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# PHY475

Prof. Mark Fox

AUTUMN SEMESTER

## PHY475: OPTICAL PROPERTIES OF SOLIDS

Prof. Mark Fox
Autumn Semester (10 credits)
Course aims and outcomes

Understand the classical theory of light propagation in solid state dielectric materials;
Understand the quantum theory of absorption and emission in solids;
Appreciate the importance of excitonic effects in solids;
Understand the origin of nonlinear optical effects in crystals.

The outcome of the course will be that the student will be familiarised with the optical phenomena
that occur in a wide range of solid state materials, based on an understanding of both the classical
and quantum theories of how light interacts with dielectric materials.
Lecture Topic
1-3

Homework

Introduction.

## The complex refractive index

4-6

Lorentz oscillators.
Dispersion and birefringence

Book chapter

7-8

Interband absorption

9-10

Excitons

11-12

Interband Luminescence

13-14

Quantum confinement

15-16

## Metals. Doped semiconductors

17-18

Phonons

10

19-20

Nonlinear optics

11

4
5
6, 8.5

Course Book: Fox, Optical properties of Solids (Oxford University Press, Second edition 2010)
These notes are to be used in conjunction with the course book. A number of hard copies are
available in the University Library, as well as an ebook that can be accessed online.

## Kittel, Introduction to Solid State Physics (Wiley)

Burns, Solid State Physics (Academic Press)
Ibach and Luth, Solid State Physics (Springer-Verlag)

Assessment: Homework: 15% (3 problem sheets), Exam: 85% (any 3 questions from 5)
Course www page: http://www.mark-fox.staff.shef.ac.uk/PHY475/

Topic 1: Introduction
Optical coefficients
Complex dielectric constant
Complex refractive index
Introduction to optical materials

Optical coefficients
propagation through
the medium
incident light

transmitted light

reflected light
Figure 1.1: Optical coefficients
Reflectivity = reflected / incident power
Transmissivity = transmitted / incident power
T + R =1 if medium is transparent

Propagation

refraction
absorption and luminescence
scattering

Figure 1.2:
Propagation of
light through a
medium

## Velocity v= c/n, n is the refractive index

I(z) = I0 exp(-z), is the absorption coefficient
T = (1-R1) exp(-L) (1-R2)
Luminescence : re-emission at lower frequency
scattering: elastic- change of direction
inelastic - change of direction and frequency

Luminescence
excited states

relaxation

Luminescence comes

emission

absorption

## out at lower frequency

than absorption due to
internal relaxation
The energy shift
between absorption
ground state
Figure 1.3: luminescence mechanisms

and luminescence is
called the Stokes shift.

## Complex optical coefficients

Complex relative dielectric constant: r = 1 + i 2
Complex refractive index: n = n + i
Absorption coefficient: = 4 /

r = n2 ; 1 = n 2 2 ; 2 = 2n
1 "
2
2
n=
\$1 + 1 + 2
2#

1/2

1 "
2
2
=
\$ 1 + 1 + 2
2#

1/2

%
'
&

1/2

1/2

%
'
&

n 1
(n 1) 2 + 2
Reflectivity: R =
=
n +1
(n +1) 2 + 2

Insulators / semiconductors
Transmission

1.0

UV visible
(a)

infrared
Al2O3

0.0
0.8 (b)
CdSe

0.0
0.1
1
10
Wavelength (microns)
Figure 1.4 : transmission spectra of
(a) sapphire (Al2O3) (b) CdSe

## Infrared absorption due

to phonons
ultraviolet/visible
absorption due to bound
electrons
position of fundamental
absorption edge depends
on the size of band gap
transparency region in
between

Metals
visible UV

infrared
Reflectivity

1.0
0.8
0.6

Figure 1.5:
Reflectivity spectrum
of silver

silver

0.4
0.2
0.0
10

1.0
Wavelength (m)

0.1

## Free electrons in the metal absorb

High reflectivity up to plasma frequency in the UV

Absorption (a.u.)

Organic materials
1.0
0.8
0.6
0.4
0.2
0.0
300

UV

visible
UV/blue band

## Figure 1.6 : Absorption

spectrum of polyfluorene

polyfluorene
(F8)
400

500

600

700

Wavelength (nm)
Strong absorption in UV/visible spectral region due to
electronic transitions
Stokes-shifted emission across the visible spectral region

Doped insulators
Transmission

1.0

sapphire

0.8

ruby

0.6

yellow/green
band

0.4
0.2

Figure 1.7:
Transmission spectra
of sapphire (Al2O3)
and ruby (Al2O3: Cr3+)

blue band

0.0

## 200 400 600 800 1000

Wavelength (nm)
Sapphire is transparent for visible wavelengths

Cr3+ ions doped into sapphire absorb in the blue and yellow/green
spectral regions, hence red colour

Lifting of degeneracies
atom
in
crystal

free atom

atom in
B field

degenerate
magnetic
levels
crystal
field
effect

Zeeman
effect

## Figure 1.8 : Lifting of degeneracies in the solid state

Crystals have directions lower symmetry than atoms or molecules
new effects due to lower symmetry e.g. lifting of degeneracies

solid

free
atom

Band formation
Figure 1.9:
Band formation in
the solid state

Interatomic separation
Free atoms have sharp absorption and emission lines
Solids have broad absorption and emission bands
Two types of bands: electronic and vibronic

## Topic 2: Dipole oscillators

Introduction
Lorentz oscillator model
KramersKronig relationships
Dispersion
Optical anisotropy & chirality

Electron oscillators
Figure 2.1: classical model of an atom.
Electrons are bound to the nucleus by springs
which determine the natural frequencies
Bound electrons (insulators, intrinsic semiconductors)
restoring force for small displacements F = k x
natural resonant frequency 0 = (k/m)1/2
0 lies in the near infrared / visible / UV spectral regions
Free electrons (metals, doped insulators)
k = 0 0 = 0

Dipole oscillators
p(t)

x(t)

t
x

+
t=0

t=

2
t=
0

Refractive index
light AC electric field at (0)
forced oscillations at
atoms lag on the driving field

Figure 2.2

p(t) = e x(t)
P=Np
D = 0 E + P = r0 E
Light emission
natural oscillations at 0
Hertzian dipoles
Absorption
light frequency = 0
resonance phenomenon
atoms absorb energy from
the light beam

Vibrational oscillators
Figure 2.3
polar molecule

Molecular physics
IR absorption at resonant frequency of the vibrational modes
Ionic crystals
IR absorption at frequency of optically-active lattice vibrations
i.e. the transverse optic (TO) phonons

Lorentz oscillators
Dielectric constant

Refractive index

30
1

6
n

10

4
2

-10

0
40

20
0

Figure 2.4
Lorentz
oscillator
with
= 51012 s-1
st = 12.1
= 10

60

100

2
140

60
100

Ne 2
1
r ( ) = 1 + +
0 m0 0 2 2 i

140
absorption at 0
= 1/ = damping rate
FWHM = ,

## Example: atomic absorption line

1700 m

0
n

3.95 10

n0 1
200,

0,
(MHz)

Lorentzian lineshape
2
( ) = 0
4 2 + 2
4
n( ) = n0 n
4 2 + 2
= 0

200,

Figure 2.5
sodium gas, N = 11017 m3 (low density n0 1)
D2 line at 589.0 nm, hyperfine component with FWHM = 100 MHz

Absorption

Refractive index

Multiple resonances
vibrational
bands

electronic
transitions

Figure 2.6
resonant frequencies:
phonons
IR
valence electrons
vis/UV
core electrons
X-ray

0
r ( ) = 1 +

IR

1011

visible UV X-ray

## 1013 1015 1017

Frequency (Hz)

fj
Ne 2

0 m0 j 0 j 2 2 i j

fj = oscillator strength
classical theory fj = 1
quantum theory fj determined
by transition probability

## Example: SiO2 glass

10

SiO2 glass

(a)

Figure 2.7
real and imaginary
part of the refractive
index for SiO2 glass

1
1,

(b)
Transparency region
between
phonon frequencies in IR
and band gap in UV

2,

10 4,
1012 1013 1014 1015 1016 1017
Frequency (Hz)

10

## Optical fibre losses

KramersKronig relationships
% ( %)
d %
0 %2 2
2
% [ n( %) 1]
2
( ) =
P
d %
0 %2 2
n( ) 1 =

## Refractive index (n) and absorption

() are the real and imaginary parts
of the same function: = n+i
Absorption and refraction are
related to each other by the
KramersKronig relationships \$

Refractive index

Figure 2.9
4
2

n at 10 m
vs band gap

0
0
1
2
Band gap wavelength (m)

11

UV transmission of glass

## (at 546 nm)

reduces UV transmission
increases refractive index at
visible frequencies

Dispersion
Wavelength (nm)
1000 600
400
300
Refractive index, n

IR

visible

Figure 2.10
glass dispersion
200

ultraviolet

Group velocity
dispersion (GVD)
d2n/d!2
GVD determines
in optical fibres
GVD = 0 near
1300 nm

1.55
1.50

d2n
d 2

=0

SiO2 glass

1.45

0.2

0.4

## 0.6 0.8 1.0 1.2

Frequency (1015 Hz)

1.4

12

Dispersive prisms
white

red

Figure 2.11
Dispersion of light by a prism

blue

## NORMAL dispersion: n increase with frequency

ANOMALOUS dispersion: occurs near resonance lines

## For Pink Floyd fans

red

red
blue

blue

anomalous dispersion ?

normal dispersion

13

## Double refraction in calcite

optic axis
109

unpolarized
light

6.2
71

e-ray
o-ray

Figure 2.12
Birefringent crystals
such as calcite
(Iceland Spar)
separate orthogonal
light polarizations
into the
o(rdinary) and
e(xtraordinary) rays

## Birefringence (optical anisotropy) : refractive index depends on

the direction of the polarization vector relative to the crystal axes

14

Optical anisotropy
optic axis
z
propagation
direction

optic axis
z
propagation
direction

(a) o-ray

y
(b) e-ray

Figure 2.13
Birefringence caused by
difference of dielectric constants
(and hence refractive index)
along the different crystal axes.

0 #& E x #
& Dx #
& 11 0
\$
!
\$
!\$ !
\$ D y ! = 0 \$ 0 22 0 !\$ E y !
\$D !
\$ 0
0 33 !"\$% E z !"
% z"
%

## Polarizing beams splitters

unpolarized
light

air gap

"

Figure 2.14
GlanFoucault
prism

o-ray

"

e-ray

optic axis
Critical angle: sin "c = 1/n
Calcite: no = 1.658, "c = 37.1; ne = 1.486, "c = 42.3
Hence choose 37.1 " 42.3

15

Wave plates
(a)

Figure 2.15

(b)

input

opt
ic a
xis

"

( no ne ) d

o-ray
output

e-ray

"
input
polarization

## Half wave plate:

!# = \$
Quarter wave plate: = / 2,

Induced birefringence
Isotropic materials are non-birefringent
Induce birefringence !n with strain or electric field
Hence photo-elastic and electro-optic effects
Kerr effect (quadratic electro-optic effect) observed in
all materials, including liquids and glass:
n = ! K E2 ; K = Kerr constant
Hence Kerr cells (see Fig. 11.8)
Contrast with linear electro-optic effect (Pockels effect)
observed only in anisotropic crystals (See Fig 11.6)

16

Chirality
Optical properties different for left or right circularly polarized
light due to chirality (helicity) of molecules or crystal
structure
Circular dichroism: different absorption for left or right
circular light
Optical activity: different refractive index for left or right
circular light.
Optical activity causes rotation of linear light: Examples:
dextrose, laevulose (fructose) [latin dexter, laevus]

d
( n nL )
R
amino acid

Magneto-optics
Induce chirality in non-chiral materials with a magnetic
field
magnetic circular dichrosim in absorbing materials
Faraday effect in transparent materials: rotation of linear
polarization by magnetic field
\$ = V B d ;
V = Verdet coefficient
B
"

input

output

Figure 2.16

17

## Appendix: Local field corrections

P
- - - - - - +
++
++++

Figure 2.8
local field applied field in dense medium
Lorentz correction:,
local = + P/30
in cubic crystal
Clausius Mossotti relationship
r 1 N a
=
r + 2
3

18

## Topic 3: Interband absorption

Interband transitions: direct and indirect
Direct gap materials
Optical orientation
Indirect gap materials
Photodetectors & solar cells

Interband absorption
Energy

upper band
Ef
Eg

!%
Ei
lower band

## Photon excites electron

from filled valence to
empty conduction band
Fundamental
absorption edge at Eg
Process creates an
electronhole pair
Figure 3.1

19

## Direct and Indirect absorption

(a) Direct band gap:
C.B. minimum at k = 0
E

Eg

Figure 3.2

## (b) Indirect band gap

C.B. minimum at k 0
E

conduction band

!%

!%

Eg

valence band
0

## kphoton = 2/ ~ 107 m1 negligible compared to B.Z. size /a ~ 1011 m1

Transitions appear as vertical lines on E k diagrams
Phonon needed to conserve momentum for indirect gap materials
Indirect absorption 2nd order process, therefore low probability

Figure 3.3

p antibonding
p

s antibonding
p bonding

Eg

conduction band
valence band

s bonding
ATOM

MOLECULE

CRYSTAL

## Four valence electrons per atom: Group IV (C, Si, Ge),

III-V compounds (GaAs, InAs, InSb, GaN .)
II-VI compounds (ZnS, ZnSe, CdSe, HgTe, . )
V.B. C.B. is p s, hence allowed transition

20

Energy (eV)

Figure 3.4

Eg

GaAs

!%

## Direct gap at 1.5 eV

Very important
optoelectronic material

-2
-4

!% > Eg

-6
L

Wave vector k

## fcc lattice Brillouin zone

kz

Symmetry points
000
X 100
010
001
K 110
L 111

L
,
X
kx

ky

Fig D.5

21

Four-band model
Figure 3.5

E
Electron (e)
band
Eg

Simplified band
structure first proposed
by Kane (1957)
valid near k = 0

"
k
Heavy holes (hh)

## Light holes (lh)

Split-off holes (so)

## ! Heavy hole transition

" Light hole transition
Split-off hole
transitions also possible

## InAs band edge absorption

2 (1012 m 2)

1.0

Figure 3.6

InAs
0.8 room temperature

## InAs is a direct gap

IIIV semiconductor
with Eg = 0.35 eV

0.6
0.4

!% < Eg : " = 0

0.2
0.0
0.3

0.4

0.5
Energy (eV)

0.6

!% > Eg :
" (!% Eg)1/2

22

Transmission (%)

Figure 3.7

45

germanium
300 K

40
35

## direct gap at 0.80 eV

B-Field quantizes motion
in direction perpendicular
to B

B = 3.6 T

30
25 B = 0
20

## Landau level absorption

when
0.86
!% = Eg + (n+) !%c
%c = eB / me
(cyclotron frequency)

15
0.78

0.80

0.82

0.84

Energy (eV)

## Spin injection (optical orientation)

E
Eg

|M12|2 MJ
hh transitions three
times stronger than lh

conduction band
J = 1/2

hh

&+

#!

lh

&+

&#

&#

lh

hh

so
so
valence band
#3/2

#1/2

+1/2

+3/2

N (+1/2) ! N (!1/2)
"=
N (+1/2) + N (!1/2)

E1 selection rule

m = 1 for
J = 3/2
J = 1/2
MJ

Figure 3.8

50% spin
polarization for
excitation

23

Absorption coefficient (m 1)

## Direct versus indirect absorption

Figure 3.9
106
105
104
103

Direct absorption is
much stronger than
indirect absorption

GaAs
silicon

102
1.0

1.2

Energy (eV)

## Silicon has indirect gap

at 1.1 eV
2.0
GaAs has direct gap at
1.4 eV

Energy (eV)

4
2 Eg = 0.66eV

Figure 3.10
direct gap

Indirect gap
at 0.66 eV

-2

Direct gap
at 0.80 eV

-4
-6

,
,
Wave vector k

24

40
20

0
0.6

60

10

291 K
phonon
emission

phonon
absorption

'1/2 (m#1/2)

80 (a)

20 K

0.7
0.8
Energy (eV)

0.9

(b) 300 K

8
6
4
2

germanium

Eg

0
0.6

0.7
0.8
Energy (eV)

Figure 3.11

0.9

at 300K :
Egind = 0.66 eV

Egdir = 0.80 eV

## (!% Egdir )1/2

direct absorption:

(108

2.5

Absorption coefficient

1)

Silicon absorption
2.0

E2
E1

1.5
1.0

silicon
300 K

Eg

0.5
0

## Indirect band gap

at 1.1 eV

4
6
Energy (eV)

10

Critical points
(van Hove
singularities) at E1
(3.2 eV) and E2
(4.3 eV)

Figure 3.12

25

## Silicon band structure

density of states g(E)
2 g(k) (dE/dk)1

Energy (eV)

4
Eg

E1

E2

## Critical points (van

Hove singularities)
whenever dE/dk = 0

-4
-8
-12
L

,
,
Wave vector k

occurs when
conduction and
valence bands are
parallel to each other:
Parallel band effect

Figure 3.13

Absorption spectroscopy

white-light
source

white-light
source

collimation lenses

scanning
monochromator

sample
in cryostat

reflection
detector

collection lenses

sample
transmission
detector
valve
vacuum pump

Figures 3.14-15

entrance slit
spectrograph
silicon
diode array
detector

computer

26

## p-i-n diodes (Appendix E)

p

Eg

Eg
Figs E.1-2

| eV0 |

li

li
z

z
Reverse bias V0 applied

V0 = 0

li

## Electric field E = (Vbi V0) / li

Vbi = built-in voltage Eg / e
V0 is negative in reverse bias

n
z

## Embed absorbing region within

p-n junction to form p-i-n diode

!%
Ipc

## Apply reverse bias V0

(i.e. V0 negative )

p
i

Photodetectors

Figure 3.16

V0

V0

li

## Electric field = (Vbi V0) / li

Vbi = built-in voltage Eg / e
Photons absorbed if !% > Eg
Creates electron-hole pairs in
i-region

Examples:
photodiodes
solar cells (V0 = 0)

## Carriers swept out by field

into external circuit to generate
photocurrent Ipc

27

!%

pi n

Ipc

R
+

Figure 3.17

V = Ipc R

ISC

Ipc

maximum
power

VOC

## Small gap: large ISC , small VOC

Large gap: small ISC , large VOC
Single junction: max efficiency ~30%
Larger for multi junction

## Solar cell efficiency

28

Topic 4: Excitons
Introduction
Wannier excitons
Excitonic nonlinearities
Frenkel excitons

Excitons

Figure 4.1

e
a

h
e

h
Free (Wannier)
small binding energy
moves freely through crystal

Tightly-bound (Frenkel)
large binding energy
localized on one lattice site

29

Figure 4.2

## Free exciton absorption

Hydrogenic series of
lines satisfying :
!% = Eg RX / n2

n=1
n=2

!% > Eg

(!% Eg)1/2
Eg

T ( RX / kB)

Photon energy

exciton,

0.8

21 K

0.4

(!% 1.425)1/2,

1.42

1.46

n=2

1.2

294 K

1.50

1.54

## Photon energy (eV)

standard purity sample
T = 21 K 294 K

(106 m 1)

(106 m 1)

1.2

n=1

Figs 4.3-4

n=3

0.8

RX

0.4
0

Eg
1.514

1.520

## Photon energy (eV)

ultra pure sample
T = 1.2 K
RX = 4.2 meV

30

Figure 4.5

## Field ionization in GaAs

F ~ 2 RX / e aX

Photocurrent

V0 = +1.00 V, 5 105 V / m
p
V0 i
n

li

aX

ionized if > F
T=5K

0
1.50

!%

V0= +1.44 V\$
0
1.51
1.52
Photon energy (eV)

GaAs parameters :
RX ~ 4.2 meV
aX ~ 13 nm
li = 1 m (typical)
F ~ 6 105 V / m
~ 1.5 106 V / m
for V0 = 0 !

Figs 4.6 - 7

GaAs, 1.2 K

## (a) Low density

Separation diameter

(106 m 1)

10
8
6
4
2
0
1.512
(b) High density
Separation diameter

low density
6 1022 m 3
2 1023 m 3

1.516

1.520

## Photon energy (eV)

NMott = [ (4/3)aX3 ]1
~ 1.1 1023 m 3 in GaAs

31

Frenkel excitons

Organic crystals

(108 m 1)

300 K

NaCl

Eg

LiF
Eg

10
12
14
Energy (eV)

Eg(eV) RX (eV)
NaCl 8.8
0.9
LiF
13.7
0.9

Absorption

Alkali halides
3

Figs 4.8 - 9

C16H10 (pyrene)

300 K
3.20

3.40
3.30
Energy (eV)

## Also: Rare gas crystals

(solid Ne, Ar, Kr, Xe)

32

Topic 5: Luminescence
Introduction
Photoluminescence
Electroluminescence
LEDs and lasers
Cathodoluminescence

Luminescence
Luminescence

## spontaneous emission in solids

Fluorescence

fast luminescence
electric-dipole allowed, R ~ ns
slow luminescence
electric-dipole forbidden, R ~ s ms

Phosphorescence

Electroluminescence
Photoluminescence
Cathodoluminescence

electrical excitation
optical excitation
cathode ray (ebeam) excitation

33

inject
electrons

NR

relaxation
EXCITED
STATE
R

Fig. 5.1

efficiency
total transition rate

!%
GROUND
STATE

R =

1
1 + R / NR

inject holes
Radiative transition rate determined by Einstein A-coefficient
R = A1
R determined by phonon population, number of traps etc

Eg

!%
holes

k=0 k
valence band

3.40

## Strong emission at the band gap

most III-V and II-VI semiconductors
linewidth kBT

Absorption

electrons

GaN
T = 4 K, Eg = 3.50 eV
Luminescence
intensity

conduction band
E

3.50
3.60
Energy (eV)

Figs 5.2 3

34

E

conduction band

phonon

Figure 5.4

electrons
Eg

!%
holes

valence band
k=0

## Low emission probability (2nd order process)

diamond, silicon, germanium, AlAs

Photoluminescence
E

electrons

conduction
band
Eg
hL

Figure 5.5

h
k
k=0

0
valence
band

holes
Density of states

## Excite using laser with photon energy > Eg

electrons and holes relax to the bottom of their bands
thermal distributions formed according to statistical mechanics
emission from Eg to top of carrier distributions

35

Classical (Boltzmann)Statistics
Figure 5.6
GaAs
T = 100 K
kBT = 8.6 meV
Eg = 1.501 eV

PL intensity (a.u.)

103
102
1.50

kBT
Eg

1.52

Rate |M|2 (h)

Energy (eV)

## Boltzmann statistics: f(E) exp(E/kBT) (occupancy factors)

I(E) Density of states fe(E) fh(E)
PL rises sharply at Eg, then decays exponentially. Linewidth ~ kBT

E
electrons
E Fc

Eg

EFv

holes
Density of states

Photoluminescence (a.u.)

Degeneracy

Figs 5.7 8

Ga0.47In0.53As, TL = 10 K
6nJ/pulse

Eg
0.80

250 ps
55 K

24 ps
180 K

0.90
1.00
Energy (eV)

## Degeneracy observed at high density and low temperatures

Emission from Eg to (Eg + EFc +EFv )

36

Photoluminescence spectroscopy
Photoluminescence (PL) spectroscopy
fixed frequency laser, measure spectrum
by scanning spectrometer

sample in cryostat
laser
mirror
PL

## PL excitation spectroscopy (PLE)

detect at peak emission,
vary laser frequency
effectively measures absorption

collection
lenses
entrance slit

Time-resolved PL spectroscopy
short pulse laser + fast detector

spectrometer

computer

detector

Electroluminescence
holes
p-type
n-type

electrons

h Eg
epitaxial
layers

substrate
current
V0

p
n

## Epitaxial growth of high

purity light-emitting layers on
substrate crystal
MBE, MOCVD, LPE .

## Forward-biassed p-n junction

Electrons and holes recombine at the
junction
photon energy ~ Eg
Figure 5.10

37

Lattice matching
substrate materials
SiC sapphire
hexagonal
AlN

## Band gap (eV)

6
4

GaAs
cubic

GaN

GaP

AlP

InP

GaAs
InN
InAs
3
4
5
Lattice constant ()

## direct band gap

indirect band gap

AlAs

visible
spectrum

InP

blue
red
fibre
optics
Figure 5.11

Figs 5.12 3

p
EFv

depletion
region

Eg

electrons
EFc

holes
(a) V0 = 0
p
eV0
(b) V0 +Eg/e

n
h = Eg

Electroluminescence

Junction electroluminescence
GaAs, Eg = 1.42 eV

1 mA
293 K
1.2

1.4
1.6
Energy (eV)

1.8

Emission at Eg
Operating voltage ~ Eg / e
Spectral width ~ kBT

38

Diode lasers

Figs 5.14 16

l
current
h
R2

Output
Gain , power ,

R1

oxide
p - AlGaAs
i - GaAs

n- GaAs
substrate

n - AlGaAs
Iin

Ith

light
output

th

metal contact

Iin

## Mirrors formed by facets (i.e. edges) of chip

Emission wavelength ~ hc / Eg
Linewidth determined by cavity modes

Cathodoluminescence
VACUUM
Primary electrons
few keV
back-scattered
electrons
penetration
depth (Re)
! 1 m
CRYSTAL

metal contact

electron
beam

Figure 5.17

## Focussed spot size ! 100nm

Primary electrons generate
secondary electrons in
excitation volume
Secondary electrons generate
eh pairs, hence luminescence
excitation
volume
cathodoluminescence

## Commercial use in cathode ray tubes

Research tool for investigating nanostructures:
Observe luminescence from electron microscope

39

40

## Topic 6: Quantum confinement

Dimensionality
Quantum wells
\$Energy levels
\$Optical transitions
\$Quantum confined Stark effect

Quantum dots
Carbon nanostructures

Fig. 6.1

Dimensionality
Dimensionality /
Confinement
bulk

2/1

quantum
well

1/2

quantum
wire

0/3

quantum
dot

Density of states

3 /0

Eg

Energy

41

## Semiconductor quantum wells

AlGaAs GaAs
crystal
growth
direction
z

e-

EgAlGaAs

EgGaAs

V.B.

h+
Single quantum well
growth
methods

substrate

## GaAs quantum wells

GaAs
substrate
C.B.

AlGaAs

b
C.B.

EgGaAs
V.B.

EgAlGaAs

MQW or superlattice

## Molecular beam epitaxy (MBE)

Metal-organic chemical vapour deposition (MOCVD)

## Infinite quantum well

E (h 2/8m*d 2)

Fig. 6.2

10

Fig. 6.3

n=3
kn = n/d

5
0
d/2

n=2

En = (!kn)2/2m* = (!22/2m*d2) n2

n=1

d/2

## symmetry about z = 0 wave functions have definite parity

n has (n1) nodes
En depends on m*, hence heavy and light holes split

42

Figs 6.45

## Finite quantum well

y = 0.85 (13.2-x2) / x

E2

n=2
n=1
z

E1
d 0 d
2
2

## Wave functions tunnel into the

barrier
wave function still identified by
parity and number of nodes
Confinement energy reduced
compared to infinite well
graphical solution to find En

y = tan(x)

8
y

V0

4
0
0

Example : GaAs/AlGaAs
V0 = 0.3 eV, d = 10 nm
mw*= 0.067me, mb*= 0.092me
E1 = 31.5 meV
c.f. infinite well: E1 = 57 meV

Figs 6.67

Optical transitions
quantum well

conduction band

!%

n=1
z

n=2

valence band

## Light polarized in x,y plane for normal incidence

Parity selection rule: n = even number
Infinite well selection rule: n = 0

43

Figs 6.89

conduction
E
band
Eg

!%

kxy

0
valence band

Absorption coefficient

2-D absorption

3-D
n=3

n=2
2-D
n=1
0
5
10
(!%#Eg) in units of (h 2/8d 2)

## Absorption density of states

Density of states constant in 2-D: g2D(E) = m / !2
Thresholds whenever ! exceeds (Eg + Een+ Ehn)
Band edge shifts to (Eg + Ee1+ Ehh1)

## GaAs quantum wells

GaAs/AlGaAs MQW
d = 10 nm

0.5
0.0

n=1 n=2
hh
hh lh
lh

hh lh
n=3

T=6K
1.6
1.8
2.0
2.2
Photon energy (eV)

(105 m 1)

Absorption (au)

## GaAs/AlAs MQW, d = 7.6 nm

1.0

Figs 6.1011

10 bulk
5

hh
lh

n=2

4
2

n =1 300 K

0
0
1.4
1.5
1.6
Photon Energy (eV)

## Excitonic effects enhanced in quantum wells: strong at room temp

Pure 2-D: RX2D = 4 RX3D
Typical GaAs quantum well: RX ~ 10 meV ~ 2.5 RX (bulk GaAs)
Splitting of heavy and light hole transitions

44

E

conduction band
J = 1/2

Eg

&+
0
hh

#!

&+

&#

lh

&#
lh

hh

so
so
valence band
3/2,

+1/2,

1/2,

Selection rules
+: m = +1,
: m = 1

+3/2,

J = 3/2
J = 1/2

MJ
Figure 6.12

Figure 6.13
(b) Ez = 107 V/m

e1
1455.0
7.4 hh1

1438.5

1800
1600
1400

1462.4

Energy (meV)

(a) Ez = 0

1447.9
9.4

200
10
0
10
Position (nm)

10
0
10
Position (nm)

## 10 nm GaAs / Al0.3Ga0.7As quantum well in an electric field

Eg (GaAs) = 1420 meV

45

pi n

!%

## GaAs MQW, d = 9.0 nm, 300 K

MQW

V0 Ez
photocurrent
Red shift of excitons
Excitons stable to high
fields (c.f. Fig 4.5)
Parity selection rule
broken
used to make modulators

## Photocurrent (arb. units)

hh1e1

lh1e1
hh2e2

(a) 0 V
1.5106 V/m

(b) 10 V
1.1107 V/m

hh1e2
hh2e1
1.4

1.5 1.6
Energy (eV)

1.7
Figs 6.1415

Figure 6.16

Emission spectrum
Zn0.8Cd0.2Se/ZnSe quantum well
PL intensity

d = 2.5 nm
300 K

0
2.4

10 K

2.5
2.6
2.7
Energy (eV)

Eg = 2.55eV (10K)
Eg = 2.45eV (300K)
Emission energy shifted from
Eg to (Eg + Ee1 + Ehh1)
Tune by changing d
Brighter than bulk due to
improved electron-hole overlap
Used in laser diodes and LEDs

46

Figure 6.17

Intersubband transitions
n-type quantum well
h

## Need z polarized light

Parity selection rule: ,
n = odd number

n=2
electrons
n=1

## Transition energy ~ 0.1 eV (~ 10 m, infrared)

Absorption used for infrared detectors
Emission used for infrared lasers (Quantum cascade lasers)

Quantum dots

Figure 6.18

Density of states

Bulk (3-D)
Quantum well (2-D)
Quantum wire (1-D)

## Quantum dot (1-D)

Eg

Energy

47

Quantum dots
Spherical dot
Cuboid dot

d
R

! 2
2
2\$
2 2 # n x n y n z &
E=
+
+
2m* #" d x2 d y2 d z2 &%

Density of states

E=

3-D

! 2 2\$
2 # Cnl &
2m* #" R2 &%

C10 = 1
C11 = 1.43
C12 = 1.83
C20 = 2
"

0
5
10
(E Eg) in units of (h 2/8d 2m*)

(a)

CdSe
10 K

D
C

Figure 6.20

(b)
6 nm

CdTe
300 K

5 nm

B
A

Energy (eV)

4 nm
1.6

Energy (eV)

## Found in semiconductor doped glass (Colour glass filters &

stained glass)
Available commercially

48

Figs 6.19, 21

m

InAs 200 nm
quantum dot

d shell

p shell

s shell

V(r)

h 2 2 nz2
2m*d z2

0
z

10 nm

GaAs
E

2, 1, 0, 1, 2,

dz

+ (n + 1)h0

dz a

Figure 6.22

## Quantum confined Stark effect

200 nm
aperture

200 m
spot

Spatially
resolved PL
Single QD

10 pA

PC
PL

Far field PL
~107 QDs

T = 10 K
1.25

1.30
1.35
Energy (eV)

1.40

2.6V

Bias voltage

T = 10 K

Photocurrent (pA)

(b)

1.250

0.6V

PL Intensity
(arb. units)

## PL Intensity (arb. units)

(a)

1.255
1.260
Energy (eV)

49

Figure 8.20

Carbon nanostructures
graphene

nanotube

## * Buckminster fullerene named after

architect R. Buckmintser Fuller

Fig. 8.21

## Graphene band structure

Ideal 2-D material
(a)

(b)

\$'

&

(c)

\$'

12

!%

16
20

EF

0
Energy (eV)

&

&
&

ky

kx
K

&

50

100

(a)

99
98
97
96
95

400

Transmission (%)

Figure 8.22

100

(b)

95
90
0

Wavelength (nm)

1 2 3 4 5
Number of layers

## After Nair et al. Science, 320, 1308 (2008).

Nanotube chirality
armchair
chiral
"

a2
a1

zig
za

## Quantum wire (1-D)

D.O.S.

Transmission (%)

Graphene transmission

(5,5)

Eg

Energy

(7,3)

(9,0)

Figure 8.23
chiral vector c = n1 a1 + n2 a2
Metallic if
n1n2 = 3m ; otherwise semiconductor

51

Nanotube transitions
E

semiconducting
nanotube

conduction band
emission
valence band

kz

density of states
E

E
conduction band

metallic
nanotube

kz

EF
valence band

density of states

Figure 8.24

s
m
E22 E11

## Energy gap (eV)

3
2
1
0
0

Es11
1
2
Tube diameter (nm)

## Normalized PL intensity (au)

SWNT ensemble
1.0

(7,5)
(8,3)
(9,1)

0.0
1.0

0.0

Figure 8.24-5

single
SWNTs
(9,1)
(8,3)
(7,5)
900 1000 1100 1200
Wavelength (nm)

52

S2(u)

S1(g)

1
0

1.2 ns

T1(g)

1.8 s
S0(g)
singlets

triplets

Absorption
(104 cm1)

Energy (eV)

(a)

Absorption

PL (a.u.)

(b)

4
Energy (eV)
3
S2
C60
2 S
1
1
0
2
3
4
5
Energy (eV)
Figure 8.27

53

54

## Topic 7: Free electrons

Free carrier reflectivity
Metals
Doped semiconductors
Plasmons (bulk & surface)
Negative refraction

Reflectivity

1.0
0.5
0.0

1
/ p

## Free electron effects observed in:

metals
doped semicondcutors

Fig 7.1

Key parameter:
Plasma frequency ,
p = (Ne2/0m0)1/2
Lightly-damped system,
r() = 1 p2/2,
R = 100% below p
transmitting above p
ultraviolet transparency
of metals

55

## The Drude model

!%p

Reflectivity

1.0

Aluminium
!%p = 15.8 eV,
= 3.6 107 1 m1

0.8
experimental data

0.6
0.4

=0
= 8.0 fs

0.2
0.0

Fig 7.2

r ( ) = 1

5
10
15
Energy (eV)

20

p2
2 + i
1/ 2

& Ne 2 #
!
p = \$\$
!

m
% 0 0"

## = 1/ = momentum scattering time = m0/Ne2, = DC conductivity

Reflectivity < 100% below p
Discrepancies caused by interband absorption transitions

## Interband transitions in Aluminium

Transition energy ~ 1.5 eV
Transitions from filled
states below EF to
empty states above EF

Energy (eV)

16
EF

12

## Very high density of

states for parallel bands

## parallel band effect

at the critical points

4
0

Wave vector k

K X

at 1.5 eV,
Fig 7.3

56

## Fig. 7.4, 7.6

Transition metals
E

1.0

optical
transitions
EF

copper

0.8
0.6
0.4
0.2

!%p

visible

Reflectivity

4s band

0.0
0 2 4 6 8 10 12 14
Energy (eV)

3d band
Density of states

## Inner d orbitals form narrow bands below the Fermi energy

threshold for optical transitions to outer half-full s band gives a
sharp absorption edge
hence characteristic colours of metals, eg copper, gold

Fig 7.5

2
0
-2
-4
-6
-8
W

## Integrated density of states

0
EF
3d
bands

X WK

Wave vector k

8 10

2
0
-2
-4
-6
copper
3d and 4s bands -8

Energy (eV)

Energy (eV)

## minimum transition energy

~ 2.2 eV (560 nm)

0
2
4
6
Density of states (states eV 1)

57

Fig 7.7

Doped semiconductors
n-type InSb at 300 K

Reflectivity (%)

100

4.0 1024
2.8 1024
1.2 1024
6.2 1023
3.5 1023

80
60
40
20
0

Plasma frequency ,
p = (Ne2/0rm*)1/2

10
20
30
Wavelength (m)

## Control plasma frequency by varying the doping density

Plasma edge in the infrared

Fig 7.8

## Free carrier absorption

E
!k 2
E=
2me*
EF

scattering
process
!%

free carrier =

Ne 2
m * 0 nc 2

k
Transitions from filled states below EF to empty ones above EF
2 /
Scattering process required to conserve momentum
Continuous infrared absorption in doped semiconductors

58

Fig 7.9

E
EF

"! #\$

!!

,
hh band
lh band

SO band

## Infrared absorption in p-type semiconductors

Impurity transitions

Fig. 7.10

## Impurity levels: En = (m*/m0)(1/r2) RH / n2

n conduction band

conduction band
donor
levels

2
1

n
2
1

n-type
material
valence band
(a) low temperature:
infrared absorption

valence band
(b) high temperature:
band tail below Eg

59

Absorption (103 m 1)

## Donor absorption in n-type silicon

Phosphorous doped Silicon

1.0

2p0

2p

3p
3p0
4p0

4p
5p

0
32

34 36 38 40 42
Photon energy (meV)

N = 1.2 10 20 m3
T = 4.2 K
me* ~ 0.5 m0
r = 12
R* ~ 45 meV

44

*
1 %
* me 1
RH
simple model: h = R &1 2 # , R =
m0 r 2
' n \$
complications due to effective mass anisotropy
*(

Fig. 7.11

Plasmons

k
Quantized plasma waves: i.e. longitudinal
oscillations of the electron plasma at p
Fig. 7.12

60

sample
!%p
Ein

Eout
!%p

## Metals: !%p ~ 320 eV

observe by electron energy
loss spectroscopy :
Eout = Ein n!%p
Ein ~ keV
Figs 7.12-13

## Doped semiconductors: !%p ~ 10 meV

Measure by Raman scattering:
!%out = !%in n!%p
plasmon
emission

plasmon
absorption

-400 -200 0
200 400
Energy shift (cm 1)
n-type GaAs, T = 300 K
N = 1.8 10 23 m3
!%p = 19 meV (150 cm1)

Surface plasmons
z

dielectric

dielectric: (d
z=0

k
metal: (m

Ezd (z)

Ez
Ezm (z)

###

+++

###

metal

+++

## Surface waves at boundary between

metal and insulator
Plasmonics: propagate energy as
surface plasmons in nano-circuits
Cannot couple directly to free-space
photons due to wave vector
mismatch: hence need for couplers
(e.g. gratings)
Figs 7.14 - 15

61

%

bulk

% = ck

%p

0
0

!sp =

(a)

1 ck /%p 2

!p

(b)

surface
% = ckx /(d

%p
%sp
0

1 ckx /%p 2

1+"d

Fig. 7.16

## Localized surface plasmons

MesoGold
pure gold
nanoparticles
suspended in
water

Absorption (a.u.)!

1.2!
0.8!

Courtesy
M. Sugden
T. Richardson

0.4!
0.0!
300!

Wavelength (nm)!

Fig. 7.17

## Colloidal gold is not gold coloured !

Localized plasma oscillations at surface of metal nanoparticles
sp ~ p/((d+2) i.e. p/3 for air-metal boundary, but varies
somewhat with size and shape

62

Negative refraction
r
II

= i)
)>0

n>0
)=0

n<0
)=0

= i)
)>0

III

n=1
"i

Figs 7.18 - 19
n<0
"r

perfect lens
)r
IV

## Need both (r and r to be negative

i.e. region III
Not possible in natural materials:
hence need metamaterial

metamaterial

63

64

Topic 8: Phonons
(Chapter 10)
Infrared active phonons
Reststrahlen
Inelastic light scattering
\$ Raman scattering

Lattice absorption
, k

## Resonant absorption when

photon frequency and wavevector match the phonon , q

, q

## Only possible for optical

phonons of ionic or polar
(partly ionic) crystals

photon

Frequency

optical branch

## Phonon must be transverse:

hence TO phonons involved
acoustic branch

Figs 10.12

## Resonance occurs in the

infrared ~ 10 100 m

65

TO phonon resonance
= 0eiqz

Figure 10.3

x+

x
TO phonon modes of ionic crystals: positive and negative ions
move in opposite transverse directions
This generates transverse electric field waves
Light resonates with these modes when the wave vectors and
frequencies match

Reststrahlen

Figure 10.4

## 100% reflectivity between TO and LO

Lyddane-Sachs-Teller relationship: lO / TO = (st / )1/2

40
20
0
-20

TO 2
2

TO

(a)

8 10 12 14
Frequency (THz)

Example:
TO = 10 THz
LO = 11 THz

Reflectivity

r ( ) = + ( st )

st = 12.1
= 10

1.0
(b)

0.0

8 10 12 14
Frequency (THz)

66

Infrared reflectivity
Reflectivity

1.0

0.0

InAs

Figure 10.5

GaAs :
TO = 273.3 cm1
LO = 297.3 cm1

GaAs

InAs :
TO = 218.9 cm1
LO = 243.3 cm1

200
240
280
Wave number (cm 1)

## Reststrahlen band observed between TO and LO

reflectivity less than 100% due to damping
damping caused by anharmonic phonon decay. Typical lifetime ~ 10 ps

Figs 10.6 7

Polaritons

## Polariton = coupled TO phonon polarization wave & photon wave

anticrossing of photon and TO phonon modes when ~ TO
modifies the dispersion of both photons and TO phonons
52
= v q

10

= vst q
LO / 2

upper branch

Calculated: TO / 2 = 10 THz,
st = 12.1, = 10

48
44

TO / 2

0
0.0
1.0
2.0
Wave vector q (106 m 1)

!\$LO

lower branch

40

Energy (meV)

/ 2 (THz)

20

36
0

1
2
3
Wave vector (106 m 1)
Raman scattering data on GaP

67

Polarons

Fig. 10.8

## free electron in a polar solid

produces a local lattice distortion
through the electron-phonon
coupling ep
modifies the effective mass to :
m** = m*(1 ep/6)1

## Polaron effects are small in III-V s (e.g. ~ 1% in GaAs) but increase as

the crystal becomes more ionic.
Organic conductors show strong polaron effects

## Inelastic light scattering

2 , k2
1 , k1
,q

Fig. 10.9

Conservation laws:
,1 = 2 ; k1 = k2 Q
Stokes scattering:
phonon emission (+ sign)
Anti-Stokes scattering:
phonon absorption ( sign)
Ianti-Stokes / IStokes = exp(!\$/kBT)

## Raman scattering: scattering from optical phonons

Brillouin scattering: scattering from acoustic phonons
Qmax = 2k ~ 106 m1 for back-scattering geometry
can only probe small wave vector phonons
Scattering can also be observed from plasmons, magnons etc

68

Fig. 10.10

laser beam

computer

scanning
laser
double
scattered
spectrometer
light

sample
in cryostat

#
CCD array
detector

collection
lenses

Fig. 10.11

## Raman signal (a.u.)

TO

200

LO
Raman scattering from TO
and LO phonons in various
III-V semiconductors using
a Nd:YAG laser at 1.06 m

GaAs
InP

1cm1 = 3 1010 Hz
= 0.124 meV

AlSb
300 K

GaP

300
400
Energy shift (cm 1)

69

Figs 10.12 13

## Klemens channel (see Klemens 1966)

1 , q1
3 , q3
1 , q1
3 , q3
2 , q2
3 phonon processes
caused by anharmonicity
in the crystal

Frequency ()

2 , q2

TO

optical
branch

TO
2
0

acoustic
branch

0
Wave vector (q)

acoustic phonons

70

## Topic 9: Nonlinear optics

(Chapter 11)
Definitions
Resonant vs non-resonant nonlinearities
Second-order nonlinearities
\$frequency doubling
\$electro-optics

third-order nonlinearities

Nonlinear susceptibility
D = 0 E + P 0 r E
P = 0 (1) E + 0 (2) E2 + 0 (3) E3 + .
% r = 1 + (1) + (2) E + (3) E2 + .
(n) = nth order nonlinear susceptibility,
(2) = 0 in materials with inversion symmetry (centrosymmetric)
ie:

## all isotropic materials (gases, liquids, glasses)

+ some crystals (eg NaCl)

## optical properties depend on the light intensity

needs large electric fields (ie high power lasers)

71

P

P
P(t)

(a)

,
t,

(b)
t

sine wave
output

(t),
small amplitude
sine wave input

Figure 11.1

P(t)

t,

(t),
large amplitude
sine wave input

distorted output
contains terms
at 2, 3 etc

## laser is tuned to the transparency region of crystal

far from resonance with any atomic transitions

N2
u

N1

Figs. 11.2-3

I(z)

I dI
dz

## laser is tuned to resonance with an atomic transition

stimulated emission reduces net absorption rate at high intensity
equivalent to Pauli blocking of upper state
saturable absorption: (I) = 0 / (1 + I / Is) ; Is = saturation intensity
(I) 0 2 I at small I ; 2 = 0 / Is
r I E2 third-order nonlinearity

72

## Second order nonlinear effects

Pi(2) = 0 jk (2)ijk Ej Ek
2

(a)

## (2) = 0 in centrosymmetric crystals

2

(b)

1+2

1 2

Fig. 11.4

Process
Frequency mixing
Frequency doubling
Down conversion

Input
1, 2
,
1

Ouptut
, 1 + 2
2,
2, 1 2,

Phase matching

(2)

k2

## Phase matching condition: 2k = k2

(conservation of momentum)
2 n() / c = n(2) 2 / c
n() = n(2)
not usually possible due to dispersion.
use a birefringent crystal with optic axis at angle :\$

1
no ( ) 2

sin 2
ne ( 2 ) 2

cos 2
no ( 2 ) 2

73

use a

2nd

nonlinear
crystal

## order nonlinear crystal

266 nm
2, 4,

nonlinear
crystal
,
2,

Nd:YAG laser
1064 nm

532 nm
2,

3,

355 nm

,
nonlinear
crystal

Figure 11.5

Electro-optic modulators
y
45

y'

z
x

E-O crystal
polarizer

output

x'

input

crossed
polarizer

## Linear electro-optic (Pockels) effect:

Field-induced birefringence: n rij E
rij = electro-optic coefficient
0 for non centro-symmetric crystal
Consider as (2) process with DC field
Use to make intensity modulators

Figure 11.6

74

## Third-order nonlinear processes

1
1+2+3
2
3
(a) Four-wave mixing

,
,
,

3,

## (d) Raman effect

Figure 11.7

Kerr cells
polarizer
input

Kerr
medium

crossed
Kerr polarizer
medium

crossed
polarizer
output

output

polarizer
E

input
E
laser pulse

Field-induced birefringence: n (3) E 2
Occurs even in isotropic materials (eg glass, liquids)
DC Kerr effect: rotate polarization with DC field
Optical Kerr effect: induce birefringence with light pulse

Figure 11.8

75

## Nonlinear refractive index

n(I) = n0 + n2 I

r = (3) E2
n = n2 I
n2 = (3) / n02 c 0

## Third order nonlinear effects found in all materials

including isotropic media e.g. glasses, liquids, gases
self-phase modulation: = 2 n L / = 2 n2 I L / ,

Figure 11.9

## soliton: balance dispersion

and self-phase modulation
propagation of high intensity
short pulses along optical fibres

Semiconductor nonlinearities

## strong Pauli blocking when

!% ~ Eg
saturable absorption
third order nonlinearity
excitonic enhancements

(103 cm 1)

Eg

40
30
20

GaInAs/InP MQW
exciton

10
0

(103 cm 1)

Figs. 11.10-11

300 K
0.7

0.9

1.1 E (eV)

6700
8
(I) =
+ 2000
1 + I / 290
6
4
2
E = 0.77 eV
0
10 102 103 104 105
I (W cm 2)

76

Fig. 11.12

15
10

3.5 eV

0
1.26545

1.26550

1.26555

Peak absorbance

102
103
104
0.1

Energy (eV)

10 100 1000
Power (nW)
N2

## Tune laser to QD exciton

Behaves as saturable two-level atom

N1

2
1

77