Phonons II.

Thermal Properties

Introduction to Solid State Physics 8/e

Kittel
Phonons: dominate thermal properties of materials and affect the electrical
transports of conductors by scatterings of electrons

Phonon generations: 1. external perturbations

2. scattering of particles
3. thermal

thermal : a system with energy level En,

⇒ probability of occupancy at temperature T

 En 
P( En )  exp  
 k BT 
Boltzmann factor (p41)
Boltzmann factor: 一權重因子，決定在溫度T時，處於熱力學平衡下，多狀
態系統中狀態i的相對機率。 exp (- Ei/ kBT)
Boltzmann factor不是機率，要表示成機率要做歸一。
將狀態i的Boltzmann factor除以系統所有可能狀態的Boltzmann factor之和Z

Plank distribution

在某一個mode中有s個phonon存在的情形，此狀態能量Es = sℏ

配分函數 Z = ∑ exp (- sℏ/ kBT) = 1/(1-exp(- ℏ/ kBT))

( x = exp (- sℏ/ kBT) < 1, ∑xs =1/(1-x) )

系統處於具能量狀態sℏ的機率 P(s) = exp ((- sℏ/ kBT) / Z

Phonon數的熱平均值 <s> = ∑sP(s) = 1/Z (∑ s exp ((- sℏ/ kBT))

= 1/(exp (ℏ/ kBT) -1)
=1/kBT
phonons
  1 s
Excitation level amplitude (n) with energy  n  
 2
 1 
 ( s  ) 
 Es   s exp  k T 
2
s sP Es  s exp  k BT  s 

B 

Average of phonons n   
s P( Es )    Es  

1 
( s  ) 
 k T
s  B  s exp  k 2T 
 B

 
d
  exp(  sx )
dx s

 exp( sx )
s


x (p44)
k BT

Plank’s distribution of <n> (average number of phonons excited per mode at )

1
n 
  
exp  1
 k BT 
普朗克分布 (Planck Distribution)
三種統計分布函數
 mod e
Thermal energy U   i
ni i

  dD( ) n( ) 

  dD( )
  
exp   1
 k BT 

D(): density of modes (states) - uniform in k space

1D D(k): density of states = number of states per unit k at k
D(k)dk: number of states from k to k+dk
Plank’s distribution of <n> (average number of phonons excited per mode at )
1
n 
  
exp  1
 k BT 

D(): density of modes (states)

1D D(k): density of states = number of states per unit k at k
D(k)dk: number of states from k to k+dk
Summary 4/21
A linear chain of length L carries N+1 particles with separation a
Boundary condition: u0(t)=0 (s=0) and uN(t)=0 (s=N)

 
us (t )  u exp  ik , pt sin( ska) where k 
 2 3 4
,
L L
,
L
,
L
,....
( N  1)
L

One mode for each interval k 
L

The number of modes per unit range of k

L 
D(k )  for k
 a

0 for k
a

(p41)
 Unbounded medium but with periodic solution over the distance L
For a large system, periodic boundary conditions u(sa)=u(sa+L)


us (t )  u exp i(ska k , pt )  where k  0,
2 4 6
L
,
L
,
L
2
One mode for each interval k 
L
L  
The number of modes per unit range of k D( k )  for  k
2 a a
L =0 otherwise
D(k )dk  dk
2
dk
D( )d  2 D(k )dk  2 D(k ) d
d

dk 2 D(k ) 2 D(k )
The number of modes per unit frequency range D( )  2 D(k )  
d d vg
dk
 4C  ka 
1D monatomic lattice  sin  
M  2

 Na 
2 
2 D( k )  2  N M max
2
D( )   
d 4C a  ka   C max
2
2
cos 
dk M 2  2

Total number of modes

4C
 /a max
L 2 M
N  D(k )dk 
 / a
2 a
  D()d   D()d
0 0
2D lattice: periodic boundary condition- N2 primitive cells within a square of side L

exp[i(k x x  k y y)]  exp[i(k x ( x  L)  k y y( x  L))]

2 4 6
k x , k y  0, , , ,....
L L L
2
1  2  L2
   2
One mode per unit area in k space:
k x k y  L  4

Number of modes with wave vector from k to k + dk in k space:

1 L2
D(k )dk  dkx dky  2 2kdk
k x k y 4
D( k ) A 1
The number of modes per unit frequency range: D( )   2 2k
d 4 vg
dk
 D(k ) V 2 1
3D lattice: D( )   3 4k
d 8 vg
dk

D()d  D(k )d 3k for each polarization

⇒ find dispersion relation and count all k values with each

frequency
 Continuum waves:
=vgk depending only on amplitude of k
2
V    d 
2 2
V  V
D( )d  D(k )d k  3 4k dk  2
3 2
 2 d
8 2  vg  v
 g 2 vg
3

The number of modes per unit frequency range for each polarization:
V 2
2
D( )  2 a quadratic dependence
2 vg 3
 Thermal energy:
 
D
 
V 
2
 
U   dD( ) n( )    d 2 3  
2 v g      
0
 exp 
 
  1 
  k BT  
each polarization

Three polarizations: 2 transverse and 1 longitudinal

 
D
 
   3V  k BT  D  
3 4x
3V x3
U  2 3  d    3    
dx  
2 vg 0      2 vg    0  exp( x)  1 
2

 exp k T   1 
  B  

x
k BT
Classical model: equipartition theorem
0.5 kBT for each excitation mode
3 translation + 3 vibration modes ⇒ 6 degrees of freedom

U= N 6 (0.5kBT) = 3N kBT
for N atoms in the crystal
Cv = 3NkB
Dulong Petit Law
Einstein model (1907): N identical oscillators of frequency 
3N
U  3N n  
exp / k BT   1
exp / k BT 
2
U   
CV  3 Nk 
B

 exp / k T   12
T
V
 B 
k T B

2
      
At low T, CV  3Nk B   exp 
 k BT   k BT 
At high T, CV  3NkB

At low T, there are systematic deviations between data and

Einstein model.
⇒ The oscillations of a solid are far from single frequency.
Debye T3 model:
Assume continuum elastic phonon mode only up to some cutoff
frequency D V 2
D( )  ,   D
2 vg
2 3

0 ,   D

Number of phonon mode for each polarization is equal to N

D D
V 2
N   dD( )   d 2 3
0 0 2 vg

1/ 3
 6 2vg 3 N 
Debye frequency D   
 V 
 
1/ 3
D  6 N 
2
Debye wave vector k D    
vg  V 
D
Debye temperature  D 
kB
D, D depend on Vg, n, ~ Vgn1/3

At very low temperature, T<< D, XD= D/T  


x3 4
0 dx( e x 1)  15

3 4 Nk BT 4
4 xD
3V  k T  x3
U 2 3 B 
2 vg    0 dx( e x  1) U
5 D
3

3
 T 
3X
D
xe 4 x 12 4 Nk BT 3  T 
CV    
CV  9 NkB  
 D 

0
dx
e x
1 
2
5 D
3
234 Nk B
 D 

(p45)
Define Debye temperature D

1/ 3
D   6 vg N 
1/ 3
vg  6 N 
2 3 2
D     
kB k B  V 
 kB  V 

D  D
xD  
k BT T
3  /T
 T  D
 x3 
U  9 NkBT  
 D 

0
dx 
 exp( x)  1 
total phonon energy
 U  3V   D  3 
 
 2 2v 3  T  0
CV  V  d 
T  g   exp( / k BT )  1 
 3V    1 D  exp( / k BT )
4
 T 
3X
D
x 4e x
 
 2 2v 3  k B  T 2  0
    d  9 NkB    dx
 g 
(exp( / k B T )  1) 2
  D  0 
e x
 12

D
x  1
T
 x3  1 
XD 3
 
0  e x  1  3
dx    x D 3

1
 D

3 T 
1  D 
XD 3
x 4e x
dx 
1
 x 
0 e x  1 2 3 D 3  T 
3

 

T>>D, T<<D,

U 3NkBT CV  T3

CV 3NkB (p46)
Only long wave length acoustic modes are thermally excited.
These modes can be treated as an elastic continuum.
The energy of short wavelength modes is too high to be populated significantly
at low temperatures.
 T3 at low temperatures
Debye and Einstein modes

T/D
Idea to understand T3 dependence:
kB
Total phonon mode:    D (or k  kD  D )
v

Each mode has energy kBT

3
 T 
U ~ 3N   k BT
 D 
3
 T 
CV ~ 12 NkB    T 3
 D 
General result for D(): the number of states per unit frequency

dS: an element of area on the

surface in K space of selected
constant frequency 

Density of states
Lattice vibrations: mode (k, )
k is in BZ,
(k): dispersion relation
D(): density of states
E(): (n+1/2)ħ

1
Phonons: number n n  

e k BT
1

Thermal properties:
Thermal energy U   dD( ) n( ) 
dU
Heat capacity CV 
dT
Plank distribution

在某一個mode中有s個phonon存在的情形，此狀態能量Es = sℏ

配分函數 Z = ∑ exp (- sℏ/ kBT) = 1/(1-exp(- ℏ/ kBT))

系統處於具能量狀態sℏ的機率 P(s) = exp ((- sℏ/ kBT) / Z

Phonon數的熱平均值 <s> = ∑sP(s) = 1/Z (∑ s exp ((- sℏ/ kBT)) = 1/(exp (ℏ/ kBT) -1)

D(): density of modes (states)

D(k)dk: number of states from k to k+dk
1D lattice

1 L2
2D lattice D(k )dk  dkx dky  2 2kdk
k x k y 4
D(k ) V 1
3D lattice: D( )   3 4k 2
d 8 vg
dk
From an harmonic term in binding potential

U 1  2U 1  3U
U ( x)  U ( x0 )  x 0 ( x  x0 )  x 0 ( x  x0 ) 
2
( x  x0 )3  .....
x 2 x 2 6 x 3
x0

1  2U 1  3U
U ( x)  U ( x)  U ( x0 )  x 0 ( x  x0 ) 
2
( x  x0 )3  .....
2 x 2 6 x 3
x0

Reset the equilibrium, let displacement x-x0  x

harmonic term
anharmonic term
  
 U ( x)   cx 2  gx 3  fx4 
dxx exp  k BT  dxx exp  k BT


x    
 U ( x)   cx 2  gx 3  fx4 
dx exp  
 k BT 
 dx exp  k BT


 cx 2  gx 3  fx4   cx 2   gx 3 fx4   cx 2  gx 3 fx4 
exp    exp   exp    exp  1   
 k BT   B 
k T  B
k T k B 
T  B 
k T k BT k B 
T
x 2 x3
e  1  x    .....
x

2! 3!

high T limit
Transport properties (non-equilibrium)
• Vibration: Ultrasonic attenuation  excite single phonon mode
 measure decay of amplitude
• Energy: Thermal conduction  apply temperature gradient 
measure heat current by phonons

Phonon thermal conductivity:

Apply temperature gradient T
 Determine heat current density jU

the flux of the thermal energy: the energy transmitted across unit area
per unit time, : thermal conductivity coefficient

Solids: heat is transported by phonons and free electrons

Metals: electronic contribution dominates the thermal conductivity
Propagations of phonons

Ballistic: no interaction, no scattering

in harmonic approximation, in perfect, infinite crystal
 no scattering  phonon modes are uncoupled

d
v  vg 
dk

Diffusion: phonons scatter random through crystal

phonons scatter in real crystal
scattering processes with boundary, defect, phonon-phonon

d
v  v g 
dk
The flux of thermal energy is based on that the process of thermal
energy transfer is a random process.
The energy diffuses through the crystal suffer frequent collisions.
Ballistic: jU  T across the whole sample

dT
Diffusive: jU  T  local
dx
jU: [Watt/m2]

jU

Thermal conductivity for diffusion is
 T 
affected by phonon properties, scattering, crystal quality, temperature
: [Watt/m/K]
Kinetic theory of gases:
consider phonons as gases
calculate diffusion in the presence of temperature gradient T
Fick’s law: dn dn dT n: concentration of molecules

dx dT dx C: heat capacity per unit volume = nc
vg = phonon velocity
l = phonon mean free path = vg
At low temperatures, l  L (sample’s
size)
Phonon propagation ~ ballistic
 = (1/3)vglCV ~ vgLCV
  CV  T3

At intermediate temperatures,
 = (1/3)vglCV = (1/3)vg2CV
 ~ eD/T
CV = constant =3NkB
Phonon-phonon scattering
Phonon displaces atom which changes the force constant C  scatter other
phonons ⇒ three phonon process (p50)

Normal Umklapp
processes processes