloch's method of proof was valid only
fork near the zone center, but the result was later generalized by Jones and
Zener,' who showed that this was actually a general characteristic of such
electronic wave packets. Their derivation showed that if $(r, t ) were expanded
in the complete set of Bloch functions of all bands,
the expansion coefficients A,(k, t ) must satisfy the identity
($
7)
1
IA,(k, t)12 = 0,
whence""
where G(x) is an arbitrary function of x. Equation (18) has the simple

physical meaning of an electronic wave packet acting as a classical particle,
being accelerated in a uniform field of force. Bloch' calculated the actual
form of the coefficients only as a perturbation expansion for small k.
""The proof will be given in Section 7
6.
463
This theory, originally developed for conduction in solids, was applied

later by Zener3 to effects seen only in insulating crystals as an attempt to
describe the interband tunneling phenomenon which now bears his name.
Zener investigated the approximate one-band, one-dimensional solution
where the usual E ( k )function is inverted to define k in terms of E, a procedure

not easily generalized to three dimensions. Zener was able to show that
the one-band expansion was a good approximation except for very large
fields.
The first tractable approximation to the exact solution of Eq. (15) was
obtained by H o ~ s t o nwho
, ~ proposed the functional form
where
k(r) = k,
(e&r/h).
(21)
This was effectively Zener's solution3 in the time domain rather than in the
(one-dimensional) space domain. Equations (20) and (21) show clearly, from
the periodicity of w,(k) and cp,(k, r) in k, that the electron moves in the direction of the field until it is reflected by the lattice (k on the Brillouin zone
boundary), then moves in the opposite direction until it is stopped by the
field, whereupon the motion is repeated. The field must be sufficiently weak
so that it will not cause an electron to jump from one band to another.
In practice, the electron travel is limited by collision effects so that full
periodic motion is never attained.
A further approach to the approximate solution of Eq. (1 5) was the crystal
momentum representation (CMR). This is an operator formalism due to
Adams, l 8 - l B C where the perturbed Hamiltonian of Eq. (15) is transformed
into an operator on the expansion coefficients in Eq. (16). This technique
was used by Kane" to treat Zener tunneling.
The first calculations of the effect of the electric field on the optical
properties of a crystal were done independently by Keldysh5 and Franz6
in 1958. Both workers treated only the M , or fundamental edge absorption
properties, using the Houston functions to obtain the now well-known
E. N. Adams. Phys. Rev. 85, 41 (1952).
Adarns, J . Chent. Phys. 21,2013 (1953).
IBbE.N. Adams and P. N. Argyres, P h p R w . 102, 605 (1956).
'"E. N. Adams, Phps. Re(>.107. 698 (1957).
E. 0. Kane, J . Phys. Chem. Solids 12, 181 (1959).
l8
l S a E .N.
''
464
D. E. ASPNES AND N. BOTTKA
electric-field induced exponential absorption tail which extends into the

forbidden gap. Franz6 derived an integral representation of the absorption
coefficient in the presence of a uniform field which was valid both above and
below the threshold energy. He evaluated this numerically and obtained
oscillations of the absorption coefficient about the zero-field value for
energies above the threshold. Due to their pioneering work, the general
effect of the electric field upon the electronic contribution to the interband
dielectric properties of solids is now known as the Franz-Keldysh effect.
Since the initial calculations of Franz and Keldysh, many workers have
contributed to the theory of the effect of the electric field upon the dielectric
properties of solids. In 1963, TharmalingamZo used the effective-mass
formalism of Elliott2 to obtain the first closed-form solution describing
electric field effects on optical absorption at the fundamental edge.
Callawayz2*22a
used the CMR to show that the absorption coefficient
should contain fine structure, called Stark steps, due to the periodicity
of the lattice. In 1965, Chester and F r i t ~ c h e Y
, ~a~~ o b y , and
~ Pen~hina~~
calculated the effect of field on the indirect absorption in solids. Measurements by Frova and Handler,26 extending to both sides of the fundamental
edge, demonstrated that the Franz-Keldysh effect did describe electroabsorption in crystals.
The advent of electroreflectance in 1965 opened new avenues for the
study of transitions above the fundamental threshold and at the same time
raised the theoretical need to explain the electric field effect of these higher
transitions. In the first effort to explain electroreflectance, Seraphin and
Bottka calculated numerically the Kramers-Kronig transformation of
Tharmalingams result to describe electroreflectance at the direct absorption
edge of Ge. These results were extended to the special case of a field parallel
to the principal axis of an M , critical point by Phillips and Seraphin,28
who showed that the effect of an electric field on a simple nondegenerate
MI-type saddle-point edge is directly related to the M o threshold. In 1966,
AspnesZ9gave the closed form analytical solution in the EMA for the effect
K. Tharmalingam, Phys. Rev. 130,2204 (1963).
R. J . Elliott, Phys. Rev. 108, 1384 (1957).
2 2 J. Callaway, Phys. Rev. 130, 549 (1963).
22*J. Callaway, Phys. Rev. 134, A998 (1964).
2 3 M. Chester and L. Fritsche, Phys. Rev. 139. A518 (1965).
2 4 Y. Yacoby, Phys. Rev. 140, A263 (1965).
C. M. Penchina, Phys. Rev. 138, A924 (1965).
2 6 A. Frova and P. Handler, Phys. Rev. 137, A1857 (1965).
B. 0.Seraphin and N. Bottka, Phys. Rev. 139, A560 (1965).
J. C. Phillips and 9 . 0 .Seraphin, Phys. Rea. Lett. 15, 107 (1965).
2 9 D. E. Aspnes, Phys. Rev. 147, 554 (1966).
6.
465
of an arbitrarily oriented electric field on the imaginary part of the dielectric

constant in anisotropic crystals. This work was later extended to describe
both real and imaginary parts of the dielectric f ~ n c t i o n . ~These
'
results
provided the theory which was needed to identify the type of transition
showed that the finite-field
involved. Recently, Rees" and Aspnes et
dielectric function is related to the zero-field dielectric function quite generally
through a convolution integral. Rees showed that a convolution concept
had fairly general validity at the fundamental absorption edge, more than
was implied by the one-electron approximation (using arguments readily
generalized to the entire Brillouin zone), and independently, Aspnes ef al.
showed that the electric field effect on the crystal dielectric properties in the
one-electron approximation could be represented by a convolution or
broadening of the zero-field function at any nondegenerate point of the
Brillouin zone. The theory was no longer restricted to the region of critical
points in the Brillouin zone nor to the assumptions of the one-electron
approximation, but could be used to calculate electric field effects in real
crystals where the optical properties are determined not only by one-electron
interactions, but also by phonon scattering, electron-hole interaction, lifetime broadening, impurity scattering, etc. Strong resonances, large-angle
scattering, and degenerate points were still excluded, however. Since strong
resonances, particularly the Coulomb interaction between the electron and
hole, assume particular importance at the critical points, this approximation
(also inherent in the former treatments) is serious. A recent series of theoretical
calculations by Enderlein and Keiper,' 2-34 utilizing many-body techniques,
have resulted in the first analytic calculation which attempts an approximate
general treatment of the Coulomb interaction together with the electric
field.14 It appears that future developments in the theory of electric field
effects on the dielectric function of solids will occur in this direction.
Having given a chronological outline of the subject, we can now consider
the more formal aspects of the electric field effect on the dielectric function.
11. Interaction of Light with Matter
3. THEDIELECTRIC
FUNCTION
For completeness, we first consider the interaction of light with matter in
order to link the theory to experiment. There are several different formalisms
which may be used to describe this interaction in terms of the properties of
'O
32
33
34
D. E. Aspnes, Phys. Rev. 153,972 (1967).

D. E. Aspnes, P. Handler, and D. F. Blossey, Phys. Rev. 166,921 (1968).
R. Enderlein and R. Keiper. Phys. S t t h s Solidi 19, 673 (1967).
R. Enderlein and R. Keiper, Phys. Status Solidi 23, 127 (1967).
R. Enderlein. Phys. Srarus Solidi 20.295 (1967).
466
the wave functions of a solid, for example the standard perturbation theory
approach used by Seitz3 or Pines,36 the Kubo formalism,37338or various
Greens function technique^.^^ We outline here the perturbation theory
approach, which has been used predominantly in the calculation of electric
field effects; a discussion of the Kubo and Greens function approaches as
applied to electric field effects can be found in Enderlein14 and P o r ~ c h , ~
respectively. A good discussion of the current operator has been given by
Callaway: and complete treatment of the general properties of the dielectric
function can be found in the article by Stern.41 The connection between
the microscopic and macroscopic forms of Maxwells equations is discussed
by J a ~ k s o n .a~
As usual, the medium is assumed to be infinite, isotropic and homogeneous.
An electromagnetic wave propagating in this medium can be described by
its electric field 8(r, t ) or its vector potential A(r, t). These quantities are
related by the equation 8(r, t ) = - (l/c)d/dt A(r, t ) in the Coulomb gage
and the field induces a microscopic current j(r, t ) in the solid, which gives
rise to a polarization p(r,t) of the microscopic charge distribution. The
propagation of the wave 8(r, t ) in the solid can be described by solving the
microscopic form of Maxwells equations,41a written in terms of e(r, t ) ,
h(r, t), p(r, t ) , and j(r, t ) , the microscopic electric and magnetic fields, and
the microscopic charge density and current, respectively. But since the
wavelength of the propagating wave is much larger than the atomic dimensions of the system, it isconvenient to perform local averages ofthesequantities
and convert Maxwells equations into macroscopic form,41awhich requires
the definition of an average displacement D(r, c), and allows the equations
to be written in the local averages of the microscopic quantities. For an
electrically neutral solid with no external current flow, the Fourier transforms of D(r, t ) , the applied electric field &(r, t ) ,and the averaged microscopic
F. Seitz, Modern Theory of Solids. McGraw-Hill, New York, 1940.
D. Pines, Elementary Excitations in Solids, Chapter 4. Benjamin, Ne\* York. 1963.
3 See, for example, the article by V. L. Bonch-Bruevich, in The Optical Properties of Solids
(Proc. Int. School Phys. Enrico Fermi, Varenna, 1965). p. 333. Academic Press. New York,
1966.
3 8 R. Kubo, Lectures in Theoretical Physics. Vol. 1 (Lectures delivered at the Summer
Institute for Theoretical Physics, Univ. of Colorado. Boulder. 1958). p. 120. Wiley (Interscience). New York. 1959.
3y A. A. Abrikosov, L. P. Gorkov. and I . E. Dzyaloshlnskii, Metody kvantovoi teorii polya
v statisticheskoi fizike, Chapter 6, Fizmatgiz, Moscow. 1962 [English Trans/.: by R. A.
Silverman. Methods of the Quantum Field Theory in Statistical Physics, Chapter 6.
Prentice-Hall, Englewood Cliffs, New Jersey 19631.
40 See Callaway, Chapter 4.
4 1 F. Stern. Solid Strife Pbys. 15. 299 (1963).
J. D. Jackson, Classical Electrodynamics, Chapters 4 and 6. Wiley. New York, 1962.
35
36
6.
ELECTRIC-FIELDEFFECTS
467
current J(r, t ) = (j(r, t)) and polarization P(r, t ) = (p(r, t ) ) are related (by
definition) as
+
= b ( k ,o)+ (4ni/o)J(k,o).
D(k, W ) = 6 ( k , o) 4nP(k, W )
(22)
For sufficiently weak fields, the current term J(k, w ) will depend linearly
on d(k, w ) in the random-phase approximation, and Eq. ( 2 2 ) can be written
(in the linear optical and random phase approximations) as42
D(k, W ) = E(k, O )* b(k, 0).
(23)
The tensor E(k, o)relating D and d in Eq. (23) is defined to be the dielectric
function. The importance of the dielectric function is that it completely
describes wave propagation in the medium on the macroscopic scale.
By matching boundary conditions among incident, reflected, and transmitted
waves a t an interface of the medium with another, the reflectance R and
transmittance T may be expressed in terms of it. The properties of the solid
enter through the source term (4ni/w)J(k,o) in Eq. (22), and E(k,co) is
calculated by evaluating the Fourier transform of the spectral average of
the microscopic current operator Jfr, t ) t o terms linear in the electromagnetic
wave perturbation A(r, t ) or d (r, t ) , using the wave functions of the system.
The microscopic current operator is ( - e ) times the probability current
density of quantum mechanics, or
where $ = $(q, r, t) represents a one-electron state of quantum number q

which is a solution of the perturbed Schrodinger equation
Although other vector potentials may also be included in the Hamiltonian

operator of Eq. (25), we show explicitly only the vector potential of the
(real) traveling wave
A(r, t)
&I
cos(k
,, r
of)
(26)
with polarization vector 2 Ik. In the linear optical approximation, only
That is. D(t) and 8 ( 1 ) are real quantities not proportional to each other at arbitrary times.
i.e., the response D(t) is dependent on the past history of the source I(r).Mathematically this
means there is a convolution relation between them in the time domain, which becomes il
multiplicative relation in the frequency domain.
468
terms to first order in A are kept and the wave function $(q, r, t ) may be
calculated to first order in A in terms of the complete set of eigenfunctions
$o(q, r, t) of Eq. (25) with A = 0. We use the dipole approximation, where
the spatial dependence of A is neglected.
If the eigenstates $o(q, r, t ) represent stationary states of a time-independent
Hamiltonian, the time dependence is separable as in Eq. (4)and the dielectric
function may be easily evaluated in general form. The first-order corrections
linear in A are calculated for the wave functions tj0(q,r,f) by standard
time-dependent perturbation theory. The current operator is evaluated with
these wave functions to terms linear in A. By taking the Fourier transform
of the resulting expression and using Eqs. (22)and (23),we have the expression
(for an isotropic crystal)
E(W) = ~ ~ ( 0
k 2)( w )
where E , ( U ) and ~ ~ are

( 0
the)real and imaginary parts of E(w),Vis the crystal
volume, Aw,., represents the energy difference between the states q' and q
E,,,
hw,.,
E,, - E,,
(28)
where P,,,is the momentum matrix element taken between constant energy
states,
p,,,
($(q', r)I(A/j)V,l$(q. r)).
(29)
9means the principal value, and (N(q)) represents the occupation probability
of the state q
where E , is the Fermi energy and (N(q)) describes the Pauli exclusion
principle and must be added as an ad hoc correction. It is convenient to
separate the real part ~ ' ( 0into
)
the Kramers-Kronig transform4' of the
imaginary part and a remainder proportional to w - ', which gives the
interband contribution to the plasma term. Since
6.
469
Eq. (27) can be written as
where the plasma frequency is given by
As an example, the dielectric function of an insulator in which the constant

energy eigenfunctions are of Bloch form is given by
where the quantum numbers q are now the wave numbers k and band
indices n, P,.,(k) is the matrix element defined in Eqs. (13) and (14),
En*,(k)= hw,,,(k) = En,(k)- En(k)
(35)
is the interband energy separation, the sum of k over the Brillouin zone has
been replaced with an integral as
(36)
and a factor of 2 has been included for spin degeneracy. The bands are
assumed to be either completely filled or completely empty, so wp = 0.
4.
GENERAL PROPERTIES OF THE
DIELECTRIC
FUNCTION
a. Optical Properties of Solids
We now indicate the connection of the dielectric function to experiment.

Since the dielectric function determines the propagation ofan electromagnetic
wave in a medium, it determines the energy loss per unit length, and also the
reflectivity by imposing boundary conditions on the surface. The solution of
470
D. E. ASPNES A N D N. BOTTKA
the one-dimensional Maxwell equation for a monochromatic transverse

wave:
where
F(r,t ) = i?60exp(ik r
iwt)
(38)
gives the relation between ~ ( wand

) the complex propagation vector k of the
wave in the solid [now treated as a macroscopic quantity since the microscopic processes are contained in the dielectric function ~ ( w ) ]
(c/w)lkl = [&((0)]
n(w) + iK(w).
(39)
Equation (39) defines the refraction and absorption indices n and ti, respectively. calculation of Poyntings vector gives the attenuation in terms of
the absorption coefficient
CL =
wE2(w)/nc,
(40)
where &(to)= cl(w)

ic,(w). The reflectivity is obtained by matching boundary conditions at an interface with an ambient dielectric function E , which
is taken to be real. The ambient dielectric function may also be described by
the refraction index n, = (E,) or the propagation vector Ik,l = (w/c)n,.
If k = Ikl and k, = IkJ, the reflectivity is
Ik
k,l/lk
+ k,J.
(41)
Modulation experiments which induce changes in the dielectric function (we

take the perturbation to be a function of an external electric field a),
AE(W 8)= E(O, 8)- E ( W , 0 ) = A E ~ ( w8)

, + i AE(u, a),
(42)
therefore induce changes in the reflectance and absorption which can be

described by the equations
+ P ( o )AE(w,6 ) ,
AR(w,b ) / R = U(O)A E ~ ( w8)

,
ACL(O,6) = Y ( O )A E ~ ( w&)
, + 6(w)AE(w,6 ) .
(43)
(44)
where the fractional coefficients CL [not to be confused with u(w.$), the

absorption coefficient], P, y, 6 are given by the following expressions in terms
of the indices n, K of the unperturbed solid and n, of the ambient.43
B. 0.Seraphin and N. Bottka. Pliys. RCV.145. 62X (1966).
6.
47 1
-Oh
?i' =
c ( n 2 + /(2)'
6=
nw
c(n2 +
ti2)-
Near the fundamental edge ti 1 0 and A R x A E ~A2, x As,.

Finally, if the perturbation AEis a function of distance and IAcl << I E ~ , then
~
be replaced by the average44
and A E must
(AE)
( A E ~+) i(Ac2)
J
- x,
for a semi-infinite solid with interface at z , in calculating AR and AM.

h. Kramers-Kronig Relations
The real and imaginary parts of the dielectric function are not independent.
Fundamental considerations of causality45 require a connection between
them and this connection is expressed by the Kramers-Kronig relation4'
J-.r
(47)
where 3represents the principal part operation. The interband contribution

to ~ ~ is
( usually
0 ) calculated from sz(w)using Eq. (32),since E,((u) is more
easily calculated theoreticalIy due to the 6 function in frequency which
appears in Eq. (32). It is only necessary to calculate the part of c 2 ( u ) associated with the function 6(wqq.- t u ) since the second 6 function gives a contribution equal to the negative of this with negative frequency argument,
required to satisfy the reality conditions on
We use only the half of
generated by 6(wqq, - w ) , in which case the interband contribution to
E~(w
must
)
be calculated from the expression3'
El(W)
44
"
+ -n2 P
D. E. Aspnes and A. Frova. Solid
w' dw'
f-
~ (Q'
,
E2(W')
+ 0)(00)
-
Strrtc C'orn/nuti. 7, 155 (1969)
J. S. Toll. P h v s . Rer. 104. 1760 (1956).
412
The changes A q ( o ) and A E ~ can

( ~ be
) related approximately by3
provided they are nonzero only in a narrow range o f o . Equation (49)neglects

contributions from the poles at w = - o and a = 0 (implied)in Eq. (48), but
is generally completely adequate for describing perturbation-induced changes.
c. Critical Points
The dielectric function of a periodic crystal exhibits features that are due
to the topological properties of the continuous, periodic eigenvalues E,(k)
which describe the energy of an electron in the Bloch state qn(k,r).45a
These appear most clearly in c 2 where the 6 function causes singularities at
certain points in the Brillouin zone, called critical points, where the gradient of the interband energy vanishes (i.e., the constant-energy surfaces are
parallel). A vanishing of the interband gradient can occur in four topologically distinct ways between two nondegenerate bands: at a maximum, at a
minimum, or at either of two types of saddle points. These singularities are
extremely important from an experimental point of view, since the dominant
perturbation-induced changes in the dielectric function occur in the vicinity
of these points. Van
has shown that the periodicity of E(k) alone
implies that E,.,(k) has a certain minimal number of critical points and that a
large number of critical points are possible between a given band pair. To
show these singularities explicitly, we transform the imaginary part of Eq.
(34) associated with 6[o,,,(k) - o]from a volume integration in k space to a
surface integration using the coordinate transformation
d3k = dE dS,.,/JV,E,.,(k)J,
(50)
where dS,., represents an element of area of the constant interband energy

surface Enrn(k)= E in k space, and dE is the energy increment in that space.
The result is
Using the properties of the 6 function and assuming the momentum matrix
element to vary slowly with k, we obtain
45aL,
Van Hove, Phys. Rev. 89, 1189 (1953).
6.
473
where
is the joint density-of-states for interband transitions. The singularities of

critical points in E , or in the joint density-of-states are now evident : they
occur where the gradient of the interband energy vanishes, i.e., when V,[E,,(k)
- E,(k)] = 0.The four types ofnondegenerate critical points can be explicitly
shown by expanding the interband energy as a function of wave vector about
the critical point k, in a power series
where the summation indices i, j represent the coordinate axes x, y , z. Since

the gradient vanishes at the critical point itself, an expansion about this
point has no terms linear in wave number, and only the constant and quadratic terms appear in the parabolic approximation. In the language of analytic
geometry, Eq. (54) describes a constant energy surface in the vicinity of k,.
The expansion coefficients can be rewritten in the coordinate system which
diagonalizes Eq. (54),
where we define the reduced mass pi as
and where me* and mh* are the effective masses of the electron and hole,
respectively. A positive reduced mass thus corresponds to a minimum in
energy along that particular direction, and a negative mass corresponds to a
maximum.
Since there are four distinct combinations of signs of the masses, there are
four types of nondegenerate critical points designated by M , through M , .
Near a local minimum [ M o ] or a maximum [ M , ] , the components of the
reduced masses are all positive and negative, respectively. With reference to
Fig. l(a-d) the surfaces ofconstant interband energy E,.,(k) are then ellipsoids
o r spheres (the critical point surface itselfbeing a surface of radius zero). Near
a saddle point [MI] the reduced masses p x and ,uYare positive, and p z is
negative; the saddle point defined by p, positive and ,ux and pl,negative is
designated as M , . In the former case, the surface of constant interband
energy is a hyperboloid of one sheet : in the latter it is a hyperboloid of two
474
I>. F.. ASPNES A N D N . BOTTKA
FIG. I . Constant energy surfaces through or near a critical point. ( a ) Surface near a local
minimum M , or maximum M , : (h)surface through a saddle point M , or M , ; Ic) surface near a
saddle point M , : (d)surface near ii saddle point M I .
sheets (the critical point surface itself being a double cone). Two points
should be emphasized at this stage, one being the quadratic approximation
assumption, the other being the interband nature of these surfaces. The
surfaces near a critical point are quadratic surfaces only in the neighborhood
of the critical point and as soon as one goes far enough away from this point
this approximation no longer holds. Degenerate critical points, such as the
doubly degenerate valence band l- point of group IV semiconductors, are
not expressible anywhere a s quadratic expansions but are more complicat-
ed.4h.4ha
As an example of the joint density-of-states function, we consider the

simplest possible case, the tight-binding approximation for the simple cubic
lattice where the energy bands have the form
U k ) = ( E g + 315,) - EI[cos(nk,/k)
+ cos(nk,/k) + c o ~ ( ~ ~ k , / k )(]5, 7 )
and the momentum matrix element is k independent. The calculated density

of states is shown in Fig. 2. The four types of critical points are evident as
square-root singularities, and their k space locations are indicated. This
G . Dresselhaus, A. F. Kip, and C. Kittel, P h j x R ~ P98.
. 368 (1955)
.IhaE.0. Kane. J . Phys. Chrm. S o M \ I . 82 ( 1956).
I
6.
475
x
Mo
MI
M;
(0001
11001
(0101
(001)
(1101
(1011
1011)
Mi
Flw
IIIII
FIG.2. The joint density-of-states for the simplest periodic energy bands. the tight-binding
approximation for the simple cubic lattice. The eight critical points and their k-space locations
and types are indicated.
is the minimum number of critical points a nondegenerate band can haveone minimum, three of each type of saddle point, and one
The
importance of critical points in all modulation experiments should now be
obvious ; a perturbation which changes the density-of-states causes the
largest relative changes to occur where the density-of-states varies most
rapidly with energy, that is, at the critical points themselves. For example,
stress and thermal modulation tend to give a derivative-like structure by
shifting the energy of a critical point, among other effects. A uniform electric
field in effect broadens the zero-field structure, a process which also results
in the greatest modifications where the unbroadened function changes most
rapidly. The remainder of this chapter will be devoted to the theoretical
description of the latter effect.
111. Electric Field Effects in the One-Electron Approximation
5. GENERAL
PHYSICAL
CONSIDERATIONS
When an electric field is applied to a crystal, basically two different
effects occur: the relative positions of the atoms in the crystal lattice shift,
and the wave functions of the electrons in the crystal become distorted. The
first effect is dominant in ferroelectric crystals or in crystals approaching
ferroelectricity, such as perovskites, but weak in other crystals ;its theoretical
description has been given by Brews4' and Zook and Casselman$8 and we
d o not consider i t further. The crystal lattice is assumed to be undistorted by
47
4"
J. R. Brews, Phys. Rev. Lett. 18, 662 (1967).

J. D. Zook and T. N Casselman. Phvv. R t v . Letr. 17.960 (1966).
476
the field, and we consider the effect of the uniform field upon the electrons
only.
The latter effect may be described qualitatively in several ways. Basically,
the application of an electric field to the crystal breaks the symmetry of the
Hamiltonian in the direction of the field by adding a potential energy term
r& r which varies linearly in position. The one-electron Hamiltonian is
therefore no longer invariant to lattice translations in the direction of the
field, and the wave vector of an electron in this direction is no longer a good
quantum number. In other words, the effect of the electric field on the quasicontinuous states in a band will be to mix those states whose wave vectors are
connected by a linear relation which we write as
k, - (e at jh),
(58)
with t being an independent variable. As the field increases, this intraband

mixing increases, which causes the bands to widen until, for high enough
fields, interband mixing occurs, allowing electrons to tunnel to higher
bands. Interband mixing is negligible for small fields except at degeneracy
points, where it cannot be neglected even for arbitrary small fields.
Degeneracy points are traditionally treated by assuming such interband
mixing to be negligible, which is not valid theoretically but appears to give
the correct experimental results.
An alternate approach to the electric field effect is to consider the
momentum of the electron to be increasing linearly in time, in response to
the electric field, as
hk = hk, - e a r .
(59)
The physical picture is that of a classical particle under uniform acceleration.2 Since Eqs. (58) and (59)are identical, we are again led to the conclusion
that the wave functions will consist of a linear combination of Bloch functions
whose wave vectors are connected by the acceleration - e b / m . It is this
acceleration or mixing which causes the photon-assisted tunneling or FranzKeldysh effect and is also responsible for Zener tunneling of electrons between
bands in high electric fields. Having emphasized the physical basis for
electric field effects in crystals, we can now explore the formal derivations of
the dielectric function in the presence of an electric field.
6. THEDIELECTRIC
FUNCTION
IN THE EFFECTIVE
MASS APPROXIMATION
Although the first treatments of the electric field effects by Franz and
Keldysh5 utilized the Houston function approach, the first closed-form
solutions of the electric field effect on the dielectric function in the vicinity of
a critical point were given in the effective mass approximation (EMA) by
several a ~ t h o r s . Since
~ ~ the
~ ~more
~ detailed
+ ~ ~ treatments
~ ~ ~ ~are* usually
~ ~
6.
477
reduced to the EMA expressions for computation, we introduce the electric

field treatment by this approach, which describes the general effects. The
method is relatively crude, neglecting nonparabolicity and fine structure
due to lattice periodicity, but the solutions represent the best approximation
available for anisotropic thresholds at the present time. In view of auxiliary
effects such as collision broadening, which tend to suppress all but the gross
structure near higher interband critical points, the EMA expressions appear
to describe experimental results at least qualitatively.
Calculations in the EMA have proceeded from an expression developed by
Elliott2 for the description of excitonic effects. This is a two-electron EMA
and does not properly belong in a one-electron discussion, but since it has
been used exclusively in the one-electron EMA treatments of the electric
field effect, we include it. It represents a certain amount of theoretical overkill
from the standpoint of the one-electron EMA, but it permits the Coulomb
interaction to be included without further effort. We first outline the derivation of Elliotts expression,21 and in so doing will develop the normalization
restrictions required on the EMA wave functions when obtaining the electric
field effects in the following section.
a. The Elliott Formalism

In light of the one-electron approximation, a semiconductor or an insulator
can be described as having a ground state represented by a number of completely filled valence bands and separated from completely empty conduction
bands by an energy gap. In the excited state, electrons are excited across the
gap into the conduction band. The one-band ground state can be written as49
$0
(N!) i2P~v(ki,ri)...cpv(kN,r~)
,
(60)
where P denotes the antisymmetric combination of one-electron Bloch

functions arising from the indistinguishability of the N electrons in a valence
band. The one-band excited state can now be described as
$
( N ! ) i 2 P V v ( kr1)
~ , . . Vc(ki,T i ) . . . Po,&,,rN),
(61)
where the wave function cpv(ki,Ti) has been changed to cpc(ki,Ti). The total k
value of this state is K = ki - ki and the total energy E ( K ) = Ec(ki)- E,(ki).
We can also think of this excited state as containing two particles, an electron
in a conduction band having wave number ki, and a hole representing the
absence of the electron in the valence band having momentum k i , charge,
and energy opposite in sign to the conduction electron. While remembering
the true representation of the wave function as Eq. (61), we can write the
49
R. J. Elliott, in Polarons and Excitons (Scottish Universities Summer School, 1962)

(C. G. Kuper and G. D. Whitfield, eds.), p. 269. Plenum Press, New York. 1963.
478
D . E. ASPNES A N D N. BOTTKA
excited state as
$ ( k l , r l ; k z 7 r z )= ( ~ ~ * ( k ~ , r ~ ) ( ~ ~ ( k ~ ~ (62)
r ~ ) ~
where the hole state represents the absence of an electron of momentum - k, .
The effective mass approximation follows by t a k i ~ ~ g ~ . ~
JT = Xo(rl) + x o ( r z ) +
W l ,rz),
(63)
where X ois the Bloch Hamiltonian of Eq. (3) and V(r,, r2) is a slowly varying
perturbing potential. We construct a trial wave function of two-band form
$ v c ( q ~ , r l ; q z , r z=)
mi32
F(ql,Rl;q2,R2)u,*(rz - R M r 1 - R A ,
(64)
where F is a slowly varying function of its variables and uc(rl - R,)and

uv(rz - R2) are Wannier functions defined in Eq. (10); $Jq1, r l ;q z , r2)must
satisfy the time-independent equation
,f$vc(q13r1 ;q21rz)
W(q,7qz)$vc(ql9rl :q29rz)*
(65)
where q, and q 2 are the relevant quantum numbers of the eigenvalue Eq. (65).
Utilizing the standard methods of the one-band EMA, we have F ( q l , qz ;
R , , R2) as the solution of
[EC(- iVXJ - Ev(iVxJ+ V(xi
XZ)
W q i qzll
F ( q 1 , x 1 ; q 2 , X 2 ) ~ x l = R l , x ~ = R 2=
0,
(66)
where q , and q2 have become the quantum numbers for Eq. (66), and x 1 and
x z are treated as continuous variables. Since $(q,, r l ;q z , r2) is to be used as

a constant energy solution for evaluating the dielectric function, it must be
normalized as
which requires the equivalent normalization of F
In the parabolic approximation, the energies E , and E, in Eq. (66) are

expanded to second order in the gradient operators. Equation (66) then representsa two-particleeffective Hamiltonian which can be separated by introducJ. C. Slater, in Encyclopedia of Physics (S. Flugge, ed.). Vol. 19, p. I . Springer-Verlag.
Berlin. 1956.
R. A. Smith, Wave Mechanics of Crystalline Solids, p. 348ff.Chapman & Hall, London,
1961.
50
6.
479
ing relative and center-of-mass (CM) coordinates5 l a

p = x, -
X2'
with conjugate momenta
MacM
+ m,*x,
m,*x,
hKCM,
(704
p p = p(Xl - X 2 ) = hK,
(70b)
where local coordinates i = x, y , z have been chosen to diagonalize the

effective mass tensors me*and mh*.and
Using Eqs. (69), Eq. (66) can be rewritten as
.f'(ql?p)FCM(q2 R) = 0
I
(72)
where the relative and C M coordinate separation has been extended to

W(q,, q2) and also to F(q, ,q 2 , R,, R2). Considering only the electric field
and the Coulomb interactions,
-2
independent of the CM coordinate ; the CM solution can be written immediately as the plane wave
FcM(K, R) = ( l/N1'') p i K.R,

W&(K)
==
( 74)
1(h2/2Mi)KiZ.
(75)
Since the Jacobian of Eqs. (69) is unity, the normalization given by Eq. (68)
remains unchanged. The normalization of F,, has been chosen in Eq. (74)
51a
The Jacobian of the transformation is unity, hence,

for any function of g(r,, r2).
5 gfr,,r2)dr dr,
fg(p, RcM)dp dR,,
480
so that by Eq. (68), f(q, p) satisfies
Cf*(cl,p)f(q, P) =
JqZq
(76)
where the sum p is over the N lattice vectors of relative coordinate space.
Thereforqffq, p) is determined by the normalization Eq. (76)and the differential equation
where q represents the numbers identifying a particular solution of Eq. (77).

Taking f(q, p) to be known, E ~ ( O ) may now be evaluated from Eq. (32).
Equations (64) and (74) show that the matrix element PqZq
in Eq. (29) can be
written as
(il(h/i)
vr1.f)
N2
6KOi
Pcvf(q, 0)
(78)
in terms of the quantum numbers K and q, where P,, is the momentum matrix
element between Bloch states cp,(k, r) and cp,(k, r) as defined by Eq. (3). The
derivation of Eq. (78) requires the usual effective mass approximation of a
k-independent momentum matrix element. We find the complete expression
( 0 )from J(w,., - o)as
for the part of ~ ~ arising
where f(q,p) is determined by Eqs. (76) and (77), and W(q) is the energy
belonging to the solution identified with the quantum number q. Equation
(79) is the equation obtained by Elliott for discussing excitonic absorption.21
Before proceeding with the electric field calculation in the EMA, we
obtain E ~ ( O ) for V(p) = 0
f(q, P)
2exp(iq * P) = /z exP(iK - P)
1
where K is the wave vector of the plane wave. We obtain for a single band
pair c, v the expression
TABLE I
THEFUNCTIONAL
DEPENDENCE
OF THE DIELECTRIC
FUNCTION
O N ENERGY
IN THE VICINITY OF THE FOUR
T Y P E OF CRITICAL.
BANDSI N THE E M A , IN THE ABSENCEOF ELECTRIC
FIELDS
POINTS FOR PARABOLIC
Critical point
Mass sign
MO
P X ? Py7
MI
P:
PLr.Py
M,
<0
PLx.Py
P:
<0
1 - B / w Z ( o1-
B/W2[2(Wg)Z
>0
Pz < 0
>0
+ B / w ~ [ ~ ( w , -) (me
~ + w)
>0
P:
P x 7 Py7
M3
E1,W
E2,W
( w~ o)u(w,
W,)~U(W-
- ( W g + W ) l 2 - (ag- W ) l Z U ( W , - W ) ]
+ B/w(w
w ~ ) ~ u (-ww g )
E/w(w - W , ) ~ U ( W - w ~ )
w)]
os)
>0
C , - B/w(w, - w)u(w, - w ) ~
C,
- B/w(w - UJ,)~
~U(UJ
- UJJ
B / w ~ ( w, o)*u(w,
- W)
(2eZI&.P,,12/m2h)(81~(,~,~c,l/h3)
: u ( x ) is the
2 unit step function; h o g is the critical point energy at the M icritical point between the bands c,v.
bThe constant C , is indeterminate due to the divergence of the EMA integrals at the M , and M , critical points.
482
after changing the sum to an integral. The analytical form of the zero-field
dielectric function at each of the four types of critical points is given in
Table I ; the real part is calculated from the imaginary part by means of the
Kramers-Kronig integral in Eq. (48).
h. Electric Field EfSects

We now consider the effect of the electric field in the EMA using the
Elliott formalism developed in the preceding section. The Coulomb interaction will be neglected on the grounds that we are dealing with solids
which have relatively weak exciton binding (for which the EMA is itself
valid). Although the Coulomb potential has a singularity at the point where
the wave function is to be evaluated [see Eqs. (77) and (79)], it should be
realized that the EMA eigenfunction f(q, p) itself does not. Moreover, if the
electric field is sufficiently strong so that its potential across the exciton
orbit exceeds the exciton binding energy, the exciton would not exist as a
bound entity and the field effect should dominate anyway. We present these
usual arguments given for the neglect of the Coulomb interaction, but the
principal reason is, of course, that the relative coordinate EMA equation
has no closed-form analytic solution when both interactions are included."
But if the Coulomb interaction is neglected, closed-form solutions for all
four critical points with an arbitrary field direction in an anisotropic solid
can be ~ b t a i n e d ~ as
~ .we
~ ' now indicate.
By choosing a local coordinate system which diagonalizes the mass tensor
in the vicinity of a critical point of energy E, = hw,, Eq. (77) in the presence
of a field becomes
which is separable in Cartesian coordinates p = ( x , y, z). Given field comand gZalong the local principal axes, the solution of Eq. (82)
ponents gX,q,,
can be written asz9
f(q, p)
CxC,Cz Ai(
-e&"x - Ex
hex
Ai(
-egLyy he,
"')Ai( -e&"z - E,
he,
, (83)
bRalph52and B l o ~ s e yhave
~ ~ performed numerical calculations based on the separation of
the relative coordinate equation which can be done in parabolic coordinates. These calculations, however, can be easily done only for isotropic (hence, M , or M , ) critical points.
(See Chapter 3 by Blossey and Handler in this volume.) Enderlein14 has also treated the
problem in a different formalism, which we consider later.
5 2 H. 1. Ralph, J . Phys. C1, 378 (1968).
5 3 D. F. Blossey. Phys. Rev. B2. 3976 (1970); B3, 1382 (1971).
51
6.
433
where the Airy function is defined as54355

Ai(x) = x
lorn
+
Srn
ds COS(+
xs) =
2n
-W
ds exp( ifs3
+ isx) ,
(84)
which is the convergent solution ofs4
d 2 Ai(x)/dx2 = x Ai(x).
The quantity hei is given by
(86)
/idi = [ e Z ~ z h 2 / 2 p i ] / 3 ,
and the normalization coefficients Ci are to be determined. The quantities

hei have the dimensions of energy and depend on the magnitude of the ith
component of the electric field to the 3 power, and on the inverse f power of
the reduced mass in the ith direction. Therefore, hOi will be independent of
the sign of the field and will have the same sign as the reduced mass in that
particular direction. The general quantum numbers qi are just the energies E , ,
and
W ( q )= E , E x E , E , .
(87)
+ + +
The normalization condition given by Eq. (76) requires some care to

evaluate. We are working in a continuum in E space, hence the summation
Eqin the expression for the dielectric function will be replaced by
+
But in order to do this, the normalization condition must also be converted

into continuous variables. Since the normalization sum is over N vectors in
the volume V, each vector is separated by a length Li= ( V / N ) l 3 ,hence
,.
and for each coordinate Eq. (76) becomes
(N/V13
dpif,*,,JEi*P i ) L e l J E i , P i )
d(Ei
Ei)?
(90)
--a,
H. A. Antosiewicz, in Handbook of Mathematical Functions (M. Abramowitz and

1. A. Stegun, eds.), Applied Mathematics Series 55, pp. 446ff.US.Department of Commerce,
National Bureau of Standards, Washington, D.C., 1964.
5 5 The Airy integral is conventionally normalized as 1/71 or K ~ .In A ~ p n e s , the
~ normalization
constant was chosen to be N to allow for either normalization. The preferred normalization
is N = n, which we use throughout, t o avoid confusion with N as the number unit of cells
in the crystal. The normalization N = K is used in Antosiewic~.~
N =K
is used in
Enderleini4 and references therein.
54
484
which allows evaluation of the normalization coefficients Ci and the direct

replacement of C, in Eq. (79) with J dE, dE, dE,. Since29
W
dtAi(t
+ x)Ai(t + y) = S(y - x),
(91)
we have, using Eqs. (83), (90), and (91),

lCil
( N / 1/)'13( elql/h28iz),
whence
d(E,
dE, dE, dE, A?(
2)3) 2)
Ai2(
Ai'(
+ Ex + E , + E, - h a )
(93)
for a single band pair (c, v) in the EMA. All four types of critical points are
included in this expression through the sign dependence of the characteristic
energies hUi according to Eq. (86). We will use Eq. (93) to calculate only
the change
A E ~ ( w8)
, =&
8) E ~ ( w01,,
(94)
2 ( ~ -
since the EMA is valid only in the vicinity of the critical point energy E,.
Contributions from other critical points will not generally interfere, so only
a particular interband transition c, v is treated. An important exception
occurs for equivalent critical points, where by crystal symmetry several
critical points a t the same energy occur at different points in the Brillouin
zone as, for example, is evident in Fig. 3. These are treated as being independent, each with its local coordinate system, and the total dielectric
function change is given by a sum over all equivalent critical points. We
discuss this more fully in Section 12.
It is of interest to write Eq. (93) in a form approximating Eq. (81), the
zero-field case. Using the integral representationz9
(95)
and the identity29
W
dt Ai(t
+ x) Ai(at + y) = 11 - u31- ' 1 3

=
S(y - x)
Ai
if
o!
1,
(96)
6.
485
FIG.3. The Brillouin zone of a diamond lattice showing the symmetry points and directions.
Points which can be connected by reciprocal lattice vectors are equivalent and have the same
energy.
we rewrite first each term in the integrand, then perform the integrals over
E x , E,, and E , . The result is
&2,,(W,
8)=
4n2e21e PCJ2
I~x414
m202
8 . 22/3n3fi4 l ~ x ~ , ~.lo1
,l
?
f
where
tI3 = ex3
+ By3 + O z 3 .
(98)
Equation (97) can be further reduced if we let
rex = AkX2/2p,, etc.,
(99)
i.e., rewrite Eq. (97) in terms ofwave vectors instead ofthe coordinate energies.
Then Eq. (93) becomes
486
The quantity 2l3hR = h0 is the characteristic energy of the electrooptic

effect, and may be defined by any of the following equivalent expressions.
22/3m =
he
(1Ola)
(101b)
= { e 2 ( 8 . vk)2[Ec(k)
- Ev(k)lk=k,}
113.
(101c)
It is independent of the sign of the field, and its sign is determined by that of
the interband reduced mass in the direction of the electric field. It should
be noted that Eq. (100) reduces, as it must, to Eq. (81) in the zero-field limit,
lim(l/~hQ~)Ai[(E
- ho)/hR]
fiR-+O
6 ( E - ho).
(102)
Equation (100) is the effective mass limit of the convolution expression

describing the effect of the electric field in terms of the zero-field dielectric
constant, which will be discussed more fully in a following section. We
note that the effect of the electric field has been to replace the 6 function of
Eq. (81) with a function of finite width (but also of unit area). The electric
field therefore acts to smooth out the structure present in the zero-field
dielectric function by averaging over a given energy range determined by
the characteristic energy hR and the properties of the Airy function.
It can be seen immediately that a simple connection exists between the
critical points M , and M , , and the points M and M , , as in the zero-field
case. The respective reduced masses p ifor the pairs ( M o ,M 3 ) and ( M I ,M 2 )
are the negatives of each other. By explicitly replacing pi with - p i in Eqs.
(100) and (101) it is seen that this is completely equivalent to replacing
( E , - ho)with ( h o - Eg),since the sign of R is that of the interband reduced
mass in the field direction, which reverses if all interband reduced masses
change sign. Therefore, given E ~ ~ ~- (ha,&)
E , and c Z M , ( E g- ha,&), the
problem has been solved, for
E2M3(Eg
ha,8)= E2Mo(hW
E , , 81,
(103a)
E2M2(Eg
ha,&) = &2M,(hW
Eg,8).
(103b)
The explicit expressions for E,(w,8)may be found by evaluating any of

the integrals derived from Eq. (93) using various expressions involving Airy
integrals. The details may be found in A~pnes.~
The results are expressed
as a difference,
A E ~ ( w8)
, = E Z ( W ,8)- EZ(W O ) ,
(104)
6.
487
02
01
3
LL
0
-0 I
-0 2
-4
-2
(0)
7
1
0.2
0.I
0
-0 I
-0.2
-0 3
-4
-2
(b)
FIG.4. The electrooptic functions of the EMA. (a) F ( x ) , representing the field-induced change
in .c2 at an M , edge; (b) C(x), representing the field-induced change in E , at an M , edge. (From
A~pnes.*~)
488
TABLE I1
CHANGES
IN
DIELECTRIC
FUNCTION
I N THE VICINITY
OF CRITICAL
POINTSINDUCEDBY
UNIFORM
ELECTRIC
FIELD,FOR PARABOLIC
BANDSI N THE EMA
THE
Critical point
Mass sign
which can be given for the entire set of critical points, with an arbitrary field
direction in an anisotropic solid, in terms of only two functions29
F(x) = n[Aif2(x)- x Ai2(x)] - ( -x)lI2u( -x),
G(x) = n[Ai(x) Bi(x) - x Ai(x) Bi(x)] + (x)u(x),
(105)
(106)
where Bi(x) is the divergent solution54 of Eq. (85). The two functions F(x)
and G(x) are shown in Figs. 4a and 4b, respectively. The expressions for
Ae2(w, 8 )for all four critical points, in terms of the functions of Eqs. (105)
and (106), are shown in Table 11, with all arguments and constants defined.
The zero-field expression for each critical point (neglecting the indeterminate
constant of M and M , in Table I) is just the contribution from the terms of
the form (+x)li2u(+x) in Eqs. (106) and (107), since the field-dependent
characteristic energy hB cancels in these terms.
Calculation ofthe real part ofthe change in the dielectric function Acl(u, 8)
follows directly from the approximate Kramers-Kronig integral defined by
Eq. (47) and the fact that F ( x ) and G(x) are the Kramers-Kronig transforms
of each other
6.
489
~-
FIG.5. A summary of the fundamental shapes associated with the changes in the real and
imaginary parts of the dielectric function in the EMA, for all types of critical points and field
orientations, as listed in Table 11. Here q = ( h m - E,)/hO. A = B8''2/wz and the sign change
for the argument x in Table I1 is shown explicitly. Line shapes of AE,(w,E) and A E ~ ( wE), are
calculated at the condition : hO = 10 meV. E , = 0.8 eV, and A = 1. (From Hamakawa ef a/.55a)
The calculated expressions of AE,(w,&) are also given in Table 11. The
functional forms of the changes AE(w,8)for all combinations of field directions and critical points are shown in Fig. 5.55a
Several features of the EMA solution are of interest since they are also
characteristic of more general results. The fact that the solutions are based
on Airy functions is not surprising since Eq. (85) is just the nondimensional
Hamakawa, P. Handler, and F. A. Germano, Phys. Rev. 167. 709 (1968)
490
FIG.6. The Airy function, describing a free particle in a uniform field of force
form of the quantum mechanical equation of a particle in a uniform field

of force. As such, the characteristics of the Airy function can be interpreted
in physical terms. The Airy function is shown in Fig. 6, together with the
linear potential describing the uniform field of force. The classical turning
point occurs at zero argument. The classical particle cannot extend beyond
the turning point, but the quantum mechanical particle can, by tunneling.
This tunneling gives rise to a tail which decreases roughly exponentially
for positive argument corresponding to the reduced probability of finding the
particle in higher potential regions. The classical particle accelerates toward
regions of negative potential, which results in a higher velocity (increasing
rate of oscillation) and a lower probability of finding the particle in a given
interval (decreasing amplitude of the oscillations). The wave function
therefore mirrors the characteristics of the classical particle. The exponential
tail of the F function, which describes the fundamental edge ( M , ) absorption,
simply reflects the penetration of the electron and hole wave functions into
the forbidden gap and the probability of making a transition for photon
energies slightly below the gap, which is zero in the absence of the field.
The oscillations above the critical point energy represent constructive
interference of the effective mass wave functions when calculating the
transition probability.
The electrooptic functions F and G defined in Eqs. (105) and (106) both
have a strong singularity at x = 0 (the energy of the critical point) and
6.
491
oscillations for negative argument, and both decay rapidly with an identifying
shape for positive argument. The sharp singularity makes the electric field
effect useful for experimentally obtaining critical point energies, and in the
presence of collision broadening effects which destroy the oscillations for
higher interband transitions, the singularity represents the most distinct
and sometimes the only structure associated with a critical point.
The change in the dielectric function depends not only on the magnitude
of the applied field for anisotropic solids, but also on the direction through
the value of the interband reduced mass. The scalar symmetry of the dielectric
function for cubic crystals is destroyed under the influence of the electric
field and becomes tensorial. Equivalently, the electric field defines a preferred
axis in the crystal, reducing the symmetry which produced the scalar dielectric
function. The dependence on field direction is extremely strong at the
saddle points M , and M , , because the reduced mass in the field direction
may have either sign, depending upon the orientation of the electric field.
This sign-dependence carries over into the characteristic energy and completely changes the functional form of A E , and A&,, depending on whether
the field direction mass is positive or negative. In this case, A E and
~ AE,
vanish on the boundaries of the negative-positive mass regions, where the
reduced mass becomes infinite, as they must in order to avoid nonphysical
discontinuities ; both functions also reduce to the same zero-field limit. The
characteristic oscillations of the electrooptical functions can appear either
above or below the critical point energy for M , and M , edges. Since the
mass is always positive for the M , edge and negative for the M , edge, no
such inversion of the oscillations is seen, and the directional dependence is
much weaker.
This concludes the discussion of the electric field effect in the EMA. The
closed-form solutions in Table I1 apply only in the region of a critical point
in the EMA one-electron formalism for a nondegenerate band and where
Coulomb interaction is neglected. The solutions are strictly valid only for
parabolic bands, and the deviations which occur in actual bands, usually
close to the critical point, would be expected to lead to only qualitative
agreement between theory and experiment. As will be seen, other reasons,
such as lifetime broadening, also cause considerable deviations, particularly
for higher interband transitions, and in fact the oscillations shown in Fig. 4
have been seen only at fundamental edges. The EMA is not readily generalized
to include nonparabolicity, and other methods must be used, as shown in
following sections. In spite of these difficulties, EMA solutions remain the
only analytic expressions for electric field effects at a general critical point,
and in practice other methods are reduced to these solutions for computational purposes. We next consider a more exact treatment, which leads to
the Stark steps and results in a convolution integral which describes the
entire electric field effect in the one-electron approximation.
492
7. ONE-ELECTRON
WAVEFUNCTIONS
IN
AN
ELECTRIC
FIELD
We now turn to methods of calculating the effect of the electric field upon
the dielectric function of a solid where the lattice periodicity of the wave
functions is taken into consideration. The advantage of beginning with the
wave functions themselves lies in the fact that the method is more general.
It reduces to the EMA, and in so doing gives a clearer insight into the
approximations made. These methods are in turn less powerful than the
method of Greens functions, but at the present stage of the theory they have
been used more extensively, and the known results apply more widely.
Using the one-electron Bloch functions as a basis, two equivalent methods
are available for the calculation of the dielectric function of a crystal in
the presence of an electric field. The first of these is the Houston
a p p r ~ a c h , - ~ . ~ which
* ~ treats the wave functions in the presence of the
field as time-dependent, with the electron momentum increasing linearly in
time as is expected of a classical particle being accelerated by a uniform
field of force. The second approach obtains directly the constant-energy
solutions of the Hamiltonian in the presence of the field in the crystal
momentum representation (CMR).13 Using the time-independent Bloch
functions as a basis, the expansion of the constant-energy wave functions in
terms of this complete set is ~ b t a i n e d . ~ .The
~ . constant-energy
~~
expansion
coefficients obtained are the wave functions in the CMR. The two approaches
differ only by a Fourier transform in time5; hence, they are simply different
aspects of the same approximation. The Houston functions are defined in
the time domain, whereas the CMR functions represent the one-electron
wave functions in the energy, or frequency, domain.
Both methods are one-electron approximations, and the results obtained
will be limited t o conditions where the Coulomb interaction is relatively weak.
A characteristic feature of both, which is absent in the effective-mass approximation, is the appearance of fine structure due to the discrete nature of the
This fine structure, the Stark steps, arises because the wave
functions must reflect the periodicity of the lattice. We will obtain the
one-electron wave functions in the presence of the electric field, in both the
Houston and the CMR representations.
a. Houston Functions
The one-electron Hamiltonian in the presence of an electric field is
= Xo
+eb-r,
(108)
where Xois the Hamiltonian of the unperturbed lattice and has as its eigen56
P. N . Argyres, Phys. Reo. 126, 1386 (1962).
L. Fritsche, Phys. Status Solidi 13. 487 (1966).
6.
493
functions the Bloch functions cp,(k, r) with energy eigenvalues E,(k) as

discussed in Section 1. For the purposes of the following discussion, we
assume that the dimensions of the solid approach infinity, so the quantum
numbers k, defined over the fundamental Brillouin zone, form a quasicontinuum. The wave equation can therefore be written as
(109)
at
where we assume time-dependent solutions $(q, r, t ) of quantum number q.

The solution of this equation has turned out to be much more difficult than
first sight would suggest. The difficulty arises from the fact that in an infinite
crystal the uniform field potential diverges and the zeroes of both energy
and coordinate have no physical significance. Further, the infinitely deep
potential well provides a sink into which all stationary solutions of Eq. (109)
in the limit -+ 0 will decay. However, it turns out that to a good approximation the solutions are describable in terms of wave functions from a single
band, and the interband terms which represent interband mixing are generally
small and easily identified. One can therefore carry out the solution of
Eq. (109) formally, although the exact physical interpretation of the wave
functions is sometimes difficult. A detailed consideration of the problems
involving finite crystals has been given by Ree~.~
Houston4 proposed the following approximate solution to Eq. (109)
where cp,F(t),r] is a Bloch function with energy E,F(t)], and k(t) is a timedependent wave vector related to the zero-field wave vector k, and to the
electric field by
k(t) = k, - [ e l ( [ - T,)/h].
(111)
The electric field is assumed to be turned on at t = To.The validity of this
approximate solution can be tested by direct substitution in Eq. (109).
Using the explicit form of the Bloch functions in Eq. (6),we obtain
- ie exp
{ -;
f n
dt E,[k(t)] exp{ik(t) r} V,,u,[k(t),
rl.
(1 12)
Since .X,$(k, r, t ) = E,F(t)]$(k, r, t ) it follows that the Houston function

57aH.
D. Rees, J. Phys. Chem. Solids 28,353 (1967).
494
satisfies Eq. (109) except for the last term on the right-hand side of Eq. (1 12).
This term represents interband tunneling, and is small for weak fields. The
electron undergoes a repetitive motion in the direction of the field, being
reflected first by the lattice [k(t) = K on the Brillouin zone boundary] and
then by the field, provided the field is sufficiently weak so that it will not cause
an electron to jump from one band to another.
F r i t ~ c h eshowed
~ ~ that by treating E,[k(t)] as an adjustable parameter an
additional term in the energy is obtained which makes the Houston approach
completely equivalent to the CMR treatment which will be outlined in the
next section. By minimizing the expectation value of Eq. (109), taken as a
matrix element between $,*[k(t), r] and $,[k(t), r] and treating E,[k(t)] as an
adjustable parameter, the energy term in Eq. (110) becomes
E,[k(t')l
+ fa?X,,"t)l
E,[k(t')l
where we define in general

X,.,(k)
= i
= Ufl[k@)l,
(113)
J"
d3r u,*.(k,r)V,u,(k, r).
The physical significance of the quantities X,.,(k) is that they represent

terms which connect optimized Houston functions between bands ; the term
with n = n represents the change in interband energy from wave function
polarization. The interband terms comprise the error term of Eq. (112).
We discuss these terms more fully in the CMR treatment. The optimized
Houston functions approximating the one-electron wave functions in the
time domain can therefore be written as5'
where k(t) is defined in Eq. (112) and U,[k(t)] is defined in Eq. (1 13).
Having a set of one-electron wave functions for the crystal in the presence
of the electric field, we can, in principle, calculate the dielectric function by
explicitly evaluating the time-dependent current operator and then taking the
Fourier transform (a procedure used by Y a ~ o b in
y ~the~ treatment of direct
and indirect transitions at M , critical points). Alternatively, we can use the
results obtained in Section 3 and calculate the dielectric function from Eq.
(27). However, this requires a set of constant-energy wave functions which
describe the electron in the crystal, and the optimized Houston functions are
not constant energy solutions. The constant energy solutions, which are
obtained directly by the CMR treatment, are calculated by taking the Fourier
transform of Eq. (115). This parallels the procedure used by Franz6 and
Fritsche.'
6.
495
In an infinite crystal, Eq. (1 1 I ) implies that for some time interval AT,
k(t AT) will differ from k(t) by a reciprocal lattice vector, i.e., k(t) and
k(t AT) are equivalent. Let K, be the minimum reciprocal lattice vector
for which equivalency is obtained, i.e.,
+
+
k(t
+ AT) = k(t) - K,
k(t) -
e& AT
.
h
hence
AT = hJK,J/eJ&I.
(117)
We note that 2n/[KF[is just the separation of the lattice planes perpendicular
to the electric field in real space. Now all terms in Eq. (115)which are dependent on k are invariant with respect to translations by reciprocal lattice
vectors. Therefore $,,(k,r,f AT) differs from $,,(k,r,t) only by the integrated factor in the exponential. If we defines7b
hG,(k,)
Dn(kL)= (l/AT)
(118)
then the increase in phase in a period AT is just G,(k,) AT, and by adding
( t - T,)G,(k,) to the phase we obtain an expression periodic in time with
period AT. This function can therefore be expanded as a discrete Fourier
series in harmonics of 2nlAT
exp[iG,,(k,) ( t
T0)]$,(k,r, t ) = N
1exP(Y
i(2nvt/AT))dh,,,(k,, r). (1 19)
Therefore5
where an unimportant phase factor exp(i2nvTo/AT) has been dropped. By

57bNotethat the integration limits in Eq. (118) require the initial and final values of k ( i ) to
differ by exactly a reciprocal lattice vector. Therefore, all possible values of k in the direction
of the field are swept out, and U , becomes independent of the component of k in the field
direction, and therefore f. We denote the two components of wave vector perpendicular to
8 by k,.
S8
The same arguments used to show 0,as a function of k, only, can also be applied to the
coefficients c#Jn.Jkl,r). since the disappearance of unimportant phase bctors is the only
consequence.
4%
using the orthonormality of the Bloch functions and the t r a n s f ~ r m a t i o n ~ ~

P
it can easily be verified that the coefficients c$,,v(k,, r) are orthonormal with
respect to the quantum numbers (n,v,k,).
By Eqs. (109) and (1 19) we have
(122)
and using the orthogonality of the functions &+,(kL,r) the expectation value
of ih(d/dt),and therefore (,Zo+ e 8 r), is a constant
The function $,,v(kl, r) is therefore a stationary solution of the perturbed

Hamiltonian t o the extent that interband terms can be neglected. The above
involved the operator ih a/& ;we show in the CMR discussion the result also
follows from the operator (2,- e b r) although it is more involved and
requires essentially the CMR derivation. Note this solution has been constructed from a linear combination of Bloch functions whose k vectors lie
parallel to the electric field, as indicated in the qualitative discussion of
electric field effects.
By Eq. (123), the electric field induces a set of energy levels equally spaced
throughout the crystal with energy spacing
Aw = ( h / l K F l ) e l b [ .
( 124)
This is the Stark step of the Stark ladder, and can be obtained quite
generally by requiring only that the Hamiltonian be periodic in the absence
of the electric field, as shown by Wannier.60 The proof is simple, and we
outline it briefly. If Xo is invariant to translations by a lattice vector and if
s9
O0
Note that N -+ m has been implicitly assumed in writing Eq. (120), for although t is a
continuous variable, k is not. Equation ( I 10) is meaningless unless the crystal volume becomes
sufficiently large to enable the quasi-continuum ofwave vectors k to be treated as a continuum,
in which case the transformation Eq. (121) is used in the sense of interchanging discrete sums
with integrals in k space. The parameter N is used in two different senses, but in the limit N ;o
the same value may be assigned to the number of cells in the volume V and the number of
terms in the Fourier e ~ p a n s i o n . ~
G. Wannier, Phys. Rev. 117. 432 (1960).
6.
there exists a solution such that

[.fo(r)
497
+ e b rI$h
W(q)$(q9 r)
(125)
then by displacement of r by a lattice vector R

[Xo(r
+ R) + e b - (r + R)]IC/(q, r + R) = W(q)$(q, r + R ) .
(126)
But since ,Xois periodic in R, we have
+ e b - r]IC/(q,r + R) = [ W(q) - e b - R]$(q, r + R ) . (127)

Therefore, if $(q, r) is a solution with energy W(q), then $(q, r + R) is also a
[Xo(r)
solution but with energy
W'
W(q) - e 8 . R .
(128)
The Stark ladder has a direct physical interpretation. Considering the wave
function $(q, r) to represent a localized electron wave packet or Wannier
function, the Stark ladder is simply the mathematical statement that the
potential energy of electrons localized on different lattice sites will vary
linearly in lattice vector in a uniform field. Since 2n/K, is the lattice plane
separation perpendicular to the electric field, Eqs. (123) and (128) are obviously equivalent, and the Stark step is simply the minimum possible energy
separation between all pairs of lattice sites.
We have shown that the Houston functions can be transformed into a set
of constant energy solutions which could be used to calculate E by Eq. (34).
First, however, we will derive these solutions in another way, using the
formalism of the crystal momentum representation.
b. The Crystal Momentum Representation

In the CMR,'8-'9 the stationary or constant energy wave functions are
obtained directly as an expansion in the complete set of Bloch functions. It
is customary to use the fundamental, or first, Brillouin zone as the domain
for defining the Bloch functions. This zone is the primitive cell (WignerSeitz cell) in the reciprocal lattice. This choice of the primitive cell is convenient because it displays in a rather obvious manner the symmetries possessed
by the lattice. But the basic definition of the fundamental Brillouin zone as
the collection of all wave vectors which cannot be connected by a vector of
the reciprocal lattice allows a wide latitude in the construction of this zone.
For the purpose of the CMR expansion, the most convenient fundamental
Brillouin zone is constructed in a manner which allows a retention of the
periodicity (and orthogonality) properties of the wave functions in the
directions perpendicular t o the applied electric field.56We therefore construct
the Brillouin zone for the purposes of the CMR expansion using the shortest
reciprocal lattice vector which is parallel to the applied electric field, namely,
498
D. E. ASPNES AND N . BOTTKA
the vector K, which was used as one of the translation vectors in the discussion concerning the optimized Houston functions. The end points in the field
direction (which we take to be x)are then equivalent, separated by thereciprocal lattice vector K, = K,P. The wave functions in the other two directions
remain periodic and orthogonal. The general constant-energy wave function
can therefore be written as the expansion
&4,, k, r)
1
c 4.(4,, k)cp,(k, r)
kx,n
(129)
which satisfies the time-independent Schrodinger equation

The q x represent quantum numbers identifying different solutions to the
eigenvalue equation. The wave functions ( q X ,k,, r) are normalized in the
usual manner
n
A set of equations for the coefficients in Eq. (129) is obtained by left multiplication of Eq. (1 30) with the Bloch function cp,*.(k,r) and integration over
the volume of the crystal, using the orthogonality properties of the Bloch
functions. The result is
{[En(k)
kx,n
- w(qx,
kl)l 6kk 6 n n
+ e& Jv d3r (prli.o<, r)xcp,(k, r)
A,(q,, k) = 0 .
( 132)
The expectation value of x can be written as a CMR operator by using the

explicit form of the Bloch f ~ n c t i o n s ~ ,
where X,,,(k) is the projection of the quantity X,.,(k) defined in Eq. ( 114) in
the field direction. The operation of the derivative on the Kronecker fi
function is formally equivalent to
where F(k) is an arbitrary function of k. Therefore, Eq. (132) becomes
6.
499
We have transformed Eq. (132) into a set of first-order differential equations
which are already diagonal in the wave vector k, but are mixed between
bands by the terms Xnn.(k).61
The quantities X,.,(k) defined6'" in Eq. (114)are interband terms describing
wave function mixing between bands. Their magnitudes have been estimated 3 , 1 9 , 5 6 and are always small for weak fields except near points of
degeneracy. As a result, an approximate equation for each coefficient
An(4,, k) can be obtained by summing Eq. (135) over n and setting each term
n individually equal to zero, rather than using the exact connected set in
Eq. (136). This is equivalent to obtaining a one-band expansion of Bloch
functions, but including tunneling. If we define
we have independent approximate equations for the coefficients A,(q,, k )
''
E,(k)
- Wn(4,,k,)
+ id-8k.X + e B X , ( k )
A,(q,, k) = 0
(142)
We digress at this point to indicate the proof of a general theorem obtained by Jones and
Zener,' represented by Eq. (18). Equation (136) is rewritten in the form4'
where
A,(q,,k, t ) = A,(4,, k ) e x ~ [ - ~ W ( q ,kJ1.
,
( 1 38)
If we multiply Eq. (137) on the left by A,*(q,, k,t), subtract the result from its complex
conjugate, and sum over n, we have
since X;,(k)
Xnn4k).But Eq. (139) has the general solution
where G is an arbitrary function. Since Eq. (136)is already diagonal in k, a general wave packet
consists of a series of Bloch functions of the same k but including coefficients A&,, k, r ) of
all bands: Eq.(l40)simplystates that thecentroid ofthis wavemovesas though its momentum
were increasing linearly in time, as first proved by Jones and Zener.'
6'BNote that the scalar Xn,"(k),the component of the vector along the field, was defined after
Eq. (133).
500
which have the general solution
where C,(q,, k) is a normalization constant. Since the functions &qX, k,, r)

are formed from Bloch functions of only one band, they may be denoted by
the band index n, and the normalization condition can be written as
The 6 functions for k and n follow immediately from the form of A,(q,, k),
and in order to obtain orthonormality we must have
Im[X,(k)]
(145)
and
"X
where the quantum numbers qx are represented by the set of integers v, and
W,'(k,) is as yet an arbitrary function k, and n.
The quantities X,.,(k) are never completely real as required by Eq. (145)
and in order to obtain a consistent approximation it is necessary to drop all
terms X,,,(k) with n' # n immediately in Eq. (136). Imaginary parts of the
X,,(k) describe transfer of eIectrons between bands, as is obvious in that
they represent an effective complex energy which affects the amplitude of the
CMR functions and prevents normalization. Working in the standard k p
representation,62 where the functions u,(k, r) are expanded in terms of the
complete set u,(O, r), it is possible to prove two general characteristics of the
interband terms X,.,(k).3' Let us define the expansion
in terms of the complete set {um(O,t))- By Eq. (8), the coefficients B,"(k)
satisfy the orthonormality condition
Cm B?*(k)B,"(k) = (1/N)6,,, .
62
M.Cardona and F. H.Pollak, Phys. Reti. 142, 530 (1966)
6.
By Eqs. (114) and (147), we have

X,.,(k)
= i
1B;*(k)
rn
V,B,"(k)
501
(149)
Consider the intraband term X,,(k). By subtracting Eq. (149)from its complex
conjugate and utilizing Eq. (148), we have
- 2 Im[X,,(k)] = X,(k) - X,,(k) = i V,
which proves the first general result ; the intraband terms X,,(k) are always
completely real.
The equations for the coefficients B,"(k) are determined by6'
-;V'
whence
+ V(r)
exp(ik.r)u,(k,r)
E,(k)exp(ik-r)u,(k,r), (151)
If the crystal satisfies inversion symmetry, we can make the usual choice of
phase of the wave functions u,(O, r). namely, real for the symmetric functions
u,(O, r) and imaginary for the antisymmetric functions. The momentum
matrix element is therefore purely real and the B,"(k) are determined by a set
of linear equations, all coefficients of which are real. Therefore, the B,"(k)
must themselves be purely real and by Eq. (149)we obtain the second general
property: all interband terms X,.,(k) must be purely imaginary in crystals
with inversion symmetry. The two general properties mean, of course,
X,,(k) = 0 for crystals having inversion symmetry.
Since X,.,(k) may, for certain cases, be large near points of degeneracy, the
solution will not be a particularly good approximation in the vicinity of
these points. Degeneracy points are a much more difficult problem, and no
theoretical work has been done with respect to applied electric fields. I t is
generally assumed that degenerate bands, such as the valence bands of the
group IV elements, can be treated as being nondegenerate, which seems to
give results which agree with experiment. We therefore keep only the intraband terms in the following discussion, and define the effective energy which
includes this correction as
as in Eq. (113).
502
The additive energy W,(k,) of Eq. (146) cannot be determined by the

orthogonality Eq. (144). It can be shown that in order to obtain an expression
for the dielectric function which reduces properly in the limit of zero field
W,(k,) must be chosen so the coefficients A,(q,, k) retain the periodicity
of the unperturbed lattice. Since the end points of the Brillouin zone are
equivalent, this condition is obtained by requiring56
A,(q,, k
+ K F ) = A,(q,, k) ;
( 154)
whence it follows immediately that

kx+Kx
K(k1)= (l!Kx)j
kx
dk, U,(k,, k;)
U,(k,),
(1 5 5 )
where gn(kl)has been defined in Eq. (118). By Eqs. (146) and (155), the energy
of the eigenfunction q5,,Jkl, r) [we substitute v for the quantum number q,]
is precisely that given in Eq. (123) which was derived from the Houston
approach. Since the normalization constant C,(v, k) is
C,,(V,k) = l/N,
( 156)
the CMR approximation gives the stationary solutions to Eq. (109) as
r).
( 157)
The identity between Eqs. (120) and (157) can be seen using Eqs. (111) and
(117) and performing minor changes in integration variables. The complete
equivalence of the Houston and CMR methods is therefore established.
Throughout the discussion, we have assumed the volume of the crystal to
approach infinity in both the Houston and CMR approaches. The need of an
infinite crystal is perhaps obvious in the CMR approach, for the assumption
of a reciprocal lattice vector parallel to the field requires an infinite set, and
also the formal interchange of differentiation of the delta function and the
coefficients A,(q,, k) requires k to form a continuum. As Fritsche has
pointed out, the CMR leads to a contradiction for finite crystals since the
additive constant energy of the Stark ladder in Eq. (123) is the band average,
and a finite crystal with a finite number of Stark steps would not have a
sufficient number of levels for arbitrarily small fields to span the entire
energy band. R e e ~ assignment
~~
of the initial Bloch energy for the additive
constant circumvents this difficulty, but the periodicity of the coefficients is
destroyed. It is perhaps less obvious that the infinity is needed in the Houston
approach, but Eq. (1 1 l), in which the momentum is taken as increasing linearly
in the continuous time variable, has already tacitly assumed that the wave
vectors form a continuum, i.e., the crystal is infinite. The mathematical
x
Cpnoc,
6.
503
difficulties associated with the solution for an infinite crystal are more
manageable than those of the finite crystal; the most careful analysis of the
latter problem has been given by R e e ~It. appears
~ ~ ~ that the main features
obtained in the treatments involving infinite crystals would not be affected
by boundary conditions on large crystals, and the finite crystal approximations are quite valid in actual practice.57a
The wave functions given by either Eq. (120) or Eq. (157) describe the
electronic states of the crystal in the presence of an electric field in the
one-electron approximation. We review the approximations inherent in
their derivation, since these determine the limits of validity of the results to
be obtained. First, these are one-electron approximation wave functions,
which means that all interelectronic interactions are neglected. The most
serious approximation is the neglect of the Coulomb interaction. Secondly,
these wave functions represent a one-band expansion, and the results will be
good to the extent that interband transfer of electrons or interband mixing
is negligible. This restricts the results in principle to nondegenerate bands,
or at least to regions removed from points of degeneracy. Thirdly, the effect
of the finite lifetime of the electron in a particular state has not been considered, but this is an extension which will be treated later. We note, however,
that the solutions are exact within the above limitations, and in particular
represent the exact solutions in terms of the wave functions of a single band.
We will now calculate the dielectric function using the constant energy
functions obtained, and discuss some of the more general features of this
solution which results from the lattice periodicity of the wave functions.
8. THE FIELD-DEPENDENT
DIELECTRIC
FUNCTION
a. General Expression
The imaginary part of the field-dependent dielectric function will now be
calculated by substituting the stationary solutions defined by Eq. (120) or
(157)intoEq.(32).Themomentum
matrixelement defined byEq.(29)between
the states (n, v, kL)and (n, v, k,) is
L
(158)
where gn(kl) is defined in Eq. ( 1 18) and Pn.,(k)is the momentum matrix
element defined by Eq. (13), and
Un,n(k) = [En(k)- En(k)l
504
D. E. ASPNES AND N . BOTTKA
where X,.,,(k) is defined in Eq. (1 14). By Eq. (32),
[e - Pi,,,(kL,k,')]
exp -
8
:
{
dk;
V)
2neb
U,,.,,(kl, k:) - -(v
+ G,,.,,(k1) - o
KX
v)
(160)
where Pn.n,v.v(kl'r
k,) and its complex conjugate have been written explicitly,
and G,,,,,(k,) has been defined b y Eq. (1 18). Since56
N
Eq. (160) can be transformed into
rX"
where we have utilized Eq. (36),performed the transformation
dk,'
c-4rs"'i2
2n
k;
-K,/Z
dk,',
Kx
-Kx/2
( 163)
and included a factor of 2 for spin degeneracy.

Suppose k fixed and consider the extension of the integration range of
k,' from K J 2 to 3Kx/2.Since P,,,,,is invariant with respect to translations
by reciprocal lattice vectors, this extension reproduces the original interval
except that an additional term
exp(iK,h/ed) [G,,.,,(k,) - 0 1
( 164)
has been generated. But this simply reproduces the term I = 1 in the sum over
1. Each similar extension reproduces further terms in the sum over I, hence
this sum can be absorbed into the k,' integration by extending the limits to
6.
505
infinity. Equation (162) then becomes
The integration variables k, and k, define a strip in (k,, k,) space, covering
(166a)
(166b)
AS shown in Aspnes et al.,31by cutting this strip into appropriate areas and
properly translating each area, the region defined by Eqs. (166) is completely
equivalent to the region
Ik,
-00
+ kl d K , ,
< k,
k, < 00
(167a)
(167b)
for the purpose of evaluating Eq. (165). The convolution formalism is obtained by defining new variables
(168a)
(168b)
whence the region of integration becomes
(1 69a)
(169b)
and
By performing elementary transformations we can write the above expression

in the following general coordinate form, valid for any choice of axes and
506
any shape of the Brillouin zone
[e
x exp
{ JIs
P,,.,(k + e l s ] [e P:,,,(k - eBs)]

i
ds' [ U,.,(k
+ e&s') - h o ]
By performing the transformation

s =
t/2h,
Eq. (171) can be written in a form illustrating its alternate interpretation as

the Fourier transform of a time-dependent current operator
(which suggests that a much simpler derivation is possible in the time

domain).
Equation (171) represents the complete description of the imaginary part
of the dielectric function of a crystal in an electric field. It shows explicitly
that the field mixes only those Bloch functions whose wave vectors lie along
a line parallel to the electric field. As B -+0, the exponent and the integral
overs reduces to z times the delta function of energy. The equation reduces to
the equivalent part of the zero-field expression, Eq. (34). Equation (171) is
also real, which may be shown by taking its complex conjugate and replacing
s with -s, in which case the expression resumes its original form. This
operation is trivial if P,,,(k) is real, as is always the case for crystals of inversion symmetry where P,,,,(k) can be formed as an expansion in k of real
quantities.62 If P,,,(k) is real, the operation & -, -8,when followed by
s'
-s' and complex conjugation, returns Eq. (171) to its original form,
showing the dielectric function to be invariant to field reversal if inversion
symmetry is present. The k dependence of momentum and nonparabolicity
effects are explicitly included, and Eq. (171) is not limited to the vicinity of
critical points, as was the result obtained in the EMA, but may be applied in
any region of the Brillouin zone (subjected to the approximation of neglecting
degeneracy point effects). Generalization of the arguments of Rees13 to the
--f
6.
507
entire Brillouin zone, to be considered in Section 10, show the convolution

expression t o have somewhat wider validity than implied in the one-electron
approximation.
The interband contribution to the real part of the dielectric function can
be obtained by calculating the Kramers-Kronig transform of Eq. (171) using
Eq. (48). However, since it is easier to transforin specific approximations, the
general expression will not be given.
b. Stark Steps
Equation (171) contains fine structure due to lattice periodicity effects, the
Stark ladder obtained by Callawayzz~z2a
in the absorption coefficient. To
show this explicitly, it is necessary to use the periodicity of P,,,(k) and
U,,,,(k), Eq. (159), and undo the integration over s (=k , / e 8 ) into its repetitive elements expressing each with its phase factor as
x exp{i J I s d s [U,,,(k
+ ebs) - ho] ,
and using the identityzza
The result is
x [1 - ( N ( n ,k))]
x ds [U,.,(k
[a * P,,,(k+ xk,] [k - P:*,(k
1.
+ e l s ) - ho] .
- xk,)]
( 176)
As seen by Eq. (176), eZ(co, ) can be interpreted as a series of 6 functions,

defined by the energies u,,,,,(kL)+ (rc&//Kx).The incremental energy is
exactly one-half of the energy increment between successive lattice planes
508
because the Stark steps enter as an average, which gives half-integral structure in the dielectric function. Equation (176) is more useful than Eq. (1 71) for
very strong fields; for weak fields only the 1 = 0 term contributes appreciably
in Eq. (176).
The Stark structure at present is principally of academic interest, for
collision broadening effects are always sufficiently large so as to prevent
the electrons from traversing a full period before undergoing a collision ;
no Stark structure has yet been observed in crystals of inversion symmetry.
Nevertheless, a certain amount of controversy has arisen concerning their
presence. Zak63 has argued that the additive constant defined in Eq. (1 18),
which has a well-determined value in the one-electron single band approximation, is not well defined if the interband terms X,,,(k) are included and
as a result the Stark structure should not appear. While the tendency of the
quantities X,.,(k) is certainly to change the amplitude of the one-band
expansion wave function in the time domain, which introduces broadening
and tends to wash out the Stark structure, no calculations of this broadening
effect are available and it is unknown whether reasonably large fields would
indeed broaden this structure unduly. The essentially negligible Zener
tunneling which occurs suggests the broadening would not be too severe.
The general proof of Wannier6' indicates that the same additive energy is
present for each step of a sequence in any event.
We should also note that the apparent drastic dependence of the Stark
separation upon the orientation of the field, in that the quantity K , is the
magnitude of the shortest reciprocal lattice vector which parallels the electric
field, is somewhat misleading. For instance, the shortest possible vector K , ,
in the (100) direction, would be expected to produce steps which were
reasonably well separated in energy. A slight misalignment of the field
would define another, much longer reciprocal lattice vector to replace K , ,
which drastically reduces the energy separation of the Stark structure.
As YacobyZ4 has pointed out, however, this would result primarily in a
broadening of the Stark structure which would occur for the (100) direction
and not wash it out completely. No calculations have yet been done to
obtain this broadening effect analytically, although it appears that Yacoby's
treatment which approximates the actual energy bands by bands of tight
binding form, is the simplest model with which to work, leading to Bessel
functions describing the field effect and the Stark steps.
The direct measurement of transitions between Stark levels has recently
been proposed. Dohler and Hacker64 have calculated the transition probability for absorption of light in the infrared, and show that spontaneous
emission should occur as well.
'' J. Zak, Phys. Rev. Lett. 20, 1477 (1968).
64
G. Dohler and K. Hacker, Phys. Status Solidi 26, 551 (1968).
6.
509
c. The Weak-Field Approximation
We now investigate the reduction of Eq. (171) to the results obtained in

the effective mass approximation. This reduction could have been made in
the derivation of the convolution formalism prior to making the geometric
transformation which changed k,, k, into q,, 4, leading to Eq. ( I 70), in
which case we would have recovered precisely the forms encountered in the
EMA for the various critical points. Franq6 Keldysh, and Callaway22
obtained their M, results in this manner. The convolution formalism leads
to an equivalent result, and in addition has the advantage of illustrating more
clearly the reason for describing the EMA results as the weak field approximati~n.~
The simplest approximation to Eq. (171) is that which leads to the EMA,
namely, assuming that the momentum matrix elements are independent of k
and that Eq. (113) may be expanded about any point in the Brillouin zone
as a power series in the electric field
U,,,(k
+ e d s ) = { 1 + sed .Vk + f . s r 2 ( e dVL)

.
+ . . .}U,.,(k).
( 1 17)
Integration of this series with respect to s in the integral in the exponent of

Eq. (171) eliminates all odd powers of s in the expansion. It is reasonable to
expect that as long as the bands are parabolic and the field not too large,
a good approximation is obtained by keeping only the zero-order and
quadratic terms in the energy expansion. If only the zero-order term were
kept, Eq. (171) would reduce directly to the zero-field result. By keeping
the quadratic term, we pick up the first nonvanishing field contribution.
Since the cubic term cancels anyway, we have in effect kept terms up to the
fourth order in the energy expansion. Note that this is also a power series
expansion in the field, and that the approximation should improve as the
field becomes smaller. For this reason, the result is called the weak-field
approximation. We therefore can write the energy to this approximation as
U,,,(k
+ e b s ) 2 U,.,(k) + +sf2e2(d V,)2U,.,(k).

*
(178)
But since
1
PI1
h2
- ---
is the interband reduced mass in the field direction, we have [neglecting the
second derivative of d X,Jk)]
U,.,(k
+ e d s ) E U,.,(k) + ( . ~ ~ e ~ h ~ & ~ / 2 p ~ , ) .
Defining a frequency
(180)
510
we can write Eq. (171) as
It Pn.,(k)I2exp
where
WA&)
{ &, dr'
i
[w:.,(k) - w
(I/h) (En,,&) + edf * [Xn,,&)
+ 4Q3t2] ,
- Xnn&)I).
(182)
(183)
By performing the t' integration and using the definition of the Airy funct i ~ nthis
, ~can
~ be written as
which is the convolution expression for the electric field effect in the weak
field EMA, obtained previously in Eq. (100).It should be remembered that
one of the assumptions in the derivation of Eq. (184) was that P,,,,, and R
depended only weakly on k. In contrast to Eq. (loo), which is valid only in
the vicinity of a critical point, Eq. (184) is valid at any (nondegenerate)
point in the Brillouin zone where the interband energy can be represented
locally as a power series expansion.
Since
it follows again that the effect of the electric field in the approximations
which lead to Eq. (184) is to replace the delta function which is obtained in
the zero-field expression with a function of unit area but of finite width.
The field therefore averages or convolutes the zero-field structure in the
dielectric function as pointed out earlier for the special case of the vicinity
of critical points. But due to the shape of ~ ~ ( 0 , 0as) shown
,
for example in
Fig. 2, we expect to find the greatest effects in the regions of the optical
spectra where ~ ~ ( 0 4is0 )
changing most rapidly with energy, i.e., in the
vicinity of critical points. In these regions the energy may be expanded
quadratically to a good approximation, the momentum matrix elements
tend to be independent of the wave vector, and the interband reduced mass
(and therefore 0)are nearly constant. These are the assumptions which lead
to the effective mass formalism, and which have been derived from more
basic considerations. The discussion following Eq. (100) applies, and we
do not repeat it here. One point of interest is that Eq. (184) may be used to
6 . ELECTRIC-FIELD
EFFECTS
511
relate the zero-field dielectric function to the finite field function in a convolution integral involving the Airy f ~ n c t i o n ' ~ provided
'~'
the parabolic
approximation is locally valid. Let Eq. (184) be transformed from a momentum space integral into a density of states form, using Eq. (50).Then, considering only a single band pair-here a completely empty conduction band and
a filled valence band-and assuming the momentum matrix element to be
independent of k, we obtain
where the integration limits can be extended to infinity because of the

functional dependence of the density of states. The function Jcv(m)was
defined in Eq. (53). But
[- dw' Jcv(o')
AilT)
oc
w' - w
Xl
-a
dodo"J,,(w") 6(w" - w ' ) Ai
(187)
and the integral over w" is just proportional to W ' ~ E , ( O ' , O ) . Therefore it
follows that
Equation (188)shows that the finite field dielectric function can be expressed
as a convolution of the zero-field function with an Airy function, provided
PcV(k)and R are roughly independent of k. If R varies on the Brillouin zone,
as for example if the range of o includes equivalent critical points, no simple
expression such as Eq. (188) can be written down. Regions of the Brillouin
zone contributing with different R values must be treated individually.
9. SPECIAL TOPICS
IN THE
ONE-ELECTRON
APPROXIMATION
a. Stark Steps in the Effective Mass Limit
The Houston and CMR approaches lead to Stark step structure in c2(w,8)
which can be obtained by approximating Eq. (176) by the same procedure
applied to Eq. (171). We have
dt exp{it[oA.,,(k)-
03
+ i+Q3t3}.
512
In the above, use was made of Eqs. (180), (181), and the transformation
t = 2hkJeG: If hKx/e& is fairly large, the integral over r becomes approximately an Airy function and we have
( 190)
which exhibits the Stark structure.22a

b. Momentum Dependence on Wave Vector
The momentum dependence on wave vector can be treated by expanding
t P,,.,,(k+ e b s ) in the series
P,,,,(k -k ebS) =
The product
becomes
- [1 + eSb
* v k
[e - P,,,,,(k + ebs)][t
+ iS2e2(b
vk)2
-I-. . .]P(k).
(191)
P,*.,(k - ebs)] in Eq. (171) therefore
[t P,,,,,(k+ ebs)][t P,*.,,(k- ebs)]
++s2{[(e&- P(k))]L - P*(k) 4- C.C.

-2[e&
P)][ e b - Vk(t - *)I),
Z
12 * P(k)J24-S ( [ e b* v k ( t P(k))]C P*&) - C.C.)

vk)2(t
* vk(t
(192)
which becomes a power series in s. But in operator calculus we have
hence the momentum matrix element dependence on k can be expressed as

an operator series on the expression obtained by treating P as k independent,
as, for example, the weak-field approximate result Eq. (184). Differentiation
of Airy functions leads to divergences for large argument, hence these results
are useful only near o = w g .
c. Indirect Transitions
Indirect transitions are responsible for the fundamental absorption edges

of a number of semiconductors and insulators, Ge and Si, for example.
The field effect for indirect transitions can be obtained within the framework developed by using a few simple extensions. The theory for indirect
transitions was worked out by Chester and F r i t ~ c h e Y
, ~a~~ o b y and
,~~
6.
513
Penchina.2s We discuss this effect only for the M, threshold in the EMA;
a discussion of Stark steps for these transitions has been given by Y a ~ o b y . ~ ~
Indirect or phonon-assisted transitions involve another degree of freedom
in that the CM energy of the electron-hole system need no longer be restricted
to zero since the phonon is able to absorb momentum. We may phenomen, dan) M o edge
ologically describe this, in the EMA expression for ~ ~ ( 0 at
by replacing the gap energy E , byz9 E , - (h2GM)/2M* hv,,, where
(h2KEM)/2M*represents the energy of the center of mass of the electron-hole
pair, and hv,, represents the phonon energy (the plus sign refers to creation
and the minus sign to absorption of a phonon in the indirect excitation
process). To lowest order it is assumed that all phonons have the energy of
the phonon required for momentum conservation from the top of the valence
band to the conduction band minimum.25 In the usual approximation of
a k independent matrix element, it is then necessary to replace the direct
transition matrix element with the indirect element, include the phonon
Boltzmann factor, then sum over all CM degrees of freedom. We have
in Eq. (100) is replaced as

where in addition, the matrix element 12 Pn.,,(0)l2
l~*Pn,,(0)lzIM12(~K,+ k $1,
+
(195)
where qKois the Boltzmann factor for the phonon, M is a factor proportional
to the indirect matrix element, and
( - ) refers to emission (absorption) of
the phonon. The expression for E ~ ~ , ~8)
( ( for
u , the M , edge can be written in
closed form in the EMA as29
+ r Ai(r) + r2
where
and 0 is defined as in Eq. (101). The change in the imaginary part of the
514
dielectric function can be represented by
[ni(r)
+ r Ai(r) + r2
i 1
dr Ai(t)
- r2u(-r)
(198)
where the zero-field expression for c2 is given by the term rZu(- r ) of the
brackets.
The indirect transition effect appears to have application only at the
fundamental edge due to the fact that it is a second order process, with
matrix elements typically lo3 less in magnitude than those for direct transitions. Indirect transition effects in higher interband transitions are therefore
negligible with respect to direct transitions. These effects can be calculated
directly from Eqs. (194) and (195) by substituting the appropriate function
E~ for a particular threshold.
More detailed calculation of indirect dielectric function by YacobyZ4
shows that Stark steps also appear at this edge. By including periodicity
effects, as done for the direct transition theory, the &function structure
again appears.
d. Collision Broadening
Following photon absorption, the presence of many interaction mechanisms in a crystal prevents the electron or hole from remaining in the state of
creation for an appreciable length of time. According to the uncertainty
principle, these interaction mechanisms introduce collision broadening.
This can be treated phenomenologically by adding an imaginary term to the
energy,30*33.34*43
which causes the state to decay with a characteristic
lifetime in the time-dependent picture. This is equivalent to Lorentzian
broadening, since the poles of the Lorentzian broadening function are
symmetrically located above and below the real frequency axis by an amount
equal to the broadening frequency in the complex w-plane. A complex
energy representing broadening may be included from the beginning in
the time-dependent current operator, and this problem has been treated
rather extensively in the Kubo formalism by E n d e r l e i r ~and
~ ~ Enderlein
and K e i ~ e r These
. ~ ~ results can be expressed in closed form in the EMA
]imit.30,34.65
65
D. E. Aspnes, Phys. Status Solidi 23, K79 (1967).
6.
515
The effect of Lorentzian broadening on the one-electron electric field

results can be obtained immediately by utilizing the fact that the function
Ai2(z)
+ i Ai(z) Bi(z) =
3/2
+ sz +
Jom$exp{i[$s3
is analytic in the upper half plane and vanishes on the infinite arc in this
plane. Since the functions F and G are generated from the integral of the
above expression, it follows that the Lorentz transform is represented by
evaluation of the residue at its U H P pole, and in the presence of collision
broadening, the function F ( o , 8)+ iG(w,8 )becomes3
r) + i q w , 8,r)
~(o
8,
,
Ai(z)Ai(w)
+ w Ai(z) Ai(w)
where
E , - ho
z=x+ir= f
h0
r,
+ ia.
r, is the broadening parameter in energy units, and

w
z exp[ - i$r].
In Table 11, F(w,8)and G(o,8)are to be replaced directly with F(w,8,r)

and G ( o , 8,r)in the presence of broadening.
The effect of broadening is shown in Fig. 7. The functions F ( x , r ) and
G(x, r t w h e r e x is defined in Eq. ( 2 0 1 k a r e shown for several values of the
dimensionless broadening parameter r. The most obvious effect is the
rounding of the singularity in the electrooptic functions which occurs at
the critical point energy. Since the electrooptic functions F ( x ) and G(x) are
scaled according to the characteristic energy h% = 223hR, the relevant
energy unit is h e and the electrooptic functions are broadened with the
broadening energy r, equal to 0, 0.5, 1.0, and 1.5h0, respectively. With
sufficiently large broadening, the subsidiary oscillations vanish and all that
remains is the small structure around the critical point energy itself, a
characteristic observed in most higher interband electroreflectance spectra.
Discussions of the phenomenological effect of collision broadening can be
found in various sources.27,30~33~34~43~66~67
b6
67
R. A . Forman, D . E. Aspnes, and M . Cardona. J . Phys. Chem. So1id.s 31. 227 ( 1970)
516
Broadening can also be expressed directly in Eq. (171). To within terms

of the order of TJho (we neglect the contribution from cK2in the prefactor),
Eq. (171) becomes
[e - P,.,(k
+ e b s ) ][e - P;,(k
x exp(-2rclsl) exp
- ebs)]
ilS
i
ds' [U,,,(k
+ ebs') - h o ~ ] .
(203)
The damping term exp( - 2rJsl) cuts off the integral over s, and could make
numerical evaluation of Eq. (171) for a given band structure practical.
e. Crystals without Centers of Inversion
In crystals without centers of inversion, the quantities X,,,(k) defined by

Eq. (114) are nonzero. The general convolution formalism shows this to
lead to a correction linear in field to the interband energy. Provided X,,(k)
is a sufficiently slowly varying function of k, it may be represented by its
k-independent term and leads only to a linear shift of the edge,6 as shown in
Eqs. (182) and (183).
An alternate method of treating the effects of X,,(k) is to expand the
exponential term containing 8 -[X,.,(k) - X,,(k)] in Eq. (171) to first
~ r d e r . ' ~ .Th
~ *e .exponential
~~
term is approximately
exp {i
J:, ds' [U,.,(k + ebs') - ho]

ds' [X,.,.(k
+ e l s ' ) - X,,(k +
The functions X,,(k) can be expressed in terms of Wannier functions using

Eqs. (114) and (12)
Xnn(k) = i
d3r un*(k, r)V,un(k r)
1exp(ik - R) jvd3r a,*(r + R) ran@)

= 1exp(ik - R)(nRlr(nO).
=
Yu. A. Kurskii and V. B. Stopachinskii, Fiz. Tekh. Poluproo. 1, 106 (1967) [English Transl.:
Sou. Phys.-Semicond. I , 81 (1967)l.
69 A. G . Aronov and G. E. Pikus, Fiz. Tuerd. Tela 10,825 (1968) [English Transl.: Sou. Phys.Solid Stare 10, 648 (1968)J
68
6.
517
0.32
1 -
-0.32
tk
1
u
I
-0.04
o'ok3i!2
I
0.02
F CO.l.0)
-0.0 I
0.004
-0 02
F
GCe,l.5)
-0 004
-0008
-4
-2
4 e
-4
-2
FIG.7. The effect of Lorentzian broadening on the functions F(x), G(x) shown in Fig. 4
where r = 1 corresponds to a broadening energy r, = he. (From Forman er
Upon substituting k .+ k ebs' in Eq. (205) and inserting in Eq. (204), the
first order correction may be calculated. The EMA expression for the
correction is rather long; it is given in Eq. (63) of Porsch." A feature of
this solution is the appearance of step-like structure due to the lack of
inversion symmetry. A discussion of this effect can be found in Kurskii and
Stopachinskii.68
518
f. One- and Two-Dimensional Critical Points

The methods used to obtain the dielectric function for three dimensions
are also applicable in one and two dimensions. It is not possible to reduce
a higher dimensional result to a lower dimensional result by letting one or
more interband reduced masses become infinite, since higher dimension
results contain integrations over k-space directions which are not present
in lower dimensions. Since only the dimension in the direction of the field
was explicitly involved in the derivation of Eq. (171), it is apparent that
Eq. (171) describes the electric field effect for any number of dimensions.
The reduction to the weak field approximation, Eq. (184), also applies, in
general, provided the k-space integration spans the appropriate dimensions
and the interband reduced mass defined in Eq. (179) is modified accordingly.
One-dimensional critical points arise in magneto-electroreflectance, and
two-dimensional structure should be appropriate to layered crystals such as
g r a ~ h i t e . ~For
completeness, we list the changes in the real and imaginary
parts of the dielectric function for all critical points in one and two dimensions
in Table I11 for a single pair of bands in the EMA. Intraband effects are
neglected. The functions used in Table 111 are defined by
u( - x)
G,(x) = 2n Ai(x) Bi(x) - ( -x)1/2
~
FAX)= n{/:
G,(x)
= Jxm
dt Ai(t) - u( - t ) ,
dt {n Gi(t) - -
The zero-field behavior of the dielectric function is given by the term involving
the unit step function in Eqs. (206H209).
g. Field EfSect on the Plasma Frequency
The effect of the electric field upon the plasma frequency has been calculated
by Enderlein and K e i ~ e rin~ the
~ Kubo formalism. The results show a
quadratic shift of the plasma edge with field. We outline the derivation and
result ;a more thorough treatment is given by Enderlein and Keiper.
The intraband part of the dielectric constant is calculated by substituting
the CMR wave functions given by Eq. (157) into Eq. (33). The zero-field
F. Aymerich and F. Bassani, NLIO~MJ
Cimrnto 488,358 (1967)
6.
519
TABLE 111"
FUNCTION
IN THE VICINITY OF CRITICAL POINTS INDUCED BY A
ELECTRIC
FIELD,
FOR PARABOLIC BANDSIN THE EMA IN ONE AND TWO DIMENSIONS
CHANGES IN THE DIELECTRIC

UNIFORM
Dimension
Type
A&1
A62
Key to the terms used in Table 111 :
pI1= p in one dimension,
F[*
$1
E 2
1 8 '
=
in two dimensions.
K , . K Lare k-space cutoff lengths in remaining dimensions
plasma frequency wpz(0) can be represented in the usual manner by an

optical mass mgpl for each filled band v
wp2(0)=
14rre2n,/m~,,,
(210)
where n, is the density of electrons in the band v . Only the lowest terms in
the field expansion need be considered since the field effect is small. Substituting Eq. (157) into Eq. (33) and calculating gives the result33
where 0 is defined in Eqs. (101). The field dependence is contained in 0'

Bz; hence the shift of the plasma edge is quadratic in field.33
520
h. Defect Electric Fields in Optical Properties of Solids

The so-called internal electric field effect on the dielectric function has
been investigated in detail by Redfield.70a*bNaturally occurring electric
fields arising at charged defects in solids (such as occurring at impurities,
dislocations, lattice defects, etc.) seem to produce significant effect on the
medium in which they are embedded. Redfield calculated the probability
distribution of the electric field strength due to a fixed defect point
and by using the Franz-Keldysh form for the local change in the absorption
coefficient he obtained the total absorption coefficient by integrating over all
field strengths weighting each value by its probability of
His model succeeds in explaining the tail in the absorption edge of
covalent solids like G ~ A s . ~His
results are in disagreement with the theory
that the shape of the edge in such materials is dependent on phonon interaction.
A similar mechanism has been proposed by Fischer70d to be responsible
for the modification of the Si absorption edge by radiation-induced defects.
i. Multiple Photon Processes ; High-Frequency Eflects
Several authors have considered the possibility of using high frequency ac

fields rather than dc fields on solid^.^^^^^^" The use of ac fields gives rise to
side bands at w f 2 n o f , where w sis the applied field, in the usual approximations. The theory involved is a generalization of the Houston function
approach, and has been treated quite thoroughly by Yacoby. We refer the
reader to this reference for the details.
IV. Generalizationsof the One-ElectronTheory
The effect of the electric field has been discussed in the one-electron
approximation, where the electron is assumed to move in a potential determined principally by the lattice and where electron4ectron interactions are
neglected. There are several arguments which are generally used to justify
the neglect of electron-electron interactions, principally the Coulomb interaction. If the electric field is large enough, it represents the dominant perturbation in the system and the neglect of the Coulomb interaction is relatively
less serious. If collision broadening exceeds in energy the average value of the
Coulomb interaction, then the Coulomb interaction can be considered as
70aD.Redfield, Phys. Rev. 130,914 (1963).
70bD.
Redfield, Phys. Rev. 130,916 (1963).
70cD.Redfield and M. A. Afromowitz, Appl. Phys. Lett. 11, 138 (1967).
70dJ.E. Fischer, Phys. Rev. 181, 1368 (1969).
7 1 Y. Yacoby, Phys. Rev. 169,610 (1968).
6.
52 1
leading to effects which are primarily washed out by collision broadening. In

these arguments, one relies on the presence of stronger perturbations to overcome the presence of the Coulomb interaction ; however, in certain cases these
arguments cannot be applied and the Coulomb interaction exerts a dominant
influence on the dielectric function. An example of this breakdown can be
found at the critical points themselves, precisely where these arguments are
needed the most, for the definition of the critical point at the Brillouin zone
location where the gradients of the conduction and valence bands are equal
is just the criterion for equal group velocities of the electron and hole. Since
photon absorption creates an electron and hole at the same point in space, the
condition of equal group velocities causes them to move together and to
interact more strongly at critical points than at other points in the zone.
Under certain conditions this interaction cannot be neglected.
Therefore, one is left with the necessity of solving the Hamiltonian with the
Coulomb term explicitly included. This is a problem so difficult, even in the
absence of the electric field, that exact EMA solutions have only been
obtained for isotropic ( M , and M , ) 2 1 s 7 2 critical points. However, approximate variational solutions are available in the EMA for a certain amount of
anisotropy, not only at the M , and M , edges7, but also for the highly anisotropic saddle point.74 Greens function methods have also made progress
on the zero field p r ~ b l e m . ~ ~ , ~ ~
Electric field effects introduce a considerable complication. In spite of
this, a certain amount of progress has been made recently in estimating their
effect. One of the methods of treating electric field effects in the Hamiltonian
containing the Coulomb interaction is to obtain the wave functions of the
effective-mass Hamiltonian n ~ m e r i c a l l y . ~These
. ~ ~ wave functions are then
properly normalized and substituted into Elliotts formalismz1 [Eq. (79)].
Ralph52and B l o s ~ e yhave
~ ~ investigated the M o isotropic edge in this way.
An elegant formalism due to EnderleinI4 introduces the electric field as a
time-dependent vector potential and obtains the dielectric function by means
of a Greens function approach. A third method introduced by Rees,
generalizes the convolution procedure, but is still not well adapted to regions
of critical points. The many-body theory of the electric field effect is at
present being developed, and anything other than an introduction would
probably become obsolete in a short time. The effective mass approach is
*B. Velicky and J. Sak, Phys. Status Solid1 16, 147 (1966).
W. Kohn and J. M. Luttinger, Phys. Rev. 98,915 (1955).

E. 0. Kane, Phys. Reo. 180. 852 (1969).
J. Hermanson. Phys. Rev. Leu. 18, 170 (1967): Phys. Rev. 166, 893 (1968).
Y. Toyozawa, M. Inoue, T. Inui, M . Okazaki, and E. Hanamura, J . Phys. SOC.Japan 22,
3
1337 (1967).
522
D.
E.
ASPNES AND N. BOTTKA
treated in detail by Blossey and Handler in Chapter 3, on electroabsorption in

this volume. We will discuss only the generalized convolution development of
Rees, and the Greens function approach of Enderlein. At present, Enderleins
formalism is the most general, and in principle can be used to calculate the
electric field effect at any critical point provided the effective mass wave
functions are known for the zero-field case, and that the EMA relative
coordinate potential satisfies certain relationships (the Coulomb interaction
satisfies these relationships to a good approximation, but not exactly). It is
expected that generalizations of Enderleins result will lead to calculations
of the electric field effect at general points of the zone and will provide the
basis for further theoretical advances in the theory of electric field effects.
10. THE GENERALIZED
CONVOLUTION
FORMALISM
The convolution formalism which was obtained in Section 8c in the oneelectron approximation can be shown to be more general than the derivation
implies. In this section the derivation due to ReesI3 will be treated, in which
the convolution formalism is obtained in the presence of additional perturbations.
The objective is to relate the dielectric functions for different fields; as a
result, the discussion will be essentially qualitative. The crucial point is that
the actual wave functions of the electrons in the crystal must still have the
phase factor which is obtained in the one-electron approximation. This in
turn depends on the absence of resonant collisions, so that the distortions
introduced in the spatial part of the wave functions due to scattering potentials
will have negligible overall effect. We generalize Rees original treatment at
the M , threshold to the entire Brillouin zone.
Let the two-particle Schrodinger equation be written as
[ H - if~(d/dt)]$~(r,
t ) = 0,
where
Hoe(re)+ H o h ( r h ) - edf. ( r h -
re)
(212)
+ v(rerr h ) ,
(213)
and t+bq(r,t ) is a solution of (six-component) quantum number q, Hoe(re)and

Hoh(rh)are the unperturbed Bloch Hamiltonians for the electron and hole,
and V(re, rh) represents interactions between electrons, holes, and the lattice.
Then t,kq(r, t ) is expanded in Bloch functions as
$q(rtr) = (1/W
kekh
C(ke, k h , q , f)(Pv(khrrh)(Pc(ke,re)r
(214)
and in addition it is assumed that the cell-periodic parts of the Bloch functions are k independent. Then
$q(r,
= (1 / N
v) 1 C(ke,kh ,q, t ) eXp(ikh * r h 4k&h
ike re)
(215)
6.
523
and
are Fourier transforms of each other. In addition to the obvious assumption

of expanding the wave function in terms of Bloch functions of only two bands,
we have made an additional assumption, namely that the interaction
potentials are time independent.
An equation of motion is now derived for t,b (r , rh, t ) which generates
q.,
the required phase factor.I3 Substituting Eq. (215) into Eq. (212) and taking
the matrix element pv*(kh,rh)qc*(ke,re) gives
(217)
(since the cell-periodic parts of the Bloch functions are neglected). If

S, =
k, - t.Et/h,
(219a)
(219b)
(219~)
then Eq. (2 17) becomes

[ E,(S,
+ t.&T/h) + E,(sh
- C&T/h)
- ih d/dT )C(S,, s h , 9, T )
V(qe,qh)c(se-qe* s h - q h * q , s ) = o .
(220)
qe+qh
If low angle scattering predominates, we can make the assumption upon

which the convolution theorem is based, namely that V(qe,qh) will have a
significant value Only near q,, qh Z 0, hence each solution of Eq. (220) will
consist of a narrow s-distribution about its mean value, which is denoted by
S. We can therefore use this assumption to expand E , (as an example) giving
E,(s,
+ e b 7 / h ) 2 E,(S, + e b z / h ) + hs, - u,(S, + e&s/h) + g,(S,, u,),
(221)
where
u,(S,
+ e&s/h) = ( l / h ) VSeE,(S,+ e&t/ri)
(222)
524
is the electron group velocity and gC(se,u,) represents higher order terms.
Higher order derivatives of E , and E , with respect to s are expected to be
generally small. By substituting Eqs. (221) and (222) into Eq. (220) and using
Eqs. (216) and (218), we have
[E,(Se
+ ed?r/h) + E,(S,
ihu,($, - ed?r/h) V,,
*tl/(re,rhrScrsh,f) =
+ V(re, r,) - ihu,(S, + e b r / h )- Vre

- ih a/& + D,(u,) + D,,(u,)]
eEr/h)
(223)
0,
where the quantum number q in Eq. (212) is now represented by the mean
values S, and s,, and the differential operators in u, and u, acting on tl/
generate g , and g,.
The equation of motion (223) utilizes explicitly the slow spatial variation
and time-independence of the interaction potentials contained in V(re, r,),
where DJu,) and Dr,(uv)describe local severe distortions, which are assumed
to occupy a negligible volume. To a first approximation which neglects the
operators D,
where X is an arbitrary function of position, and

=
df
~ ~ u c , v ( ~ )
is the classical distance the electron (hole) moves in time 7.Thus X describes
the particle displacement and the exponential involving V(re, rh) gives the
phase distortion by refraction from the scattering centers. This solution will
not describe the wave function near these centers where D is important, but
if we make an adiabatic approximation to the effect that each core function is
determined by incident velocity alone and that the incident velocity changes
slowly enough so that the core function can follow, then the wave function I)
in the core regions must join to the shallow potential solution. Then, to a
good approximation, the position-independent phase factor
6.
525
will also apply in these regions. The entire solution can therefore be approximated by
(227)
Rather than completing the derivation by the method of Rees, we note
that his additional approximations of ( 1 ) taking the momentum matrix
element to be slowly varying in S (and therefore T), (2) expanding the energy
( E , E,) to quadratic terms as in Section 8c, and (3) including momentum
conservation between initial and final states (which may involve creation or
annihilation of a phonon), the dielectric function may be calculated as in the
one-electron approximation. The convolution expression again is obtained
in the weak-field limit, but instead of calculating the momentum matrix
elements using the Bloch wave functions, we now use the more general wave
functions defined in Eq. (227). The convolution expression is therefore valid
to the extent that a spatially independent phase factor can be defined as in
Eq. (227).
Rees actual method of proof of the convolution equation (188) is somewhat different than that used in Section 8c, and involves the absorption
coefficient for the M o edge. The transition probability is calculated and the
absorption coefficient reduced to the form
J-
P(F, w ) = ,I1/,
T(w)Ai2[+1(W - w ) ] dw,
(228)
where 1 = l/n. The convolution expression is derived by transforming Eq.

(228)into the time domain and using the Fourier convolution theorem, which
states that the transform of a convolution of two functions is the product of
the transforms of the functions. It is therefore possible to obtain the transform
of the field-independent factor T(o as
) a proportionality factor which disappears upon taking a ratio for two different fields. The Fourier transform of
Ai2(x) is given directly by its integral repre~entation,,~
and in general as
Rees shows for the M , edge, the relation
w ~ ~ ( wF,)
, Ai[
($
- $)(cot
- a)] dw
(229)
is obtained, where SZ is the characteristic frequency defined in Eq. (101). If
F, = 0, Eq. (188) is obtained.
It has therefore been shown that the convolution result is more general
than is implied by the one-electron approximation derivation. Convolution
526
D . E. ASPNES A N D N. BOTTKA
expresses the effect of the electric field at general points of the zone, and
automatically takes into account the differences in reduced mass in the field
direction for equivalent critical points which are oriented at different angles
to the field. Unfortunately, the adiabatic approximation which underlies
Rees' derivation tends to break down in the vicinity of critical points.77 In
the next section we discuss another method of attack, used by Enderlein,14 in
which the electric field is introduced as a time-dependent vector potential and
leads to equations of a different form. However, neither method is rigorously
applicable in the vicinity of critical points where Coulomb effects are present,
and one must resort to numerical solutions in these cases.
11. THE ELECTRIC
FIELDAS
VECTORPOTENTIAL
In this section, we consider an alternative method of describing the effects

of a uniform electric field, where the electric field is treated as a time-dependent vector potential. This method has been used by Enderlein14 in an
attempt to describe electric field effects in the presence of the Coulomb interaction. Although Enderlein's results are not correct,'' the formalism which
he used is itself of interest, and we outline it in this section.
In all previous sections, the uniform electric field has entered the Hamiltonian through spatially dependent potential energy terms of the form
V(r) =
ecp(r) = e 8 r .
(230)
In general, d is a function of both scalar potential cp(r) and vector potential

A(r),s'
i a
d(r, t ) = -~-A(r, t ) - Vcp(r, t )
c at
Equation (231) shows it is also possible to describe a uniform field 6' in terms
of a vector potential A(r, t). The two methods of description are equivalent, as
we now show.
" There
exists experimental verification that the Airy convolution may give reasonable results
even in the presence of Coulomb effects. Rees" has measured the change in absorption
induced by the electric field at the (degenerate) fundamental direct edge of GaAs, and obtains
an excellent fit with the convolution of the measured absorption by treating the reduced
mass an adjustable parameter. Using his convolution formalism, with broadening energy
hR, an interband reduced mass of0.065me is calculated. The interband reduced mass is known
to be 0.037m,.79 Since hR depends on the cube root of the reduced mass, the discrepancy is
magnified.
H. D. Rees, Solid State Commun. 5, 365 (1967).
l9 Q. H. F. Vrehen, J. Phys. Chem. Solids 29. 129 (1968).
J. D . Dow, Phys. Srarus Soiidi 34,K71 (1969).
Jackson,41" pp. 179-183.
6.
527
The Hamiltonian of i electrons in the presence of an electromagnetic

field contains both scalar and vector potential terms q(r, t ) and A(r, t ) asB2
+ 1 V(ri,rj),
i.j
(232)
where the last term on the right-hand side represents the interelectronic
potential and the potential between the electrons and the lattice. By the
definition of A(r, t ) and q(r, t ) , it follows that Maxwells equations (and therefore the dielectric function) are invariant with respect to a gauge transformation
A(r, t ) = A(r, t )
+ VA(r, t ) ,
I d
~p(r,
t ) = ~ ( rt ), - - -Nr,
c at
t),
(233a)
(233b)
where A(r, t ) is an arbitrary scalar function. In previous sections, we have

chosen A(r, t ) = 0 and q(r, t ) = - 8 r, which represents the electric field as a
spatially dependent scalar potential. By Eq. (233b), the choice
A(r, t ) =
-ctb
-r
(234)
eliminates the scalar potential and replaces it with a time-dependent vector

potential, expressing Eq. (232) as a Hamiltonian in the time gauge
H
m(p, -
=
I
+ 1V(ri,rj).
(235)
i.j
The invariance of the physical problem with respect to the gauge transformation guarantees the equivalency of Eqs. (232) and (235).
Different methods of calculation must be used to obtain e 2 from Eq. (235),
as compared to the procedures outlined for Eq. (232) in Section 4. Equation
(235) does not possess constant-energy solutions, and the formalisms described earlier d o not apply. Without going into the details, we note that the
dielectric function can be obtained from the eigenfunctions of Eq. (235)
through the method of Greens functions, and in the two-particle approximation the imaginary part is given as a summation of Greens functions over
the complete set of operators for creation and annihilation of Wannier functions by the expression 14.
L I . Schlff. Quantum Mechanics. Chapter 10 McGraw-Hill. New York. 1955
528
where
G(R1, R2: Rl, R2; t ) = iu(t)([a~R,(t)a~R,(t),

ac~j(o)av~i(o)]). (237)
In the two-particle EMA, G(R 1 , R2 :R

the equation14
[:hi
R, : t ) is given as the solution of
- H(R1, R2 :t ) G(R1, R2 ;R1, R2 : t ) =
-a([)
In terms of the EMA Hamiltonian
H(R,, R 2 ; t ) = W, - iVR2- -8
h
- W, iVR, -
6R,Ri 6R2Rj.
+
:)
-8
V(Rl
(238)
R2),
(239)
provided the interparticle potential is sufficiently weak so that the crystal
can be represented by the dielectric constant c0 (Wannier e ~ c i t o n ) . *In~the
parabolic band approximation,
+ (h2/2mZj)kj2,
W,(k)
E,
W,(k)
- (h2/2mEj)kj2.
(240a)
(240b)
(summation over j = x, y, z is assumed in Eqs. (240), and throughout), and

me*and mh*are the electron and hole effective masses, respectively. Equation
(239) becomes
ih2 e t 8 a
e2t2g2
j
V(Rl - R2),
(241)
rnzi A a R 1 ,
2pi
which may be separated ih the usual manner into center-of-mass and
relative coordinates, by defining the CM and relative coordinates as in
Eqs. (69H71),giving
+-
+-2-
H(R,,R2 ; t ) = H(R,p; t )
- E , - - - h2
a2
2Mj aRj2
-t
e 2 t 2 g 2 ihet
+ -&j2Pj
Pj
apj
h2 a2
2Pj a P j 2
+ V(p).
Therefore, the Greens function can be written as

G(Ri,R2;R,,R2;t)
(242)
G(R,p;R,p;t )
= iu(t)
2 exp[iK - (R - R)] x,*(p, O)xq(p,t ) ,
(243)
K.q
83
Note that Eq. (239) differs from Eq. (66) only by the gauge transformation of Eqs. (234).
6.
529
where
and
E,
e2t2gj2+ i herb.
2 - a
+ E,, + ___
2Pj
apj
pj
Here E,, = h2Kj2/2Mj, and q represents a general quantum number

describing the solutions xq(p, t )of Eq. (245). The EMA equation has therefore
been replaced with an equation where the electric field enters in a bilinear
term in time and space and a quadratic term in time, rather than the term
egjrj which appears in the usual EMA formalism. Defining
dj3 = e2gj2/2hpj,
d3 =
cOj3,
(246a)
(246b)
l j= e q / p j ,
xq(p, t ) = x,(p, t ) exp( - io,t - io,,t
i+Q3t3),
(246c)
Eq. (244) is transformed into

at
a2
h2
i h t l V, - 2pj a P j 2
= {ihtk.
v, + HO(P)JX,(P, r),
(247)
where
~ , ( p )=
+ v(p)
h2/2pja 2 / a p j 2
(248)
is the relative coordinate Hamiltonian with 8 = 0 and H , is assumed to

have a complete set of stationary, properly normalized eigenfunctions
Cp,(PX where
HO(Pbq(P) = E,Cp,(P).
(249)
These results may be substituted in Eq. (236), yielding c2 in terms of
~ ( pt ,) . This form can be simplified by noting that the coordinates R, ,R,, R,,
and R2 may be replaced by the relative and CM coordinates R,R ,p, and p,
since the Jacobian of the transformation is unity. This also leads to

6R,,RIzSR2.R2s
-+ So, do,.. The center-of-mass sums over R, K, and R can be
= 0) which expresses
performed in order, giving K = 0 (and therefore oCM
530
conservation of momentum. After these calculations, Eq. (236) becomes

E&,
8 )= Re
jr
4ne21e. Pcy12
dt exp[i(o - w,)t] exp
m2w2h
where the functions x,(p,r) are the solutions of Eq. (247) subject to the
boundary condition of Eq. (244). In the continuum, Xq -+ Jd3q and bqaq-,
6(q - q) in Eqs. (244) and (250).
We have essentially followed the procedure used by Enderlein,I4 which
is correct to this point. Enderlein continues with a derivation ofan expression
for limp,, xq(p, t),but this has been shown to be incorrect by Dew." Before
discussing Enderleins expression, we first obtain the formal solution for
xq(p,t ) and show the approximation inherent in Enderleins result (which
limits its general applicability and in particular prevents its use in treating
exactly the effects of the Coulomb interaction).
The connection between Eq. (247)and time-dependent perturbation theory
is obvious. The general solution can be written formally in terms of the
time-ordering operator T as84
where the time-ordering operator is necessary since in general b V, does

not commute with H,(p). The functions xq(p,t ) can be obtained in principle
to arbitrary orders by summing the appropriate Feynman diagram^.'^
If the operators l V, and H,(p) commute, the time-ordering operation
is not necessary and the operators can be integrated directly as commuting
numbers. The result in this special case is exactly what would be obtained
by straightforward integration of the first order differential Eq. (247), or84a
xq(PI
rb
- v,, H,(p)l
exp[ - f t 2 i * V 1 exp[ - (i/WH,(p)r] xq(p,01,
= 0.
(252a)
(252b)
A natural choice for the starting functions xq(p,0) in either case is the complete
set of constant-energy eigenfunctions cp,(p) of H , , given by Eq. (249), which
already diagonalize H , and satisfy the normalization condition of Eq. (244).
8 4 See, for example, Arbikosov et
Chapter 2.
84aEquation(252a) is not a general solution to Eq. (247) because the factor t in (ihrl . V,) leads
upon integration to a factor f in this term: -(i/h)t[(ih/2)ti. V, + Zo(p)] does not commute
with [ihrp.V, + 3?o(pp)unless A. V,, commutes with .Wo(p). This is easily seen by direct
substitution of Eq. (252a) into Eq. (247).
6. ELECTRIC-FIELDEFFECTS
531
If Eq. (252b) is also satisfied, the eigenfunctions cp,(p) are in addition eigenfunctions of the operator 3L V,, or the momentum operator in the nontrivial
case of 8 # 0.
We are now in a position to discuss Enderleins expression. Enderlein
uses an iterative procedure to obtain
which is assumed to give the correct limiting form for p + 0 for all Hamiltonians such that
lim [A V,, H , ]
P-0
0,
i.e., Eq. (253) is taken to be valid for all systems where the potential energy
has inversion symmetry. The justification of this assertion is based on the
commutation of k V, with H , at the point p = 0, which simplifies the
iteration procedure so that it appears that the solution of Eq. (252a) is valid
at p = 0, although in general it is not correct for p # 0. As Dow points out,80
the physical equivalent of this procedure is to neglect everywhere the force
exerted on a particle simply because it is in a potential well having inversion
symmetry, i.e., zero force at the origin, whereas the force exerted for p # 0
must influence the value of the wave function at p = 0 even though the
force is zero at that point. However, the error is still more subtle : the interaction is only partly neglected in the calculation of the time evolution of x,
and is in fact correctly incorporated into the initial condition xq(p, 0) = cp,(p)
since cp is the exact solution of the Hamiltonian with the inversion-symmetric
interaction included. This is immediately seen by showing that Eq. (253)
is exactly equivalent to Eq. (252a), which gives the time evolution of if
3L V, commutes with H , . We note the translation operator is given formally
as
expf -x,
V) cp(x) = cp(x
xo),
(255)
and therefore Eq. (252a) can be written in the form
exp( - ; H1 , r )
cpq( p
z1t i ) ,
(256)
which is just Eq. (253).Therefore, Enderleins expression gives an approximation where the timeevolution of x is calculated from the exact initial condition,
but where all diagrams which take into account the noncommutativity of
532
l . V and H, are neglected.84b In particular, the calculated results of

Enderlein14 for the Coulomb interaction at an isotropic M a edge are not
exact because the Coulomb potential - e 2 / p does not commute with the
gradient operator, and therefore Eq. (253) is not applicable. This results in
certain qualitative errors in Enderlein's calculated results :the lowest exciton
line moves to higher e n e r g i e ~ ,in
' ~contrast to the results of numerical integration by Ralph,52 B l o ~ s e y Dow,
, ~ ~ and second-order perturbation theory.84c
Also, the second lowest, doubly degenerate exciton line is calculated to split
and broaden syrnmetri~ally,'~
whereas it should broaden a~ymmetrically.~~
These points are discussed more fully in Chapter 3 by Blossey and Handler
in this volume.84d
The equivalency of the vector potential approach and the Elliott formalism
can be demonstrated directly for three special cases which can be solved
exactly in the vector potential method. In the zero-field limit, for which the
commutator Eq. (252b) is trivially satisfied,
xqlp,4
exp[ -(i/@HO(p)tl(P&,
0)
= exp[ - iwq(p7O)I(P,(P,
0)-
(257)
Upon substituting into Eq. (250) and using the fact that
dt eiW'= i Y ( l / w )+ n 6(w),
Elliott's equation is recovered
gives an example where Eq. (254) is satisfied, yet Eq. (253) gives clearly incorrect
results when calculating c2. In this case, the relative coordinate interparticle potential is
assumed (for simplicity) to be a one-dimensional harmonic oscillator potential ) K z 2 in the
field direction. The harmonic oscillator is exactly solvable with or without the field present,
and it is known that the effect of the uniform electric field is simply to shift the center of oscillation, and all energy levels by the same amount so that the level separation remains unchanged. Use of Eq. (253)leads to a broadening of the zero-field levels, which is incorrect. The
harmonic oscillator potential is therefore an example of a system which satisfies Eq. (254)
and fails to give the correct expression for on the basis of Enderlein's assumption.
84cH. A. Bethe and E. E. Salpeter, ''Quantum Mechanics of One- and Two-Electron Atoms,"
pp. 228ff. Academic Press, New York, 1957.
u4dForcompleteness, we note there are several typographical errors in Eqs. (14) and (15) of
Enderlein14: the operator 8"-'/as"- '( 1 + s) in Eq. (14) should be replaced by the operator
[8/8s(l + ~ ) ~ ] n - the
' : factor Dm2(1 + 2s) in Eq. (15) should be [P,(1 + 2s)I2. Also, n-"
normalization of the Airy integral is used throughout. Equation (14) should also be multiplied by )n" : Eqs. (B2) and (B3) by ( 4 ~ )'.- These equations are normalized to the natural
z ~ the
~ ~ hydrogen
unit of volume rO3 in terms of the length ro defined by Landau and L i f ~ h i t for
atom.
u4eL. D. Landau and E. M. Lifshitz,"Quantum Mechanics," pp. 116122. Pergamon Press,
Oxford, 1965.
8 4 b ~ ~ ~ U O
6.
533
A second example which leads to an exact solution is that of the free particle,
where H , = p2/2m and Eq. (252b) is again satisfied. Then
xk(p, t)
exp(i3t2L k) exp( - iokt)exp(ik r),
(260)
since V, and H, are both diagonal operators in the plane wave eik.r.This
expression can be substituted into Eq. (250), which can be reduced by
expressing the k (or q) space integration in Cartesian coordinates, interchanging the k and r integrations, defining an integration variable
k j + (Ljpj/2h)t
(261)
for each Cartesian coordinate j , and using the definitions of 3, and H in
Eqs. (246).The time integration is then in standard Airy function form which
can be changed to
kj'
which is the Airy convolution form of the Franz-Keldysh effect. It is also

possible to obtain an explicit solution of Eq. (247) for the uniform electric
field potential by factoring Eq. (247) into Cartesian coordinates (note in
this case, Eq. (252b) is not satisfied). The solution is the product of solutions
for each coordinate, the jth solution of which is
It can be shown that the effect of adding a uniform electric field in this
manner as a scalar potential merely tends to invert the initial gage transformation, and that the electric fields of the vector and scalar potentials
subtract vectorially in the result, as they must.
In general, it is no easier to solve Eq. (247) than to solve the equivalent
equation in the Elliott formalism. In particular, it cannot be applied to the
Coulomb problem to obtain exact results. The vector potential and scalar
potential methods are equivalent, and provide different methods of attack
on a particular problem. Which method to use would depend on the problem
to be solved.
V. Analysis of Electroreflectance
In the past four years, one of the main uses of electric field effect upon
solids has been to aid experimentalists in identifying interband transitions
occurring in crystals. Since most of the interband transitions occur above
the fundamental gap, the technique of electroreflectance has been ideally
suited for this task. Here one observes localized structure which can be
534
correlated to transitions occurring at specific regions in the band structure.

The main objectives of these experiments have been not only to locate the
spectral position of these structures, but also, if possible, to identify the
symmetry of the transition, i.e., its location in k space within the Brillouin
zone associated with this structure. Even when properly done, this task
has turned out to be quite difficult. Also, the experiments were often overinterpreted and open to controversy, particularly in light of recent band
structure calculations.8s As a consequence, electroreflectance and associated
modulation reflectance techniques suffered a credibility gap. It is the purpose
of this section to focus attention upon this problem and to give possible
alternatives which bypass some of the arbitrariness associated with the
interpretation of experimental data.
12. ARIR EXPRESSION
IN
THE
EMA
The expression for A R / R in the EMA for a single nondegenerate critical

point has already been given in Eq. (43).The functional forms of A E ,and A E ~
appear in Table 11. Equation (43),however, is not written in its most general
form, and before we make this apparent, it will be instructive to list again
the approximations and assumptions made in deriving the analytical
expressions of Table I1 and to consider their applicability in describing
electroreflectance.
The expressions in Table I1 describe the electric field effect upon the
dielectric function in the one-electron approximation. The derivation makes
the following assumptions :
(a) nondegeneracy of band at point of transition,
(b) no phonon4ectron interaction,
(c) no electron4ectron interaction,
(d) all the states in the valence band are filled while in the conduction band
all are empty,
(e) the parabolic band approximation,
(f) only dipole interaction considered, and
(g) field is homogeneous in the crystal.
Thus, when invoking the EMA theory in analyzing experimental data, these
facts must be kept in mind in order to achieve an honest comparison between
experiment and theory.
Since in real crystals not all of these assumptions hold, we must either
minimize them, circumvent them, or simply ignore them. Fortunately, most
of the above-mentioned approximations [with the exception of (a)] can be
'' F. Herman, R. L. Kortum. C. D. Kuglin. and J. L. Shay. in "IILVI
Semiconducting Compounds" (Proc. 1967 Int. C o d . Providence) (D. G. Thomas. ed.). p. 503. Benjamin. New
York and Amsterdam, 1967.
6.
535
justified partially or in full either experimentally or theoretically. In order

to encompass degenerate critical points, we simply make the nd lzoc assumption that they behave as individual critical points and assume them to be
effected by the perturbation as if they were nondegenerate.*" Having
emphasized the limitations of EMA we can now generalize Eq. (43).
Within the EMA, the structure observed in experiment is classified
according to symmetry of the transition (location in the Brillouin zone) and
the type of critical point (whether M , , M , , M , , or M 3 ) . With reference to
Fig. 3, a transition at r (center of the Brillouin zone) is necessarily an M,,
while at A, X , C, etc., the transition can be any one of the four types. This is
a direct consequence of the symmetry and the quadratic approximation
assumed in the EMA. Thus, when calculating the perturbed dielectric function for a given type of transition we must use the proper analytical functions
given in Table 11. In addition to the type of critical point it is necessary to
consider the number of equivalent branches of the star of k of the critical
point. Thus instead of Eq. (43) we must now
where q is the total number of equivalent branches of the k star for the given
transition and where CL and fi are the normalized fractional coefficients in
terms of E , and c2 given in Eqs. (45).43
For calculation purposes it is convenient to extract the polarization
matrix element IL Pcv12from B in Table I1 and write it as cos' @lPcJ2,
where
0 is the angle between L (polarization vector) and the momentum matrix
IPcv12.The term cos2 @IPcVIz
gives us a way to incorporate in the theory
the strength and the selection rule associated with the t r a n s i t i ~ n . ~ If,
~ . in
~'
addition, we consider the possibility of degeneracy, Eq. (264) will have the
Anisotropy in electroabsorption originating at the degenerate valence band maximum of

CdTe has been interpreted by V. S. Bagaev, T. Ya. Belousora. Yu. N. Berozashuili. and
L. V. Keldysh at the fnr. Con!: Phys. Srmiconducr.. Moscow, 1968(published in the Proceedings
by title only) to be a result of degeneracy. This anisotropy. however, appears to be small.
*' N. Bottka and U. Roessler, Solid Srrtre Cornniuti. 5. 939 (1968).
8'aJ. C. Phillips, Phys. Reti. 146, 584 (19661.
*' F. Aymerich and F. Bassani. N u o w C'itwnro 568. 295 (1968).
'' The selection rule is strictly determined by the symmetry of Pcy.Then cosz H represents
an outside measure whether we can or cannot excite this particular transition once the
selection rule is known. For cubic crystals in case of no perturbation the total contribution
from the k stars to normal incidence reflectance is always a constant and hence there is no
polarization dependence. In Eq. (265).on the other hand, the symmetry-breaking character
of the perturbation will cause polarization discrimination.
90 P. T. McElroy, Ph.D. Thesis, Harvard Univ., Cambridge, Massachusetts, 1968 (unpublished).
8b
536
form
AR/R =
Y.1
c c o s 2 @(ki)7:IP(kiE:12[a
m,n i
A&
+ fl A&]
m,n i
wheref(ki)F! is defined as the polarization factor and Di as the dynamical

factor expressing the effect of perturbation on the dielectric function ;c and v
label the bands, while y and A are the order of degeneracy of these bands.
Equation (265) describes the normal incidence electroreflectance from a
crystal assuming dipole transition between states E,(k) and E,(k) which are
q . I - and q . y-order degenerate. Equation (265) is in its most general form.
For computational reasons, however, it is helpful to redefine Di.Since both
f(ki) and Di must be evaluated in their local frame of reference, it is useful
to define a transformation matrix T which aligns the z axis of the crystal
frame of reference with that of the principal axis of the symmetry point
(local frame of reference). The Eulerian angles are a natural choice for
such a transformation (see Fig. 3). (See Eq. (266), p. 537.)
Now we can redefine 8 in Table I1 as
where
e3 = (e2l8I2/2fvL,)b(5,v, 6) + br(i, v, 6) + ch(i, v, S)l,

b
Px/Pyr
c = PJPZ
(267)
(268)
in local coordinate and where p , r, and h are angular functions relating the
direction of the electric field 8 in the crystal frame to that of the local frame
of reference for the particular k star. Thus, in the local frame of reference
the field is just
b = T I
(269)
and
:
a = l812p,
(270a)
&;
\&I%,
a: = lb12h.
(270b)
(2704
Choosing I in polar coordinates
6,
6 sin ( cos y ,
(271a)
d,
d sin ( sin y ,
(271b)
6, =&cos 5 ,
91
(271c)
H. Goldstein, Classical Mechanics, Chapter 4. Addison-Wesley, Reading, Massachusetts,

1959.
6.
537
538
it follows immediately from Eqs. (269) and (270) that
[(cos 6 cos [ - cos 4 sin [ sin 6) sin ( cos y + (cos 6 sin [

+ cos U] cos [ sin 6) sin 4 sin y + sin 6 sin U] cos (I2
[(-sin6cos[ - cosqsin[cosS)sin(cosy + ( - s i n 6 s i n i
+cos U] cos [ cos 6) sin 4 sin y + cos 6 sin U] cos (I2,
(272b)
[sin U] sin [ cos y sin ( - sin 4 cos [ sin ( sin y
(272c)
+ cos U] cos (I2.
(272a)
Thus, knowing 8 and the symmetry of the transition, the value of D i is

easily determined.
Now we have at our disposal an algebra for calculating the theoretical
value of A R / R for any interband transition within the EMA.
13. SYMMETRY
CHARACTER
OF ARIR
Since Eq. (265) is determined once d and the symmetry of the transition
is known, one could justly ask whether a direct comparison between experimental and theoretical A R / R would yield information as to the symmetry
and type of transition. As seen from Eq. (265), Table 11, and Fig. 5, however,
this algebra is quite complicated, and a direct line-shape comparison between
them is indeed ~nrealistic.~
We must identify the symmetry of the transition
by some other means. An alternate way would be to use the symmetry properties of,/; and Di themselves and extract symmetry information from them by
performing systematic operations on them, e.g., rotating the polarization
vector, changing the direction of the electric field, taking the ratio of A R / R
measurements for two polarizations as a function of field direction or vice
versa, etc. The signatures obtained by performing such operations should
be unique for a given symmetry of transition (provided they are seen in the
e~perirnent).~~
As an example, let us consider a conflict of assignment for a nondegenerate
transition in Ge where the symmetry of the transition could be either that
of A or A, say. The selection rule in both cases, say, is such thatq2.
f(ki) = A ( [ , u],6) = COS 0,
+ COS
0,=
j= I
C),
(273)
Aside from the fundamental edge of the material. which is necessarily a single star of k
critical point contribution to ARIR, the superposition of the stars of k for higher transition
will wash out any singular character which might differentiate them from one another.
92r
The reason for choosing ratios is to cancel out unknown parameters such as field strength.
field inhomogeneities, etc.
92bThisis an arbitrary assumption. We also assume that the applied field does not change
the selection rules in question. For calculating selection rules see for instance F a l i c o ~ . ~
92cL. M. Falicov, Group Theory and Its Physical Applications. Univ. of Chicago Press,
Chicago, Illinois, 1966.
92
6.
539
TABLE I V "
THEPRINCIPAL DIRECTIONS
OF A
Transition
X
6 equivalent
WITH ASSOCIATED
Direction
A
8 equivalent
direction
AND
EULERIAN
ANGLES
314n
ni4
54" 44
54" 44
I
2
3
[1111
[ITI]
514n
54" 44
[Ti11
714n
54" 44
1
2
3
[@311
[0 101
[ 1001
0
n
ni2
0
n2
n2
[ T i 11
"Because of fourfold and threefold rotational symmetry about the principal axes, 6 = 0.
where @' = T& and where 0;is the angle between the jth component of the
star k and i and the polarization vector i? in the local frame of reference.
In polar coordinates (in the crystal frame), Z has components
ex = sin 4 cos $,
(274a)
e,, = sin 4 sin II/,
(274b)
e,
(274c)
COS~,
<
and ifwe substitute the angles 4 and $ in Eqs. (272)for and y the polarization
factor is justf;. = p
r. In addition, due to the symmetry of A and A we can
define in Eq. (267) a longitudinal and transverse effective mass with respect
to the principal axes, thus
Table IV lists the principal directions of A and A with the associated subscripts and Eulerian angles necessary to align the z axis of the crystal with
them. Since most electroreflectance experiments are done at normal incidence
to the plane of reflection, it is convenient to define two classes of geometrics:
one where the Poynting vector of the polarized light is perpendicular and
the other where it is parallei to the electric field vector. These are designated
by experimentalists as transverse and longitudinal.
Table V shows the results for A R / R for A and A in a transverse geometry
where the plane of symmetry and electric field orientation are along principal
directions. Both the electric field and polarization vector have a degree of
freedom in the plane of reflection (see Fig. 3). For high symmetry directions
the equivalent Di are listed and it is indicated whether or not there is a
6 . ELECTRIC-FIELDEFFECTS
541
542
polarization dependence. Discrimination of polarization between the two

transitions is evident from this table.92dThere is still an indeterminacy as
far as the type of critical point (M,, M , , M , , or M,) and the effective mass
ratio. In principle, this indeterminacy can be narrowed by fitting the five
experimental configurations in Table V to the five unknowns. This could
done by doing field shift measurements on the structures. If in all five configurations the satellite peaks shift in one direction, the assignment would be
an M , or M , ( M o , if the shift is to higher frequencies and M , , if to lower);
if the shift is in both directions, it will necessarily be a saddle point of type
M , or M,. The final selection should be based on the effective mass ratio
which satisfies the five experimental configurations.
Table VI shows the results for A R / R for A and A in a longitudinal geometry
where the electric field vector is perpendicular to and the polarization vector
is in the plane of reflection.
With the aid of such tables and the corresponding experiments, a much
broader base of analysis would be established. Recently, a series of experiments on Ge demonstrated the presence of such signatures. Work is under
way to study them systematically and arrive at a unique identification of
structure.93
VI. Conclusion
We have discussed the effect of the uniform electric field on the dielectric
properties of solids as calculated by several different methods. These include
the one-electron effective mass approximation, where the formalism developed
by Elliott is used to evaluate electric field effects. The equivalent one-electron
methods of the crystal momentum representation and the Houston function
approach have been treated in detail, and have been used to obtain the
strong-field convolution form of the electric field effect, and the Airy convolution weak-field limit. After treating various special topics, many-body effects
are approximately considered with the generalized convolution formalism,
and the equivalent problem is formulated in the vector potential or time
gage. Finally, a discussion of symmetry information and the interpretation
of experimental results are given.
92dForthe (100) plane of symmetry, if we define the signature to be S = AR ( 5 = 0, 4 = n/?)
AR(5 = 0, I p = 0), then S = 1 and S # 1 for A and A transitions, respectively, while for
S = AR (5 = n/4, 4 = - n/4)/AR (5 = n/4, 4 = ~ 1 4 )S. = 1 and S # 1 for A and A. respectively. Thus for the two field orientations we obtain a clear-cut discrimination between the
two transitions. Also note, that (due to symmetry) this particular choice of signature gives
the same diagnostic results even when we make no specific assumptions about the form of
fJli.For further information about signatures see Seraphin.""
9 3 ' N . Bottka and J . E . Fischer, Phys. Rcz'. B3, 2514 (1971).
6.
543
There are numerous problems still to be solved concerning the effect of an

electric field on the dielectric function. Foremost among these are manybody effects, for with the exception of numerical computation at isotropic
M , and M , critical points, nothing is quantitatively known about the effect
of the electric field upon excitonic or Coulomb-affected band structure at
other critical points. Equally important from the point of interpreting
experimental symmetry information is the calculation of Coulomb and
electric field effects on matrix elements, which have generally been assumed
to be slowly varying. Also, there is no formalism which quantitatively describes the effects of degeneracy at a critical point. Although experimental
results appear to be described by ignoring degeneracy effects, a quantitative
theoretical treatment which indicates the validity of this procedure would
be welcome. Likewise, no computations of the electric field effect at general,
more complex regions of the Brillouin zone, such as the 2-symmetry regions
of group IV and 111-V compounds, have yet been done. Such calculations
would necessarily have to be performed numerically, and in order to make
computation feasible, broadening would have to be included initially in the
strong-field convolution integral in order to obtain reasonable convergence
of the kernel function. I t is also important to choose a system where the
Coulomb interaction is relatively less important, i.e., materials with large
static dielectric constant. One might expect reasonable results from calculation near the A structure in G e ; Saravia and B r ~ s have
t ~ ~calculated the
piezoreflectance spectrum in this region in the one-electron approximation
and have obtained reasonably good agreement with experiment.
We hope that this review of the theoretical literature of the electrooptic
effect may serve as a stimulus for further work on these problems.
ACKNOWLEDGMENTS
The authors wish to acknowledge numerous useful conversations with J. H. Aspnes. D. F.
Blossey, J . D . Dow. E. 0. Kane, J . C. Phillips, and B. 0.Seraphin.
94
L. R. Saravia and D. Brust, Solid Stare Commun. 7,669 (1969).
Author Index
Numbers in parentheses are footnote numbers and are inserted to enable the reader to locate
those cross references where the authors name does not appear at the point of reference in the
text.
A
Abagyan, S. A,, 73
Abowib, G., 48
Abraham, A., 56
Abrikosov, A. A., 466,530
Adachi, E., 227
Adams, E. N., 235, 284,463, 492(18), 497(18,
18a, 18b, 18c)
Adler, E., 414
Afromowitz, M. A., 520
Agekyan, V. T.,421,425(33), 426
Aggarwal, R. L., 22, 153, 154, 170, 174,
183(47), 185(47), 198, 202, 203, 211, 212,
213, 214, 215, 216, 217, 218. 219, 220(34),
221, 222, 223, 224, 225(47), 226(47), 227
(47), 228, 229(27, 47), 230(47), 231(27).
232, 233(27, 47), 234(27), 235(47), 236(28,
47), 237(28), 238(28), 239(28,47), 24 I , 242,
243, 247, 248, 249, 251, 252, 253, 254, 443,
452,453
427,433(56)
Akimoto, 0..
Albers, W. A., Jr., 42, 87, 91(55), 148, 149,
152, 187(21), 206(21), 247(21)
Alferieff, M. E., 32, 263
Allen, P. B., 97
Anastassakis, E., 310,447
398
Anderegg, M _,
Anderson, R. L., 260(22), 313
Andrew, A. A,, 97
Antoci, S., 398
Antosiewicz, H. A., 483,488(54), 510(54)
Arai, T., 451
Argyres, P. N., 284, 463, 492, 497(18b, 56).
499(56), 502(56), 504(56)
Arnold, E., 48
Aronov, A. G., 153, 164, 516
Ascarelli, G., 152, 199, 246, 247, 248,422
Ashar, K. G., 260(22), 313

Ashley, E. J., 67
Aspnes, D. E., 16, 17, 19, 23, 24, 26, 29(17),
30, 38(23), 53, 64, 65(15a), 95, 104(16),
126, 127, 128, 129, 130(199), 131, 132,
133, 134, 135, 136(199), 139(199), 140(199),
142, 145, 146, 147, 257, 260(38, 72). 283,
284,287,290(126), 296(125, 126), 299(126),
305(38), 306(38), 307(38), 310, 312, 313,
320, 322, 464, 465, 471, 472(30), 476(29,
30), 482(29, 30), 483, 484(29), 486. 487,
488(29), 492(31), 500(31), 505, 509(31),
511(31), 513(29), 514, 515, 517(66), 525(29)
Assenov, I., 398
Aubrey, J. E., 435,439(77), 442
Avdeeva, L. A,, 288(140), 289, 301(140),
302(140), 303(140), 304(140), 308(140),
309(140), 310(140)
Axe, J. D., 260(23), 313
Aymerich, F., 28, 45(22), 78, 399, 518, 535
Bagaev, V. S., 535

Bagguley, D. M. S., 152, 153, 203, 246, 247,
248
Bailey, P. T., 234
Balashov, A. A., 397, 398(86)
Baldini, G., 399
Ballaro, S., 260(24), 313
Balslev, I., 47, 152, 198119). 240, 260(77, 78),
314, 317, 322, 326, 374, 375, 376, 377,
401,419,420,421(28,30), 423,424,427(43),
428(28), 429(39), 433(57a), 437, 438, 440,
441,442,452,453(28,29.30), 455,456
Balzarotti, A,, 206, 260(24, 85), 313, 314,
321, 324(24), 329, 333, 380, 384, 385. 392,
393, 398,459
545
546
AUTHOR INDEX
Bansigir, K . G., 433

Bardeen. J., 217, 356
Bashara, N. M., 100
Bassani, F., 28,45(22), 53,55,78,281,518,535
Batz, B., 15, 152, 187(18), 206(18), 207(18),
260(86, 92), 314, 317,320, 321, 324, 325(19,
39), 326(19), 332, 347(19), 349, 374, 376.
380, 381, 382, 383(19), 384, 386, 397(39),
400(39), 452
Baumgardner, C. A,, 147
Beaglehole, D., 430,432(66), 456(66)
Becker. W. M., 79. 227
Bell, E. E.. 326
Bell, R . L , 246
Belousora. T. Ya.. 535
Bendorius. R., 139
Bennett. H . E., 10, 67
Benoit a la Guillaurne, C., 424, 440
Berglund. C. N.. 206. 260(87), 314. 317.
319(12), 324(12), 325, 357, 374, 377, 378.
379. 452. 459
Bergstresser, T. K . , 27, 53(20), 55(20), 69,
78(20), 79
Berozashuili, Yu. N.. 535
Bethe, H. A,, 269, 532
Bhargava, R. N., 424,440
Biellman, J., 266, 293( 1 18). 308
Bienenstock. A,, 400
Bir. G. L., 184,405, 416,417,419,438.439
Blaser, R . , 39
Blatt, F. J., 217, 221, 356
Bleil, C. E., 42, 87(55), 91(55), 148(55, 272).
149(55. 272), 152, 187(21), 206(21), 247(21)
Blinowski, J., 186
Bloch, F., 457, 462
Bloom, A . I., 439
Bloom. D . S.. 69
Blossey, D. F., 24, 29(17), 64(17), 260, 264.
268(95), 272(95), 275, 276, 277, 278, 279.
281, 282, 284, 288, 289, 296(95), 299,
302(152). 309, 312, 465, 482, 486(3l),
492(31), 500(31), 505(31), 509(31), 511(31),
521, 532
Blount, E . I., 460,498( 16)
Boddy, P. J . , 39, 101, 102, 121,260(39,40,41),
307(41), 308(41), 313, 322
Boer, K. W.. 290,458
Bonfiglioli, G., 198, 323,459
Bordure, G., 227,229
Borysheva, A. I., 426
Bottka. N., 8, 9. 15, 18(3. 4). 19, 20, 22(3), 23,

27. 28,29(4, 17). 3 3 , 37(3, 34). 45, 51(3). 53.
57. 60(19), 62(1 lo), 63, 64(11, 15d), 65(3).
66(19), 68(3), 75(4), 78(19), 95(4), 103(4,
15d), 104(16), 105(4), 110. 117, 119(187),
121. 122(19,63), 123, 124(187. 188). 130(11).
131(16), 136, 139, 146(211, 212), 147(211),
257. 260(25, 55, 56, 57, 58), 313, 314, 329.
382(45), 464, 470, 514(43), 515(27. 43).
535(43), 542
Brahms, S., 294, 295
Brattain, W. H.. 20.39. I21
Braunstein, R.. 199. 239, 323. 374. 377. 378.
396,400.432,436,452
Brecher. A,, 247. 248( 122)
Brews, J. R.. 100,475
Briggs. M . . 75
Britsyn. K . T., 290, 458
Brooks. H.. 405.417
Broser. 1.. 147, 397
Brout, R., 359
Brovetto, P., 198. 323. 459
Brown. R . N., 170, 21 1, 242. 247, 248, 249,
250( 123). 252( 123)
Brust, D., 15, 53, 55, 56, 28 I 543
Buckman, A . B., 100. 129. 146
Buehler, E., 140
Bultius, K., 439
Bulyanitsa. D. S.. 426
Burckel, J. (see Schmitt-Burckel, J.)
Burger, R . M., 439
Burke, W . J., 446
Burstein, E., 97, 221, 310,441. 447
Busca, G., 198, 323
Butler, J . F., 254, 255
Button, K. J., 219,223,227,247,248
~
Calawa, A. R., 254. 255

Callaway, J., 284, 3021127, 1281, 458, 464,
466, 476(22, 22a). 492(22, 22a). 499(40),
507, 509, 512(22a)
Cardona, M., 8, 16, 21(15c). 30, 32, 38, 42.
45. 46, 47(70, 71). 48. 49. 54. 55(93).
56, 57, 58, 60, 61(113), 62, 63(54), 65(54j,
66, 67(43, 74). 68, 69. 72, 73, 74, 76(74),
78, 79, 80, 81, 82, 86, 87(64), 88, 89, 90, 91,
92(15c), 93, 94(15c), 95, 98, 100, 103(15c),
105(64), 129, 130(199), 136(199), 139(199).
547
AUTHOR INDEX
Cardona--continued
140(199), 142, 146, 147, 152, 153, 154(15),
187(15), 198, 205(15), 225, 227(89), 229,
231, 233, 239, 240(105), 243(89), 247(89),
248(89), 251(89), 252(89), 257, 260(2&30,
50,6244,69, 72, 84, 89,90), 294,295, 313,
314,317,320,322(22), 323,324(15), 325(15).
329(15, 22), 331(15), 332(15), 333(15, 36),
35 I( 19, 352(36), 364( 15, 46), 369( 15, 36),
374(15), 380(15, 22), 381(15, 36), 383(15,
22), 384(15), 386(15), 387(15), 388(15),
389(15), 390(15), 391(15), 395, 397(15),
398(15), 399, 400(15, 89), 401, 402, 419,
421, 423(30a), 424, 426, 427, 432, 433(44a,
59, 70a), 440(30a), 442(30a), 447, 451,
452(70, 70a), 459, 500, 501(62), 506(62),
515, 517(66)
Casselman, T. N., LOO, 475
Cerdeird. F., 49, 147
Chadderton, L. D., 426
Chamberlain, J. M., 238
Chen, J. H., 70,260(31), 313
Chen, Y. S., 102, 260(41), 307(41), 308(41),
313
Cherepanov, V. I., 426
Chester, M., 56, 260(32, 73), 286, 313, 314,
464,492(23), 5 12
Chiarotti, G., 260, 309, 31 1
Church, A. B., 317, 322(14a), 323
Clark, C. D., 446
Cohen, M. L., 27, 53(20), 55, 78(20), 79, 96,
97, 360, 400. 401
Collins. T. C., 86, 426
Cronburg, T., 227
Crowther, P. A., 421, 444,445, 446, 454
Cuevas, M., 454,455
Cuff, K. F., 254, 255
Dakhovskii, I. V., 441, 442

Damaskova, S., 290
Dash, W. C., 45, 53(66), 56(66), 408,430(14),
454( 14)
Daunois, A., 137, 142
Davisson, J. W., 441
Dean, P. J.. 419,421.444.445.446.454
de Groot, S. R., 409
Deiss, J. L., 137, 142
Del Signore, G., 260

Del Sole, A., 128
Dexter, R. N., 153, 203, 221
Dickey, D. H., 454
Dimmock, J . O., 238, 261,263,365,454
Dohler, G., 508, 520(64)
Doering, G., 440
Dolisi, Y., 142
Donovan, T. M., 66
Dow, J. D., 132, 134,264,274( 116), 29611 16),
526, 530, 531(84b)
Dresselhaus, G. F., 152, 153. 212(23), 221,
241(23), 247,248,261, 266, 284,453,474
Dresselhaus, M. S., 152, 153,212(23), 241(23),
453
Drews, R. E., 260(33), 313, 323, 381(35)
Drude, P., 433
Duke, C. B., 31, 32,263, 369
Duncan, W., 237
Dzhioeva, S. G., 140, 142, 397
Dzyaloshinskii, 1. E., 466, 530(39)
E
Ehrenreich, H., 14, 15,45, 53(14,66), 56(66),
75, 173,239,240,408,430(14),439,454(14)
Elinson, M. I., 288(140), 289, 301(140),
302(140), 303(140), 304(140), 308(140),
309( 140), 3 1O( 140)
Ellett, M . R.,254,255(127)
Elliott, R. J.. 31, 235. 262, 267(104), 276,
284,293,319,365,367(17,66),368,375(66),
421,448,464,477,480,521
Emtage, P. R., 440
Enderlein, R., 264, 289, 290, 459, 460, 465,
466,482.483,514,515(33,34), 518,519(33),
520(33), 521,526,527(14), 528(14), 530, 532
Engeler, W. E., 152, 187(16), 198, 199, 200,
202, 260(79-82), 314, 322, 422, 423, 430,
432(65), 452,453,456,459
Eppley, R. W., 317, 322(14a)
Erlbach, E., 414,421
Esaki, L., 97
Euwema, R. N., 427,433(57)
Evangelisti, F., 21, 65, 128, 208
Everett, C. R., 436
Evtuhov, V., 179
Eyglunent, B., 141
548
AUTHOR INDEX
F
Falicov, L. M., 538
Fan, H. Y., 79, 223, 227, 356, 359(58), 360,
362(61), 363,365(58), 434
Faraday, M., 152
Feher, G., 397,418,440
Feinleib, J., 36, 38, 50, 53(40), 82(39, 40).
83(40), 99, 145(44), 153, 154(24,26), 205(24.
26), 206(26), 207, 209(24), 210(24). 21 l(24).
212(24), 221(24), 223(24), 243(24, 26),
244(26), 247(26), 248(26), 249(26), 250(26),
251(26), 252(26), 260(34,88), 313,314,326,
380, 394(84). 395,452
Feldman, A., 49, 260(93), 314, 432,435, 442,
452
Feotilov, P.P., 446
Feuerbacher, B., 398
Filinski, I., 227, 260(94), 314
Fischer, J. E., 11, 13, 33, 37(34), 53(34), 117,
119, 121, 124(187, 188), 136, 137, 138(217),
139, 140(217), 142(217), 143(217), 144,
146(211-213), 147, 260(35), 313, 321, 329,
520, 542
Fischler, S., 441,442(107), 443(107)
Fisher, P., 443, 444(110)
Fitton, B., 398
Flinn, I., 75
Fong, C. Y., 79,401
Foord, R., 196
Forman, R. A,, 45, 87(64), 89, 90, 91, 98,
105(64), 129, 130, 136, 139, 140, 146,
260(72), 314, 515, 517
Fowler, A., 199
Franz, W., 167, 259, 284, 458, 463, 464. 476,
492(6), 509, 516(6)
French, B. T., 260(36), 313
French, C. S., 317, 322(14a), 323
Frenkel, J., 261
Fridrikh, Kh., 397
Fritsche, L., 286,464,492(23), 494,496, 502,
512
Fritzsche, H., 152, 187(16), 198(16), 199(16),
200(16), 260(79), 314, 322, 422, 423(38).
430(38), 441,442,452(38),454,455,456(38),
459
Frohlich, H., 333, 353
Frova, A., 16, 17, 19,21,53,56,65,95, 101, 102,
126, 127, 128, 132(15a), 133(190), 134, 135,
142(15a), 146, 152, 187(14), 204, 208, 259.

260(12, 13, 37-41), 290, 305, 306, 307, 308,
3 13, 320,322,464,47 1
Fujiwara, S.. 142
Fukai, M., 142
G
Gabriel, C. J., 152
Gahwiller, Ch., 32, 45, 70(60. 61), 98, 101,
138(60, 61). 142. 309
Garfinkel, M., 152, 187(16), 198(16), 199(16),
200(16), 202, 260(79-82). 314, 322, 422,
423(38), 430(38), 432(65), 452(38), 453.
456(38, 65), 459
Garrett, C. G. B., 20
Gavini, A., 225. 427. 433(59)
Gay, J. G., 42,43(56), 149(56),247
Geballe, T. H., 441,442(103)
Gebaver, R., 262,278(107)
Georgobiani, A. N., 397
Gerhardt, U., 45, 56, 60(68), 427. 430, 431,
432,433, 454(64), 456
Germano, F. A., 9, 22(5), 27(5), 38, 63(5, 36.
46), 64(5,47), 65(5,46,47), 66(5,47), 105(5,
45, 46), 260(21, 28), 285(21). 296(18, 20).
297(20), 298(20), 299(20), 300(20), 301(20),
305(38), 306(38), 307(38), 313, 320,322121).
489
Gerischer. H., 39
Ghosh, A. K., 57, 61, 65, 66, 67, 68, 141,
2 6 0 ( 4 2 4 ) , 3 I3
Gilgore, A., 199
Gilleo, M. A., 234
Glass, A. M.,422, 440,454(36)
Glosser, R., 82, 84, 137, 138, 140, 142, 143,
145(214)
Gobeli, G. W., 152, 187(17), 199, 410,
430(17). 452, 455, 459
Gobrecht, H., 39, 40, 41, 43, 62, 66, 106(48),
128
Goldstein, H., 536
GorKov, L. P., 466, 530(39)
Goroff, I., 439, 440,442
Goryunova, N . A,, 140
Gradshteyn, I. S., 272
Grandolfo, M., 206, 260(85), 314, 321,
324(24), 329, 333, 380, 384, 385, 392, 393,
398, 459
549
AUTHOR INDEX
Grant, P., 145

Grassano, V. M., 309, 31 l(163)
Grasso, V., 260(24), 313
Greenaway, D. L., 56,68(120), 77
Gross, E. F., 293, 405, 417(4), 421, 424,
425(33), 426(4)
Grossman, M.,293
Groves, S.H., 36, 37, 50, 53(40), 82(39, 40).
83(40), 92, 94, 153, 154, 205, 206(26), 207,
209, 210, 211, 212, 221, 223, 243, 241, 245,
246, 247, 248, 249(26), 250(26), 251(26),
252(26), 326, 380(43), 452
Groves, W. 0..4 4 W 4 2
Grynberg, M., 186, 426
Guastavino. F.. 227
Gubler, W., 435, 439(77), 442(77)
Gutsche, E.,88,90(158), 260(45,46), 302,313,
3 14
H
Hacker, K.,508, 520(64)
Hansche, H. J., 458
Hall, J. J., 440, 441
Hall, L. H.. 217, 356
Halpern, J., 219, 221, 223
Hamakawa, Y.,9, 22, 27, 38, 63(5, 46), 64,
65(5, 46, 47). 66, 105(5, 45, 46). 132, 135,
139, 141(229), 142, 146, 239, 260(21), 285,
296, 297, 298, 299, 300, 301(20), 313, 489
Hammer, R., 260(23), 313
Hanamura, E., 31, 319, 369, 373( 18), 374(79,
81), 521
Handler, P., 9, 22(5), 24, 27(5), 29(17), 38, 56.
63(5, 46), 64(5, 17, 47). 65, 66(5, 47). 85,
105(5, 45, 46), 129, 132, 134(197, 198), 139,
152, 187(14), 204, 259, 260(12, 13, 21, 38,
47, 75). 284,285(21), 290,291,292, 296(18,
20), 297(20), 298(20), 299(20), 300(20), 301,
302(75), 305(38), 306(38), 307(38), 3 10, 3 12,
313, 314, 320, 322(21), 464, 465, 486(31),
489, 492(31), 500(31), 505(31), 509(31),
511(31)
Hanscho, H. J., 290
Hansen, J. R., 439
Hansen, W. N., 100, 260(51), 314
Hanus, J., 394, 395
Harbeke, G., 32,82,98, 142. 309
Haraldson. S.,237
Harrick, N . J., 259
Harris. F. C., 404, 409(2), 449(2), 450

Hasegawa, H., 184, 413, 415, 418, 427,
433(56)
Hattori, K., 142
Hayes, T. M., 400
Hayes, W., 448
Hein, F., 39, 40(48), 41(48). 43(48). 62(48),
66(48), 106(48), 128(48)
Heitler, W., 359
Henningsen, T., 435,439(77), 442(77)
Henrion, W., 70, 324, 325(40). 380. 392
Hensel, J. C., 213, 221,418,440, 441
Henvis, B. W., 152, 441
Herman, F.. 53, 55, 69(88). 79. 98, 316, 534
Hermanson, J., 131, 369, 521
Herring, C., 405,439,441, 442(103)
Hess, R. B., 8, 18(3), 22(3), 35, 37(3), 51(3),
63(3, 36), 64, 65(3), 67(36), 68(3, 36),
260(57), 314, 317
Higginbotham, C. W., 69, 227, 229, 231. 243,
248, 251, 252, 424, 433
Hill, D. E., 234
Hilsum, C., 263
Hobden, M.V., 235
Hobson, G. S.,436,438,447
Hodge, C. V., 147
Hoffmann, B., 85, 86, 138
Hoffmann, R.-A., 147, 397
Hoffmann-Perez, M., 39
Hopfield, J. J., 87, 302, 426, 429
Houston, W. V., 284,458,463, 492,493
Howard, W. E., 97
Hurych, Z., 399
I
Ikeda, K., 142
Iliev, M., 398
Ilisavsky, U. V., 439
lmatake, A.. 400
Inoue, M., 31, 319, 369, 373(18), 374(79, 81),
52 1
Inui,T.. 31. 319, 369, 373(18). 374(79,81), 521
Irzhikyavichyus, A. E., 141, 146(241)
Isaacson, R . A,. 397
Ishibashi, Y., 145
lto, Y., 260(71), 314
Ivanov, V. S.,397, 398(85, 86)
lwasa, S . , 203, 310, 452
Iyengar, K.S.,433
550
AUTHOR INDEX
J
Jackson, J. D., 466, 526
Jasperson, S., 129, 132(198), 134(198), 139
(198). 260(75), 301(75). 302(75), 314
Javan, A., 203,452
Jessop, H. T., 404,409(2), 449(2), 450(2)
Johnson, E. J., 221, 223, 227, 316, 339(2),
360(2)
Jones, G. D., 448
Jones, H., 457,462, 476(2), 499
Jones, R.,196
Jones, R.L., 443
Jones, V. 0..
139
Jsrgensen, M.H., 439,442
Kahn, A. H., 436,437

Kahn, S. A., 137
Kane, E. O., 53, 54, 55, 62(87), 66, 79, 152,
173, 178, 181, 187(17), 199, 246, 284, 410,
430, 432, 452, 455, 456(67), 459, 463, 474,
497(19), 499(19), 521
Kaplyanskii, A. A., 405, 411, 413, 414,
417(4), 421,424(33), 425,426,443,446
Kastalskii, A. A,, 440
Kavaliauskas, J., 140, 141, 146(241, 242)
Kavalyauskas, Yu.F.(see Kavaliauskas, J.)
Keffer, C., 400
Keiper, R., 289, 290, 465, 514(33), 515(33),
518, 519(33), 520(33)
Keldysh, L. V., 167, 259, 284, 458, 463, 476,
492(5), 509, 535
Keyes, R. J., 254
Keyes, R. W., 235,405,434( 1 I). 439( 11)
Khan, S. A.. 137
Kingston, R. H., 20
Kip, A. F., 221,247,248(120), 474
Kittel, C., 221, 247, 248(120), 352(54), 353,
406, 407(13), 417, 419(22), 460, 461(17),
474,498( 17)
Klauder, L.T., 42,43(56), 149(56), 247
Kleiner, W. H., 184, 201, 247, 248(119), 405,
418,422,441,442(107), 443(107)
Kleinman, L., 55,96, 97(163), 439, 440, 442
Kline, J. S.,57, 61, 62, 98(113)
Knox, R. S . , 261, 365
Kobayashi, M., 235, 239(1 lo), 240
Koda, T., 427, 428,433(55, 57)

Koenig, S. H., 434,435,439(75, 77). 440,441.
442(77)
Koeppen,S., 129,132(197,198), 134(197,198).
139(198), 260(75), 301(75), 302(75), 314
Kohn, W., 154,155,170,428,441,521
Koike, N., 235,239(1 lo), 240
Kopylovskii, B. D., 397, 398(85, 86)
Kortum, R.L., 53, 55, 69(88), 79(89), 98, 316,
534
Kosicki, B. B., 231
Koster, G . F., 41 I , 413
Krag, W. E., 441, 442, 443(107)
Kruse, P. W., 190, 194(54), 195
Kubo, R.,466
Kuglin, C. D., 53, 55, 69(88), 79(89), 254,
255(127), 316, 534
Kummel, U., 290,458
Kurskii, Yu.A,, 516, 517
Kwan, C. C. Y., 399
Kyser, D.. 45. 77(62). 78, 92(62). 136. 137.
138(62), 139, 146(211), 147(211), 260(52),
314
Lambert, L. M., 260(48), 314

Lanczos, C., 262
Landau, L. D., 155,532
Lange, H., 70, 88, 90(158), 260(45, 46). 302.
313, 314, 324, 325(40), 380, 392
Langer, D. W., 427,428,433(55,57)
Langreth, D. C., 363
Lao, B. Y ., 132, 134(206,207)
Laude, L. D., 198,402
Lavallard, P., 424, 440
Lawaetz, P., 439, 440,441
Lax, B., 22, 50, 51, 152-154, 158, 167, 170,
174, 178(37), 183(37, 47), 184(37), 185(47),
187(12), 202(34), 203, 207, 210(75), 212,
217(34, 37)- 218(34), 219, 220(34), 221,
222(34), 223,224(47), 225(47), 226(47), 227,
228(47), 229(27, 47), 230(47), 231(47), 232
(47). 233(27, 47), 234(47), 235(47), 236(28,
47), 237(28), 238(28), 239(28, 47), 247,
248(122), 251,252(125), 253(125), 254,429,
439
Ledell, J., 48
Leheny, R. F., 140
551
AUTHOR INDEX
Lenz, J., 56
Leonov. E. I . . 140
Lettenberger, R., 49
Levialdi, S., 198, 323
Lifshitz, E. M., 155, 532
Lin, P.J., 96, 97(163, 165)
Litton, C. W., 86,426
Lowdin, P., 415,438(21)
Loudon, R.,235,428
Lucien, L. D., 421,423(30a), 440,442
Ludeke, R., 36, 53(38), 91(38), 92, 260(83),
314
Luth, H., 141,447
Lukes, F., 13, 14, 42, 56, 62(105), 63(53),
79, 260(49), 314
Luttinger, J . M., 154, 155, 170, 173, 179,428,
441, 521
M
McCoy, J . H., 147, 397
Macdonald, H. F., 448
McElroy, J. D., 397
McElroy, P.,21,65, 68,69(126), 260(28), 313,
535
Macfarlane, G. G . , 217, 298
McGlauchlin. L. D., 190, 194(54). 195(54)
McIntyre, J . D., 145
McLean, T. P., 298, 316, 363, 367(1), 375(1),
376, 377,419,421(26), 422, 428
McNatt, J . L., 141,260
McQuistan, R. B., 190, 194(54), 195(54)
McWilliam, I. G., 323
Madelung, O., 263
Maradudin, A. A,, 343
Markel, K., 144
Marple, D. T. F., 75, 263
Martynenko, G . P., 424
Matatagui, E., 260(89, 90), 314, 317, 324,
325, 329(15), 331(15), 332(15), 333, 351,
364(15), 369(15), 374, 380, 381(15), 383,
384, 386(15), 387, 388, 389, 390, 391, 395,
397, 398, 399, 400(15), 459
Matukura, Y., 439
Mavroides, J. G., 152, 153, 212, 227, 238,
240, 254,439,453
Maycraft, G. W., 446
Medveder, V. N., 446
Mell, H., 71
Mindt. W.. 39
Mishra, V. K., 227,239, 240
Mitchell, D. L., 96, 97(164), 249, 250( 123),
2521123). 254. 255
Mitchell, E. W. J., 446
Mohler, E., 137,427.456(58)
Mollwo, E., 56, 85, 86
Montroll, E. W., 343
441,
, 442
Morin, F. .I.
Moskalenko, S. A., 426
Moss, T. S., 152, 187(11), 204, 259, 290(9),
409, 450( 16), 458
Mourzine, V., 443
Mula, G., 399
Muto, T., 360
Nahory, R. E., 42, 44(58), 130, 147, 148,206,

246(69), 247(69), 402
Nanns, J., 260(88), 314
Narita, S., 235, 239, 240
Nathan, M . I., 424,440
Neustadter, S. F., 20
Newrnan, R.. 436
Nii, R., 254, 255
Nikitenko, V. I., 424
Nikitine, S., 137, 142, 266, 293. 308, 365
Nilsson, N. G . , 147
Nilsson, P.O., 432
Nishino, T., 132, 135, 139, 141, 142, 146, 239
Nobile, M., 399
Nordheim, L., 98
Nye. J. F., 406, 409(12)
0
Oherly, J . J., 441
Okazaki, M., 31. 319, 369, 373(18), 37479, 71),
521
Okuyama, M., 139, 141, 142(229), 146(229),
239
Oliver, C. J., 196
Onton, A., 443,444
Oppenheimer, J. R., 262(108), 263
Orlov, V. M., 140
Ortenberger, I . B., 98
Osipov, Yu.V., 422, 429, 454(37)
Otmezguine, S., 399
552
AUTHOR INDEX
Overhauser, A. W., 261,439

Owen, J., 152
Oyama, S., 360
P
Paige, E. G. S., 300, 302, 363,436, 438,447
Palik, E. D., 152, 247, 248, 251, 252, 254,
2 5 3 130)
Palrnieri, G., 198, 323
Parke. Y.S., 86,426
Parmenter, R. H., 98
Parsons, B. J., 100, 137. 140, 145
Parsons. R . B.. 426
Patek, K., 290
Patel, C. K. N., 147, 148.206,246(69), 247(69)
Paul, W., 36,45,47,48(69), 53(38),91(38),92,
231,260(83), 314,404,441(1)
Payne, R. T., 301,441
Peierls, R. E., 261
Penchina, C. M., 260(37), 286, 306, 313, 464.
513
Perov, P. I., 288, 289, 301, 302(140), 303,
304, 308, 309, 310
Perregaux, A.. 152, I99
Pettit, G. D., 80
Philipp, H. R., 10, 14, 15, 45, 53(6, 14, 66),
56(6, 66), 316,408, 430(14), 454(14)
Phillips, J. C., 28, 31, 53, 5 5 , 62, 107(25),
280,281,282(122), 316,341(4), 343(7), 347,
369, 464. 535
Picus, G. S..221, 247, 248(121)
Pidgeon, C. R., 36, 37, 50, 53(40), 82, 83, 92,
94, 153, 154, 170, 205, 206, 207, 209(24),
210(24), 21 1(24), 212(24), 221(24), 223(24),
242, 243, 244, 245, 246, 247, 248, 249, 250,
251,252, 326,380(43), 451,452
Pike, E. R., 196
Piksis, A. H., 405,446(5), 4546)
Pikus, G. E., 184,405,416,417,419,438, 516
Pilkuhn, M . H., 75
Piller, H., 137, 140, 144, 152. 227
Pinczuk, A., 447
Pines, D., 466
Pollak, F. H., 8, 16, 21(15c), 38, 42, 46, 47,
48, 49, 54, 55(93), 57, 60, 61(113), 62(15c,
74, 113), 63(54), 65(54), 66, 67(43, 74),
68, 69, 72, 73(15c, 133). 74(15c), 76(74).
78, 79(15c), 80(1, 15c, 43). 81(15c), 82(1,

15c, 54), 86, 88(1Sc), 89(15c), 91(15c),
92( 15c). 93( 15c). 94f 15c), 98( 1131, 103fl5c),
152, 154(15), 187(15), 198,205(15),227(89).
229,231,233(90), 243(89), 247(89), 248(89),
251(89), 252(89), 260(26-30, 50, 62, 63, 84).
313, 314, 320, 322(22), 329(22), 380(22),
383(22), 401, 402, 404, 421, 423(30a), 424,
426,432,433(44a, 70a), 440(30a). 442(30a),
447,452.500.501(62), 506(62)
Porsch, M., 460,466, 516(15). 517,527(15)
Potter, R. F., 65
Powell, J. A., 153. 203(31)
Praddaude. H. C., 50
Pressley, R. J.. 446
Prostak, A., 100, 260(51), 314
Przhevuskii, A . K., 446
Q
Quarrington, T. E., 298
Radkowski, A., 360, 362(60)

Ralph, H. I., 32,264,274( 1 I>), 296(11 9 , 482,
521, 532
Ramdas, A. K.. 79,443,444(110)
Rausch von Traubenberg, H., 262,278(107)
Raymond, F., 399
Redfield, D., 264, 274(116), 296(116), 520
Rees, H. D., 289,300, 302,459,460,465,493,
502, 503, 506. 511(13), 521, 522, 523(13),
526
Reese, W. E., 80
Reguzzoni, E., 398
Rehn, V., 45, 76, 77(62, 140). 78, 81. 82(140),
92(62), 98(140), 137, 138(62). 139, 141,239,
240,260(52,74), 314,515
Reik, H. G., 439
Reine, M.. 50, 153, 167. 170, 174, 183. 185,
198, 223, 224, 225, 226, 227. 228. 229. 230.
231, 232(47), 233-239
Reiss, R., 266, 293( 118)
Reynolds, D. C., 86,426
Ribbing, C. G.. 237
Riccius, H. D., 260(53), 314
Rindner, W., 439,440
AUTHOR INDEX
Ringeissen, J.,' 308

Riskaer, S., 424,427(43), 435,436,442
Risken, H., 439
Roberts, V., 217, 298
Robinson, M. L. A,, 246, 247(114), 248(114,
117)
Rogachev, A. A,, 260(54), 314
Rogers, K. T., 246
Roessler, U., 27, 28, 45(19), 60(19), 66(19),
78(19), 110(19), 122(19),260(25), 313,535
Rosei. R., 309, 311(163)
Rose-Innes. A. C., 454
Roth, L. M., 158, 178, 183, 184, 201, 210(75),
212, 217, 219, 221, 223, 227(83e), 405. 418,
422
Rowe, G. A,, 32
Rowe, J. E., 131, 133, 134, 135, 138, 198,
260(64), 314,323,333(36), 352(36). 369(36),
381(36), 400, 401, 402, 426, 432, 433, 453,
459
Rubenstein, M., 138
Rubin, L., 22, 212
Runciman, W. A., 446
Ryvkin, S. M., 260(54), 314,440
Ryzhik, I. M., 272
S
Safarov, V. I., 402

Sak, J., 32, 131, 369, 374(82), 521
Salpeter, E. E., 269, 532
Samoggia, G., 260, 398
Sandell, B., 432
Sander, T. M.. 441,442(104)
Sandrock, R., 71,430,432(66), 456(66)
Saravia. L. R., 55( 103). 56, 543
Saslow, W., 79, 96, 97(165)
Schaldach, M., 39, 40(48), 41(48), 43(48),
62(48), 66(48), 106(48), 128(48)
Schawlow, A. L., 405,446,454
Schecter, D., 442
Schiff, L. I., 527
Schmidt, E., 42, 56, 61, 62(105), 63(53). 79,
128, 260(49), 314
Schmidt-Tiedemann, K. J., 433, 434, 435,
436, 442
Schmitt-Burckel, J., 266, 293(118). 308
Schneider, E. E., 237
Schreiber, P., 199, 323, 374(34), 377(34).
378(34), 396(34), 400(34). 452
553
Schrieffer, J. R..21
Schulz, H.-J., 147, 397
Scouler, W. J., 260(88, 91). 314, 325, 393,
394(84), 395
Segall, B., 31,263, 304,369
Seiler, D. G., 227
Seitz, F., 339, 466
Seliger, H., 146
Sell, D. D., 66,430, 432, 456(67)
8,9, 10, 11, 13, 14, 15, 18(3,4),
Seraphin, B. 0..
19, 20, 21(2), 22, 23(2), 29(4), 33, 35, 37(3.
34),45,51(3),53,57,58,59.60,62(110, 111).
63. 64, 633). 67(36), 68(3. 36). 75, 76, 77,
78(2, 15c, 136), 82, 84, 95, 103(4, 15d).
105(4), 106, 117, 119, 121(187), 122(63),
123, 124(187), 130(11). 137, 138(214-217).
l40(2 14-217). 142(214-217). 143(214-2 I7),
144, 146, 149, 152, 154, 187(13), 205, 239,
257,259,260(35, 55-61). 213. 314, 317,320,
321, 322(20), 329, 382(45), 384(20), 452,
458, 460. 464, 470, 514(43), 515(27, 43).
535(43), 542
Shaklee, K. L., 8, 16, 21(15c), 32, 38, 42, 46.
47(71), 49, 57(15c, 74), 62(15c, 74), 63(54),
65(54), 67(43, 74), 68, 69(126), 72, 73,
74(15c), 76(74), 78(15c, 74, 134), 79(15c).
80(1, 15c, 43), 81(15c), 82(1. 15c, 54), 86,
88(15c), 89(15c), 91(15c), 92(15c), 93(15c),
94(15c),98(134), 103(15c),152,154,187(15),
205,231,233(90), 239,240(105),260(2&30,
62, 63, 64,69, 84), 313, 314, 320, 322(22),
323,329(22), 333(36), 352,369(36), 380(22),
381(36), 383(22), 400, 401, 402, 424. 432,
452(70), 453, 459
Shaldin, Yu.. V., 140
Shatas, R . A., 454
Shay, J . L., 42, 44(58), 53, 55(88), 79(89),
130, 140, 147, 148,206, 246, 247. 316, 534
Shen, Y.R.,138,400,401,432,452(70b)
Shestatskii, S. N., 98, 142, 260(65), 314
Shiff, L. I . , 339
Shileika, A. Yu., 139. 140, 141, 146. 424
Shlimak, I. S., 402
Short, R. A., 53, 55, 69(88)
Sileika. A. (see Shileika. A. Yu.)
Skettrup, T., 427, 433(57a)
Slater, J . C., 478
Smith, A. P., 424
Smith, J. E., Jr., 440
Smith, R. A., 263, 341, 356(52), 369(52), 478
554
AUTHOR lNDEX
Smith, S. D., 451

Smith, U., 251,252(125), 253(125), 254(125)
Snavely, B. B., 260, 302(67)
Sobolev, V. V., 98, 142, 260(65), 308, 314
Somma, F., 398
Spicer, W. E.,79
Spitzer, W. G., 434, 438
Stadler, H. I., 145
Stager, C. V., 446
Stern, F., 14, 318, 326(16), 328(16), 335(16),
466,468(41), 470(41), 471(41)
Stevenson, J. R., 251, 252
Stiles, P. J., 97
Stillman, G. E., 238
Stokes, J., 401
Stokowski, S. E.. 432
Stoller, P. J ., 199
Stopachinskii, V. B., 140, 142, 397, 398(85,
86), 516, 517
Stoyanov, S., 398
Stradling, R. A,, 153, 203(31), 227, 238, 239.
240, 246, 247( 114). 248( 1 14)
Stuke, J., 45, 70,71,72, 145, 260(68), 302(68),
314
Sturge, M. D., 76,239, 302,446
Subashiev, V. K., 73, 139, 141
Sugano, S., 405,446(5), 454(5)
Summers, C. J., 451
Suzuki, K., 213,221
T
Taft, E. A., 10, 53(6), 56(6), 316
Tanton, G. A,, 454
Tauc, J., 56,316,334, 343(5), 358(5)
Taylor, D. J., 153,203(31)
Teitler, S., 247, 248(121)
Tharmalingam, K.,167, 284, 302(133), 464,
476(201
Theriault, J . P., 247, 248(119)
Thomas, D. G., 85,86,87, 302,404,419,424,
425,426,427.429.454
Thompson, A. G., 73,78,82,98(134,144,145),
138, 239, 240, 260(69, 70, 90), 314, 317,
324(15), 325(15), 329(15), 331(15), 332(15),
333(15), 351(15), 364(15), 369(15), 374(15),
380( 15). 38 1( 1 3 , 383(1 9 , 384( 1 9 , 386( 1 3 ,
387( 15). 388( 15), 389(1 9 , 390(15 ) , 391( 1 5 ) ,
397(15), 398(15),400(15),459
Thull, R.,39, 40(48), 41(48), 43(48), 62(48),

66(48), 106(48), 128(48), 146
Tiemann, J . J., 152, 187(16), 198(16), 199(16),
200(16), 202, 260(79, 80, 81, 82), 314, 322,
422, 423(38), 430, 432(65), 452(38), 453.
456(38,65).459
Titkov, A. N ., 402
Tohver, H. T., 246,247, 248
Toll, J. S., 471
Tomiyama, S . . 260(71), 314
Toyozawa, Y., 31, 288, 319, 368, 369, 372.
373, 374(79, 81). 521
Treusch, J., 71
Tsu, R., 97
Tung, Y., 97
Tuomi, T. O., 400,401
Turner, R., 260(53), 314
Turner, W. J., 80
Tyler, W. W., 436
U
Uemura, Y., 400
Usui, S., 91
Van Dyke, J. P., 98

Van Hove, L., 280, 316, 343(6), 347, 472.
475(45a)
van Vliet, K. M., 195
Vasquez, F., 98
Vavilov, V. S., 142,290,397,398(85),458
Vecchia, P., 398
Velicky, B., 32, 131, 369, 374(82), 521
Verie, C., 399
Vishnubhatla, S. S., 141
Vogt, E., 405,417,439
Volfson, A. A., 139, 141
Vorobev, Yu., V., 140
Vrehen, Q. H. F., 50, 152, 153, 165. 166.
167. 181, 187(12), 207, 208, 212, 221. 233,
235,238,239,240,526
W
Wagemann, H. G., 39
Wagoner, G., 247, 248( 120)
Wallis, R. F., 96, 97(164),221, 247. 248(121)
555
AUTHOR INDEX
Walter, J . P., 400

Walton, A . K., 227, 239, 240, 436
Wang, E. Y., 42, 87, 91(55), 148, 149. 152,
187(21), 206(21), 247
Wanke, E., 198, 323
Wannier. G. H., 261, 365, 369. 496. 508
Wardzynski, W., 426
Warschauer, D. M., 404. 441(1)
Watanabe, N., 91
Weil, R., 440,441. 442
Weiler, M. H.. 50
Weill, G . , 399
Weinreich, G . , 441, 442
Weinstein, F. C., 132, 134
Weiser, G., 45, 70, 71, 72, 145. 260(68),
302(68). 314
Weiss, G . H., 343
Welkowsky, M., 199, 323. 374(34), 377(34).
378(34), 396(34), 400(34), 432, 452(70c),
452
Wendland, P. H., 56, 260(32, 73), 313. 314
Wernick. J. H.. 140
Whelan, J. M.. 438
White, H . G., 441, 442(104)
Whiting, J. S . S., 153. 203(31)
Williams, E. W., 76, 77(140), 81, 82(140),
98(140), 141, 239,240, 260(74), 314, 515
Williams, J . E., 454
Williams, L. R., 254, 255(127)
Williams, R., 38, 259, 290(8), 302(8). 308(8),
458
Wittry, D. B., 147, 397
Wolfe, C. M., 153, 236(28), 237(28), 238
Wonson, R.,440
Wood, C., 399

Woolley. J. C., 78, 82. 98(144, 145). 141, 239,
240(105), 260(69, 70), 314, 399
Woodruff, T., 55
Wortman, J . J., 439
Y
Yacoby, Y., 260(76), 286, 314. 464, 492(24).
494,508,512,513, 514,520
Yafet, Y ., 235
Yoffe, A. D., 426
Z
Zak. J., 508
Zakhartshenya, B. P., 421,424(33)
Zawadski, W., 50
Zeeman. P., 151
Zeiger, H. J., 221,254,441,442(107),443(107)
Zemel, I. N., 254, 255(130)
Zener, C., 457,462,463,476(2), 499(3)
Zentrallab, P., 436
Zharkova, T. N., 140
Zook. J. D.. 16, 100, 101,475
Zucca. R. R. L., l38,400,401,432,452(70b)
Zuteck, M. D., 154, 202(34), 203(34),217(34),
218(34), 219(34), 220(34), 221(34), 222(34)
Zwerdling, S., 152, 158. 178(37). 183(37),
184(37), 210, 212, 217(37). 219, 221(37),
223, 227, 247,248, 429
Subject Index
AlSb (continued)
indirect gap, 263
ionization field, 263
piezoabsorption, 421
piezobirefringence, 424
reflectance, wavelength-modulated, 400.
423
Rydberg energy, effective, 263
Amorphous materials, electroreflectance
germanium films, 144
si!icon films, 145
Anisotropy
conductivity ( r m - I). 436
piezoabsorption ( 7 - l r n - l 436
Absorption 268, see also Electroabsorption.

Magnetoabsorption, Thermal modulation spectroscopy, Wavelength
modulation spectroscopy
coefficient, see Absorption coefficient
excitonic, 268-282.480
Hamiltonian in parabolic coordinates, 269.
270
interband momentum matrix element, 268
intervalence band transitions, 436--438
line broadening, 368
exciton effect, 368
stress modulation, 420
thermal modulation, 374380
wavelength modulation, 374-378, 420
Absorption coefficient, 167,268,316, 327,470
differential form, 470
electron-hole interactions, 366-368
elementary theory, 338-341
fundamental edge, near, 335,367
exciton effects, 367. 368
direct, 367
indirect, 367
indirect transitions, 357, 420
magnetic field effects, 167, 168
modulated transmission experiments. 357
stress modulation, 420
wavelength modulated, 420
AgBr, piezoabsorption. 422
Airy function, 24, 483, 484, 490, 510, 51 1
AlSb
absorption, wavelength-modulated, 401,
402
phonon identification, 402
stressed, 402
deformation potential constants, 4 4 0 4 4 2
electroreflectance spectra, 72, 73
direct gap, 72
indirect edge, 72
B
Band-filling effects, 95, 137, 42, 147, scualso
Population effects
InSb, 142, 143
Band gap, see Energy gap
Band parameters, see also specific materials
determination, magnetooptical effects, 152
GaAs, 237-240
GaSb, 227
germanium, 221
nonparabolicity, 220-222
InAs, 250-252
InSb, 243,247,248
Band shift, see also Energy levels, Energy gap
broadening parameter, 359-364
strain, 415419.422, 423,428,438
temperature, 358-365
self energy, 359, 360
thermal expansion, 359, 360
Bands in magnetic field, see also Energy
levels, Landau levels
degenerate, 170-178
nonparabolic, 178-182
simple, 1 5 6 156
split-off, 177-182
557
558
SUBJECT INDEX
BaTiO, , transverse electroreflectance, 45,

101
Birefringence, 404, 409
piezoeffects, 424,433
GaAs, 424,433
germanium, 424,433
Bloch functions, 470
Broadening effects, 514517, see also Line
shapes
C
(CdHg)Te alloys, thermoreflectance, 399
CdS
absorption, temperature-modulated, 374.
379. 380
electroabsorption spectra, 301-304
electroreflectance, transverse, 45, 87, 88
energy gap, 263
exciton effects, 149, 302
photoreflectance, 42, 43, 87
piezooptical effects, 426
thermoreflectance. 380, 391, 392, 398
exciton effects, 398
CdSe
electroreflectance spectra, 88-90
energy gap, 263
CdSnP,, electroreflectance spectra, 140
CdTe
deformation potential constants, 440
dielectric constant, thermal modulation,
390
energy gap. 263
ground-state exciton, 424
strain, excitons, 405
thermoreflectance spectra, 390, 391, 398
Cesium, thermoreflectance, 395. 396
Characteristic energy, electrooptical effect,
24,25, 29-31,483,486
line shape, 29
Compliance tensor, 406,407

Conductivity, 433
anisotropy ( m - ' ) ,436
piezoabsorption (anisotropy T - l m - I ) .
436
piezoeffects. 434
piezoresistance, 434
repopulation effects, 434
Convolution formalism, generalized, 521533
electron-electron interactions. 520-533
Convolution integral. 465, 485. 505, 506. 510.
51 1, 522-526
Copper
electroreflectance, 99, 100
piezoreflectance, 432
critical point studies, 432
reflectance. wavelength-modulated, 401
Coulomb interactions. see also Electronhole interactions, Excitons
effect of electric field, 31, 32. 482. 531, 532
Critical points. 3-5, 29, 32, 44. 102, 108-121,
280-285, 312, 313, 316, 317, 331,
343-352, 370, 373, 464, 465, 472475,481,486-489,491, 534
analysis, electroreflectance versus cyclotron
resonance, 1 0 4 1 0 6
analytical, 343, 344
definition, 3, 280, 316, 343, 472
degenerate, 535, 543
excitons, 374
fluted, 347
identification, 23,26, 281
importance in modulation effects, 475
one- and two-dimensional, 518, 519
parameters, 102
piezooptical studies, 430-433
symmetry analysis, 107. 108
symmetry via piezoelectroreflectance, 48
topographical features, 103, 104. 344346
transition energy, 103
types, 26,27,281. 346346,473
Crystal momentum representation 463, 497503, see also Zener tunneling
inversion symmetry, 501
cu,o
electroabsorption, 293-295
exciton spectra, 293-295
phonon spectra, 295
electroreflectance. 98, 142
SUBJECT INDEX
Cu,O (continued)
excitonic features, 98, 142, 425, 426
ground state, 425
strain, 405, 421
excitons, 405, 421
Current operators, 467, 506
time dependent, 506
Cyclotron resonance, compared with electroreflectance, 1 0 4 106
D
Deformation, see also Strain
homogeneous, 406
Deformation potentials, 416, 423,439-442
constants for various semiconductors, 440442
tensor, 416
Density of states, see also Density of states
function, Interband density of states
joint, 343-347,473475
simple bands, 356
Density of states function, 3, see also Critical
points, Density of states. Interband
density of states
joint. 316, 343-347,473475
Detectivity. fractional, 191-1 97
Diamond
electroabsorption, 310
impurity-level piezospectroscopy, 444,445
piezoabsorption, 42 I
Dichroism. 409
piezoeffects, 433,436438
Dielectric constant, 327-338, see also Dielectric function, Kramers-Kronig relations
complex, 327, 335-338
differential form, 330-333, 350-352
dispersion, 333
dissipation, 333
electric field effect, 285, see also Electric field
effects o n dielectric function
exciton effects, 37CL374
free-carrier contribution, 433
imaginary part, 268, 327, 348, 350, 370
critical point, at, 348
related to optical transition matrix ele.
ment, 268
559
Dielectric constant (continued)

interband magnetooptical, 156160
lifetime broadening, 331, 335, 348, 514516
Lorentz parameter, 331-333, 336, 348,
364, 368,372, 514,515
modulated, 160-167,329-338, 347-352
critical points, at, 347-352, 408
crossed field, 165, 167
electric field, 164, 165
magnetic field, 163, 164
stress, 160-162, 408
thermal, 347-352.384384
InSb, 388
silicon, 384-386
wavelength, 347-352
real part. 327, 349, 350
strain shift, 4 0 8 4 1 1, 434
nonlinear variation, 410
Wannier exciton, 528
Dielectric function, 3, 409, 461, 465, see also
Dielectric constant, Electric field
effects on dielectric function,
Kramers-Konig relations
basic theory, 465469
convolution integral representation, 485,
505, 506, 510, 511, 522-526, see
also Convolution formalism
critical points, near, 3-5, 15, 27, 464, 472,
481, 486489. 491, 534, see also
Critical points
depth dependence, 1622.471
effective mass approximation, 4 7 W 9 1
electric-field effects, 17, 23-28, 4 8 U 8 8 ,
503-506, 516, 527, 530
effects on Coulomb interactions, 31, 32
mixing of states, 24
one-electron approximate, 23-28
symmetry breaking, 23, 491
field dependence, 503-51 1
convolution formalism, 505, see also
Convolution integral
general expression, 503-507
Stark steps, 507, see also Stark steps
weak-field approximation, 509-51 1
general expressions, 468,469,480
general properties, 469-475
imaginary part, 3
electric field, 506
indirect transitions, 512-514
560
SUBJECT INDEX
Dielectric function (continued)

inhomogeneous medium, 16-22
interband contribution, 507
internal electric fields, 520
charged defects, 520
absent, 516
line shapes, 29-31, 105
collision broadening, 514-516
plasma term, 468
electric-field effect, 518
polarization, 409
real part, 507
interband contribution, 507
strain, 409-41 1,434
tensorial character. 23,. 409
Differential coefficients, 9-13, 329.470, see
also Fractional coefficients
absorption, 470
reflectance, 9-13, 329,470
Dispersion relations, 333-335, see also
Kramers-Kronig relations
Dissipation, 333
E
Effective masses, see Mass, effective: specific
materials
Elastooptical tensor, 410, 432
differential piezoreflectance spectra, 432
Electric-field effects 276-290, 458$ see also
Electroabsorption, Electric-field
modulation, Electrooptical effect,
Hydrogen atom in electric field,
Stark splitting
atomic shifts, 475
breaking of selection levels, 97, 111, 112,
293
critical points, near, 281-286, 481, 4 8 6
489,491, 534
dielectric constant, 285, 457ff
effective-mass approximation, 476-491
field dependence, 503-51 1
convolution formalism, 505
weak-field approximation, 507
on dielectric function, 457-543, see also
Dielectric function
Electric field effects (conrinued)

on dielectric function (continued)
absorption, 470
fractional coefficients, 470, see also
Differential coefficients
Airy function, 483, 490, 510. 51 I, see also
Airy function
characteristic energy. 483, 486, see also
Characteristic energy
collision broadening, 514516
Lorentzian. 514-516
convolution integral. 465, 505. 506. 510.
51 1
critical points, 464, 465, 472475. 481,
486489,491, 534
crystal momentum approach, 463, 497503
interband terms. 499
absent, 516
depth dependence, 471
electron4ectron interactions included.
520-533
effective-mass approach. 521. 522
electric field as vector potential. 526533
equivalence to Elliott formalism, 532.
533
time-ordering operator. 530
generalized convolution formalism,
522-533
numerical solution. 521
electrooptical functions, 487, 488, 490, see
also Electrooptical functions
electroreflectance, analysis, 533-542
crystal reference frame transformation
matrix. 536-538
effective mass approximation, 534538
longitudinal, 539, 541, 542
symmetry character, 538-542
transverse, 539, 540, 542
excitonic absorption, 480
field-dependent dielectric function, 50351 1
convolution formalism, 505

weak-field approximation, 509-51 1
general discussion, 457-465
56 1
SUBJECT INDEX
Electric field effects (continued)

on dielectric function (continued)
high-frequency effects, 520
indirect transitions, 512-5 14
Stark steps, 514
inversion symmetry absent, 516
Kramers-Kronig relations, 471. 472. see
also Kramers-Kronig relations
multiple-photon processes, 520
one-electron approximation, 475-520
Coulomb interaction neglected, 482
effective-mass approximation. 476-491
dielectric function near critical
points. 481,486, 489,491
electrooptical functions, 487. 490,
517
wave function approach, 492-503
crystal momentum representation,
497-503
Houston functions. 492497
interband mixing, 493
reflectance, 470
fractional coefficients. 470, see also
Differential coefficients, Reflectivity
symmetry breaking, 491
unsolved problems, 543
zero-field case, 465475
absorption coefficient, 470, see also
Absorption coefficient
absorption index, 470
basic theory, 4 6 5 4 6 9
general properties, 4 6 9 4 7 5
position-dependent case, 471
propagation vector, 470
refractive index, 470
electronxlectron interactions, 520-533
electron wave function distortion, 475476
one-electron wave functions, 492-503
plasma frequency, 518
Stark steps, 277,464,496, 507, 51 I , 512
effective-mass limit, 51 1, 512
indirect transitions, 514
symmetry breaking, 491
vector potential for electric field, 526-533
equivalence to Elliott formalism, 532,
533
weakly bound exciton limit (zero electronhole interaction), 283-288
Electric-field modulation. 2, 6, 152, 187, 2 0 4

206,260. see also Electroabsorption,
Electroreflectance
dielectric constant, 164167
magnetoreflectance. 207-21 2, 243-245.
247-25 1
Electroabsorption, 257-3 14, see also Electrooptical effect, Electrooptical functions, Electric-field modulation,
Modulation techniques, Modulation,
Electric-field effects
advantages over electroreflection, 31 1, 312
broadening, 288-290, 313
critical points, 280-285, 312
C U ~ O293-295
,
exciton spectra, 293-295
phonon spectra, 295
defect and impurity studies, 309, 310
diamond, 310
field-induced ionic charge, 310
electron-hole interaction neglected, 283288
direct transitions, 284286
excitonic theory, 268-288.312
experimental methods, 290, 291
pn junctions, 291, 292
transparent electrodes, 290, 291
GaAs, 300,302
germanium, 295-301
direct edge, 295-301
indirect edge, 306, 307
phonon energies. 307
reduced mass, 307
Hamiltonian in parabolic coordinates,
269,270
Pbl,, 308-310
energy gap, 309
reduced mass, 309
silicon, indirect edge, 305, 306
phonon energies, 305, 306
reduced mass, 306
theory and experiment compared, 288290
TiO, 307,308
Wannier excitons, 268-282
interband matrix element, 268
Electron-hole interactions, 31, 312, 313, 365374, see also Coulomb interactions,
Excitons, Wannier exciton
562
SUBJECT INDEX
Electron-hole interactions (continued)

breaking of translational symmetry, 265
fundamental edge
above, 368-374
at, 365-368
Electron-lattice interactions, 29-31, see also
Electron-phonon interaction
lifetime broadenings effects, 29, 30, 352
relaxation energy, 29
Electron-phonon interaction, see also Electron-lattice interaction
broadening, 352, 364
Lorentzian, 364
energy level shift, 352
nonpolar crystals, 352
optical matrix element, 353
polar crystals, 353
transitions, 354
Electrooptical effect, 25, see also Electric-field
effects, Electroabsorption, Electricfield effects (on dielectric function)
anisotropies, 108-1 11
characteristic energy, 24, 25, 29-31, 483,
486, see also Electrooptical energy
high frequency effects, 520
linear behavior, 137-1 39
multiple-photon processes, 520
response characteristics, 113-1 17
Electrooptical energy 270, see also Characteristic energy, Electrooptical effect
(characteristic energy)
Electrooptical functions, 26, 105, 487, 488.
490, 515, 517
lifetime broadening, 105,515-517
Electroreflectance, 1-149, 458, 464, 533, see
also specific materials
analysis of spectra, 122-139
versus cyclotron resonance, 1 0 4 1 0 6
anisotropies, 23, 108-1 11
combination techniques, 45
magneto-, 50, 51
crossed fields, 50, 51
piezo-, 4 5 4 9
roto-, 49
contrasted with piezoreflectance, 30
cyclotron resonance, vs., 104-106
electric-field depth dependence, 16-22, 128,
129
electrolytic method, 3 7 4 2 , 52, 53, 146,
205
Electroreflectance (conrinued)
electrolytic method (continued)
Helmholtz layer, 38
hysteresis, 39
interfacial capacity, 39
response, 40-42. 146
surface conditions, 42
electron beam, 147
exciton effects, 131, 132. 141, 142
experimental findings, 51-102. 139-145
experimental methods, 33-51. 145-147
detection, 33
electrolytic, 3 7 4 2 , 52, 205
field effect, 35-37, 204. 205
photoreflectance, 42-44.206
relative modulation depth. 33
surface barrier, 34. 35. 52
ultraviolet, 33
field-effect method. 35-37, 145. 146. 2 0 4
206,
dry sandwich. 37, 53
heterojunction. 146
p-n junction, 204, 205
thin-film techniques. 36
modulation frequency limit, 37
wet-sandwich, 36
field nonuniformity, 128, 129
general discussion, 1-7. 51-54
line shapes, 32. 106, 107, 129, 131-135
linear effects, 137-139
longitudinal, 539, 540, 542
phenomenological aspects, 7-22
photomodulation. 4 2 4 4 , 147-149
response characteristics. 113-1 17
spectra signatures, 121-125
field-induced shift, 122
lifetime broadening, 129-131
peak size, 121
polarization ratio, 123-125
position, 122, 123
surface barrier, 34. 52
effective field, 35
normal incidence, 35
transverse incidence, 35.44,45
surface parameter control, 126-128
symmetry analysis, 107, I I 7- I2 I. 135-1 37,
538-542
theoretical concepts, 22-32
Coulomb interactions, 31, 32. s t v U ~ S O
Exciton effects
SUBJECT INDEX
Electroreffectance (continued)
theory applied to measurement, 533-542
crystal reference frame transformation
matrix. 536-538
effective mass approximation. 534-538
symmetry character. 538-542
Ellipsometry. modulated, 100
Energy gap
temperature coefficient, 360
temperature shift, 360. s w also Band shift
nonpolar crystals. 360, 362
polar crystals, 360, 363
self-energy term, 360-362
variation with composition, 99
Energy levels, see also Impurity state5
broadening, 359-364
energy dependence, 364
electron-phonon interaction, 352
magnetic field effects. see a/so Landau levels
degenerate bands, 170-178
nonparabolic bands. 178-182
selection rules, 182-184
simple bands, 1 5 6 156
split-off band, 177-182
stress effects, 184187
strain splitting. 41 1-415. 422. 428. 438
temperature effects, 358-365
Excitons. 31. 32. 261. 421-427. see ulso Coulomb interactions, Wannier excitons.
Electron-hole interactions. specific
inaterials
absorption, 480
binding energies. 263. 366
stress shifts, 428, 429
CdTe, 424,425
critical points, at, 374
Cu,O, 425
direct, 365
energy levels, 366
electroabsorption, 268-288, 312
electroreflectance spectra, 131, 132, 141. 142
Frenkel type (localized), 261
fundamental edge
above, 368-374
at, 365-368
hyperbolic, 401, 433
indirect, 367
ionization field, 262. 263, 270
phonon interaction, 367
Rydberg, 366
563
Excitons (continued)
stress splitting, 423, 428, 429
Wannier type (nonlocalized), 261-283. 365
Extinction coefficient. 168. 326, 329
differential form. 329
F
Fractional coefficients. 9. 470, see ulso Differential coefficients, Reflectivity, differential coefficients, Seraphin coefficients
absorption. 470
reflectance, 9-13, 329,470
oblique incidence, 11. I2
Franz-Keldysh effect. 18. 22. 23. '59. 646.476
Free-carrier optical effects. 433-438
interband transitions, 436-438
intervalence bands. 437.438
piezodichroism, 436-438
intraband transitions, 433-436
conductivity, 423
dielectric constant, 433. 434
piezobirefringence, 435, 436
germanium, 435.436
silicon, 435. 436
piezodichroism. 436
Fresnel's equations. 8. 9
differential form, 9
coefficients, 9- I3
c
g-factor, 178. 179
GaAs. 237, 239, 240
GaSb. 227.231
germanium, 221
InAs. 252
InSb, 248
GaAs
abqorption, temperature-modulated. 374
377
band parameters, 237-240
conduction band parameter$. 237. 238
deformation potential constdnts, 440
effective mass. 238-240
564
SUBJECT INDEX
GaAs (continued)
electroabsorption edge, 300, 302
electroreflectance spectra, 74-79, 139. 141,
142
fundamental edge, 76
spin-orbit splitting, 77
exciton effects, 142, 148, 149
exciton energy, 234
fundamental edge. magnetoreflectance,
233-236
g-factor, 237, 239, 240
hyperbolic excitons, 401,433
interband magnetooptics, modulated, 233240
magnetoreflectance
spectra. 233-241
split-off edge, 236-240
photoreflectance, 42
piezoelectroreflectance,47.48
piezoemission. 423
exciton splitting, 423
piezoreflectance, 423,424,432,433
principal gap, 240,263
reflectance
modulated, 27, 28
wavelength-modulated, 400, 401
temperature dependence, band structure, 400
reflectivity differential coefficients, 1 I , 329
Rydberg energy, effective. 263
semi-insulating, transverse electroreflectance, 45
line shape, 45
thermoreflectance, 397
valence band parameters, 239, 240
split-off band, 77,239-240
(GaAs)P alloy, electroreflectance, 98, 141,
239
spin-orbit splitting, 141, 239
(Ga1n)As alloys, electroreflectance, 98, 141
Ga(1nSb) alloys, electroreflectance spectra,
141
principal gap, 141
GaP
absorption, wavelength-modulated, 401
exciton peaks, 401
deformation potential constants. 440442
electroreflectance spectra, 73, 74, 139
direct edge, 73
reflectance, wavelength-modulated, 400
GaSb
band parameters, 227
deformation potential constants. 440
effective mass, 227, 231
g-factor, 227, 231
magnetoreflectance
fundamental edge, 222-229
modulated, 222-233
piezoemission, 423
principal conduction band parameters. 224.
227,230
principal gap, 79, 224. 230, 263
reflectance, wavelength-modulated. 400
Rydberg energy. effective, 263
valence band parameters, 224, 227-233
heavy hole, 227
light hole, 227
GaSe, thermoreflectance spectra, 398
Germanium
absorption
temperature-modulated, 374,376
wavelength-modulated, 374. 375. 402
band parameters, 21 1
deformation potential constants, 439442
dielectric function, 9, 17
space-charge-field effects, 17
direct conduction band parameters, 21 5.
22 1
direct edge, 63,207-216,295-301
electric-field modulated magnetoabsorption and magnetoreflectance, 207212
electroabsorption, 295-30 1
565
SUBJECT INDEX
Germanium (continued)
stress-modulated magnetoreflectance,
212-216
direct gap, 63, 210, 296
effective mass, 200, 221. 222
electroabsorption, 295-302. 306, 307
direct edge. 295-302
phonon energies. 307
reduced mass, 307
electroreflectance, 19-22, 63-68, 134, 135.
139, 142
electrolytic technique, 39-43
exciton, stress splitting. 424. 428, 429
g-factor, 221
impurity level piezospectroscopy, 443
indirect conduction band parameters, 221,
222
indirect edge. 216-222
magnetoabsorption, 21 7-219
magnetopiezoabsorption, 220
magnetopiezotransmission, 218-222
indirect gap, 263
interband magnetooptics, modulated. 207222
ionization field. 263
magnetoreflectance. 207-222
piezoabsorption, 421,422
piezobirefringence, 424,433,435, 436
piezodichroism, 436
piezoelectroreflectance, 46-48
piezoreflectance, 422,423, 431,432
reflectivity differential coefficients, 9, 329
stress effect on band edge, 46,220
stress perturbation of valence band, 41 141 3.41 8,422,423
surface-field effects, electroreflectance, 1922
temperature-modulated absorption. 374,
376
thermoreflectance, 38G-383, 397, 398
valence band parameters, 2 13-21 5,221
heavy hole, 215,221
light hole, 215, 221
split-off band, 216, 221
Germanium-silicon alloys, electroreflectance
studies, 61, 62, 98, 99
GeTe, electroreflectance spectra. 95

Gold
electroreflectance, 99, 100, 145
thermoreflectance, 393, 394
Graphite, thermoreflectance spectra, 333, 380.
392, 393, 398
oblique incidence, 398
Gray tin
electroreflectance spectrum. 68-70
stress effects, 419
H
Hamiltonian, see also Hydrogen atom in
electric field
crystal momentum approach, 463, 497503
interband terms, 499
electron4ectron interactions included.
520-533
effective mass approach, 521, 522
electric field as vector potential. 526533
equivalence t o Elliott formalism. 532,
533
time-ordering operator, 530
generalized convolution formalism, 522533
numerical solution, 521
one-electron(externa1electric field), 492-497
interband mixing, 493
Stark steps, 496
parabolic coordinates (external electric
field), 269,270
radiation field, 339
two-particle (external electric field), 478-482
center-of-mass coordinates, 479
conjugate momenta, 479
Heavy-hole band, see also Valence bands.
degenerate
stress splitting, 185-187
HgSe, electroreflectance spectra, 93
HgTe, magnetoreflectance spectra. 94
Houston functions, 463,492-497
Hydrogen atom in electric field, 269-283. see
also Hamiltonian
Stark splitting, 277-280
WKB approximation, 272
566
SUBJECT INDEX
lnSb (continued)
dcformation potential constants. 440
dielectric constant, thermal modulation.
Impurity states, 441-447
388
deep levels, 443-446
effective mass, 248
electroreflectance specii-a, 82, 83, 140
piezospectroscopy. 443-4415
g-factor. 248
shallow levels. 441-444
interband magnetooptics. modulated. 241stress splitting. 443
248
lnAs
band parameters, 250-252
magnetoelectroreflectance data, 82.83.241
conduction band parameters. 252
247
magnetoreflectance
effective mass. 252
electroreflectance spectra. 81. 82
fundamental edge. 241-247
g-factor. 252
piezoemission, 423
interband magnetooptics, modulated, 247.
249-252
principal gap, 243. 263
reflectance spectra
magnetoreflectance
thermal modulation. 387-390
fundamental edge, 247.239-251
spectra, 247-251
wavelength modulation, 388.400
Rydberg energy. effective. 263
split-off edge, 247, 249-251
principal gap. 249. 263
valence band parameters. 246-248
reflectance. wavelength-modulated. 300
split-off band, 82. 243, 248
Rydberg energy, effective. 263
wavelength modulation spectra. 333. 152.
thermoreflectance spectra, 398
38 I , 389
lnterband density of states. 3. 280. 473. S O P
exciton effects. 398
valence band parameters, 252
also Density of states function
split-off band. 82. 250, 252
singularity (critical point). 3. 280. 4 7 2 4 7 5
In(AsP) alloys, electroreflectance spectra, 141 lnterband effective mass. 102-103. 157, 473.
principal gap, 141
509, scc ulso Mass. effective
spin-orbit splitting. 141
lnterband energy surface. 24. 25
I1nAs)Sb alloys, electroreHectance. 98, 141
reduced effective mass. 102-104
principal gap. 141
saddle point, 25, 26
Indirect transitions. see Transition, opttcal
temperature coefficient. 364
Inhomogeneous perturbations, 16-22. 471
Intcrband transitions. S K Y u l o Modulated
see ulso Modulation
interband magnetooptics. TransiInP
tions, optical
direct gap. 263
magnetic field. 1 5 4 187
electroreflectance spectra. 80. 81
allowed, 157. 182-184
direct edge. 80
crossed electric field. 165
spin-orbit splitting. 80
forbidden. 165
GaAs. 233-237
reflectance. wavelength-modulated. 400
GaSb. 222-233
germanium, 207-222
thermoreflectance spectra, 368, 387
InAs. 247-251
InSb
InSb. 241-247
band parameters. 243, 247. 248
PbTe. 251-254
conduction band parameters. 248
selection rules. 157. 182-lX4
1
567
SUBJECT INDEX
Interband transitions (continued)

magnetic field (continued)
stress effect. 186187
Ionization field, 262-264
exciton ground state. 270
selected semiconductors, 263
Line shapes (continued)

interband magnetooptical transition. 158166
modulation, 161-166
interpretation. 132-1 35
phonon effects, 352. 364
KBr, electrooptical effects. 427

K1, electrooptical effects, 427
Kramers-Kronig relations, 10, 159, 268, 333335. 348, 349, 471, 472, see ~ J ~ SDiO
electric constant
differential form, 13-15. 334,472
stress derivative, 422
KTaO, temperature-modulated absorption.
374, 380
K T a 0 3 : KNbO,, electroreflectance, 101
Magnetoabsorption (modulated). 167, 168. s w

also Magnetooptical effects, Modulation interband magnetooptics.
Modulation techniques. specific materials
crossed field. 165, 207
dielectric constant, 163-167
crossed field, 165
germanium
direct edge, 207-216
electric-field modulated, 207-210
indirect edge, 217-222
Magnetoelectroreflectance. SO, 51. 207
crossed fields, 51, 207
GaAs. 233-240
GaSb. 223-233
germanium, 154.207-2 I2
direct edge. 207-212
indirect edge. 216-222
line shape analysis, 208
InAs, 154. 247-251
InSb. 154,241-247
line shape analysis, 208
PbTe, 251-254
Magnetophotoreflectance, 246, 247, sec also
Photoreflectance
Magnetopiezoeffects. see also Piezoreflectance, Stress, Stress modulation
GaAs, 233-241
GaSb, 223-233
germanium, 212-220
direct edge, 2 12-2 15
Magnetoreflectance (modulated). 6, 169. 380.
see also Magnetoelectroreflectance.
Magnetooptical effects, Modulation
techniques, Modulated interband
magnetooptics, Stress modulation,
specific materials
GaAs, 233-240
GaSb, 223-233
L
Landau ladders, 6
Landau levels, 154-159, 169-184. s w also
Energy levels, magnetic field effects
germanium and 111-V compounds. 169-184
modulation. 6, 51
stress effect. 184- 187
two-band model, 154156
Lattice vibrations, scc also Phonons
local modes, 448
piezooptical studies. 448
Light-hole band, see also Valence bands.
degenerate
Line shapes
dielectric function. 29-31. 370-373
broadening, 29, 30, 105, 331-333. 335338, 348, 514516
electric-field modulated magnetoreflectance, 208
electroabsorption spectra, 287-290
broadening, 288-290
collision. 289
Gaussian, 288
Lorentzian, 288-290
electroreflectance spectra, 32, 106, 107
collision broadening. 129
exciton effects, 131. 132
568
SUBJECT INDEX
Magnetoreflectance (continued)
germanium, 207-222
InAs, 247,249-25 I
InSb, 241-247
PbTe, 251-254
sensitivity considerations, 188-190
Mass, effective, 178, 179, see also specific
materials
anisotropy, 436
conductivity ( r m - I), 436
piezoabsorption (~-m-),
436
GaAs, 238-240
GaSb, 227,231
germanium, 220-222
InAs, 252
InSb, 248
PbTe, 254
reduced, interband, 24, 25, 102-104, 157,
269,473, 509
Mg,Ge, electroreflectance, 98
Mg,Si, electroreflectance, 98
Mg,Sn, electroreflectance, 98
Magnetooptical effects, 151-255, see also Modulated interband magnetooptics
magnetic-field modulation, 203, 204
advantages, 204
limitations, 204
magnetoabsorption, 167, 168, 207, 208,
216-222, see also Magnetoabsorption
electric-field modulated, germanium
direct edge, 207, 208
stress modulated, germanium
indirect edge, 22C222
magnetoreflection, see also Magnetoreflectance
electric-field modulated. germanium. direct edge, 207-212
stress modulated, 212-215
Modulated interband magnetooptics, 151255, see also Magnetooptical effects,
Modulation techniques, Magnetoelectroreflectance, Magnetoabsorption, Magnetoreflectance
experimental results, 207-255
GaAs fundamental edge, 233-236
split-off valence bans, 2 3 6 2 4 0
GaSb fundamental edge, 222-229
split-off valence band, 229-233
Modulated i nterband magnet oopt ics

(continued)
Ge direct edge, 207-21 6
electric-field modulated magnetoabsorption and magnetoreflectance,
207-2 12
line-shape analysis, 208
stress-modulated magnetoreflectance.
212-216
Ge indirect edge, 216-222
InAs fundamental edge, 247-251
InSb fundamental edge, 241-247
parameter-finding computer program.
228
PbTe fundamental edge, 251-255
interband transitions, 154187, 203
Landau levels, 154-159. 183, 184
modulation techniques, 187-207, see also
Modulation techniques
electric field, 204-206
fractional detectivity, 192
magnetic field, 203, 204
noise, 189-197
photodetector choice, 197
sensitivity considerations, 188-197
stress, 199-203
temperature, 206, 207
wavelength, 197-199
Modulation, 1-7, 317, 459, see also Electroabsorption, Modulation techniques.
Dielectric constant, Modulated interband magnetooptics
absorption differential coefficients, 470
critical point considerations, 475, see also
Critical points
homogeneous, 8-15
inhomogeneous, 1622,471
reflectivity differential coefficients, 9-1 3,470
symmetry breaking, 5-7, 23, 28,4&49
Modulation techniques, 1-7, 152-154, 187207, 317, see also Modulation, Electroreflectance, Magnetoreflectance,
Piezoreflectance, Thermoreflectance,
Magnetooptical effects, Electroabsorption
band structure analysis, 7
detector choice, 197
detector noise, 194-197
electric field, 2,6, 152, 187,204-206,260,459
external (wavelength), 187, 188
SUBJECT INDEX
Modulation techniques (continued)

instrumentation, 320-326. 452
internal. 187, 188
magnetic field, 6, 153. 163. 187, 203. 204
noise equivalent power, 189-197, see ulso
Noise
dark, 190
fractional, 189-197
photo, 42, 152, 187, 206, 246
sensitivity. 188. 198
stress, 2, 5,6, 152, 160, 187,199-203,260,459
temperature, 2,6. 152, 187,206,207,260,459
wavelength, 152, 187, 197-199,459
Momentum matrix element, 461. 468, 512. S C P
also Transitions. optical
Nickel, thermoreflectance. 394, 395

NiO, electroreflectance spectra, 141
Noise, modulation systems, 190-197
detector, 19&197
current, 194
dark current, 195
generation-recombination, 194, 195
shot, 195--197
thermal, 194, 195
Noise-equivalent power, 189-197
dark, 190
fractional, 189-197
Nonparabolicity, band, 178-182
germanium. 220-222
0
Optical anisotropy, 409-41 1, see also Piezooptical effects
birefringence (double refraction), 409
dichroism (absorption anisotropy), 409
dielectric function, 409
dielectric tensor, 4 0 9 4 1 I
Maxwell's equation, 409
polarization, 409
PbI,
electroabsorption, 308-310
energy gap, 309
reduced mass, 309
569
Pbl, (continued)
electroreflectance. 98. 142
energy gap, 263
excitonic features, 98. 142
(PbSn)Te alloys, electroreflectance spectra.
95-98
PbTe
effective mass, 254
reduced, 254
electroreflectance spectra, 95-98
fundamental gap, 253
interband magnetooptics, modulated. 251255
magnetoreflectance
spectra, 251-255
Phonons, 447, see also Lattice vibrations
stress effects, 447
germanium, 447
silicon, 447
Photoreflectance, 4 2 4 4 , 147-149, 187, 206,
246. see also Magnetophotorefleclance
Piezoabsorption. 41 9-427, s w u l m Piezooptical effects
anisotropy ( ~ - mI )-, 436
conductivity (anisotropy rm- I ) . 436
dichroism, 433,436-438
direct transitions, germanium, 422
indirect transitions. 419-422
AgBr. 422
AISb. 421
Cu,O, 421
diamond, 421
Gap, 421
germanium, 420. 421
silicon, 421
Piezoelectroreflectance. 45-40. see u f u Piezomodulation, Piezoreflectance. Stress,
Piezooptical effects
Piezoemission, 423, 424
GaAs, 423
GaSb, 423
InSb, 423
Piezomodulation. 260, sec2 ulso Stress. Stress
modulation, Magnetopiezoeffects.
570
SUBJECT INDEX
Piezooptical effects, 403-456. ser also Magnetopiezoeffects, Piezoelectroreflectance, Piezoreflectance, Strain,

Stress, Stress modulation, Optical
anisotropy, Piezoabsorption
alkali halides, 427
critical point investigations, 430-433
exciton effects, 421-427
experimental arrangement, 449-456
compensation methods, 449
differential techniques, 451-453
interference method (piezobirefringence).
449,450
oscillatory stress. 455, 456

static stress. 453
various modulation parameters, 452
free carrier. 433-438
interband. 436-438
piezodichroism. 436,438
intraband, 433-436
conductivity, 433
dielectric constant. 433, 434
piezobirefringence, 435. 436
piezodichroism, 436
fundamental edge, near, 419-427
direct transitions, 422-427
general discussion, 403-408
anisotropic, 404
degeneracy, lifting. 404
isotropic (hydrostatic), 403
germanium, 420-422
higher energy interband transitions. 430433
lattice vibrations, 447, 448

macroscopic theory, 405-41 1
silicon. 421
11-VI compounds. 424-427
111-V1 compounds, 422-424
Piezoreflectance, 2. 5, 422. 423, 430. . s w also
Stress. Magnetopiezoeffects, Piezoelectroreflectance, Piezooptical effects
AlSb direct edge. 423
CdTe, 425
copper. 432
differential measurements. 432
electroreflectance, contrasted. 30
GaAs. 423,432
germanium. 422,423,432,433
Piezoresistance, 434
band extrema splitting. 439
strain gauges. 439
Piezospectroscopy. 443. sec also Impurity
states
Piezotransmission, SCP Piezoabsorption
Plasma frequency, 469, 518, 519
contribution to dielectric function, 468,469
electric-field effect. 518. 519
Polarization, 409, 467
factor, 536
matrix element. 480. 535
Population effects, 96. 142. W E olso Bandfilling effects
Potassium. thermoreflectance. 395, 396
Poynting vector, 327
Pressure. see Stress
R
Reflectance. 1-22, 268, 470, SYP also Electroreflectance, Reflectivity. Piezoreflectance. Thermoreflectance. Photoreflectance. Magnetoreflectance. Modulation techniques, Stress
fractional coefficients, 470
modulation, sensitivity considerations. IRXI90

Reflection coefficient. complex. 14
Reflectivity. 1-22, 316. 327-330. s w olso
Reflectance
differential coefficients, 9-1 3. 329
Brewster angle, 329
GaAs. 329
germanium, 329
normal incidence. 10
oblique incidence. 11. 12, 329
silicon, 329
electric-field induced changes. 470. 534532.
. s w ulso Electric field effects
phase angle. 328, 335
space-charge-field effects, 17 -20
Refractive index. 168. 268. 326. 329.470
complex, 326
Repopulation effects, 434, 335. 438
SUBJECT INDEX
Rubidium, thermoreflectance, 395, 396

Rydberg energy, effective, 262-265
selected semiconductors. 263
S
Sb,Te, -,Sex, thermoreflectance, 399

Schrodinger equation
hydrogen atom in electric field, 269
parabolic coordinates, 269
W K B approximation, 272
Selection rules, 111, 182-184, 341-343
breaking, by electric field, 97, 111, 112, 293
magnetoabsorption, 182-1 84
Selenium
absorption, wavelength-modulated, 401
reflectance, wavelength-modulated, 40 I
stress, 401
transverse electroreflectance, 45, 70-72
Seraphin coefficients, 9, 470, 471, see also
Fractional coefficients
Silicon
absorption
temperature-modulated, 374, 377, 378
wavelength-modulated, 374378,40 1.402
phonon energies, 402
stress, 402
deformation potential constants, 44G442
dielectric constant, thermal modulation,
384386
electroabsorption, 305, 306
phonon energies, 305, 306
reduced mass, 306
electroreflectance measurements, 5460,139
indirect edge, 56
impurity level piezospectroscopy, 443, 444
piezobirefringence, 435,436
piezoelectroreflectance, 47, 60
reflectivity differential coefficients, 10, 329
rotoelectroreflection, 49
thermoreflectance, 329, 380, 384386, 397
Silver
reflectance, wavelength-modulated, 396
571
SnTe, electroreflectance spectra, 95-98

Spin-orbit coupling, 179, see also Spin-orbit
splitting, Split-of band
Spin-orbit splitting, 8, 54, 170, 173-182, see
also specific materials, Spin-orbit
coupling
GaAs, 239
GaSb, 231
germanium, 21 1
InAs, 250
InSb, 243
ZnS, 397
Split-off band, 177-182, see also Spin-orbit
splitting, specific materials
SrTiO,
prezoreflectance, 432
rotoelectroreflectance, 49
Stark splitting, 277-280, see also Stark steps
Stark steps, 464, 496, 507, 511, 512, see also
Stark splitting
effective mass limit, 511, 512
Stiffness tensor, 406,407
Strain, 23, 184-187, see also Piezoreflectance,
Magnetopiezo effects, Modulation,
Stress, Piezooptical effects, Piezoabsorption
anisotropic, 403
band edge shifts, 415-419
complex dielectric tensor, 409-41 1
conductivity tensor, 434
deformation potential tensor, 416,423
constants for various semiconductors,
440-442
degeneracy lifting, 404,411
valence band, 41 2, 438
dielectric constant shift, 408
dielectric tensor, 434
energy-level splitting, 41 1-41 5
transitions, 4 1 3 4 1 5
excitons, 404
impurity-level splitting, 443-446
isotropic (hydrostatic), 403, 407
tensor, 406,408
Stress, see atso Strain, Stress modulation,
derivative of reflectance, 422
572
SUBJECT INDEX
Stress (continued)
energy-level perturbation, 184187
exciton splitting, 423, 428, 429
isotropic (hydrostatic), 407
laser tuning, 440
modulation, 2, 5, 6, see also Stress modulation
absorption, 420
dielectric constant. 160-162
reflectance, 199-203
phonons, 447,448
repopulation effects, 434, 43.5
tensor, 405
uniaxial, 407, 408
valence band perturbation, 184187, 412.
418,422,423,428,438
Stress modulation, 2, 5, 6, 152, 160, 187, 199203, 212, 218-222, 420, 430, see also
Piezomodulation, Piezooptical
effects
dielectric constant, 160- 163
magnetoabsorption, 216221
magnetoreflectance, 21 1-216, 223-243, 247.
249,251,252
Surface states, studied by modulation techniques, 260
Symmetry analysis, electroreflectance, 107,
117-121, 135-137, 538-542
critical points, 107, 108, 118
Temperature modulation, 2, 6, 152, 187, 206,

207,260, see also Thermoreflectance,
Thermal modulation spectroscopy
experimental techniques, 320-326, 396, 397
nonpolar crystals, 362
polar crystals, 363
Thermal modulation spectroscopy, 3 1 5 4 2
dielectric constant, 347-352
exciton effects, 365-374
fundamental edge
above, 368-374
at, 365-368
instrumentation, 320-326, 396, 397
absorption, 325
Thermal modulation spectroscopy (conrinued)

oblique incidence, 321
reflectance, 321
transmission, 322
nonpolar crystals, 360. 362
phenomenological relationships. 326338
polar crystals, 360, 363
reflectance data, see Thermoreflectance
transmission (absorption) data, 374380
CdS, 374. 379, 380
GaAs, 374, 377
germanium, 374, 376
KTaO, , 374, 380
silicon, 374, 377, 378
Thermal reflectance. see Thermoreflectance
Thermoreflectance, 2, 312, 324, 396, sre also
Temperature modulation. Thermal
modulation spectroscopy
advantages and limitations, 312
(CdHg)Te alloys, 399
CdS, 380,391, 392.398
CdTe, 390, 391,398
cesium, 395, 396
experimental techniques, 321,396, 397
fundamental edge, near, 335-338
GaAs. 397
G a p , 397
GaSe, 398
germanium, 380-383. 398
gold, 393, 394
graphite, 333, 380, 392, 393, 398
InAs. 398
InP, 386, 387
InSb, 387-390
nickel, 394, 395
potassium, 395, 396
rubidium, 395, 396
Sb,Te,-,Se,, 399
silicon, 329, 380, 384386
silver, 399
thermal conductivity determination, 399
ZnGeAs,, 399
ZnS, 397
ZnSnAs,, 399
TiO,
electroabsorption, 307, 308
electroreflectance, 102
Transfer effects, see Repopulation effects
Transitions. optical, 340-342, 354, 4 3 U 3 8 .
see also Interband transitions
SUBJECT INDEX
Transitions optical (continued)

critical points. near. 363. 364
direct. 342
free carrier effects, 433438, see U ~ S OFree
carrier optical effects
interband, 4 3 6 4 3 8
intraband, 433336
indirect (phonon assisted), 354358. 361,
5 12-5 14
absorption coefficient. 357
intermediate states, 355
Stark steps, 514, .see ulso Stark steps
interband, 538
electroreflectance, 536-538
intervalence bands, 436-438
matrix element, 267. 268. 341. 353, 369. SLV
also Momentum matrix element
strain-split levels, 41 3-41 5
strain-split sublevels, 41 3-41 5
symmetry, 342, 538
symmetry identification. 538-542
Transmission. 330, sec also Absorption
modulated. 330, 357, see ulso Thermal
modulation spectroscopy, Wavelength modulation spectroscopy,
Piezoabsorption
fundamental edge, at, 335-338
thermal. 374-380
wavelength, 374-378
v
Valence bands. degenerate, Fee also specific
materials
band parameters, 173
energy levels in magnetic field, 170-178
stress effects, 184-187. 412, 418, 422. 423,
428,438
transitions. 436-438
Van Hove smgularities, 370-374
W
Wannier exciton (nonlocalized), 261-283,
528. see also Excitons, Coulomb
interactions
573
Wannier exciton (nonlocalized) (conrinurd)

binding energies, 263
breaking of translational symmetry. 265
electric-field effect, 262-267
ionization field, 262, 263, 270
transitions, allowed and forbidden. 267,
268
matrix element 267
Wannier functions, 461
Wave functions. Landau. 155. 170. I71
Wavelength modulation, 152. 187, 197-199.
see also Wavelength modulation
spectroscopy
absorption. 420
advantages. 198
instrumentation, 198, 199
limitations, 198
magnetoreflectance, 223, 224
Wavelength modulation spectroscopy, 31 5402. see ulso Wavelength modulation
absorption, 326. s c v ulso transmission (absorption) data
broadening, 364, 374
energy dependence, 364
dielectric constant, 347-352. 401
exciton effects. 374,401
InSb, 333, 352
instrumentation, 32;-326,400
phenomenological relationship. 326-338
reflectance data, 381, 388, 399-401
AISb, 400, 423
copper, 401
GaAs, 400,401
Gap. 400
GaSb, 400
germanium, 400
InAs, 400
InP, 400
InSb, 381, 388, 389,400
selenium, 401
silicon. 400
transmission (absorption) data. 374-378,
401.402
AISb, 401,402
Gap, 401
germanium, 374, 375.402
silicon. 374, 376378, 401, 402
Wavelength wobbler. 198, 199
Weak-field approximation. electric-field
effects, 509-51 1
574
SUBJECT INDEX
Z
Zeeman effect, 151-153

Zener tunneling, 463,476
ZnGeAs,, thermoreflectance, 399
ZnO
electroreflectance spectrum, 85, 86, 138,
141
fundamental edge, 85
piezooptical effects, 426,427
ZnS
energy gap, 263
ZnS (continued)
transverse electroreflectance, 45, 90
ZnSe
energy gap, 263
transverse electroreflectance, 45, 91, 142
ZnSnAs,, thermoreflectance, 399
ZnTe
energy gap, 263

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(Semiconductors and Semimetals 9) R.K. Willardson and Albert C. Beer (Eds.) - Modulation Techniques-Academic Press (1972)

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SEMICONDUCTORS

ACADEMIC PRESS New York and London

COPYRIGHT 1972, BY ACADEMIC

ACADEMIC PRESS, INC.

New York, New York 10003

United Kingdom Edition published by

24/28 Oval Road, London NWl

LIBRARY OF CONGRESS CATALOa CARD NUMBER:

PRINTED IN THE UNITBD STATES OF AMERICA

hydrostatic pressure, nuclear irradiation, and nonuniformity of impurity

Semiconductors and Semimetals

Volume 2 Physics of 111-V Compounds

Volume 3 Optical Properties of 111-V Compounds

CONTENTS OF PREVIOUS VOLUMES

H. Y. Fan, Effects of Free Carriers on the Optical Properties

Volume 4 Physics of IIEV Compounds

Volume 5 Infrared Detectors

Volume 6 Injection Phenomena

Volume 7 Applications and Devices: Part A

CONTENTS OF PREVIOUS VOLUMES

Volume 7 Applications and Devices: Part B

Volume 8 Transport and Optical Phenomena

3. Inhomogeneous Modulation of the Reflecting Medium

Various modulation parameters define a whole family of modulated

less ambiguous the assignment becomes. However, this interplay introduces

and has produced results in a number of new materials. We can expect

XI. Electroreflectance in Phenomenological Description

a. Diflerential of Fresnels Equation

We assume in this section that the dielectric function E = s1 is, of the

FIG.1. The fractional coefficients a and B in Eq. (2) for Ge.

applies. For normal incidence of light, it has the form

Its total differential with respect to and E~ provides a phenomenological

We will express the coefficients a and j in a mixed notation. Although

where no is the refractive index of the nonabsorbing medium of incidence.

FIG. 2. The fractional coefficients a and fi in Eq. (2) for Si

values of both coefficients,calculated from experimental values for

In the analysis of a modulated-reflectance spectrum, the discussion of the

B. 0. Seraphin and H. E. Bennett, in Semiconductors and Semimetals (R. K. Willardson

FIG. 3. The fractional coefficients a and

B in Eq. (2) for GaAs.

* J. E. Fischer and B. 0.Seraphin, Solid State Commun.5, 973 (1967).

Angle of incldence (DEG)

where we use the following definitions

t = no sin (b0 tan 40,

The incident medium, refracting but not absorbing, is described by no,

b. Diflerential Kramers-Kronig Relations

Photon energy (eV)

FIG. 5. Electroreflectance response A R d R , at the (2.1/2.3)-eV doublet in Ge, at 300"K,

If AR/R is known from experiment for a sufficiently large range of photon

"See, for example, p. 98 of Philipp and Ehrenreich.I4

FIG.6. Line shape of A E (broken

In electroreflectance, it is assumed that the electric field acts on c 2 . The

Equation (13) establishes peculiar transformation relations between A&, and

E(z) = EOe"- K z +&)I

of the wave equation, where q(z) is a complex z-dependent phase and K

E. Aspnes and A. Frova, Solid State Commun. 7, 155 (1969).

dz' AE(z')= - 2iK(z, - zd)&,

indiscriminately. The uniform field approximation results for

in which case ( A E ) + A&.

Commun. 7,497 (1969).

through a solution of Poisson's equation according to' 5 e * 1 5 f

where L , is the Debye length of 0 . 7 5 ~assumed in Aspnes and Frova's

Agreement with the pattern of Fig. 8 is satisfactory. The crossover occurs