Instructor:

Welcome to
Andrei Sirenko
Associate Professor at the Dept. of Physics, NJIT

Phys 446: http://web.njit.edu/~sirenko

Solid State Physics / Optical 476 Tiernan

Properties Office hours: After the classes or by appointment

973-596-5342
Class Schedule:

Fall 2007 Friday 2:30pm - 5:25pm | TIER-108

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Course Elements:
Textbooks:
M. A. Omar, “Elementary Solid State Physics”, Addison-Wesley, 1993.

Plan for today: Charles Kittel, Introduction to Solid State Physics, 8th Edition, Wiley, 2004.

Supplemental texts:
• H. Ibach, H. Lüth, “Solid-State Physics. An Introduction to Principles of Materials
Science”, Springer, 2003.
• J. S. Blakemore, "Solid State Physics”, Third Edition, Cambridge University Press,
1985
• Introduction to the Course • P. Yu and M. Cardona, “Fundamentals of semiconductors”
• N. W. Ashcroft and N. D. Mermin, “Solid State Physics”

• Crystals Lecture Slides

Demonstrations in the Experimental Lab at NJIT

• Lab tour – Raman Scattering in Diamond

– High-Resolution X-ray Diffraction in Silicon wafer
– Transmission in InP-based multilayer device structure
– Micro-beam Photoluminescence in InGaAsP-based waveguide device structure

Grade Components:
– Homework: 10 %
– Research project: 10 %
– Two in-class exams: 15% each;
– Final exam: 50%

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 Course Goals:
This course integrates theory of Solid State Physics with experimental
demonstrations in the Research Physics Lab. The course will provide a
valuable theoretical introduction and an overview of the fundamental
applications of the physics of solids. This course includes theoretical description
of crystal and electronic structure, lattice dynamics, and optical properties of
different materials (metals, semiconductors, dielectrics, magnetic materials and
superconductors), based on the classical and quantum physics principles.
Several advanced experiments of X-ray diffraction, Raman Scattering,
Photoluminescence, etc., will be carrier out in the Research Physics Lab
followed by their theoretical discussion.

To help you with your research projects and future jobs

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Outline of the course:

• I. Crystal structure, symmetry and types of chemical bonds. (Chapter 1)
• The crystal lattice
• Point symmetry
• The 32 crystal classes
• Types of bonding (covalent, ionic, metallic bonding; hydrogen and van der Waals).

• II. Diffraction from periodic structures (Chapter 2)

• Reciprocal lattice; Brillouin zones
• Laue condition and Bragg law
• Structure factor; defects
• Methods of structure analysis
• HRXRD. Experimental demonstration in the Physics Lab using Bruker D8 Discover XRD

• III. Lattice vibrations and thermal properties (Chapter 3)

• Elastic properties of crystals; elastic waves
• Models of lattice vibrations
• Phonons
• Theories of phonon specific heat; thermal conduction.
• Anharmonicity; thermal expansion
• Raman Scattering by phonons. Experimental demonstration in the Physics Lab using Ar-laser/SPEX 500M, CCD –based Raman Scattering setup

• IV. Electrons in metals (Chapters 4–5)

• Free electron theory of metals
• Fermi Statistics
• Band theory of solids

• V. Semiconductors (Chapters 6–7)

• Band structure.
• Electron statistics; carrier concentration and transport; conductivity; mobility
• Impurities and defects
• Magnetic field effects: cyclotron resonance and Hall effect
• Optical properties; absorption, photoconductivity and luminescence
• Basic semiconductor devices
• Photoluminescence. Experimental demonstration in the Physics Lab using Nd:YAG laser/SPEX –based Photoluminescence setup

• VI. Dielectric properties of solids (Chapters 8)

• Dielectric constant and polarizability (susceptibility)
• Dipolar polarizability, ionic and electronic polarizability
• Piezoelectricity; pyro- and ferroelectricity
• Light propagation in solids

• VII. Magnetism (Chapters 9)

• Magnetic susceptibility
• Classification of materials; diamagnetism, paramagnetism
• Ferromagnetism and antiferromagnetism
• Magnetic resonance
• Multiferroic Materials

• VIII. Superconductivity (Chapter 10)

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 Scope and Requirements
Lectures:
¾ Presentation of the concepts and techniques of SSP.
¾ Demonstrations.
¾ Lecture quiz (periodically)
Required for Phys-774
¾ Lectures are not a substitute for reading the textbook
and independent literature search
Read ahead; you’ll get more from lecture.
¾ Slides will be posted on the course web.
Use these as a study guide/note taking aid
PHYS 432 (E&M-I )

Familiarity with basic principles of quantum mechanics

(Schrödinger equation, wave function, energy levels, spin)

Knowledge of basics of statistical physics (classical statistics,

Bose-Einstein and Fermi-Dirac statistics)

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Exams:
There will be two in-class exams and a final exam.
Homework
• Allowed to use lecture notes and formula sheets.
• Assignments (10 in total) will be due weekly, usually on Fridays. • Not allowed to discuss the problems with other students.
Assignments are due at the beginning of class.
• Homework problems, lectures, and text readings will form the Academic honesty
basis of the exam problems.
Students are encouraged to:
Project • discuss the lectures and textbook material
• work together on homework problems
Students will perform a research project on a selected topic of • study together for exams
contemporary solid state physics (of their choice) by reviewing
scientific journal articles focusing on the effect chosen. A formal But not allowed to:
report (~7 pages) will be required. • present other people’s work as your own (including copying
another student's homework as well as using of problem
solutions found in the Internet or elsewhere)
• discuss problems or questions during exams
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 Today: crystal structures
Lecture 1-1

“…What do you know about crystals ?

“They make nice chandeliers !?..”

Superman Returns

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Today: crystal structures (Omar Ch. 1.1.-1.6.)

Crystal: atoms are arranged so that their positions are periodic in all
three dimensions
Atoms are bound to one another →
well defined equilibrium separations;
many identical atoms →
minimum energy requires every
identical atom to be in
identical environment → 3D periodicity rn = n1 a1 + n2 a2 + n3 a3
Ideal crystal: perfect periodicity

Real crystals are never perfect:

•surface
•impurities and defects
•thermal motion of atoms (lattice vibrations)
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 Lecture 1 Andrei Sirenko, NJIT 17 Lecture 1 Andrei Sirenko, NJIT 18

Basic definitions
The periodic array of points is called crystal lattice.
For every lattice point there is a group of atoms (or
single atom) called basis of the lattice
a3
Don't confuse with a1, a2, a3 - basis vectors
parallelogram formed by the basis vectors – a2
unit cell a1
if a unit cell contains only one lattice point, it is
called a primitive cell (minimum volume)

Bravais lattices – all lattice points

are equivalent

2D case – 5 Bravais lattices in the next slide

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 7 crystal systems and 14 Bravais lattices in 3D
triclinic monoclinic orthorhombic
a≠b≠c a≠b≠c a ≠ b ≠ c, α = β = γ = 90°
P C P C I F

tetragonal rhombohedral cubic hexagonal

a = b ≠ c, (trigonal) a = b = c, a = b ≠ c,
α = β = γ = 90° a = b = c, α = β = γ = 90° α = β = 90°
P I α = β = γ ≠ 90° P I F γ = 120°
simple cubic bcc
fcc

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simple cubic

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Lecture 1 Andrei Sirenko, NJIT 25 Lecture 1 Andrei Sirenko, NJIT 26

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 Lecture 1 Andrei Sirenko, NJIT 29 Lecture 1 Andrei Sirenko, NJIT 30

Examples Elements of symmetry

In addition to periodicity (translation) each lattice can have other
rock salt perovskite (e.g. BaTiO3) diamond (Si, Ge)
symmetry properties:
zincblende (GaAs ...)
• Inversion center I
• Reflection (mirror) plane
• Rotation axes. Only 2-, 3-, 4-, and 6-fold rotations are compatible
with translation invariance
• Rotation-inversion axes
Point symmetry
Every crystal lattice may be described by a particular
What are the Bravais lattices for these structures?
combination of symmetry operations determined by symmetry of
How many atoms are in the basis, and what are their positions?
the basis and the symmetry of the Bravais lattice.
fcc cubic fcc There are 32 crystal classes (point groups)
Combining with translational symmetries, one obtains 230
space groups
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 Elements of symmetry Symmetry group example: C3v
• Inversion center I • Inversion center I
• Reflection (mirror) plane • Reflection planes: 3
• Rotation axes. Only 2-, 3-, 4-, and 6-fold rotations are compatible • Rotation axes. Only 3- fold rotation
with translation invariance
• Rotation-inversion axes

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Symmetry group example: O (cube) Symmetry group example: O (cube)

• Inversion center I • Inversion center I
• Reflection planes • Reflection planes
• Rotation axes total: 24 elements (48 with i: Oh ) • Rotation axes total: 12 elements

Lecture 1 Andrei Sirenko, NJIT 35 Lecture 1 Andrei Sirenko, NJIT 36

 Notation for crystallographic directions and planes: Summary
Miller indices (see demonstration)
• A crystal lattice is a periodic array of the points related by
Crystal directions: rn = n1 a1 + n2 a2 + n3 a3 [n1 n2 n3]
translation operation: rn = n1 a1 + n2 a2 + n3 a3
If there are several equivalent directions: 〈 n1 n2 n3 〉 • To form a crystal, we attach to every lattice point an
identical group of atoms called basis

Crystal planes:
• 7 crystal systems and 14 Bravais lattices
• 32 crystal classes (point symmetry groups)
If a plane intercepts the axes at x, y, z and basis vectors are a, b, c,
• Crystallographic directions and Miller indices; dhkl
then one can obtain three numbers
⎛a b c⎞
⎜⎜ , , ⎟⎟
⎝x y z⎠ Continue with interatomic forces and types of bonds in solids
and reduce to the set of smallest integers (hkl) – Miller indices -
represent a set of parallel planes
If there are several equivalent nonparallel sets of planes: {hkl}
Lecture 1 Andrei Sirenko, NJIT 37 Lecture 1 Andrei Sirenko, NJIT 38

Some examples of reciprocal lattices

Reciprocal lattice
1. Reciprocal lattice to simple cubic lattice
Constricting the reciprocal lattice from the direct lattice:
a1 = ax, a2 = ay, a3 = az V = a1·(a2×a3) = a3 ⇒
Let a1, a2, a3 - primitive vectors of the direct lattice; T = n1a1 + n2a2 + n3a3
Then reciprocal lattice can be generated using the primitive vectors b1 = (2π/a)x, b2 = (2π/a)y, b3 = (2π/a)z ⇒
reciprocal lattice is also cubic with lattice constant 2π/a

2. Reciprocal lattice to bcc lattice

a(x − y + z )
1
a (− x + y + z )
1 a2 =
where V = a1·(a2×a3) is the volume of the unit cell a1 =
2 2
We have bi·aj = δij
a(x + y − z ) V = a1 ⋅ a 2 × a 3 = a 3
1 1
a3 =
2 2
2π
⇒ b1 = (y + z ) b 2 = (x + z ) b 3 = 2π (x + y )
2π
a a a
Lecture 1 Andrei Sirenko, NJIT 39 Lecture 1 Andrei Sirenko, NJIT 40
 2π
got b1 = (y + z ) Brillouin zones
a
Determine all the perpendicular
bisecting planes in the reciprocal
2π
b2 = (x + z ) lattice
a
First Brillouin zone - the Wigner-
2π
b3 = (x + y ) Seitz cell of the reciprocal lattice
a
but these are primitive Second Brillouin zone: Higher Brillouin zones:
vectors of fcc lattice

So, the reciprocal lattice to bcc is fcc.

Analogously, show that the reciprocal lattice to fcc is bcc

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Brillouin zones of cubic lattices

Summary

First BZ of bcc lattice ™ Reciprocal lattice is defined by primitive vectors:

First BZ of fcc lattice

™ A reciprocal lattice vector has the form G = hb1 + kb2 + lb3

It is normal to (hkl) planes of direct lattice
™ First Brillouin zone is the Wigner-Seitz primitive cell of the
reciprocal lattice
™ Simple cubic → cube; bcc → Rhombic dodecahedron;
fcc → truncated octahedron (figures on the previous slide)

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 Solid State Physics Interatomic forces
Lecture 1-2
What holds a crystal together?
Attractive electrostatic interaction
We already know:
between electrons and nuclei –
• crystal lattice; 7 crystal systems; 14 Bravais lattices the force responsible for
cohesion of solids
• 32 point symmetry groups (crystal classes)
• Crystallographic directions and Miller indices; dhkl

Interatomic potential V
Force:
equilibrium ∂V ( R )
position F ( R) = −
∂R
R0
CONTINUE with: F(R) < 0 for R > R0 :
Inter-atomic forces and types of bonds in solids. attraction
F(R) > 0 for R < R0 :
binding energy repulsion
Lecture 1 Andrei Sirenko, NJIT 45 Lecture 1 Interatomic distance R NJIT
Andrei Sirenko, 46

Types of bonding II. Covalent crystals

I. Ionic crystals – Electron pair bond: usually one electron from each atom
Usually involve atoms of strongly different electro-negativities – Electrons tend to be localized in part between the two atoms
(Example: alkali halides). – The spins of electrons in the bond are anti-parallel
αe 2 A – Gap between fully occupied and unoccupied states → dielectrics
U ( R) = − N +N n or semiconductors
4πε 0 R R
Directionality of covalent bonds. Example: carbon
attractive Hybridization. 2s22p2 → 2s2px2py2pz : sp3 tetrahedral configuration
(Coulomb) repulsive
Also possible sp2: 2s2px2py – planar (graphite, fullerenes)
Ionic bond is strong remaining pz : interlayer π-bonding
(binding energy - few eV/pair)
Covalent polar bond (many compound semiconductors) –
⇒ hardness, high melting T
intermediate case between non-polar and ionic bond. Described by
electrons are strongly localized effective ionic charge or fractional ionic character (between 0 and 1:
⇒ insulators in solid form 0 for Si or diamond, 0.94 for NaCl). Covalent bond is also strong,
KCl: energy per molecule vs R
Typical crystal structures: NaCl, CsCl (from Kittel) binding energies of several eV per atom
Lecture 1 Andrei Sirenko, NJIT 47 Lecture 1 Andrei Sirenko, NJIT 48
 III. Metals
Hexagonal and fcc close packed structure
– Most elements in periodic table
– High electrical and thermal conductivity
– High density
hcp fcc
– Considerable mechanical strength, but plasticity

These properties can be explained considering the metallic type of bond

Example: alkali metals – single electron weakly bound to atom – easily
delocalized.
In contrast to covalent bonding, electronic wave functions are very extended
compared to interatomic distances. Why total energy is reduced ?
Partially occupied electronic bands – electrons can move freely
Group II metals – two s electrons – should be fully occupied...
but overlapped with empty p-states
Transition metals: d-electrons are more localized – form covalent-like bonds; s both have coordination number 12 –
and p-electrons again form a common band maximum possible for spheres
Metals crystallize in closely packed structures (hcp, fcc, bcc)
Lecture 1 Andrei Sirenko, NJIT 49 Lecture 1 Andrei Sirenko, NJIT 50

IV. Van der Waals bonds Summary

Inert gases: outer electronic shells are full – no ionic or covalent forces
Weak interatomic forces due to quantum fluctuations of charge → arising
dipole moments cause a weak attractive force
Can be described in the quantum-mechanical model of two linear oscillators
(given in Kittel) → results in R-6 dependence of potential
Binding energy in order of 0.1 eV
Crystal structures are fcc (electronic distribution is spherical, atoms pack as
closely as possible)
Van der Waals forces are also responsible for bonding in organic molecular
crystals. Molecules are weakly bound; often form low-symmetry crystals
They also exist in covalent or ionic crystals, but negligible
V. Hydrogen bonds
Formed between two strongly electronegative atoms (F, O, N) via H
Example: ice Binding energy is also ~0.1 eV
Lecture 1 Andrei Sirenko, NJIT 51
™Repulsive interaction between atoms is primarily due to
electrostatic repulsion of overlapping charge distributions and
Pauli principle
™Several types of attractive forces:
• Ionic crystals – electrostatic forces between "+" and "-" ions
• Covalent bond: overlap of charge distributions with
antiparallel spin
• Metals: reduction of kinetic energy of electrons in free state
compared to the localized state of a single atom
• Secondary forces (Van der Waals, hydrogen) become
significant when the other bonds are impossible, e.g. in inert
gases
™Physical properties are closely related to the type of bonding
Lecture 1 Andrei Sirenko, NJIT 52
 Indexing system for crystal
planes
Condensed Matter Physics • Since crystal structures are
obtained from diffraction
Crystals (continued) experiments (in which
particles diffract from
planes of atoms), it is useful
to develop a system for
Andrei Sirenko indexing lattice planes.
• We can use the lattice
constants a1, a2, a3, but it
turns out to be more useful
to use what are called Miller
Indices.
Index
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Rules for determining Miller Indices Examples of Miller Indices

• (1) Find the intercepts on
the axes in terms of the
An example:
lattice constants a1, a2, a3.
• (2) Take the reciprocals
of these numbers and then
reduce to three integers
having the same ratio,
usually the smallest of the Intercepts: a, ∞,∞
three integers. The result, Reciprocals: a/a, a/∞, a/∞ Intercepts: a, a,∞ Intercepts: a,a,a
= 1, 0, 0 Reciprocals: a/a, a/a, a/∞ Reciprocals: a/a, a/a, a/a
listed as (hkl), is called the Miller index for this plane : (1 0 0) = 1, 1, 0 = 1, 1, 1
index of the plane. (note: this is the normal vector for this plane) Miller index for this plane : (1 1 1)
Miller index for this plane : (1 1 0)
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 Examples of Miller Indices
Intercepts: 1/2a, a,∞
Reciprocals: 2a/a, a/a, a/∞
= 2, 1, 0
Miller index for this plane : (2 1 0)
Lecture 1 Andrei Sirenko, NJIT 57
Notes on notation
• (hkl) might mean a single plane, or
a set of planes
• If a plane cuts a negative axis, we
have minus signs in the (hkl) (ie.
(hkl))
• Planes are denoted with curly {001} face
brackets (hkl)
• A set of faces are denoted {hkl}
• The direction of a crystal (for
example, along x for a cubic crystal)
is denoted with [uvw] (ie. The [100]
direction)
• In cubic crystals, the direction [hkl] [100]
is perpendicular to the plane (hkl) direction
having the same indices, but this
isn’t necessarily true for other
crystal systems
[001] direction
Lecture 1 Andrei Sirenko, NJIT 58

Examples of common structures: NaCl structure

(1) The Sodium Chloride (NaCl) Structure (LiH,
MgO, MnO, AgBr, PbS, KCl, KBr) Crystal a
• The NaCl structure is FCC LiH 4.08 Å
• The basis consists of one Na atom and
one Cl atom, separated by one-half of
MgO 4.20
the body diagonal of a unit cube
• There are four units of NaCl in each
MnO 4.43
unit cube NaCl 5.63
• Atom positions:
a
• Cl : 000 ; ½½0; ½0½; 0½½ AgBr 5.77
Na: ½½½; 00½; 0½0; ½00
• Each atom has 6 nearest neighbours of PbS 5.92
the opposite kind
KCl 6.29
Often described as 2
interpenetrating FCC
KBr 6.59
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 (2) The Cesium Chloride (CsCl)
structure CsCl structure
(CsBr, CsI, RbCl, AlCo, AgZn, BeCu, MgCe, RuAl, SrTl)
Crystal a
• The CsCl structure is BCC
BeCu 2.70 Å
• The basis consists of one Cs
atom and one Cl atom, with AlNi 2.88
each atom at the center of a CuZn 2.94
cube of atoms of the opposite
kind CuPd 2.99
• There is on unit of CsCl in each AgMg 3.28
unit cube LiHg 3.29 a
• Atom positions:
NH4Cl 3.87
• Cs : 000
• Cl : ½½½ (or vice-versa) TlBr 3.97
• Each atom has 8 nearest CsCl 4.11 Why are the a values smaller for the
neighbors of the opposite kind CsCl structures than for the NaCl (in
TlI 4.20
general)?
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Closed-packed structures
Closed-packed structures
• There are an infinite number of ways to
organize spheres to maximize the packing
fraction.

The centers
of spheres
at A, B, and
C positions
(from Kittel)

There are different ways you can pack spheres together. This shows two ways,
one by putting the spheres in an ABAB… arrangement, the other with ACAC….
(or, what does stacking fruit have to do with solid state physics?) (or any combination of the two works)
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 (3) The Hexagonal Closed-packed (HCP)
The FCC and hexagonal closed-packed structures (HCP) are
structure formed from packing in different ways. FCC (sometimes called
Be, Sc, Te, Co, Zn, Y, Zr, Tc, Ru, Gd,Tb, Py, Ho, Er, Tm, Lu, Hf, Re, Os, Tl the cubic closed-packed structure, or CCP) has the stacking
arrangement of ABCABCABC… HCP has the arrangement
• The HCP structure is made up of stacking spheres in a ABABAB… ABABAB…. [1 1 1]
[0 0 1]
configuration
• The HCP structure has the primitive cell of the hexagonal lattice, with a basis of FCC
two identical atoms HCP (CCP)
• Atom positions: 000, 2/3 1/3 ½ (remember, the unit axes are not all (looking
perpendicular) along [111]
• The number of nearest-neighbours is 12. direction

Rotated
three times
ABAB ABCABC
sequence sequence

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Conventional HCP unit cell

HCP and FCC structures

Crystal c/a
He 1.633
• The hexagonal-closed packed Be 1.581
(HCP) and FCC structures both Mg 1.623
have the ideal packing fraction of
0.74 (Kepler figured this out Ti 1.586
hundreds of years ago) Zn 1.861
• The ideal ratio of c/a for this Cd 1.886
packing is (8/3)1/2 = 1.633 (see
Problem 3 in Kittel) Co 1.622
• Why aren’t these values perfect Y 1.570
for real materials? Zr 1.594
• Why would real materials pick
HCP or FCC (what does it matter Gd 1.592
if they pack the same?) Lu 1.586
Lecture 1 Andrei Sirenko, NJIT 67