Phys 446:

Solid State Physics / Optical

Properties
Lattice vibrations:
Thermal, acoustic, and optical properties

Fall 2015

Lecture 4 Andrei Sirenko, NJIT 1

Solid State Physics

Lecture 4
Last weeks:
(Ch. 3)
• Diffraction from crystals
• Scattering factors and selection rules for diffraction

Today:
• Lattice vibrations: Thermal, acoustic, and optical
properties
This Week:
• Start with crystal lattice vibrations.
• Elastic constants. Elastic waves.
• Simple model of lattice vibrations – linear atomic chain
2
• HW1 and HW2 discussion

1
 Material to be included in the 1st QZ

• Crystalline structures. Diamond structure. Packing ratio

7 crystal systems and 14 Bravais lattices
• Crystallographic directions n
and Miller indices d hkl  12
 h2 k 2 l 2 
 2  2  2 
a b c 
• Definition of reciprocal lattice vectors:

• What is Brillouin zone

• Bragg formula: 2d·sinθ = mλ ; k = G

• Factors affecting the diffraction amplitude:

Atomic scattering factor (form factor): f a   n(r )e ik rl d 3 r
reflects distribution of electronic cloud.
sin Δk  r 
r0
In case of spherical distribution f a   4r 2 n(r ) dr
0
Δk  r

• Structure factor F   f aj e
2i ( hu j  kv j  lw j )

where the summation is over all atoms in unit cell

• Be able to obtain scattering wave vector or frequency from

geometry and data for incident beam (x-rays, neutrons or light)

2
 Material to be included in the 2nd QZ
TBD

Elastic stiffness and compliance. Strain and stress: definitions and

relation between them in a linear regime (Hooke's law):
 ij   Cijkl  kl  ij   Sijkl kl
kl kl

 u Ceff  u x Ceff
• Elastic wave equation:
2 2
 sound velocity v 
t 2  x 2 

• Lattice vibrations: acoustic and optical branches

In three-dimensional lattice with s atoms per unit cell there are
3s phonon branches: 3 acoustic, 3s - 3 optical
• Phonon - the quantum of lattice vibration.
Energy ħω; momentum ħq
• Concept of the phonon density of states
• Einstein and Debye models for lattice heat capacity.
Debye temperature

Low and high temperatures limits of Debye and Einstein models

• Formula for thermal conductivity 1
K  Cvl
3
• Be able to obtain scattering wave vector or frequency from
geometry and data for incident beam (x-rays, neutrons or light)
6

3
 7

Elastic properties
Elastic properties are determined by forces
acting on atoms when they are displaced from
the equilibrium positions

Taylor series expansion of the energy near

the minimum (equilibrium position):

U 1  2U
U ( R)  U 0  ( R  R0 )  ( R  R0 )  ...
R R0 2 R 2 R0
U
For small displacements, neglect higher terms. At equilibrium, 0
R R0

So, ku 2  2U
U ( R)  U 0  where k
2 R 2 R0
8
u = R - R0 - displacement of an atom from equilibrium position

4
 U
force F acting on an atom: F   ku
R
k - interatomic force constant. This is Hooke's law in simplest form.
Valid only for small displacements. Characterizes a linear region in which the
restoring force is linear with respect to the displacement of atoms.

Elastic properties are described by considering a crystal as a homogeneous

continuum medium rather than a periodic array of atoms
In a general case the problem is formulated as follows:

• Applied forces are described in terms of stress ,

• Displacements of atoms are described in terms of strain .
• Elastic constants C relate stress  and strain , so that  = C.

In a general case of a 3D crystal the stress and the strain are tensors

Stress has the meaning of local applied “pressure”.

Applied force F(Fx, Fy, Fz)  Stress components ij (i,j = 1, 2, 3)
x  1, y  2, z  3
General case for stress: i.e ij
 ij
Fj 
x j

 ij
V
 Fi dV  
V
x j
dV    ij dS j
S

Shear forces must come in pairs: ij = ji (no angular acceleration)
 stress tensor is diagonal, generally has 6 components
10

5
Stress has the meaning of local applied “pressure”.
Applied force F(Fx, Fy, Fz)  Stress components ij (i,j = 1, 2, 3)
x  1, y  2, z  3
General case for stress: i.e ij  ij
Fj 
x j

Hydrostatic pressure – stress tensor is equivalent to a

scalar: i.e xx =yy =zz

 p 0 0 
ˆ  [ ij ]  0  p 0 
 
0 0  p 

Stress tensor is a “field tensor” that can have any symmetry not
related to the crystal symmetry. Stress tensor can change the
crystal symmetry
11

Stress has the meaning of local applied “pressure”.

Applied force F(Fx, Fy, Fz)  Stress components ij (i,j = 1, 2, 3)
x  1, y  2, z  3
Compression stress: i = j, i.e xx , yy , zz

Fx
 xx 
Ax

Shear stress: i ≠ j, i.e xy , yx , xz zx , yz , zy

Fy
 yx 
Ax

Shear forces must come in pairs: ij = ji (no angular acceleration)
12
 stress tensor is diagonal, generally has 6 components

6
 Strain tensor ui
3x3  ij 
x j

In 3D case, introduce the

displacement vector as
u = uxx + uyy + uzz
Strain tensor components are defined as
 xx 0 0 u x
 xx 
  x
ˆ  [ ij ]  0  yy 0 
u
0 0    xy  x
 zz  y
V ' dV Share deformations:
  xx   yy   zz  Tr (ˆ )
dV  xx   yy   zz  Tr (ˆ )  0
Can be diagonalized in x-y-z coordinates at a
ˆ certain point of space
In other points the tensor is not necessarily 13
diagonal

Strain tensor components are defined as

ui
 ij 
x j

u x
 xx 
x

u x
 xy 
y

Since ij and ji always applied together, we can

define shear strains symmetrically:

1  ui u j 
 ij   ji    
2  x j xi 


So, the strain tensor is also diagonal and has 6 components

14

7
 Elastic stiffness (C) and compliance (S) constants
relate the strain and the stress in a linear fashion:  ij   Cijkl  kl
kl
This is a general form of the Hooke’s law.
 ij   Sijkl kl
6 components ij, 6 ij  36 elastic constants kl

Notations: Cmn where 1 = xx, 2 = yy, 3 = zz, 4 = yz, 5 = zx, 6 = xy

For example, C11 Cxxxx , C12 Cxxyy , C44 Cyzyz
Therefore, the general form of the Hooke’s law is given by

15

Elastic constants in cubic crystals

Due to the symmetry (x, y, and z axes are equivalent) C11 = C22 = C33 ;
C12 = C21 = C13 = C31 = C23 = C32 ; C44 = C55 = C66
Also, the off diagonal shear components are zero:
C45 = C54 = C46 = C64 = C56 = C65
and mixed compression/shear coupling does not occur:
C45 = C54 = C46 = C64 = C56 = C65

 the cubic elastic stiffness

tensor has the form:

only 3 independent constants

16

8
 Elastic constants in cubic crystals

Longitudinal compression  xx F A
C11  
(Young’s modulus):  xx u L
L

Transverse expansion:  xx
C12 
 yy

Shear modulus:  xy F A
C44  
 xy 

17

Uniaxial pressure setup

for optical characterization of correlated oxides
Pressure control
•Variables:

Uniaxial pressure
Temperature
External magnetic field

Measured sample properties:

Far-IR Transmission / Reflection

Optical Raman scattering
cryostat

sample
Low T

18

9
 Elastic waves
Considering lattice vibrations three major approximations are made:
• atomic displacements are small: u << a , where a is a lattice
parameter
• forces acting on atoms are assumed to be harmonic, i.e.
proportional to the displacements: F = - Cu
(same approximation used to describe a harmonic oscillator)
• adiabatic approximation is valid – electrons follow atoms, so that
the nature of bond is not affected by vibrations

The discreteness of the lattice must be taken into account

For long waves  >> a, one may disregard the atomic nature –
solid is treated as a continuous medium.
Such vibrations are referred to as elastic (or acoustic) waves.

19

Elastic waves
First, consider a longitudinal wave of compression/expansion

mass density 
segment of width dx at
the point x;
elastic displacement u

 2u 1 F  xx
    where F/A = xx
t 2 A x x
Assuming that the wave propagates along the  xx  C11 xx
[100] direction, can write the Hooke’s law in the form
u  2 u C11  2 u x
Since  xx  x get wave equation: 
x t 2  x 2 20

10
A solution of the wave equation - longitudinal plane wave
u ( x, t )  Aei ( qx t ) where q - wave vector; frequency ω = vLq

C11
vL  - longitudinal sound velocity

Now consider a transverse wave which is controlled by shear stress
and strain:

In this case

 2u  xy u
  where  xy  C44 xy and  xy 
t 2 x x
- transverse
 wave equation is  2u C44  2u x C44 sound velocity
 vT 
t 2  x 2  21

Two independent transverse modes: displacements along y and z

For q in the [100] direction in cubic crystals, by symmetry the
velocities of these modes are the same - modes are degenerate

Normally C11 > C44  vL > vT

We considered wave along [100]. Ceff

In other directions, the sound velocity depends v
on combinations of elastic constants: 
Ceff - an effective elastic constant. For cubic crystals:

Relation between ω and q - dispersion relation. For sound ω = vq

22

11
 Model of lattice vibrations
one-dimensional lattice: linear chain of atoms

harmonic approximation:
force acting on the nth atom is

equation of motion (nearest neighbors interaction only):

 2u
M 2  Fn  C (un 1  un )  C (un 1  un )  C (2un  un 1  un 1 )
t
M is the atomic mass, C – force constant
Now look for a solution of the form u ( x, t )  Aei ( qxn t )
where xn is the equilibrium position of the n-th atom  xn = na

obtain
23

 the dispersion relation is

Note: we change q  q + 2/a the atomic displacements and

frequency ω do not change  these solutions are physically identical

 can consider only

i.e. q within the first Brillouin zone

The maximum frequency is 2 C

M 24

12
 25

At the boundaries of the Brillouin

zone q = /a  un  A(1) n e  it
standing wave
Phase and group velocity

phase velocity is defined as v p 
q
d C qa
group velocity vg  vg  a cos
dq M 2
vg = 0 at the boundaries of the Brillouin zone (q = /a) 
26
no energy transfer – standing wave

13
 27

Long wavelength limit:  >> a ; q = 2/ << 2/a  qa << 1

small q - close to the center of Brillouin zone

4C qa C
 sin  qa - linear dispersion
M 2 M

C
v p  vg  a - sound velocity for the one dimensional lattice
M

28

14
 Diatomic lattice

one-dimensional linear chain, atoms of two types: M1 and M2

Optical Phonons
can interact with light

For diamond
Optical phonon
frequency is  1300 cm-1
 7700 nm
29
(far-IR)

Model of diatomic lattice

one-dimensional linear chain, atoms of two types: M1 and M2

Treat in similar way, but

need two equations of
motion:

Again, look for a solution of the form u n  A1e i ( qna t )

u n 1  A2 e i ( q ( n 1) a t )
30
Substitute this solution into equations of motion

15
get system of two linear equations for the unknowns A1 and A2

In matrix form:

determinant of the matrix must be zero 

Solve this quadratic equation, get dispersion relation:

Depending on sign in this formula there are two different

solutions corresponding to two different dispersion curves
31

Note: the first Brillouin zone is now

from -/2a to +/2a

The lower curve - acoustic branch, the upper curve - optical branch.
at q = 0 for acoustic branch ω0 = 0; A1 = A2
 the two atoms in the cell have the same amplitude and the phase
dispersion is linear for small q

for optical branch  1 1 

0  2C    M1A1 +M2A2 = 0
at q = 0  M1 M 2 
 the center of mass of the atoms remains fixed. The two atoms move out of
32
phase. Frequency is in infrared – that's why called optical

16
 33

34

17
35

36

18
 37

Summary
 Elastic properties – crystal is considered as continuous anisotropic
medium
 Elastic stiffness and compliance tensors relate the strain and the
stress in a linear region (small displacements, harmonic potential)
Hooke's law:  ij   Cijkl  kl  ij   Sijkl kl
kl kl
 Elastic waves  u Ceff  u x
2 2 sound velocity Ceff
 v
t 2  x 2 
 Model of one-dimensional lattice: linear chain of atoms
 More than one atom in a unit cell – acoustic and optical branches
 All crystal vibrational waves can be described by wave vectors
within the first Brillouin zone in reciprocal space
What do we need? 3D case consideration
38
Phonons. Density of states

19
HW1
Compute the theoretical density of NaCl based on its crystal structure.

Cl- For NaCl structure, the

crystal lattice parameter is
Na+ a a= 2 ( r Na+ + r Cl -),
where r is ionic radius.

a M 4(A Na  A Cl )
 
V a3 NA
4 ions (22.99  35.45) g/mol

2[(0.102x10  0.181x10  7 )]cm3 (6.023x10 23 )ions/mol
7

 2.14 g/cm 3
(actual  2.16g/cm 3 )
39

Vibrations in three-dimensional lattice.

Phonons
Phonon Density of states
Specific heat

(Ch. 3.3-3.9)

40

20
 Three-dimensional lattice
In simplest 1D case with only nearest-neighbor interactions we had
equation of motion solution
u
2
M  Fn  C (un 1  un )  C (un 1  un ) u ( x, t )  Aei ( qxn t )
t 2
In general 3D case the equations of motion are:

 2 u n
M   Fnm
t 2
m ,

N unit cells, s atoms in each 

3N’s equations
Fortunately, have 3D periodicity 
Forces depend only on difference m-n
Write displacements as
1
u n i ( x , t )  ui (q)ei ( qrn t )
M 41

substitute into equation of motion, get

1
  2ui (q)   Fnmij e iq(rm rn )u j (q)  0
M M
, j m

Dij ( q ) - dynamical matrix

  2ui (q)   Dij (q)u j (q)  0

,j phonon dispersion
curves in Ge

 
Det Dij (q)   2 1  0 
- dispersion relation
3s solutions – dispersion branches
3 acoustic, 3s - 3 optical
direction of u determines polarization
(longitudinal, transverse or mixed)
42
Can be degenerate because of symmetry

21
 Phonons
• Quantum mechanics: energy levels of the harmonic oscillator are quantized
• Similarly the energy levels of lattice vibrations are quantized.
• The quantum of vibration is called a phonon
(in analogy with the photon - the quantum of the electromagnetic wave)
Allowed energy levels of the harmonic oscillator:
where n is the quantum number
A normal vibration mode of frequency ω is given by u  Aei ( qr t )
mode is occupied by n phonons of energy ħ momentum p = ħq
Number of phonons is given by Planck function: 1
(T – temperature) n 
e  kT  1
The total vibrational energy of the crystal is the sum of the energies of the
individual phonons:
(p denotes particular
43
phonon branch)

44

22
45

46

23
 Density of states
Consider 1D longitudinal waves. Atomic displacements are given by:
u  Aeiqx
Boundary conditions: external constraints applied to the ends
Periodic boundary condition:
Then eiqL  1  condition on the admissible values of q:
2
q n where n  0 ,  1,  2 , ...
L
ω
regularly spaced points, spacing 2π/L
dω
Number of modes in the L
dq
interval dq in q-space : 2
Number of modes in the frequency
range (ω, ω + dω): L dq q
D( )d  dq
2
D(ω) - density of states
47
determined by dispersion ω = ω(q)

Density of states in 3D case

Now have
iq y L
Periodic boundary condition: eiq x L  e  eiq z L  1
 l, m, n - integers

Plot these values in a q-space,

obtain a 3D cubic mesh
number of modes in the spherical
shell between the radii q and q + dq:

V = L3 – volume of the sample

 Density of states 48

24
 Few notes:
• Equation we obtained is valid only for an isotropic solid,
(vibrational frequency does not depend on the direction of q)
• We have associated a single mode with each value of q.
This is not quite true for the 3D case: for each q there are 3 different
modes, one longitudinal and two transverse.
• In the case of lattice with basis the number of modes is 3s,
where s is the number of non-equivalent atoms.
They have different dispersion relations. This should be taken into
account by index p =1…3s in the density of states.

49

Lattice specific heat (heat capacity)

Defined as (per mole) C 
dQ
If constant volume V
dT
The total energy of the phonons at temperature T in a crystal:

E   nqp  p (q)  0 (the zero-point energy is chosen as the

q, p
origin of the energy).

1
n  - Planck distribution Then
e  kT  1
replace the summation over q by an integral over frequency:

Then the lattice heat capacity is:

50
Central problem is to find the density of states

25
 Debye model
• assumes that the acoustic modes give the dominant contribution
to the heat capacity
• Within the Debye approximation the velocity of sound is taken a
constant independent of polarization (as in a classical elastic
continuum)
The dispersion relation: ω = vq, v is the velocity of sound.
In this approximation the density of states is given by:
Vq 2 1 Vq 2 1 V 2
D( )   
2 2 d dq 2 2 v 2 2 v 3
Need to know the limits of integration over ω. The lower limit is 0.
How about the upper limit ? Assume N unit cells is the crystal, only
one atom in per cell  the total number of phonon modes is 3N 
13 Debye
 6 2 v 3 N 
  D  
V
 
  v 6 2 n
13
frequency
51
 

The cutoff wave vector which corresponds to this frequency is

modes of wave vector larger than qD are not

allowed - number of modes with q ≤qD
exhausts the number of degrees of freedom

Then the thermal energy is

where is "3" from ?

where x ≡ ħω/kBT and xD ≡ ħωD/kBT ≡ θD/T

Debye temperature:

52

26
 The total phonon energy is then

where N is the number of atoms in the crystal and xD ≡ θD/T

To find heat capacity, differentiate

So,

In the limit T >>θD, x << 1,  Cv = 3NkB - Dulong-Petit law

53

Opposite limit, T <<θD : let the upper limit in the integral xD  

Get

 within the Debye model at low

temperatures Cv  T3

The Debye temperature is

normally determined by
fitting experimental data.

Curve Cv(T/θ) is universal

– it is the same for
different substances
54

27
 Einstein model
The density of states is approximated by a δ-function at some ωE :
D(E) = Nδ(ω – ωE) where N is the total number of atoms –
simple model for optical phonons

Then the thermal energy is

The heat capacity is then

The high temperature limit is the same as that for the Debye model:
Cv = 3NkB - the Dulong-Petit law

At low temperatures Cv ~ e-ħω/kBT - different from Debye T3 law

Reason: at low T acoustic phonons are much more populated  the
55
Debye model is much better approximation that the Einstein model

Real density of vibrational states is much more complicated than those

described by the Debye and Einstein models.
This density of states must be taken into account in order to obtain
quantitative description of experimental data.

The density of states for Cu.

The dashed line is the Debye
approximation.
The Einstein approximation
would give a delta peak at
some frequency.

56

28
 Summary
 In three-dimensional lattice with s atoms per unit cell there are
3s phonon branches: 3 acoustic, 3s - 3 optical
 Phonon - the quantum of lattice vibration.
Energy ħω; momentum ħq
 Density of states is important characteristic of lattice vibrations;
It is related to the dispersion ω = ω(q). 2
Vq 1
Simplest case of isotropic solid, for one branch: D ( ) 
2 d dq
2

 Heat capacity is related to the density of states.

 Debye model – good when acoustic phonon contribution dominates.
At low temperatures gives Cv  T3
 Einstein model - simple model for optical phonons (ω(q) is constant)
 At high T both models lead to the Dulong-Petit law: Cv = 3NkB
 Real density of vibrational states is more complicated 57

29