CH5 Phonon II.

Thermal Properties

A technician holding a silica fibre thermal

insulation tile, seconds after being removed from
a furnace at 1300 oC. The tiles lose 90% of their
heat within moments. Such tiles are used on the
underbody, wings and other areas of the Space
Shuttle.
https://www.youtube.com/watch?v=Pp9Yax8UNoM
 Heat Capacity

 Heat capacity is the measure of how much energy to raise the temperature of a unit mass of an

object.

 Two heat capacities: constant volume, CV , and constant pressure, CP . For a gas CP >CV . For

a solid CP ≈ CV .

 The contribution of the phonons (lattice vibrations) to the heat capacity of a crystal is called

the lattice heat capacity.

 Classical result: C ≈ 3NNcell kB , where N is the number of atoms in a unit cell and Ncell is the

number of cells in the crystal.

 Phonon Heat Capacity
• Phonons: dominate thermal properties of materials and affect the electrical transports of
conductors by scatterings of electrons
• The contribution of the phonons to the heat capacity of a crystal is called the lattice heat
capacity and denoted by Clat.

How are phonons created or excited in a crystal?

➢ External perturbations – vibrations or sound transducer

➢ Scattering of particles – energy transferred into lattice vibrations

➢ Thermal (KBT) – excited at any finite temperature (T≠0K)

The energy of the phonon in a solid

The energy of a phonon 𝑬 = ℏ𝝎
𝑼 = 𝒌𝑩 𝑻 = 𝝉
The momentum of a phonon 𝑷 = ℏ𝒌
Thermal phonons: consider a system with n phonons with energy level En
𝟏
Excitation level amplitude (n) → 𝑬 = 𝐧 + 𝟐 ℏ𝝎

Average of phonons

σ𝒔 𝒔 𝐞𝐱𝐩 −𝒔ℏ𝝎 Τ𝝉 𝒂 𝟏
𝐧 𝝎, 𝑻 = = = (let 𝒂 = 𝐞𝐱𝐩 − ℏ𝝎 Τ𝝉 )
σ𝒔 𝐞𝐱𝐩 −𝒔ℏ𝝎 Τ𝝉 𝟏 − 𝒂 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏

Planck distribution of 𝐧 𝝎, 𝑻 : average # of phonons excited per mode at ω

 Planck distribution of 𝐧 𝝎, 𝑻

• Thermal energy for a collection of phonons of frequencies 𝝎𝑲,𝒑

ℏ𝝎
𝑼 = ෍ න 𝒅𝝎𝑫𝒑 𝝎
𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏
𝒑
𝝏𝑼 𝒙𝟐 𝐞𝐱𝐩𝒙
(let 𝒙 = ℏ𝝎 Τ𝝉) 𝑪𝒍𝒂𝒕 = = 𝒌𝑩 ෍ න 𝒅𝝎𝑫𝒑 𝝎
𝝏𝑻 𝐞𝐱𝐩𝒙 − 𝟏 𝟐
𝒑
Density of states in 1D dimension

Density of states (modes): D(k) ≡ number of states per unit K at K

• Consider a 1D chain of total length L carrying N+1 particles (atoms) at a separation a

L

a
fixed 0 1 2 ……… N fixed

0 𝝅 𝝅 ………
𝑵𝝅 𝝅
or 𝒂
or 𝑳
𝑳 𝑵𝒂

𝝅 𝟐𝝅 𝟑𝝅 𝟒𝝅 𝑵−𝟏 𝝅
𝒖𝒔 𝒕 = 𝒖 𝟎 𝐞𝐱𝐩 −𝒊𝝎𝑲,𝒑 𝒕 sin 𝒔𝑲𝒂 where 𝑲 = 𝑳 , , , , … … ,
𝑳 𝑳 𝑳 𝑳

At s=0 and N, no motion at all. 𝑳 𝝅

for 𝑲 ≤ 𝒂
𝑫 𝑲 = 𝝅
The number of modes per unit range of K 𝝅
𝟎 for 𝑲 > 𝒂
Density of states in 1D dimension

• Consider the medium as unbounded, but require that the solutions be periodic over a large
distance L, → 𝒖 𝒔𝒂 = 𝒖 𝒔𝒂 + 𝑳

1
N
2
… 𝟒𝝅 𝟐𝝅 0 𝟐𝝅 𝟒𝝅 …
a − − 𝑳 𝑳
𝑳 𝑳
3
𝒖𝒔 𝒕 = 𝒖 𝟎 𝐞𝐱𝐩 𝒊 𝒔𝑲𝒂 − 𝝎𝑲 𝒕
L
… 𝟐𝝅 𝟒𝝅 𝑵𝝅
𝑲 = 𝟎, ± ,± ,……,
𝑳 𝑳 𝑳

N particles, N modes 𝑳 𝝅 𝝅
for − ≤ 𝑲 ≤
𝒂 𝒂
𝑫 𝑲 = 𝟐𝝅
The number of modes per unit range of K
𝟎 otherwise
For 1D monoatomic periodic lattice
𝑳 𝒅𝑲 𝑳 𝒅𝝎 𝟐𝑫 𝑲
The number of modes 𝑫 𝝎 𝒅𝝎 = 𝒅𝝎 = = 𝒅𝝎
𝝅 𝒅𝝎 𝝅 𝒅𝝎Τ𝒅𝑲 𝐯𝒈

group velocity

𝑫 𝑲
𝑫 𝝎 = Singularity at vg=0, determined by ω(k) from dispersion relation
𝐯𝒈

𝟒𝑪 𝐾𝑎 𝑵𝒂Τ𝝅 𝑵 𝑴 𝝎𝟐𝒎𝒂𝒙
𝝎= sin 𝑫 𝝎 = = 𝟐
𝑴 2 𝟒𝑪 𝒂 𝐾𝑎 𝝅 𝑪 𝝎𝒎𝒂𝒙 − 𝝎𝟐
𝑴 𝟐 cos 2

𝑫 𝑲 𝑫 𝝎 Total No. of modes

𝝅
𝒂
𝑳 𝑳 𝟐𝝅
𝟐𝝅 𝑵 𝑴
𝑵 = න 𝑫 𝑲 𝒅𝑲 =
𝟐𝝅 𝒂
𝝅
𝝅 𝑪 −
𝒂
𝝎𝒎𝒂𝒙 𝟒𝑪Τ𝑴
𝑲 𝝎 = න 𝑫 𝝎 𝒅𝝎 = න 𝑫 𝝎 𝒅𝝎
𝝅 𝝅
− 𝟒𝑪Τ𝑴 𝟎 𝟎
𝒂 𝒂
Density of states in 2D dimension
• There is one allowed value K per area:
𝟐 𝟐
𝟐𝝅 𝟐𝝅
e.g. for a 2D lattice (K space) =
𝑵𝒂 𝑳

• Thus, within the circle of radius K, there are

approximately allowed wavevectors
𝟐
𝑳
𝝅𝑲𝟐
𝟐𝝅

Number of modes with wavevector from K to K+dK

in K-space
𝟐𝝅
𝟏 𝑳𝟐
𝑳 𝑫 𝑲 𝒅𝑲 = 𝒅𝑲𝒙 𝒅𝑲𝒚 = 𝟐𝝅𝑲𝒅𝑲
∆𝑲𝒙 ∆𝑲𝒚 𝟒𝝅𝟐

The number of modes per unit frequency range

𝑳 = 𝟏𝟎𝒂
𝑫 𝑲 𝑨 𝟏
𝑫 𝝎 = = 𝟐𝝅𝑲
𝒅𝝎Τ𝒅𝑲 𝟒𝝅𝟐 𝐯𝒈
Density of states in 3D dimension

• Periodic boundary conditions over N3 primitive cells within a cube of side L:

𝐞𝐱𝐩 𝒊 𝑲𝒙 𝒙 + 𝑲𝒚 𝒚 + 𝑲𝒛 𝒛 ≡ 𝐞𝐱𝐩 𝒊 𝑲𝒙 𝒙 + 𝑳 + 𝑲𝒚 𝒚 + 𝑳 + 𝑲𝒛 𝒛 + 𝑳

Number of modes with wavevector from K to K+dK in K-space

𝟏 𝑽
𝑫 𝑲 𝒅𝑲 = 𝒅𝑲𝒙 𝒅𝑲𝒚 𝒅𝑲𝒛 = 𝟑 𝟒𝝅𝑲𝟐 𝒅𝑲
∆𝑲𝒙 ∆𝑲𝒚 ∆𝑲𝒛 𝟖𝝅

The number of modes per unit frequency range

𝑫 𝑲 𝑽 𝟐
𝟏
𝑫 𝝎 = = 𝟒𝝅𝑲
𝒅𝝎Τ𝒅𝑲 𝟖𝝅𝟑 𝐯𝒈

𝝎𝒎𝒂𝒙
𝑽 𝟒𝝅𝑲𝟑
𝑵 = න 𝑫 𝝎 𝒅𝝎 =
𝟖𝝅𝟑 𝟑
𝟎
Debye Model for Density of states
• For each polarization, assume the velocity is
taken as constant, and follows a classic elastic
𝑫 𝝎 𝒅𝝎 is the number of states
within the surfaces of constant ω continuum waves:
and ω+dω
𝝎 = 𝐯𝑲, (v: sound velocity)

𝑽𝝎𝟐
𝑫 𝝎 = a quadratic dependence !
𝟐𝝅𝟑 𝐯 𝟑

• If there are N primitive cells in the crystal, the

total No. of acoustic phonon modes is N.
𝟔𝝅 𝟐𝐯𝟑𝑵
Cutoff frequency 𝝎𝟑𝑫 = ൗ𝑽

𝝎𝑫 𝟐 𝟏Τ𝟑
𝑫 𝝎 𝒅𝝎 = 𝑫 𝑲 𝒅𝟑 𝑲 Cutoff wavevector 𝑲𝑫 = = 𝟔𝝅 𝑵ൗ𝑽
𝐯
• On the Debye model, the no. of the modes of wavevectors are not allowed to be larger than KD

for each polarization type:

𝝎𝑫
𝑽𝝎𝟐 ℏ𝝎
𝑼 = න 𝒅𝝎𝑫𝒑 𝝎 𝒏 𝝎 ℏ𝝎 = න 𝒅𝝎
𝟐𝝅𝟑 𝐯 𝟑 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏
𝟎

There are three polarizations : 2 transverse + 1 longitudinal

𝝎𝑫 𝒙𝑫
𝟑𝑽ℏ 𝝎𝟑 𝟑𝑽𝒌𝟒𝑩 𝑻𝟒 𝒙𝟑
∴𝑼= න 𝒅𝝎 = න 𝒅𝒙 𝒙 (let 𝒙 = ℏ𝝎 Τ𝝉)
𝟐𝝅𝟑 𝐯 𝟑 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏 𝟐𝝅𝟑 𝐯 𝟑 ℏ𝟑 𝒆 −𝟏
𝟎 𝟎

Define: 𝒙𝑫 ≡ ℏ𝝎𝑫 Τ𝒌𝑩 𝑻 ≡ 𝜽𝑫 Τ𝑻

ℏ𝐯 𝟔𝝅𝟐 𝑵 𝟏Τ𝟑
𝜽𝑫 (Debye temperature) = ∙ ൗ𝑽
𝒌𝑩
𝟑 𝒙𝑫
𝑻 𝒙𝟑
𝑼 (Total phonon energy) = 𝟗𝑵𝒌𝑩 𝑻 න 𝒅𝒙 𝒙
𝜽𝑫 𝒆 −𝟏
𝟎
 𝝎𝑫
𝝏𝑼 𝟑𝑽ℏ𝟐 𝝎𝟒 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉
𝑪𝑽 (heat capacity) = = න 𝒅𝝎
𝝏𝑻 𝟐𝝅𝟐 𝐯 𝟑 𝒌𝑩 𝑻𝟐 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏 𝟐
𝟎
𝟑 𝒙𝑫
𝑻 𝒙𝟒 𝒆𝒙
= 𝟗𝑵𝒌𝑩 𝑻 න 𝒅𝒙
𝜽𝑫 𝒆𝒙 − 𝟏 𝟐
𝟎

Dulong and Petit law: 𝐶𝑉 = 3𝑁𝑘𝐵

high T (T ≫ 𝜽𝑫 ) 𝑪𝑽 → 𝟑𝑵𝒌𝑩

𝟑
𝟏𝟐𝝅𝟒 𝑻
low T (T ≪ 𝜽𝑫 ) 𝑪𝑽 → 𝑵𝒌𝑩
𝟓 𝜽𝑫

𝑇 < 0.1𝜃𝐷 , obey𝑠 𝑇 3 law

Low temperature heat

capacity of solid argon
• At T is sufficiently low, only low wavelength acoustic modes are thermally excited. These are
the modes that may be treated as an elastic continuum with macroscopic elastic constants.

The excited modes: ℏ𝝎𝑻 = ℏ𝐯𝑲𝑻

The allowable modes: ℏ𝝎𝑫 = ℏ𝐯𝑲𝑫

The No. of the possible modes: 𝟑𝑵

𝟑
𝑻
The No. of the excited modes: 𝟑𝑵
𝜽
𝟑
𝑻
the phonon energy 𝑼 = 𝟑𝑵𝒌𝑩 𝑻
𝑲𝒂 ≪ 𝟏 𝜽𝑫
𝟏/𝟐 𝟑
𝒅𝝎 𝑪𝒂𝟐 𝑻
𝒗𝒈 =
𝒅𝑲
≈
𝑴 heat capacity 𝑪𝑽 = 𝟏𝟐𝑵𝒌𝑩
𝝎
= = 𝒗𝒑
𝜽𝑫
𝑲
Einstein Model for Density of states

• Consider N oscillators of the same frequency ω0 and in one direction (Assume that each atom
vibrates independently of each other)
𝟑𝑵ℏ𝝎
𝑼 = 𝟑𝑵 𝒏 ℏ𝝎 =
𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏

𝟐
𝝏𝑼 ℏ𝝎 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉
𝑪𝑽 = = 𝟑𝑵𝒌𝑩 𝟐
𝝏𝑻 𝝉 𝐞𝐱𝐩 ℏ𝝎 Τ𝝉 − 𝟏
density of states can be written as
𝑫 𝝎 = 𝟑𝑵𝜹 𝝎 − 𝝎𝟎 Dulong and Petit law:
𝐶𝑉 = 3𝑁𝑘𝐵
ℏ𝝎𝑬 Τ𝒌𝑩 𝑻 ≡ 𝜽𝑬 Τ𝑻

high T (T ≫ 𝜽𝑬 ) 𝑪𝑽 → 𝟑𝑵𝒌𝑩
𝟐
𝜽𝑬 𝜽
− 𝑻𝑬
low T (T ≪ 𝜽𝑬 ) 𝑪𝑽 → 𝟑𝑵𝒌𝑩 𝒆
𝑻
 The comparison between Debye and Einstein models

Debye (1912) Einstein (1907)

Atoms vibrate collectively in a wave-like each atom vibrates independently of each

fashion other

𝑫 𝝎 = 𝑽𝝎𝟐 Τ𝟐𝝅𝟑 𝐯 𝟑 𝑫 𝝎 = 𝟑𝑵𝜹 𝝎 − 𝝎𝟎

(from a simple dispersion relation 𝝎 = 𝐯𝑲) (Quantum mechanical)

More correct to exp. data at low T CV decreases too rapidly at low temperatures.

Often treated in acoustic mode (T3 law) Often used to approximate the optical modes

Phonon Energy x Average number of Phonon Energy x Average number of

phonons x number of modes phonons
General Result for D(ω)

𝑫 𝝎 is the number of states per unit frequency range.

𝒅𝝎
𝐿 3 𝑑3𝐾 = 𝑑𝑆𝝎 𝑑𝐾⊥ 𝑑𝑆𝝎 𝑑𝐾⊥ = 𝑑𝑆𝝎
𝛻𝐾 𝝎
𝑫 𝝎 𝒅𝝎 = න 𝑑3𝐾
2𝜋 𝑠ℎ𝑒𝑙𝑙
𝒅𝝎
𝛻𝐾 𝝎 𝑑𝐾⊥ = 𝑑𝝎 = 𝑑𝑆𝝎
v𝑔

3
𝐿 𝒅𝝎
𝑫 𝝎 𝒅𝝎 = න 𝑑𝑆𝝎
2𝜋 𝑠ℎ𝑒𝑙𝑙 v𝑔

3
𝐿 𝑑𝑆𝝎
∴𝑫 𝝎 = න
2𝜋 𝑠ℎ𝑒𝑙𝑙 v𝑔
 The Debye solid The actual crystal

cutoff of ωmax in
different k direction

Measured curve is complex because the 3-D zone has a relatively complicated shape, and
the transverse and longitudinal modes have different dispersions
 Anharmonic Crystal Interactions

For the harmonic theory For the anharmonic theory

• Two lattice waves do not interact; a

single wave does not decay or change
form with time.
• No thermal expansion All should be considered
in real crystal
• Adiabatic and isothermal elastic
constants are equal
• The elastic constants are independent
of P and T
• CV becomes constant at high T (T > θ)
 Thermal expansion
∞
‫׬‬−∞ 𝒅𝒙 𝒙 𝐞𝐱𝐩 −𝜷𝑼 𝒙 𝟑𝒈
𝒙 = = 𝒌 𝑻
∞
‫׬‬−∞ 𝒅𝒙 𝐞𝐱𝐩 −𝜷𝑼 𝒙 𝟒𝒄𝟐 B

𝟏
𝜷≡
𝒌B 𝑻

𝑼 𝒙 = 𝑐𝑥 2 − 𝑔𝑥 3 − 𝑓𝑥 4

Lattice constant of solid

argon as a function of
temperature
The asymmetry of the mutual
repulsion of the atoms

Softening of the vibration at

large amplitudes
 Thermal Expansion
• The size change of solids with temperature can be characterized by a coefficient of linear
expansion α. 𝟏 𝝏𝒍
𝜶= 𝒍𝟎 is the origin length
𝒍𝟎 𝝏𝑻 𝑷

1. At 0 K, the total energy of the atom is potential. the atoms sit at a (0K).
2. When T increase, the average energy of the system increase correspondingly. The atoms
vibrate like springs. The position of the atoms has been redefined at their average location.

3. The average position of the atoms

increases with T, following the line ab.
4. In general,
𝟏 𝟏
𝜶∝ 𝒐𝒓
𝑻𝒎 𝑬𝒍𝒂𝒕𝒕.
 Thermal Conductivity
In solids, heat is transported by phonon and free electrons.

phonon electron

hot 𝑇 + ∆𝑇 cold

• Thermal conduction is a measure of how much heat energy is transported through a material
per unit time.
• Phonons have energy and momentum and, therefore, can conduct heat.
• From kinetic theory, we know that the steady-state flow of heat can be expressed as

the thermal conductivity coefficient (𝜅)

𝑑𝑇 1 𝑑𝑇 1 𝐶: the heat capacity of phonons

𝑗𝑼 = −𝜅 = − 𝐶𝜐𝑙 𝜅 = 𝐶𝜐𝑙 𝜐: the phonon velocity
𝑑𝑥 3 𝑑𝑥 3
𝑙: the phonon mean free path
• In metals, thermal current is carried by both electrons and phonons. In insulators, only
phonons can be carriers.
• For metals, it is electronic contribution that dominates the thermal conductivity.
• This does not mean that insulators are necessarily poor thermal conductors.
• The collection of phonons are similar to an ideal gas

Ashcroft and Mermin, Chaps 23, 24

Thermal Resistivity of Phonon Gas

𝒍: the phonon mean free path

• determined by two process:

➢ Geometrical scattering (dominate at low T): scattering from crystal imperfection, such as
point defects, dislocations, grain boundaries, etc.
➢ Scattering by other phonons (dominate at high T)

Phonon-phonon scattering is a
result of the anharmonic vibration
𝟏
𝒍∝ at high T
𝑻
Propagations of phonons

• In real situation, the thermal conduction is a diffusion process: Phonons scatter, random walk
through crystal.
✓ The phonons are locally thermal equilibrium.
Normal process
𝑲𝟏 + 𝑲𝟐 = 𝑲𝟑

crystal momentum is conserved, the flux is unchanged in momentum on collision.

Umklapp process

𝑲𝟏 + 𝑲𝟐 = 𝑲𝟑 + 𝑮

crystal momentum is not conserved, a large net change in phonon momentum in

each collision event.
 Umklapp process

• Normal process (N process): G=0

• Umklapp process (U process): G≠0, occurs at high T (T ~ θ), because all phonon modes are
excited (𝒌𝑩 𝑻 > ℏ𝝎𝒎𝒂𝒙), a proportion of phonon momentums reverse the traveling direction.
• must conserve energy.

boundary scattering

𝐞𝐱𝐩 − 𝜽Τ𝟐𝑻

phonon scattering
 Imperfections

At low T, assume l is At intermdiate and high

large enough to cross T, assume U process
the whole sample dominate:
(diameter: D).
𝑪 = 𝒄𝒐𝒏𝒔𝒕. = 𝟑𝑵𝒌𝑩
𝜿 ≈ 𝑪𝝊𝑫 ∝ 𝑻𝟑
1 1
𝜅 = 𝐶𝜐𝑙 = 𝐶𝜐 2 𝜏
(𝑪𝑽 ∝ 𝑻𝟑 ) Debye 3 3
∝ 𝐞𝐱𝐩 − 𝜽Τ𝑻
 Homework

Problem # 1, 4