4 - Phonon II Thermal Properties

Solid State Physics
Phonon II
Thermal Properties
- Lattice Heat Capacity
- Density of State (DOS)
- Einstein and Debye Model
- Thermal Conductivity
1
2023 Fall K. H. Kao 高國興
Experimental Heat Capacity C
- C (T  0) = aT + bT3 for metal. C (T  0) = bT3 ≡ Clat for insulator.
- In 1819 Dulong and Petit experimentally found that specific Clat
for many substances are close to a constant value at high temperature.
Dulong-Petit value ≈ 25 J mole–1 K–1
Heat Capacity (× 104 J kilomole-1K-1)

Solid Ar
Einstein Temperature
2 K. H. Kao 高國興
Particle Statistics
- Particle statistics is a tool describing/bridging individual behavior of
particles and ensemble observation.
- f(E) = probability of occupancy of each state at energy E.
Maxwell-Boltzmann Fermi-Dirac Bose-Einstein
Category Classical Quantum Fermion Quantum Boson
Example Gas Electron Photon/Phonon
Distribution 1 1 1
f MB ( E )  f FD ( E )  f FD ( E ) 
Function e E / k BT e E / k BT  1 e E / k BT  1
Properties of No limit to number Never more than 1 No limit to number
Distribution of particles per state particle per state of particles per state
Lattice Heat Capacity
- Two main contributions to the heat capacity of a crystal: electrons and
phonons, the later is called lattice heat capacity Clat.
- Total energy Ulat of phonons at a temperature T in a crystal
U lat  U K , P  nK , P K , P
ℎ𝜔
P K P K
- <nK,P> is the mean occupancy of phonon at temperature T. 𝑥≡ 𝑘𝐵 𝑇

K , P 
- U lat      dDP ( ) .
P K exp(  K , P / k BT )  1 P exp( / k BT )  1
U x 2
exp( x)
-C  lat
 k B   dDP ( ) .
lat
T P exp( x)  1 2
Dp(ω)dω = number of phonon modes of

polarization p btw ω and ω + dω.
The central problem now is to find

density of state DOS D(ω)
Solid State Physics
Phonon II
Thermal Properties
5
Phonon States and Density of State
- Dispersion relation: ω (energy) vs k (λ).
- Displacement u is proportional to sin(kx) = sin(ksa).
- Only certain k values are supported by crystal, allowed k values are
phonon modes: k = ±π/L, ±2π/L, ±3π/L, …, ±Nπ/L.
- If L increases, more allowed k values. More atoms more states.
- Density of state (DOS) of a system describes the number of modes per
unit energy at a given energy level. DOS = D(E) ≡ dN/dE.
- dN = D(E)dE = D(ω)dω = D(k)dk.
dE
λmax = 2L kmin = 2π/ λmax = π/L

s=1 2 a N N+1 dE
λmin = 2a kmax = 2π/λmin = π/a
 0 
k
DOS of Periodic Boundary Conditions
- In general, atom at the ends would not be fixed as previous slide.
- With an unbounded 1D medium, we consider solutions being periodic over
a large distant L  u(x=sa) = u(x=sa+L), where u = uoexp[i(kxx–ωt)].
Allowed kx = ±2π/L, ±4π/L, …, ±Nπ/L  Δkx = 2π/L.
Number of states per unit length of kx  1/Δkx = L/2π.
- Total states N involved in vector K, N = K(L/2π).
- Number of states dN increases with dK, dN = (L/2π)dK.
- D1D(K) = dN/dK = L/2π.
- In 2D, exp[i(kxx+kyy)] = exp[i(kx(x+L)+ky(y+L))],
Allowed kx,ky = ±2π/L, ±4π/L, …, ±Nπ/L  Δkx,Δky = 2π/L.
Number of states per unit area ρ2D = (1/Δkx)(1/Δky) = (L/2π)2.
- Total states N involved in vector K, N = (πK2)(L/2π)2 = (L2/4π)K2.
- Number of states dN increases with dK,
dN = (2πKdK)(L/2π)2 = (L2/2π)KdK.
- D2D(K) = dN/dK = (L2/2π)K.
- In 3D, exp[i(kxx+kyy+kzz)] = exp[i(kx(x+L)+ky(y+L)+kz(z+L))],
Allowed kx,ky,kz = ±2π/L, ±4π/L, …, ±Nπ/L  Δkx,Δky, Δkz = 2π/L.
Number of states per unit volume ρ3D = (1/Δkx)(1/Δky)(1/Δkz) = (L/2π)3.
- Total states N involved in vector K, N = (4πK3/3)(L/2π)3 = (L3/6π2)K3.
- Number of states dN increases with dK,
dN = (4πK2dK)(L/2π)3 = (L3/2π2)K2dK.
- Volume of specimen V ≡ L3.
- D3D(K) = dN/dK = (V/2π2)K2. D3D(ω) = dN/dω = (V/2π2)K2(dK/dω).
Solid State Physics
Phonon II
Thermal Properties
10
Einstein Model
- In 1907 Einstein assumed D3D(ω) = 3Nδ(ω – ωo) for N oscillators in 3D,
meaning all oscillators have the identical frequency ωo.
 K , P  3No
U lat      dDP ( )  .
P K exp(  K , P / k BT )  1 P exp(  / k BT )  1 exp( o / k BT )  1
2
 U lat   o  exp( o / k BT ) ex
Clat     3Nk B    3Nk B x 2
,
 T V  k BT  exp( o / k BT )  1 (e  1)
2 x 2
where x  o / k BT . Einstein t emperature  E  o / k B .

- At high T, θE << T  x ~ 0, Clat ≈ 3NkB ≈ Dulong-Petit value 25 Jmol–1K–1.
- At low T, x  ∞, Clat ~ 3𝑁𝑘𝐵 (𝜃𝐸 𝑇)2 exp(− 𝜃𝐸 𝑇). But experiments show Clat ~ T3.
Einstein model fails because thermal energy is insufficient to excite optical phonons.
ω D(ω)
ωo
k ω
ωo
ω
Debye Model
K
- D3D(ω) = dN/dω = (V/2π2)K2(dK/dω)  dK/dω = ?
- In 1912 Debye assumed the wave velocity is a constant for each polarization
 ω = vgK, meaning acoustic phonons only  D3D(ω) = (Vω2)/(2π2vg3).
- If a monatomic lattice and 3 acoustic branches possess the same vg,
 
U lat    dDP ( )  3 dD( )
P exp(  / k BT )  1 exp(  / k BT )  1
3V D 3 3Vk B4T 4 xD x3

2 2 v g3 
0
d
e  k BT

 1 2 2 v g3  3 0
dx x ,
e 1
where x   / k BT and xD   D / k BT   D / T .
Debye temperature  D   D / T  (v g / k B ) 6 2 N / V  13
3
 U lat  3V 2 D  4 e  k T B
T  xD x 4e x
Clat    
 T V 2 v g k BT
2 3 2 0
d
e  k B T
1
2
 9

Nk  
B
 D 

0
dx
e x

1
2
.
𝑇 3 𝑥𝐷 𝑥 4 ∙1
- When T >> θD, 𝐶𝑙𝑎𝑡 ≈ 9𝑁𝑘𝐵 0
𝑑𝑥 2 = 3𝑁𝑘𝐵 = 25 𝐽 ∙ 𝑚𝑜𝑙 −1 𝐾 −1 .
𝜃𝐷 𝑥
ω
Debye Model
K
T >> θD, Clat ≈ 3NkB ~ 25 J mole–1 K–1
Dulong-Petit value ≈ 25 J mole–1 K–1
4  k BT 3
 U  3V 2
D e T  xD x 4e x
Clat   lat   2 3
 T V 2 vg k BT
2 
0
d
e k BT
1
2
 9 Nk B  
  D 

0
dx
e x

1
2
.
ω
Debye Model
3Vk B4T 4 xD x3
- U lat  2 3 3 0 dx x , where x   / k BT and xD  D / k BT   D / T . K
2 vg  e 1
 
Debye temperature  D  D / T  (vg / k B ) 6 2 N / V .
13
 
x3 
  x  exp(  sx)dx  61 / s 4   4 / 15.
xD
- When T  0, xD  ∞, 0 dx x
3
e  1 0 s 1 1
3
T 
U lat  3 Nk BT / 5 D  Clat  Nk B   .
4 4 3
 D 
- At low T, T3 approximation is quite good, meaning only long wavelength
acoustic phonon are thermally excited.
- For actual crystals, T may be necessary to be below T = θD/50 to see pure
T3 behavior.
Solid Ar
Einstein vs Debye Model
- Principle difference btw Einstein and Debye models is in the
assumption about phonon frequency spectrum.
- Einstein: D3D(ω) = 3Nδ(ω – ωo), Debye: D3D(ω) = (Vω2)/(2π2vg3).
D(ω) D(ω)
ω Debye
Einstein ω
Solid State Physics
Phonon II
Thermal Properties
16
Phonon Gas
- Agents of heat transfer in metal = electrons + phonons, in insulator = phonons.
- Some behavior of phonons (electrons) is analogical to classical gas molecules.
Thermal Conductivity with Phonon
- Thermal conductivity coefficient κ of a solid is defined with respect to a
steady-state flux of thermal energy jU through a long rod with a
temperature gradient dT/dx, dT
jU   .
dx
- dT/dx implies scattering events, namely collisions with defects, boundary and
other phonons, in the thermal flux.
- The mean length btw two collisions is defined as mean free path ϑ.
- Assuming a phonon with heat capacity c and mean free path ϑ moves from a
region at T + ΔT to a region at T, it satisfies dT dT
T  x  vx ,
dx dx
where vx is drift velocity along x direction and τ is mean free time btw collisions.
Net flux of energy is dT 2 1 dT 1 dT
jU  n(cT )vx  nc vx   ncv 2   Cv ,
dx 3 dx 3 dx
where ϑ ≡ vτ and C ≡ nc.
jU
- κ = 1/3Cvϑ.
High T Low T
Normal and Umklapp Scattering
- Normal scattering process (N process): K1 + K2 = K3. Total momentum of
the two phonons remains the same  zero thermal resistivity.
- Umklapp scattering process (U process): K1 + K2 = K3 + G.
Total momentum of the two phonons changed  finite thermal resistivity.
- All longer K must translate back into the 1st BZ.
- Which process is dominating at low temperatures?
N process U process
Mean Free Path and Thermal Conductivity
- Mean free path ϑ is mainly dominated by collisions with crystal boundary,
defects, impurities and other phonons.
- At high T, ϑ  1/T in agreement with many experiments. This is due to
# of excited phonons  T, collision frequency of a phonon  #
 ϑ  1/T. κ  Cvϑ  1/T.
- At low T # of phonons can be neglected, ϑ ≈ constant, dominated by
crystal boundary and defects. κ  Cvϑ  T3.
ϑ
κ  T3
κ  1/T
NaF
Exercise 1
Exercise 2

4 - Phonon II Thermal Properties

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Solid State Physics

Dulong-Petit value ≈ 25 J mole–1 K–1

Heat Capacity (× 104 J kilomole-1K-1)

- <nK,P> is the mean occupancy of phonon at temperature T. 𝑥≡ 𝑘𝐵 𝑇

Dp(ω)dω = number of phonon modes of

The central problem now is to find

where x  o / k BT . Einstein t emperature  E  o / k B .

T >> θD, Clat ≈ 3NkB ~ 25 J mole–1 K–1

Dulong-Petit value ≈ 25 J mole–1 K–1

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