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# Phonons: Thermal Properties

Phonons can be created by thermal excitation of the lattice and play a very important role in
the thermal properties of materials. We will now look at two such properties:
1. Heat capacity, which can be treated within the harmonic approximation.
2. Thermal conductivity, which requires us to go beyond the harmonic approximation
and consider interactions between phonons (anharmonic effects)

Heat capacity
The total heat capacity of a crystal can be written as
௣௛௢௡௢௡௦ ௘௟௘௖௧௥௢௡௦ ௠௔௚௡௘௧௜௖
‫ܥ‬௏ = ᇣᇧ
‫ܥ‬௏ᇧᇤᇧ
ᇧᇥ + ‫ܥ‬
ᇣᇧ
௏ᇧᇤᇧ ᇧᇥ + ᇣᇧ
‫ܥ‬௏ᇧᇤᇧᇧᇥ
௔௟௟௦௢௟௜ௗ௦ ௠௘௧௔௟௦௢௡௟௬ ௠௔௚௡௘௧௦௢௡௟௬

## For a non-magnetic insulator, ‫ܥ‬௏ is only due to phonons

߲ℰ
‫ܥ‬௏ = ൬ ൰
߲ܶ ௏
Note, for solids ‫ܥ‬௏ ≈ ‫ܥ‬௉ .

## Dulong & Petit law

Classically, if we think of a solid as ܰ atoms, equipartition theorem would give
1
ℰ = 6ܰ × ݇஻ ܶ
2
Where the factor of 6 comes from 6 degrees of freedom per atom (KE + PE × 3 spatial
degrees of freedom each). Hence
‫ܥ‬௏ = 3ܰ݇஻
This is known as the Dulong and Petit law (~1819). It holds for some solids at room
temperature but fails at low temperature where a quantum mechanical treatment is
necessary.

## Simple harmonic oscillator

Let’s first take a look at the heat capacity of a single quantum harmonic oscillator (QHO).
The energy eigenvalues are
1
ℰ௡ = ൬݊ + ൰ ℏ߱
2
To find the average thermal equilibrium occupancy 〈݊〉 of this QHO (i.e., how many phonons
are in mode ߱ at a given temperature), we use the usual statistical mechanics approach.
݁ ିℰ೙ /௞ಳ ் ∑௡ ݊൫݁ ିℏఠ/ଶ௞ಳ ் ൯݁ ି௡ℏఠ/௞ಳ ்
〈݊〉 = ෍ ݊‫݌‬௡ = ෍ ݊ =
ܼ ∑௡ (݁ ିℏఠ/ଶ௞ಳ ் )݁ ି௡ℏఠ/௞ಳ்
௡ ௡

4-1
ିℰ೙ /௞ಳ ்
where ‫݌‬௡ is the probability of state ݊ being occupied and ܼ = ∑௡ ݁௡ is the partition
function. Cancelling out the two terms in brackets,
∑௡ ݊݁ ି௡ℏఠ/௞ಳ ் ݇஻ ܶ ଶ ߲ ln ‫ܣ‬
〈݊〉 = =
∑௡ ݁ ି௡ℏఠ/௞ಳ ் ℏ߱ ߲ܶ
ିଵ
where ‫∑ = ܣ‬ஶ௡ୀ଴ ݁
ି௡ℏఠ/௞ಳ ்
= 1 + ݁ ିℏఠ/௞ಳ் + ݁ ିଶ԰ఠ/௞ಳ ் + ⋯ = ൫1 − ݁ ିℏఠ/௞ಳ் ൯ (geometric
series). Now,
݇஻ ܶ ଶ ߲ (−ln(1 − ݁ ିℏఠ/௞ಳ் )) ݇஻ ܶ ଶ 1 ℏ߱ ିℏఠ/௞ ்
〈݊〉 = = ൬− ݁ ಳ ൰
ℏ߱ ߲ܶ ℏ߱ ݁ ିℏఠ/௞ಳ் ݇஻ ܶ
which simplifies to
1
〈݊〉 =
݁ ℏఠ/௞ಳ ் −1
This is just the Bose-Einstein factor, the same as the well-known expression for the Planck
distribution for black body radiation. Therefore, the average energy of this oscillator is
1 1 ℏ߱
ℰ̅ = ൬〈݊〉 + ൰ ℏ߱ = ℏ߱ + ℏఠ/௞ ்
2 2 ݁ ಳ −1

## We can now calculate the heat capacity of the QHO

߲ℰ̅ 1 ℏ߱
‫ܥ‬௏ = ቆ ቇ = ℏ߱ ൬− ℏఠ/௞ ் ൰ ൬− ൰ ݁ ℏఠ/௞ಳ ்
߲ܶ ௏ ݁ ಳ −1 ݇஻ ܶ ଶ

ℏ߱ ଶ ݁ ℏఠ/௞ಳ்
‫ܥ‬௏ = ݇஻ ൬ ൰
݇஻ ܶ (݁ ℏఠ/௞ಳ் − 1)ଶ
ℏఠ
or, defining a characteristic temperature Θ ≡
௞ಳ

Θ ଶ ݁ ஀/்
‫ܥ‬௏ = ݇஻ ൬ ൰
ܶ (݁ ஀/் − 1)ଶ
஀ ଶ
In the low-temperature limit, as ܶ → 0, ݁ ஀/் ≫ 1 and ‫ܥ‬௏ →  ݇஻ ቀ ቁ ݁ ି஀/் .

஀ ஀ ଶ ଵ
In the high-temperature limit, as ܶ → ∞, ݁ ஀/் ≈ 1 + + ⋯ and ‫ܥ‬௏ →  ݇஻ ቀ ቁ మ = ݇஻ ,
் ் ౸
ቀଵା ିଵቁ

as expected from equipartition.

## Einstein’s theory of heat capacity in solids

Einstein considered the solid as a collection of ܰ simple QHOs all with the same frequency
12
߱ா (corresponding to typical optical mode frequency ~10 Hz). If we define an Einstein
temperature as Θா = ℏ߱/݇஻ , then in 3D
Θ୉ ଶ ݁ ஀ు /்
‫ܥ‬௏ = 3ܰ݇஻ ൬ ൰
ܶ (݁ ஀ు /் − 1)ଶ
For ܶ ≫ Θா , ‫ܥ‬௏ ≈ 3ܰ݇஻ , i.e. we recover the law of Dulong and Petit.

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For ܶ ‫  ا‬ȣா , ‫ܥ‬௏ ‫஀ି ݁ ן‬ు Ȁ் . This explains qualitatively the observed decrease of ‫ܥ‬௏ at low
temperature, but experimental data do not decrease as quickly— to explain this we need low
frequency (acoustic) phonons.

Einstein theory fit (dashed line) to experimental heat capacity data for diamond (open
circles); Θா = 1,320 K. Reproduced from Einstein’s seminal 1907 article in Annalen der
Physik [vol. 22, pp. 180-190].

## Total lattice energy

To calculate the total lattice energy at a certain temperature more accurately we need to
sum up the contributions from all phonon modes, i.e., over all ‫ ܓ‬and for all branches ݆
1
ࣟ ൌ ෍ ෍ ԰߱‫ܓ‬ǡ௝ ൬݊൫߱‫ܓ‬ǡ௝ ൯ + ൰
2
‫ܓ‬ ௝

Since the spacing between the states ȟ݇ ൌ ʹߨȀ‫ ܮ‬is very small compared to ʹߨȀܽ, the width
1
of the Brilouin zone , we can replace the sum with an integral

1
ࣟ ൌ න ݃(߱)԰߱ ൬݊(߱) + ൰ ݀߱
଴ 2
where ݃ሺ߱ሻ is the density of states such that the number of states between ߱ and ߱ ൅ ݀߱ is
݃(߱)݀߱. In reality, ݃(߱) is a complicated function of ߱, so we need some approximations.

Debye theory
Einstein assumed a single frequency ߱ா . Debye took into account different frequencies
assuming a linear dependence of ߱ on ݇, i.e., ߱ ൌ ‫ݒ‬ௌ ݇. We now know these as acoustic
phonons (though Debye’s theory predates the phonon theory of lattice dynamics and was
based on classical elasticity). The assumptions of the model are:

ଶగȀ௅
Typically ̱ܽͳͲିଵ଴ m, ̱݇ͳͲିଶ mିଵ so that ~10଼
1
ଶగȀ௔

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- The crystal is harmonic (the phonon modes are independent)
- Elastic waves are non-dispersive (߱ ൌ ‫ݒ‬௦ ݇)
- The crystal is isotropic
- There is a high-frequency cut off ߱஽ chosen in such a way that the total number of
ఠವ
modes is correct, i.e. that per branch ∫଴ ݃(߱)݀߱ ൌ ܰ, the number of atoms in the
crystal

Density of states
We now need an expression for the density of states.
ଶగ
In 1D, the states are separated by ȟ݇௫ = , where ‫ ܮ‬is the dimension (length) of the crystal.

ଶగ
In 2D, the allowed states form a grid with spacing ȟ݇௫ ൌ ȟ݇௬ = .

Consider an annulus of radius ݇ and thickness ݀݇. The area occupied by 1 state in k-space
ଶగ ଶ ௅ ଶ
is ቀ ቁ or, equivalently, there are ቀ ቁ states per unit area. So within the annulus area
௅ ଶగ
௅మ
ʹߨ݇݀݇ there are ʹߨ݇݀݇ (ଶగ)మ states, hence in 2D

‫ܮ‬ଶ
݃(݇)݀݇ ൌ ݇݀݇ሺʹሻ
ʹߨ
where ݃(݇) is the density of states (DOS).
ଶగ ଷ
In 3D, we have to consider a shell of volume Ͷߨ݇ ଶ ݀݇. The volume of each state is ቀ ቁ or

௅ ଷ ௅య
there are ቀ ቁ states per unit volume. Hence ݃(݇)݀݇ ൌ Ͷߨ݇ ଶ (ଶగ)య ݀݇or using ܸ ൌ ‫ܮ‬ଷ
ଶగ

ܸ ଶ
݃(݇)݀݇ ൌ ݇ ݀݇ሺ͵ሻ
ʹߨ ଶ
The corresponding DOS per unit frequency ݃ሺ߱ሻ is given by

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݃(߱)݀߱ = ݃(݇)݀݇
ܸ ଶ ݀݇
݃(߱) = ݇ (in 3D)
2ߨ ଶ ݀߱
per branch of the dispersion curve (e.g., for a monoatomic crystal in 3D there are 2T and 1L
branches).
To calculate the Debye frequency ߱஽ , we use
ఠವ
ܰ=න ݃(߱)݀߱ (per branch)

## Using Debye’s approximation for the dispersion ߱ = ‫ݒ‬௦ ݇

݀݇ 1 ܸ ߱ଶ
= → ݃(߱) = ଶ ଷ
݀߱ ‫ݒ‬௦ 2ߨ ‫ݒ‬௦
Therefore
ఠವ
ܸ ߱ଶ ܸ 1 ߱஽ ଷ ଷ
6ܰߨ ଶ ଷ
ܰ=න ݀߱ = ൬ ൰ →  ߱ ஽ = ቆ ቇ ‫ݒ‬௦
଴ 2ߨ ଶ ‫ݒ‬௦ଷ 2ߨ ଶ 3 ‫ݒ‬௦ ܸ
With three acoustic branches, the total lattice energy
ஶ ஶ
This is 3 because we are 1
considering 3D (?) ℰ = 3න ℏ߱݃(߱)݀߱ + 3 න ℏ߱݃(߱)݊(߱)݀߱
଴ 2
ᇣᇧᇧᇧᇧᇧᇤᇧᇧᇧᇧᇧᇥ ଴
ℰೋು

## can now be written as

ఠವ
ܸ ߱ଶ 1
ℰ = ℰ௓௉ + 3 න ℏ߱ ଶ ଷ ℏఠ/௞ ் ݀߱
଴ 2ߨ ‫ݒ‬௦ ݁ ಳ −1

௏ ଵ ଷே
or, using =
ଶగమ ௩ೞయ య
ఠವ

9ܰ ఠವ ℏ߱ଷ
ℰ = ℰ௓௉ + ଷ න ݀߱
߱஽ ଴ ݁ ℏఠ/௞ಳ ் − 1
Noting that the zero-point energy ℰ௓௉ is independent of temperature and therefore doesn’t
contribute to the heat capacity, we can now calculate the heat capacity as
߲ℰ 9ܰ ఠವ ℏ߱ଷ ℏ߱
‫ܥ‬௏ = = ଷන ݁ ℏఠ/௞ಳ ் ൬− ൰ ݀߱
߲ܶ ߱஽ ଴ −(݁ ℏఠ/௞ ்
ಳ − 1)ଶ ݇஻ ܶ ଶ

## Learn these substitutions as they 9ܰ ఠವ ℏଶ ߱ସ ݁ ℏఠ/௞ಳ்

= න ݀߱
make everything easier. ߱஽ଷ ଴ ݇஻ ܶ ଶ (݁ ℏఠ/௞ಳ் − 1)ଶ
Letting ‫ = ݔ‬ℏ߱/݇஻ ܶ, ݀߱ = (݇஻ ܶ/ℏ)݀‫ ݔ‬and the limits of integration become ߱ = 0 → ‫ = ݔ‬0
and ߱ = ߱஽ → ‫ = ݔ‬ℏ߱஽ /݇஻ ܶ = Θ஽ /ܶ, so that
9ܰ ஀ವ /் ℏ ݇஻ ܶ ସ ‫ ݔ‬ସ ݁ ௫
‫ܥ‬௏ = ଷ න ൬ ൰ ݀‫ݔ‬
߱஽ ଴ ܶ ℏ (݁ ௫ − 1)ଶ
ܶ ଷ ஀ವ /் ‫ ݔ‬ସ ݁ ௫
‫ܥ‬௏ = 9ܰ݇஻ ൬ ൰ න ݀‫ݔ‬
Θ஽ ଴ (݁ ௫ − 1)ଶ
ℏఠ
In the high-temperature limit, as ܶ → ∞, ‫= ݔ‬ → 0 so that the integrand in the above
௞ಳ ்
expression can be approximated to

4-5
‫ ݔ‬ସ (1 + ‫ ݔ‬+ ‫ ݔ‬ଶ /2 + ⋯ )
≈ ‫ݔ‬ଶ
(1 + ‫ ݔ‬+ ‫ ݔ‬ଶ /2 + ⋯ − 1)ଶ
ଵ ஀ವ ଷ
which integrates to ቀ ቁ and therefore the heat capacity in the high temperature limit
ଷ ்

‫ܥ‬௏ → 3ܰ݇஻
consistent with the Dulong & Petit law.
In the low-temperature limit, as ܶ → 0, ‫ ∞ → ݔ‬and we can replace ߱஽ in the upper limit of the
integration with ∞. The integral then becomes a standard integral

‫ݔ‬ସ݁ ௫ 4ߨ ସ
න ݀‫ݔ‬ =
଴ (݁ ௫ − 1)ଶ 15
This is the the low temperature T -> 0 result
and for the 3D model

12 ܶ ଷ
‫ܥ‬௏ → ܰ݇஻ ߨ ସ ൬ ൰
5 Θ஽
This expression gives good agreement with experiment.

4-6
Density of states as a function of frequency for (a) the Debye solid and (b) an actual
crystal structure. The spectrum for the crystal starts as ߱ଶ for small ߱, but
discontinuities develop at singular points. Reproduced from Kittel’s book.

(a) Dispersion relation for a diatomic crystal. (b) Dispersion relation within the Debye
approximation.

(a) Heat capacity of solid argon at low temperature plotted against ܶ ଷ . (b) Comparison
of Debye and Einstein models. Inset shows the difference in behaviour at low
temperatures. Experimental data for silver. Reproduced from Kittel.

4-7
Anharmonicity
So far, we have considered our interatomic potential to be harmonic, i.e., our model springs
exert the same force whether extended or compressed and the spring constant is
independent of the magnitude of the displacement. The Harmonic approximation works well
for small deviations from the equilibrium positions but for large displacements (high ܶ) it

Core
repulsion

Harmonic approx.
(symmetric)

Coulomb/van der
Waals attraction

For a more accurate description, we need to go beyond the harmonic terms in the expansion
(‫ ݎ‬− ܽ)ଶ ߲ ଶ ܷ (‫ ݎ‬− ܽ)ଷ ߲ ଷ ܷ
ܷ(‫ )ܽ(ܷ = )ݎ‬+ ቆ ଶቇ + ቆ ଷቇ +⋯
2 ߲‫ ݎ‬௥ୀ௔ ᇣᇧᇧᇧᇧᇧᇧᇧᇤᇧᇧᇧᇧᇧᇧᇧᇥ
ᇣᇧᇧᇧᇧᇧᇧᇧᇧᇤᇧᇧᇧᇧᇧᇧᇧᇧᇥ 6 ߲‫ ݎ‬௥ୀ௔
ு௔௥௠௢௡௜௖௔௣௣௥௢௫௜௠௔௧௜௢௡ ௔௡௛௔௥௠௢௡௜௖௧௘௥௠௦

## The consequences of including the anharmonic terms include:

1. Thermal expansion—the average interatomic distance 〈‫( ܽ > 〉ݎ‬it costs less energy to
expand than to contract)
2. Phonons interact with each other—they are no longer pure normal modes. In an
anharmonic crystal, a phonon (lattice wave) causes momentary local
contraction/expansion of the lattice. This causes a second phonon to ‘see’ a different
spring constant and the modes are therefore not independent; phonons scatter off
each other and this determines the thermal conductivity of the solid.
We will not discuss thermal expansion here as this was covered in PHAS1228.

4-8
Conservation laws for phonon-phonon collisions
Phonon-phonon collisions obey the following conservation laws

## ǣ԰‫ ܓ‬૚ ൅ ԰‫ ܓ‬૛ ൌ ԰‫ ܓ‬૜

energy: ℏωଵ + ℏωଶ = ℏωଷ

but we must not forget that phonon momentum is only defined modulo a reciprocal lattice
vector and therefore one distinguishes between two types of scattering events:

st
1. The resulting wavevector ‫ ܓ‬૜ lies within the 1 BZ. This is known as a ‘Normal’ event
(N). In an N event, two phonons travelling to the right combine to produce a phonon
travelling to the right.
st st
2. The resulting wavevector ‫ ܓ‬૜ lies outside the 1 BZ but can be translated into the 1
2
BZ by a reciprocal lattice vector ۵. Such events are called ‘Umklapp’ events (U) . In a
U event, two phonons travelling to the right combine to produce a phonon travelling
to the left!
Heat flow carried by phonons is unaffected by N events but is impeded by Umklapp
scattering and therefore U events contribute to thermal resistivity ቀ1ൗthermal conductivityቁǤ

Thermal conductivity
Thermal conductivity ߢ relates the steady-state flow of heat across a solid to the temperature
݀ܶ
݆௨ ൌ െߢ
݀‫ݔ‬
thermal current density [Wmିଶ ] = −thermal conductity [Wmିଵ K ିଵ ] × temp. gradient [Kmିଵ ]

2
‘Umklapp’ means ‘flip-over’ in German. Umklapp events were discovered by Peierls.

4-9
From kinetic theory of gases:
1
ߢ = ‫ݒ‬ҧ ݈‫ܥ‬ሚ௏
3
where ‫ݒ‬ҧ is the average particle velocity, ݈ is the mean free path and ‫ܥ‬ሚ௏ is the specific heat
per unit volume.
Importantly, particle conservation is not used in the derivation of this result and therefore it
3
can be applied to phonons, which are bosons and hence do not conserve particle number.

hot cold
end end

## phonons created phonons destroyed

(more phonons) (less phonons)

In metals, electrons contribute to ߢ (we will evaluate this contribution later); in insulators, the
only contribution is from phonons.

## Kinetic theory of gases

Imagine that the two ends of a solid are held at
different temperatures. Moving by Δ‫ ݔ‬from ܶ + Δܶ to ܶ,
the particle (phonon) gives up energy ܿΔܶ, where ܿ is
the specific heat per particle (if ݊ is the particle density
per unit volume, ܿ = ‫ܥ‬ሚ௏ /݊).
If the time between collisions (scattering time) is ߬
݀ܶ ݀ܶ
Δܶ = Δ‫= ݔ‬ ‫߬ ݒ‬
݀‫ݔ‬ ݀‫ ݔ‬௫
where ‫ݒ‬௫ is the component of the velocity along ‫ݔ‬. The thermal current density is then
݆௨ = ณ
݊ × (−ܿΔܶ)
ᇣᇧᇤᇧᇥ × 〈‫ݒ‬
ต ௫〉
ௗ௘௡௦௜௧௬ ௛௘௔௧ ௩௘௟௢௖௜௧௬

݀ܶ
= −݊ܿ〈‫ݒ‬௫ 〉ଶ ߬
݀‫ݔ‬
Therefore ߢ = ݊ܿ〈‫ݒ‬௫ 〉ଶ ߬ = ‫ܥ‬ሚ௏ 〈‫ݒ‬௫ 〉ଶ ߬. For an isotropic distribution of velocities, 〈‫ݒ‬௫ 〉ଶ = 〈‫ݒ‬௬ 〉ଶ =
ଵ ଵ ଵ
〈‫ݒ‬௭ 〉ଶ = 〈‫〉ݒ‬ଶ, so that ߢ = ‫ܥ‬ሚ௏ 〈‫〉ݒ‬ଶ ߬ = ‫ܥ‬ሚ௏ 〈‫݈〉ݒ‬, or
ଷ ଷ ଷ
1
ߢ = ‫ܥ‬ሚ௏ ‫ݒ‬ҧ ݈
3
Only Umklapp collisions contribute.
(Remember, ‫ܥ‬ሚ௏ is the heat capacity per unit volume)

3
In fact, it works even better for phonons because the speed of sound ‫ݒ‬ௌ is a constant for acoustic
phonons not too close to the BZB, unlike ‫ ݒ‬for ideal gas particles, which follows the Maxwell-
Boltzmann distribution.

4-10
Temperature dependence of thermal conductivity
The temperature dependence of the thermal conductivity is determined mostly by ‫ܥ‬ሚ௏ and ݈ (‫ݒ‬ҧ
is approximately constant). The mean free path ݈ is inversely proportional to the number of
phonons.
High T (ܶtΘ஽ ): all phonon modes up to ℏ߱஽ are excited; there are many phonons with large
enough |݇| to produce U-events. The number of phonons is proportional to the thermal
energy (݇஻ ܶ), hence ݈ ∝ ܶ ିଵ . The heat capacity is approximately constant (classical value).
Intermediate T (ܶ~Θ஽ ): U-processes start to freeze out as average energy of phonons
decreases. The number of phonons ~ exp(−Θ஽ /ܶ), hence ݈ ∝ exp(Θ஽ /ܶ).
Low T (ܶ ≪ Θ஽ ): all U-processes switch off. ݈ is limited by the size and shape of the crystal.
The temperature dependence comes entirely from ‫ܥ‬ሚ௏ ~(ܶ/Θ஽ )ଷ.

crystal
size

limited by limited by

4-11
Thermal conductivity of natural abundance
(1.1% 13C) diamond (lower squares),
isotopically enriched (0.1% 13C) diamond
(upper squares), together with the low
temperature data of Slack (circles) and the
high temperature data of Vandersande et al.
(plusses). Reproduced from Wei et al. Physical
Review Letters 70, 3764 (1993).

## Thermal conductivity of isotopically pure LiF

showing the effect of boundaries for
sandblasted crystals. Mean crystal widths: (A)
7.25 mm, (B) 4.00 mm, (C) 2.14 mm, (D) 1.06
mm. Reproduced from Thatcher Physical
Review 156, 975 (1967).

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