CHAPTER 2

Lattice Dynamics I

SOUND WAVES
LATTICE VIBRATIONS OF 1D CRYSTALS
chain of identical atoms
chain of two types of atoms

LATTICE VIBRATIONS OF 3D CRYSTALS

PHONONS
HEAT
CAPACITY
FROM
LATTICE
VIBRATIONS
ANHARMONIC EFFECTS
THERMAL CONDUCTION BY PHONONS

Crystal Dynamics

Concern with the spectrum of characteristics vibrations of a

crystalline solid.

Leads to;
consideration of the conditions for wave propagation in a
periodic lattice,
the energy content,
the specific heat of lattice waves,
the particle aspects of quantized lattice vibrations
(phonons)
consequences of an harmonic coupling between atoms.

Crystal Dynamics

These introduce the concepts of

forbidden and permitted frequency
ranges, and
electronic spectra of solids

Crystal Dynamics

In previous chapters we have assumed that the atoms were

at rest at their equilibrium position. This can not be entirely
correct; Atoms vibrate about their equilibrium position at
absolute zero.

The energy they possess as a result of zero point motion is

known as zero point energy.

The amplitude of the motion increases as the atoms gain

more thermal energy at higher temperatures.

In this chapter we discuss the nature of atomic motions,

sometimes referred to as lattice vibrations.

In crystal dynamics we will use the harmonic approximation ,

amplitude of the lattice vibration is small. At higher amplitude
some unharmonic effects occur.

At T>0 ions vibrate with an amplitude that depends on temperature because

of lattice symmetries, thermal vibrations can be analyzed in terms of collective
motion of ions which can be populated and excited just like electrons unlike
electrons, phonons are bosons (no Pauli principle, phonon number is not
conserved). Thermal lattice vibrations are responsible for:
Thermal conductivity of insulators is due to
dispersive lattice vibrations (e.g., thermal conductivity of
diamond is 6 times larger than that of metallic copper).
They reduce intensities of diffraction spots and
allow for inellastic scattering where the energy of the scatter
(e.g., neutron) changes due to absorption or creation of a
phonon in the target.
Electron-phonon interactions renormalize the
properties of electrons (electrons become heavier).
Superconductivity (conventional BCS) arises from
multiple electron-phonon scattering between time-reversed
electrons.

Lattice dynamics above T=0

5

Crystal Dynamics

Our calculations will be restricted to lattice vibrations of

small amplitude. Since the solid is then close to a position
of stable equilibrium its motion can be calculated by a
generalization of the method used to analyse a simple
harmonic oscillator.The small amplitude limit is known as
harmonic limit.

In the linear region (the region of elastic deformation), the

restoring force on each atom is approximately proportional
to its displacement (Hookes Law).

There are some effects of nonlinearity or anharmonicity

for larger atomic displacements.

Anharmonic effects are important for interactions between

phonons and photons.

Crystal Dynamics
Atomic

motions are governed by the forces exerted on

atoms when they are displaced from their equilibrium
positions.

To

calculate the forces it is necessary to determine

the wavefunctions and energies of the electrons within
the crystal. Fortunately many important properties of
the atomic motions can be deduced without doing
these calculations.

Hooke's Law
One

of the properties of elasticity is that it takes about

twice as much force to stretch a spring twice as far.
That linear dependence of displacement upon
stretching force is called Hooke's law.

Fspring k .x
Spring constant k

It takes twice
as much force
to stretch a
spring twice
as far.

2F

Hookes Law

The

point at which the Elastic Region ends is called the

inelastic limit, or the proportional limit. In actuality, these
two points are not quite the same.

The

inelastic Limit is the point at which permanent

deformation occurs, that is, after the elastic limit, if the
force is taken off the sample, it will not return to its
original size and shape, permanent deformation has
occurred.

The

Proportional Limit is the point at which the

deformation is no longer directly proportional to the
applied force (Hooke's Law no longer holds). Although
these two points are slightly different, we will treat them
as the same in this course.

SOUND WAVES
It
corresponds waves
to the atomic
a long
.
Mechanical
are vibrations
waves with
which
propagate
through a material medium (solid, liquid, or gas) at
a wave speed
on in
the
and
Presence
of atomswhich
has nodepends
significance
thiselastic
wavelength
inertial
properties
thatwillmedium.
Theredue
areto two
limit,
since
>>a, so of
there
no scattering
the
basic
types
of
wave
motion
for
mechanical
waves:
presence of atoms.
longitudinal waves and transverse waves.
Longitudinal Waves

Transverse Waves

SOUND WAVES
Sound

waves propagate through solids. This tells us

that wavelike lattice vibrations of wavelength long
compared to the interatomic spacing are possible. The
detailed atomic structure is unimportant for these
waves and their propagation is governed by the
macroscopic elastic properties of the crystal.

We

discuss sound waves since they must correspond

to the low frequency, long wavelength limit of the
more general lattice vibrations.

At

a given frequency and in a given direction in a

crystal it is possible to transmit three sound waves,
differing in their direction of polarization and in
general also in their velocity.

Elastic Waves
A

solid is composed of discrete atoms, however when

the wavelength is very long, one may disregard the
atomic nature and treat the solid as a continous
medium. Such vibrations are referred to as elastic
waves.

Elastic Wave Propagation (longitudinal) in a bar

At the point x elastic displacement is
U(x) and strain e is defined as the
change in length per unit length.

x+dx

dU
e
dx

Elastic Waves

According

to Hookes law stress S (force per unit area)

is proportional to the strain e.

S C.e

C = Young modulus

x+dx

To

examine the dynamics of the bar, we choose an

arbitrary segment of length dx as shown above. Using
Newtons second law, we can write for the motion of this
segment,

2u
( Adx) 2 S ( x dx) S ( x) A
t
Mass x Acceleration

Net Force resulting from stresses

Elastic Waves

Equation

of motion

S C.e

2u
( Adx) 2 S ( x dx) S ( x) A
t

S
S ( x dx) S ( x) dx
x
2u
2u
( Adx) 2 C 2 Adx
t
x

2u
2u
2 C 2
t
x

u Ae

du
dx
u
S C.
x
S
2u
C. 2
x
x
e

Cancelling common terms of Adx;

Which is the wave eqn. with an offered

soln and velocity of sound waves ;

i ( kx t )

k = wave number (2/)

= frequency of the wave
A = wave amplitude

vs k
vs

C/

Jadi,

kecepatan gelombang mekanik

dalam batang (secara umum zat padat)
bergantung pada besaran elastik bahan
tersebut, yakni modulus young. Karena
perambatan gelombang tersebut
bergantung pada besaran elastik maka
gelombang yang bersangkutan disebut
gelombang elastik

PHYS 624: Crystal Lattice Vibrations:

Phonons

17

Bentuk Penyelesaian dari Persamaan Gelombang :

PHYS 624: Crystal Lattice Vibrations:

Phonons

18

Ruang-q satu dimensi

Kisi Diskrit

Kisi Malar / Kontinyu

19

jumlah ragam gelombang elastik yang

mempunyai bilangan gelombang antara q
dan q+dq (dalam interval dq)

PHYS 624: Crystal Lattice Vibrations:

Phonons

20

RAPAT KEADAAN
Jumlah ragam gelombang seperti pada persamaan
gelombang diatas untuk setiap satuan volume.
g(q)dq

Dapat juga diungkapkan sebagai fungsi frekuensi sudut

, yaitu g()d; yang menyatakan jumlah ragam
gelombang elastik persatuan volume dengan frekuensi
antara dan +d (dalam interval d).
hubungan dispersi

21

Dispersion Relation

The

relation connecting the frequency and wave

number is known as the dispersion relation.

vs k
At small
At long

* Slope of the curve gives

the velocity of the wave.

k (scattering occurs)
k 0 (no scattering)

When k increases velocity

decreases. As k increases further,
the scattering becomes greater since
the strength of scattering increases
as the wavelength decreases, and
the velocity decreases even further.

PERAMBATAN GELOMBANG ELASTIS DALAM ZAT PADAT

UNTUK KASUS TIGA-DIMENSI

PHYS 624: Crystal Lattice Vibrations:

Phonons

Volume yang
23
ditempati oleh satu
titik dalam ruang-q.

Rapat Keadaan G() Dalam Ruang Tiga-dimensi Dari

Rambatan Gelombang
Jumlah ragam gelombang (dalam bola berjejari q) adalah perbandingan antara
volume bola dan volume yang ditempati oleh satu titik dalam ruang-q.

Ingat:

24

Speed of Sound Wave

The

speed with which a longitudinal wave moves

through a liquid of density is

VL

C = Elastic bulk modulus

= Mass density

The velocity of sound is in general a function of the direction

of propagation in crystalline materials.
Solids will sustain the propagation of transverse waves, which
travel more slowly than longitudinal waves.
The larger the elastic modules and smaller the density, the
more rapidly can sound waves travel.

Sound Wave Speed

Speed of sound for some typical solids

VL values are comparable with direct observations of speed of sound.

Sound speeds are of the order of 5000 m/s in typical metallic, covalent
and ionic solids.

Sound Wave Speed

lattice vibrational wave in a crystal is a

repetitive and systematic sequence of atomic
displacements of
longitudinal,
transverse, or
some combination of the two

An equation of motion for any displacement can be

They can be characterized by
produced by means of considering the restoring forces
A
propagation
velocity, v
on
displaced
atoms.
Wavelength
As
or wavevector
a result we can
generate a dispersion relationship
between
frequency
and wavelength
between angular
A frequency
or angular
frequencyor=2
frequency and wavevector.

Gelombang elastik pada zat padat ini dapat

disebabkan baik oleh gelombang mekanik
(bunyi / ultrasonik) maupun oleh gelombang
termal (inframerah). Kedua gelombang
tersebut dapat menyebabkan gelombang kisi.
Untuk selanjutnya, paket-paket energi
getaran kisi disebut fonon. Fonon dapat
dipandang sebagai kuasi partikel seperti
halnya foton pada gelombang
cahaya/elektromagnet
PHYS 624: Crystal Lattice Vibrations:
Phonons

28

BEBERAPA EKSITASI ELEMENTER PADA ZAT PADAT

GELOMBANG

PARTIKEL

Gelombang elektromagnet

Foton

Gelombang elastik/getaran kisi

Fonon

Gelombang elektron kolektif

Plasmon

Gelombang magnetisasi

Magnon

Gelombang elektron +
deformasi elastik
Gelombang polarisasi

PHYS 624: Crystal Lattice Vibrations:

Phonons

Polaron
Eksiton

29

Lattice vibrations of 1D crystal

Chain of identical atoms
Atoms interact with a potential V(r) which can be

written in Taylors series.

r a

V (r ) V (a)

V(R)

This equation looks like as the potential energy

associated of a spring with a spring constant :

d 2V
K
2
dr

r0=4
Attractive
min

d 2V
...........

2
dr r a

Repulsive
0

r a

We should relate K with elastic modulus C:

Force C

r a
a

Force K (r a )

C Ka

Monoatomic Chain
The simplest crystal is the one dimensional chain of identical
atoms.
Chain consists of a very large number of identical atoms
with identical masses.
Atoms are separated by a distance of a.
Atoms move only in a direction parallel to the chain.
Only nearest neighbours interact (short-range forces).

Un-2

Un-1

Un

Un+1

Un+2

Monoatomic Chain

Start

with the simplest

case
of
monoatomic
linear chain with only
nearest
neighbour
interaction
Un-1

Un

Un+1

If one expands the energy near the equilibrium point for the nth
atom and use elastic approximation, Newtons equation becomes
..

m u n K (un 1 2un un 1 )

Monoatomic Chain

The force on the nth atom;

The force to the right;

K (u n 1 u n )
The force to the left;

K (u n u n 1 )

Un-1

Un

Un+1

The total force = Force to the right Force to the left

..

m u n K ( 2u n u n 1 u n 1 ) 0
Eqns of motion of all atoms are of this form, only the
value of n varies

Monoatomic Chain

All

atoms oscillate with a same amplitude A and

frequency . Then we can offer a solution;
0

un A exp i kxn t

dun
0

un
i A exp i kxn t
dt
.

d 2 un
2
u n 2 i 2 A exp i kxn0 t
dt
..

0
n

na

Undisplaced
position

xn na un

..

u n 2un
Displaced
position

Monoatomic Chain

Equation of motion for nth atom

..

mu n K (un 1 2un un 1 )
2

m A e

i kxn 0 t

K Ae

m A e
2

m A e

i kna t

i kna t

2A e

K Ae

Ae

i kna ka t

i kna t

i kxn 0 t

Ae

ika

2A e

2A e

i kna t

i kna t

Cancel Common terms

m 2 K eika 2 e ika

i kxn10 t

k ( n 1) a

kna

k ( n 1) a

kna

i kxn10 t

Ae

Ae

i kna ka t

i kna t

ika

Monoatomic Chain

m 2 K eika 2 e ika

eix eix 2 cos x

eika e ika 2 cos ka

m 2 K 2 cos ka 2
2 K (1 cos ka)
2
2 ka
m 4 K sin
2
4K
2
2 ka

sin
m
2
4K
ka

sin
m
2

max

4K
m

1 cos x

2 sin 2

Maximum value of it is
1

K c :
semacam
konstanta pegas

Monoatomic Chain

versus k relation;

max 2

K
m

Vs / k
C

/a

/a

2/a

Normal mode frequencies of a 1D chain

The points A, B and C correspond to the same frequency, therefore
they all have the same instantaneous atomic displacements.
The dispersion relation is periodic with a period of 2/a.

Monoatomic Chain

Note that:

4K
ka
sin
m
2

In above equation n is cancelled out, this means that the eqn.

of motion of all atoms leads to the same algebraic eqn. This
shows that our trial function Un is indeed a solution of the
eqn. of motion of n-th atom.

We started from the eqn. of motion of N coupled harmonic

oscillators. If one atom starts vibrating it does not continue
with constant amplitude, but transfer energy to the others in
a complicated way; the vibrations of individual atoms are not
simple harmonic because of this exchange energy among
them.

Our wavelike solutions on the other hand are uncoupled

oscillations called normal modes; each k has a definite w
given by above eqn. and oscillates independently of the other
modes.

So the number of modes is expected to be the same as the

number of equations N. Lets see whether this is the case;

Establish which wavenumbers are possible for our one dimensional chain.
Not all values are allowed because nth atom is the same as the (N+n)th as
the chain is joined on itself. This means that the wave eqn. of
Na p

Na 2
2

Nk
p
p
k
a

un A exp i kxn0 t

must satisfy the periodic boundary condition

un u N n
which requires that there should be an integral number of wavelengths in
the length of our ring of atoms

Na p
Thus, in a range of 2/a of k, there are N allowed values of k.

Monoatomic Chain

What is the physical significance

2/aof wave
numbers outside the range of
?
un

x
a
un

Monoatomic Chain

This value of k corresponds to the

maximum frequency; alternate atoms
oscillate in antiphase and the waves
at this value of k are standing waves.

2a;k 2 k

a
White line :

4 7a 7a k 2 8 1.14
7a 7a
4
a
4
Green line :
3 7a 7a k 2 6 0.85
7a 7a
3
a
3
u
n

x
u a
n

-k relation

Monoatomic Chain

The points A and C both have same

frequency and same atomic displacements
C

They are waves moving to the left.

The green line corresponds to the point B
in dispersion diagram.

The point B represents a wave moving to

the right since its group velocity (d/dk)>0.
u

k
-k relation (dispertion diagram)
-/a

The point B has the same frequency and

displacement with that of the points A and C
with a difference.

K
m
Vs / K

/a

2/a

The points A and C are exactly

equivalent; adding any multiple of
2/a to k does not change the
frequency and its group velocity, so
point A has no physical significance.
k=/a has special significance

=90o

ka
n 2
2m k4K sin
k= n/aa
2

Bragg reflection
at
2 obtained
n n2can
nbe

u a
n

For the
range of k ()
2a whole
2d sin90
1 4 2 43 d a

At the beginning of the

chapter, in the long
wavelength limit, the
velocity of sound waves has
been derived as

c Ka

Vs c

Using elastic properties, lets

see whether the dispersion
relation leads to the same
equation in the long limit.
If is very long;

ka pp 1

2a 2
k
2m 4 K
4

so

m
a

sin ka ka

Vs
a
k
m

K a2
m

Monoatomic Chain

Since

there is only one possible propagation

direction and one polarization direction, the 1D
crystal has only one sound velocity.
In this calculation we only take nearest neighbor
interaction although this is a good approximation
for the inert-gas solids, its not a good
assumption for many solids.
If we use a model in which each atom is
attached by springs of different spring constant
to neighbors at different distances many of the
features in above calculation are preserved.
Wave equation solution still satisfies.
The detailed form of the dispersion relation is
changed but is still periodic function of k with
period 2/a
Group velocity vanishes at k=()/a
There are still N distinct normal modes
Furthermore the motion at long wavelengths
corresponds to sound waves with a velocity given by
(velocity formul)

Gelombang Murni Dan Gelombang Paket

45

Kecepatan Rambat Gelombang Untuk Kisi Malar

Persamaan gerak hubungan antara dan bil gelombang q

Kecepatan fasa dan

Kecepatan grupnya :

46

Kecepatan Rambat Gelombang Untuk Kisi Diskrit

47

Chain of two types of atom

Two

different types of atoms of masses M and m are

connected by identical springs of spring constant K;
(n-2)

(n-1)
K

(n)
K

(n+1)
K

(n+2)
K

a)

a
b)
Un-2

Un-1

Un

Un+1

Un+2

This is the simplest possible model of an ionic crystal.

Since a is the repeat distance, the nearest neighbors
separations is a/2

Chain of two types of atom

We

will consider only the first neighbour interaction

although it is a poor approximation in ionic crystals
because there is a long range interaction between the
ions.

The

model is complicated due to the presence of two

different types of atoms which move in opposite
directions.
Our aim is to obtain -k relation for diatomic lattice
Two equations of motion must be written;
One for mass M, and
One for mass m.

Chain of two types of atom

Un-2

Un-1

M
Un

Un+1

Equation of motion for mass M (nth):

mass x acceleration = restoring force
..
M u n K (un1 un ) K (un un1 )
K (un1 2un un1 )
Equation of motion for mass m (n-1)th:
..

mu n K (un un1 ) K (un1 un2 )

-1

..

mu n K (un 2un1 un2 )

-1

M
Un+2

Chain of two types of atom

M
Un-2

m
Un-1

M
Un

Un+1

M
Un+2

Offer a solution for the mass M

un A exp i kxn0 t

xn0 na / 2

For the mass m;

un A exp i kxn0 t
-1

: complex number which determines the relative amplitude

and phase of the vibrational wave.
..
u n 2 A exp i kxn0 t

Chain of two types of atom

For nth atom (M):

..

M u n K (un1 2un un1 )

2 MAe

MAe
2

kna
t
2

kna
t
2

K Ae

K Ae

k n 1 a

2 Ae

kna
t
2

Ae

k n 1 a
t
2

ka
2

M K e 2 e

ka

2 M 2 K 1 cos
2

kna
t
2

ka
2

2 Ae

kna
t
2

Ae

kna

t
2

Cancel common terms

ka
2

eix e ix 2 cos x

ka
2

Chain of two types of atom

For the (n-1)th atom (m)

..

m u n 1 K (un 2un 1 un 2 )
A me
2

mAe
2

k n 1 a
t
2

kna
t
2

ka
2

kna
t
2

K Ae

i
K Ae

kna
t
2

2 Ae

2 Ae

k n 1 a
t
2

kna
t
2

k n 2 a

Ae
ka
2

Ae

kna

t
2

Cancel common terms

me

ka
2

ka
2

K 1 2 e e

ka
ka
i
i

2 m K e 2 2 e 2

eix e ix 2 cos x
2

ika

ka
m 2 K cos
2

2 ka
2

Chain of two types of atom

ka
M 2 K 1 cos
2

ka

2
m K cos
2

for M

for m

Now

we have a pair of algebraic equations for and

as a function of k. can be found as

2 K cos(ka / 2)
2K 2M

2
2K m
2 K cos( ka / 2)
A

quadratic equation for 2 can be obtained by crossmultiplication

Chain of two types of atom

2 K cos( ka / 2)
2K 2 M

2
2K m
2 K cos(ka / 2)

ka
4 K cos ( ) 4 K 2 2 K 2 ( M m) 4 Mm
2
2

4 K 2 (1 cos 2 (

ka
)) 2 K 2 ( m M ) 4 Mm 0
2

2
m

M
sin
(ka / 2)
4
2
2
2K (
) 4 K
0
mM
mM

The two roots are;

m2

b b 2 4ac
x1,2
2a

K (m M )
m M 2 4sin 2 ( ka / 2) 1/ 2

mK [(
)
]
mM
mM
mM

This is Solution I (-): ACOUSTICAL BRANCH FREQUENCY

Chain of two types of atom

versus k relation for diatomic chain;

/a

Optical Branch
Upper branch is due to the
+ve sign of the root.

B
C

/a

2/a

Acoustical Branch
Lower branch is due to the
-ve sign of the root.

Normal
mode contains
frequencies
of acells
chain
two types
of atoms.
If the crystal
N unit
weofwould
expect
to find
At A, the two atoms are oscillating in antiphase with their centre
2N normal modes of vibrations and this is the total number of
of mass at rest;
atoms
and
hence
the total
number of and
equations
motion for
at B, the
lighter
mass
m is oscillating
M is atof
rest;
mass
Misand
m.
at C, M
oscillating
and m is at rest.

Chain of two types of atom

As

there are two values of for each value of k, the

dispersion relation is said to have two branches;

/a

Optical Branch
Upper branch is due to the
+ve sign of the root.

B
C

/a

2/a

Acoustical Branch
Lower branch is due to the
-ve sign of the root.

The dispersion relation is periodic in k with a period

2 /a = 2 /(unit cell length).
This result remains valid for a chain of containing an
arbitrary number of atoms per unit cell.

Chain
Chainof
oftwo
twotypes
typesof
ofatom
atom

Lets examine the limiting solutions at 0, A, B and C.

In long wavelength region (ka1); sin(ka/2) ka/2 in
-k.
2

1,2

K (m M )
m M 2 4sin (ka / 2) 1/ 2

mK [(
)
]
mM
mM
mM

KmM

m M
4 k a

K

mM
mM 4
mM
12

KmM
mM
2 2

1 1
k
a
2

mM
m

12

1 x 1 x 2
UseTaylorexpansion:forsmallx
12

KmM
mM

mM
2 2
k a
1 1
2
2(m M )

Chain of two types of atom

Taking +ve root; sinka1

max opt
2

(max value of optical branch)

2K m M
mM

2K M
Taking -ve root; (min value of acoustical brach)
2 K cos(ka / 2)
2 2
2 2
K
m

mMk
a
Kk
a
min acus.2

2(m M ) 2
mM
2(m M )

By substituting these values of in (relative amplitude)

equation and using cos(ka/2) 1 for ka1 we find the
corresponding values of as;

M

m
OR

Chain of two types of atom

Substitute 2
min ac

2
min ac

into relative amplitude

2K 2M

2 K cos(ka / 2)

2 2

K(k a )

2(m M)

This solution represents long-wavelength sound waves in the

neighborhood of point 0 in the graph; the two types of atoms
oscillate with same amplitude and phase, and the velocity of
sound is

Optical

vs

B
C

Acoustical

/a

/a

k
2/a

w
K
a

k
2(
m

M
)

1/ 2

Chain of two types of atom

Substitute
max op

into relative amplitude we obtain,

2K 2 M

2 K cos(ka / 2)

2K(m M)

mM

2
max op

Optical

B
C

Acoustical

k
/a

/a

2/a

M
m

This solution corresponds to point A in

dispersion graph. This value of shows
that the two atoms oscillate in
antiphase with their center of mass at
rest.

Chain of two types of atom

other limiting solutions of equation 2 are for ka= ,

i.e sin(ka/2)=1. In this case

The

M m
K (m M )
4

mK

Mm
Mm
Mm
2

2
max ac

1/ 2

K (m M ) mK ( M m)

Mm

2
max ac

2K

(C)

OR

2
min op

2K

(B)

At max.acoustical point C, M oscillates and m is at rest.

At min.optical point B, m oscillates and M is at rest.

Acoustic/Optical Branches
The

acoustic branch has this name because it gives

rise to long wavelength vibrations - speed of sound.

The

optical branch is a higher energy vibration (the

frequency is higher, and you need a certain amount of
energy to excite this mode). The term optical comes
from how these were discovered - notice that if atom
1 is +ve and atom 2 is -ve, that the charges are
moving in opposite directions. You can excite these
modes with electromagnetic radiation (ie. The
oscillating electric fields generated by EM radiation)

Transverse optical
mode for
diatomic chain

Amplitude of vibration is strongly exaggerated!

Transverse acoustical mode for

diatomic chain

What is phonon?
Consider

the regular lattice of atoms in a uniform solid

material.
There should be energy associated with the vibrations
of these atoms.
But they are tied together with bonds, so they can't
vibrate independently.
The vibrations take the form of collective modes which
propagate through the material.
Such propagating lattice vibrations can be considered
to be sound waves.
And their propagation speed is the speed of sound in
the material.

Phonon

The

vibrational energies of molecules are

quantized and treated as quantum harmonic
oscillators.
Quantum harmonic oscillators have equally
spaced energy levels with separation E = h.
So the oscillators can accept or lose energy only
in discrete units of energy h.
The evidence on the behaviour of vibrational
energy in periodic solids is that the collective
vibrational modes can accept energy only in
discrete amounts, and these quanta of energy
have been labelled "phonons".
Like the photons of electromagnetic energy, they
obey Bose-Einstein statistics.

CHAPTER 2
CRYSTAL DYNAMICS II

PHONONS
Quanta of lattice
vibrations
Energies of phonons are
quantized

E phonon

h s

p phonon

PHOTONS
Quanta of electromagnetic
radiation
Energies of photons are
quantized as well

E photon
~a0=10-10m

hc

~10-6m

p photon

Energy of harmonic oscillator

Obtained by in a classical way of considering the normal
modes that we have found are independent and
harmonic.

1
n n
2

Make a transition to Q.M.

Represents equally spaced

energy levels

Energy, E

Energy levels of atoms

vibrating at a single
frequency

It is possible to consider n as constructed by adding n excitation

quanta each of energy to the ground state.

1
0
2
A transition from a lower energy level to a higher energy level.

1
1

n2 n1
2
2

n2 n1 h h
14 2 43
unity

absorption of phonon

 The

converse transition results an emission of

energy
phonon with an
.
Phonons are quanta of lattice vibrations with
an angular frequency
.
of
Phonons are not localized particles.
Its momentum is exact, but position can not
be determined because of the uncertainity
princible.
However, a slightly localized wavepacket
can be considered by combining modes of

slightly
.
different and


Assume waves with a spread of k of
; so this wavepacket will
10a
be localized within 10 unit cells.

This wavepacket will represent a fairly localized phonon moving with

d .
group velocity

dk

Phonons can be treated as localized particles within some limits.

Energy of
phonons

1D crystals

Multiply by

Crystal momentum

Phonons are not conserved

They can be created and destroyed during collisions .

Thermal energy and lattice

vibrations
Atoms vibrate about their equilibrium position.
They produce vibrational waves.
This motion is increased as the temperature is
raised.
In a solid, the energy associated with this vibration and perhaps also
with the rotation of atoms and molecules is called as thermal energy.

Note: In a gas, the translational motion of atoms and molecules

contribute to this energy.

Therefore, the concept of thermal energy is fundamental to an

understanding many of the basic properties of solids. We would like to
know:
What is the value of this thermal energy?
How much is available to scatter a conduction electron in a metal;
since this scattering gives rise to electrical resistance.
The energy can be used to activate a crystallographic or a magnetic
transition.
How the vibrational energy changes with temperature since this gives
a measure of the heat energy which is necessary to raise the
temperature of the material.
Recall that the specific heat or heat capacity is the thermal energy
which is required to raise the temperature of unit mass or 1gmole by
one Kelvin.

Heat capacity from Lattice vibrations

The energy given to lattice vibrations is the
dominant
contribution to the heat capacity in most solids. In non-magnetic
insulators, it is the only contribution.
Other contributions;
In metals from the conduction electrons.
In magnetic materials from magneting ordering.
Atomic vibrations leads to band of normal mode frequencies from zero
up to some maximum value. Calculation of the lattice energy and heat
capacity of a solid therefore falls into two parts:
i) the evaluation of the contribution of a single mode, and
ii) the summation over the frequency distribution of the modes.

Energy and heat capacity of a harmonic

oscillator, Einstein Model
_

Pn n
n

Avarage energy of a harmonic

oscillator and hence of a lattice
mode of angular frequency at
temperature T

The probability of the oscillator being in this

level as given by the Boltzman factor

exp( n / k BT )

Energy of oscillator

1
n n h
2

1
n

exp

/
k
T

B

_
2
2

n0

exp

/
k
T

B

2

n0

Pn n
n

(*)

1 h
z exp[(n )
]
2 k BT
n 0

z e h / 2 kBT e 3h / 2 kBT e 5 h / 2 kBT .....

z e h / 2 kBT (1 e h / kBT e 2 h / kBT .....
z e h / 2 kBT (1 e h / kBT ) 1
According to the Binomial expansion for x1 where x h / k BT

Eqn (*) can be written

1 z
2
k BT
k BT
(ln z )
z T
T
_
e h / 2 kBT
2
k BT
ln

T 1 e h / kBT
_

h / 2 k BT
h / k BT

ln
e

ln
1

k BT 2

k BT
T
_

k BT 2

h / k BT
ln 1 e

2
k
T

h k B h / kBT
e
2 2
2k B h k B T

2 2
h / k BT
4 k BT
1

1
h e h / kBT
h
h / k BT
1

e
2

1
h
h h / kBT
2
e
1
_

x'
(ln x)
x
x

1
h
h h / kBT
2
e
1
_

This is the mean energy of phonons.The first term in the above

equation is the zero-point energy. As we have mentioned before even
at 0K atoms vibrate in the crystal and have zero-point energy. This is
the minimum energy of the system.
The avarage number of phonons is given by Bose-Einstein
distribution as
_

(number of phonons) x (energy of phonon)=(second term in )

n( )

1
e

k BT

The second term in the mean energy is the contribution of

phonons to the energy.

k BT

Mean energy of a
harmonic oscillator
as a function of T

2
T

low temperature limit

k BT

2
e kBT 1
_

Since exponential term

gets bigger

1
Zero point energy
2
_

Mean energy of a
harmonic oscillator as
a function of T

k BT

2
T
high temperature limit

h = k BT

is independent of frequency of
oscillation.
This is the classical limit because the
energy steps are now small compared with
the energy of the harmonic oscillator.
So that
is the thermal energy of the
classical 1D harmonic oscillator.

2
x
e x 1 x ..........
2!

k BT
e
1
k BT
_
1

2
1
1
k BT
_
1
k BT
2

kBT

Heat Capacity C
Heat

capacity C can be found by differentiating the average energy of

phonons of
1

2
e kBT 1
_

d
Cv

dT

Let

h k B

k BT

h
k BT

k BT

Cv k B
2
k
T
B
2

Cv k B
T

e
e

h
k BT

e 1

k BT

Plot of Cv

Cv k B
T

as a function of T

e 1

where

h
k

Specific heat vanishes

exponentially at low Ts and tends to
classical value at high temperatures.

Cv

kB
Area=

h
kB

h
The features are common to all
2 quantum systems; the energy tends
to the zero-point-energy at low Ts
T
and to the classical value of
Boltzmann constant at high Ts.

Plot of Cv

as a function of T

Specific heat at constant volume depends on temperature as shown in

figure below. At high temperatures the value of C v is close to 3R,
where R is the universal gas constant. Since R is approximately 2
cal/K-mole, at high temperatures Cv is app. 6 cal/K-mole.

Cv

3R

T, K

This range usually includes RT.

From the figure it is seen that Cv is
equal to 3R at high temperatures
regardless of the substance. This fact
is known as Dulong-Petit law. This law
states that specific heat of a given
number of atoms of any solid is
independent of temperature and is the
same for all materials!

Classical theory of
heat capacity of solids
The solid is one in which each atom is bound to its side by
a harmonic force. When the solid is heated, the atoms vibrate
around their sites like a set of harmonic oscillators. The
average energy for a 1D oscillator is kT. Therefore, the
averaga energy per atom, regarded as a 3D oscillator, is 3kT,
and consequently the energy per mole is
=3NkBT 3RT
where N is Avagadros number, kB is Boltzmann constant and
R is the gas constant. The differentiation wrt temperature
gives;
d
Cv 3R 3 6.02 1023 (atoms / mole) 1.38 1023 ( J / K )
Cv
dT
J
Cal
Cv 24.9
;1J 0.2388Cal Cv ; 6
( K mole)
( K mole)

Einstein heat capacity of solids

The theory explained by Einstein is the first quantum theory of

solids. He made the simplifying assumption that all 3N vibrational
modes of a 3D solid of N atoms had the same frequency, so that the
whole solid had a heat capacity 3N times

2
eT

Cv k B
2

T
T
e 1

In this model, the atoms are treated as independent oscillators, but

the energy of the oscillators are taken quantum mechanically as

This refers to an isolated oscillator, but the atomic oscillators in a

solid are not isolated.They are continually exchanging their energy
with their surrounding atoms.

Even this crude model gave the correct limit at high temperatures, a
heat capacity of

3 Nk B 3R

Dulong-Petit law where R is universal gas constant.

 At high temperatures, all crystalline solids have a specific heat of

6 cal/K per mole; they require 6 calories per mole to raise their
temperature 1 K.
This arrangement between observation and classical theory break
down if the temperature is not high.
Observations show that at room temperatures and below the
specific heat of crystalline solids is not a universal constant.
Cv
cal
6
Kmol

h
kB

T
Cv 3 R

In all of these materials

(Pb,Al, Si,and Diamond)
specific heat approaches
constant value asymptotically
at high Ts. But at low Ts, the
specific heat decreases
towards zero which is in a
complete contradiction with
the above classical result.

The Discrepancy of Einstein model

Einstein

model also gave correctly a specific heat tending to

zero at absolute zero, but the temperature dependence near
T=0 did not agree with experiment.

Taking

into account the actual distribution of vibration

frequencies in a solid this discrepancy can be accounted using
one dimensional model of monoatomic lattice

Density of States
According to Quantum Mechanics if a particle is constrained;
the energy of particle can only have special discrete energy
values.
it cannot increase infinitely from one value to another.
it has to go up in steps.

 These

steps can be so small depending on the system that the

energy can be considered as continuous.
This is the case of classical mechanics.
But on atomic scale the energy can only jump by a discrete
amount from one value to another.

Definite energy levels

Steps get small

Energy is continuous

 In

some cases, each particular energy level can be

associated with more than one different state (or
wavefunction )
This energy level is said to be degenerate.

density of states ( ) is the number of discrete states

per unit energy interval, and so that the number of states
between and d will be ( )d .

The

There are two sets of waves for solution;

Running waves
Standing waves
Running waves:
0

4
L

2
L

2
L

4
L

6
L

These allowed k wavenumbers corresponds to the running

waves; all positive and negative values of k are allowed. By
means of periodic boundary condition
an integer

Na 2
2
2
L Na p

k
pk
p
p
k
Na
L

Length of
the 1D
chain

These allowed wavenumbers are uniformly distibuted in k at a

density of R k between k and k+dk.
running waves

L
R k dk
dk
2

Standing waves:
0

2
L

3
L

6
L

5
L

7
L

4
L

3
L

2
L

In some cases it is more suitable to use standing waves,i.e. chain

with fixed ends. Therefore we will have an integral number of half
wavelengths in the chain;
n
2
2 n
n
L ;k
k
k
2

2L
L
These are the allowed wavenumbers for standing waves; only
positive values are allowed.
2
k
p
L

for
running waves

k p
L

for
standing waves

These allowed ks are uniformly distributed between k and k+dk

at a density of S (k )
L
S (k )dk dk

L
R k dk
dk
2

DOS of standing wave

DOS of running wave

The density of standing wave states is twice that of the running waves.
However in the case of standing waves only positive values are
allowed
Then the total number of states for both running and standing waves
will be the same in a range dk of the magnitude k
The standing waves have the same dispersion relation as running
waves, and for a chain containing N atoms there are exactly N distinct
states with k values in the range 0 to / a .

The density of states per unit frequency

range g( ):
number of modes with frequencies and +d will be
g()d.
g() can be written in terms of S(k) and R(k).
The

dR
dn

modes with frequency from to +d corresponds

modes with wavenumber from k to k+dk

dn S (k )dk g ( )d

dn R (k )dk g ( )d ;

Choose standing waves to obtain

g ( )

g ( ) S (k )

dk
d

Lets remember dispertion relation for 1D monoatomic lattice

4K
2 ka

sin
m
2
2

d
2a K K kaka
a
cos
cos
dk
2 mm 2 2

K
ka
2
sin
m
2
1 m1
1
g ( ) S (k )
a KK
ka
ka
cos
a
cos
2 2
m

1
g ( ) S (k )
a

m
1
K cos ka / 2

sin x cos x 1 cos x 1 sin x

2

1
g ( ) S (k )
a

m
K

1
ka

1 sin 2

4
4

ka
2 ka
cos 1 sin
2
2
Multibly and divide

Lets remember:

g ( ) S (k )

1
a

2
4K 4K
2 ka

sin
m
m
2

2Na
LN 2 2 1 2 1/ 2
max
g ( )

2
a max
2
True density of states

L
S (k )dk dk

L Na
4K
2
2 ka

sin
m
2
4K
2
max
m

g ( )

2N 2
2 1/ 2
g ( )
max

m
K

True density of states by

means of above equation

max

K
2
m

constant density of states

K
True DOS(density of states) tends to infinity at
m
since the group velocity d / dk goes to zero at this value of .

max 2 ,

Constant density of states can be obtained by ignoring the

dispersion of sound at wavelengths comparable to atomic spacing.

The energy of lattice vibrations will then be found by

integrating the energy of single oscillator over the distribution
of vibration frequencies. Thus

h
1
h h / kT g d
2
e
1
0

Mean energy of a harmonic

oscillator

2N 2
2 1/ 2
max for 1D

One can obtain same expression of g ( ) by means of using

running waves.
It should be better to find 3D DOS in order to compare the
results with experiment.

3D DOS
Lets do

it first for 2D
Then for 3D.

L
Consider a crystal in the shape of 2D box with crystal
lengths of L.

ky

kx

Standing wave pattern for a

2D box

Configuration in k-space

Lets calculate the number of modes within a range of

wavevector k.
Standing waves are choosen but running waves will lead
same expressions.
Standing waves will be of the form
U U 0 sin k x x sin k y y
Assuming the boundary conditions of
Vibration amplitude should vanish at edges of
x 0; y 0; x L; y L
Choosing
p
q
kx
; ky
L
L

positive integer

ky

y
L
0

Standing wave pattern for

a 2D box

kx

Configuration in k-space

The allowed k values lie on a square lattice of side / L in

the positive quadrant of k-space.
These values will so be distributed uniformly with a density
2
L
/

per unit area.

of
This result can be extended to 3D.

Octant of the crystal:

kx,ky,kz(all have positive values)
The number of standing waves;
L

V 3
L
3
s k d k d k 3 d k

1
4 k 2 dk
L /
8
V 1
3
s k d k 3 4 k 2 dk
8
2
Vk
s k d 3k 2 dk
2
ky
Vk 2
S k 2
2
3

kz
dk

kx

is a new density of states defined as the

Vk 2
k 2
2
number of states per unit magnitude of in 3D.This eqn
can be obtained by using running waves as well.
(frequency) space can be related to k-space:
dk
g k
g d k dk
d
Lets find C at low and high temperature by means of
using the expression of

High and Low Temperature Limits

Each of the 3N lattice
modes of a crystal
containing N atoms

3 Nk BT

d
C
dT

C 3 Nk B

h
T ? if
This result is true only
kB

At

low Ts only lattice modes having low

frequencies can be excited from their ground
states;
Low frequency
long

sound waves

vs k

vs
k


k 1
dk 1
vs

k
vs
d vs
2
V 2
vs 1

g
2 2 vs

and

Vk 2 dk
g 2
2 d

at low Ts

vs depends on the direction and there are two transverse,

one longitudinal acoustic branch:
V2 1
V 2 1 2
g
g
3
2
3
2
3
2 vs
2 vL vT
Velocities of sound in
longitudinal and
transverse direction

h
1
h h / kT g d
2
e
1
0

Zero point energy= z

h
V 2 1 2
1
h h / kT 2 3 3 d
2
e
1
2 vL vT
0

h
V 1 2
h 3
x
z 2 3 3 h / kT
d
k BT

2 vL vT 0 e

k BT
3

x
k BT
3
h
x

k
T
h 3
h

B
d

0 eh / kT 1
0 e x 1 4 4h dx
k BT
d
dx
V 1 2 k BT
h
z 3 2 3 3 4 3 3
h 2 vL kvBTT h x 15
0 eh / kT 1 d 2 h3 0 e x 1dx 3
22 4 4 3k3BT
d V2 2 1 1214
Cv
V3 k3B 33 kB34154 T at low temperatures
dT 15
30h vL vvLT vT h

How good is the Debye

approximation
at low T?
1
d
2
2 k BT
2
Cv
V k B 3 3

dT 15
v
v
h

L
T

The lattice heat capacity of solids thus

T 3varies as
at low temperatures; this is
law.
T 3 referred to as the Debye
Figure illustrates the excellent aggrement
of this prediction with experiment for a
non-magnetic insulator. The heat
capacity vanishes more slowly than the
exponential behaviour of a single
harmonicoscillatorbecausethevibration
spectrum extends down to zero
frequency.

The Debye interpolation scheme

g ( )

The calculation of
is a very heavy calculation for 3D, so it
must be calculated numerically.
Debye obtained a good approximation to the resulting heat
capacity by neglecting the dispersion of the acoustic waves, i.e.
assuming

s k

for arbitrary wavenumber. In a one dimensional crystal this is

equivalent to taking g ( ) as given by the broken line of density of
states figure rather than full curve. Debyes approximation gives the
correct answer in either the high and low temperature limits, and the
language associated with it is still widely used today.

The Debye approximation has two main steps:

1. Approximate the dispersion relation of any branch by a linear
extrapolation of the small k behaviour:
Einstein
approximation
to the
dispersion

Debye
approximation
to the
dispersion

vk

D
Debye cut-off frequency
2. Ensure the correct number of modes by imposing a cut-off
frequency D , above which there are no modes. The cut-off
freqency is chosen to make the total number of lattice modes
correct. Since there are 3N lattice vibration modes in a crystal
having N atoms, we choose D so that
D

g ( )d 3N

g ( )

V 1 2
( )
2 2 vL3 vT3
2

V
1
2
(

) D3 3 N
2
3
3
6
vL vT

9N 2
g ( ) 3
D

V 1 2 D 2
( ) d 3N
2 2 vL3 vT3 0
V
1
2
3N
9N
(

2 2 vL3 vT3
D3
D3

g ( ) / 2

The lattice vibration energy of

1
h
E ( h h / kBT )g ( ) d
2
e
1
0
becomes

9N D 1
h
9N
E 3 ( h h / kBT ) 2 d 3
D 0 2
e
1
D
and,

9
9N
E N hD 3
8
D

h 3
d
2

h 3
e h / kBT

d
1

h 3 d
e h / kBT 1

First term is the estimate of the zero point energy, and all T dependence is
in the second term. The heat capacity is obtained by differentiating above eqn
wrt temperature.

The heat capacity is

9
9N
E N hD 3
8
D

dE
dT

h 3 d
e h / kBT 1

dE 9 N
CD
3
dT D

h2 4
e h / kBT
d
2
2
h

/
k
T
k BT e B 1

Lets convert this complicated integral into an expression for

the specific heat changing variables to x
h
x
k BT

d kT

dx
h

and define the Debye temperature

hD
D
kB

kT
x
h

The Debye prediction for lattice specific heat

T
CD 9 Nk B

3 /T
D

x 4e x

dx

where
CD

hD
k
k T B h

dE 9 N k BT

dT D3 h

2
k BT

D / T

x 4e x

e x 1

dx

How does

Climit
at high and low temperatures?
D
High temperature T ? D

X is always small

x2
x3
e 1 x

2!
3!
x

x 4 (1 x)
2

x
2
2
2
x
x
1

1

x 4e x

x 4 (1 x)

T
T ? D CD 9 Nk B

3 /T
D

x 2 dx 3Nk B

How does CD limit at high and low temperatures?

Low temperature

T = D

For low temperature the upper limit of the integral is infinite; the
integral is then a known integral of
4. 4 /15

T
T = D CD 9 Nk B

3 /T
D

x 4e x

dx

3
We obtain the Debye T law in the form

12 Nk B 4 T
CD

Lattice heat capacity due to Debye

interpolation scheme
C
Figure shows the heat capacity
3Nk B T
between the two limits of high and
1
low T as predicted by the Debye
interpolation formula. 3 D / T
T
x 4e x
CD 9 Nk B
dx

2
x
D
0 e 1
Because it is exact in both high and low T
limits the Debye formula gives quite a good
T / D
representation of the heat capacity of most solids,
1
even though the actual phonon-density of states
Lattice heat capacity of a solid as
predicted by the Debye interpolation
curve may differ appreciably from the Debye
scheme
assumption.
Debye frequency and Debye temperature scale with the velocity of sound in
the solid. So solids with low densities and large elastic moduli have high D . Values of
for D
various solids is given in table. Debye energy
h D
can be used to
estimate

the
maximum
energy inCs
a solid. Fe
Solid
Ar phononNa
D (K )

93

158

38

457

Cu

Pb

KCl

343

105

2230

235

Anharmonic Effects
Any real crystal resists compression to a smaller volume than its equilibrium value
more strongly than expansion due to a larger volume.
This is due to the shape of the interatomic potential curve.
This is a departure from Hookes law, since harmonic application does not produce
this property.
This is an anharmonic effect due to the higher order terms in potential which are
ignored in harmonic approximation.

V (r ) V (a )

r a
2

d 2V
....................

2
dr

r a

Thermal expansion is an example to the anharmonic effect.

In harmonic approximation phonons do not interact with each other, in the absence
of boundaries, lattice defects and impurities (which also scatter the phonons), the
thermal conductivity is infinite.
In anharmonic effect phonons collide with each other and these collisions limit
thermal conductivity which is due to the flow of phonons.

Phonon-phonon collisions
The coupling of normal modes by the unharmonic terms in the
interatomic forces can be pictured as collisions between the phonons
associated with the modes. A typical collision process of

phonon1

1 , k1

3 , k3
After collision another phonon is
produced

phonon2

2 , k 2

and
3 1
2

h3 h1 h2

conservation of energy

hk3 hk1 hk2

conservation of momentum

k3 k1 k2

Phonons are represented by wavenumbers with

k
a
a
If k3 lies outside this range add a suitable multible of 2 to
a
bring

k3 k1 k2
k
a
a
it back within the range of
. Then,
n 2
This phonon is indistinguishable
becomes
k3
k1 k2
from a phonon with wavevector

where

k3

k1 , k2 , and k3 are all in the above range.

Longitudinal

Transverse

a
n Normal
0 process

Phonon3 has k p
a

3'

a
n Umklapp
0 process

3
2

(due to anharmonic effects)

; Phonon3 has k f
and Phonon3=Phonon3
a

Thermal conduction by phonons

Aflowofheattakesplacefromahotterregiontoacoolerregion

whenthereisatemperaturegradientinasolid.
Themostimportantcontributiontothermalconductioncomesfrom
theflowofphononsinanelectricallyinsulatingsolid.
Transportpropertyisanexampleofthermalconduction.
Transport property is the process in which the flow of some
quantityoccurs.
Thermalconductivityisatransportcoefficientanditdescribesthe
flow.
The thermal conductivity of a phonon gas in a solid will be
calculated by means of the elementary kinetic theory of the
transportcoefficientsofgases.

Kinetic theory
In the elementary kinetic theory of gases, the steady state flux of a property P
in the z direction is

1 _ dP
flux l
3 dz

Angular average

Constant average speed for

molecules
In the simplest case where P is the number density of particles the transport
coefficient obtained from above eqn. is the diffusion coefficient D 1 l
.
Mean free path

IfP is the energy densityE

then the flux W is the heat flow per unit area so
that
1 _ dE 1 _ dE dT

W l
l
3 dz 3 dT dz

Now dE / dT is the specific heat C per unit volume, so that the thermal
conductivity;
1 _
K
l C
3

Works well for a phonon gas

Heat conduction in a phonon and real gas

The essential differences between the processes of heat
conduction in a phonon and real gas;
Phonon gas

Real gas

Speed is approximately constant.

No flow of particles

Both the number density and energy

density is greater at the hot end.

Average velocity and kinetic energy per

particle are greater at the hot end, but the
number density is greater at the cold end,
and the energy density is uniform due to the
uniform pressure.

Heat flow is primarily due to phonon

flow with phonons being created at the
hot end and destroyed at the cold end

hot

cold

Heat flow is solely by transfer of kinetic

energy from one particle to another in
collisions which is a minor effect in phonon
case.
hot

cold

Temperature dependence of thermal conductivity

K

Vanishes exponentially at
low Ts and tends to classical
value
at highkTs
B

1 _
K l C
3

Approximately equal to
velocity of sound and so
temperature independent.

Temperature dependence of phonon mean free length is determined by

phonon-phonon collisions at low temperatures
Since the heat flow is associated with a flow of phonons, the most effective
collisions for limiting the flow are those in which the phonon group velocity
is reversed. It is the Umklapp processes that have this property, and these are
important in limiting the thermal conductivity

Conduction at high temperatures

At temperatures much greater then the Debye temperature D the heat capacity is
given by temperature-independent classical result of

C 3Nk B

T 1

The rate of collisions of two phonons phonon density.

If collisions involving larger number of phonons are important, however, then the
scattering rate will increase more rapidly than this with phonon density.

At high temperatures the average phonon density is constant and

the total lattice energy
T;
phonon number
T , so

Scattering rate

T and mean free length

Then the thermal conductivity of

1 _
K l C
3

Experimental results do tend towards this behaviour at high temperatures

as shown in figure (a).

K (Wcm 1K 1 )

10

K (Wcm 1 K 1 )

10

1
T

10-1
5

10 20

50 100

T (K )

(a)Thermal conductivity of a quartz

crystal

T3

10-1

5 10 20

50 100

T (K )

(b)Thermal conductivity of artificial

sapphire rods of different diameters

Conduction at intermediate temperatures

Referring figure a
At T< D ; the conductivity rises more steeply with falling temperature,
although the heat capacity is falling in this region. Why?
This is due to the fact that Umklapp processes which will only occur if there are
phonons of sufficient energy to create a phonon with k3 / a . So
Energy of phonon must be

the Debye energy ( k D )

The energy of relevant phonons is thus not sharply defined but their number
is expected to vary roughly as
when T = ,
e D / bT
D
where b is a number of order unity 2 or 3. Then
D / bT
l

e
This exponential factor dominates any low power of T in thermal conductivity,

such as a factor of

T3

from the heat capacity.

Conduction at low temperatures

l

for phonon-phonon collisions becomes very long at low Ts and eventually

exceeds the size of the solid, because
number of high energy phonons necessary for Umklapp processes decay
exponentially as

D / bT
e
is then limited by collisions with the specimen surface, i.e.

Specimen diameter

T dependence of K comes from

12 Nk B T
CD

D
4

Cv

which obeys

T3

law in this region

Temperature dependence of

Cv

dominates.

Size effect

When the mean free path becomes comparable to the dimensions of the sample,
transport coefficient depends on the shape and size of the crystal. This is known as a
size effect.

If the specimen is not a perfect crystal and contains imperfections such as

dislocations, grain boundaries and impurities, then these will also scatter phonons. At
the very lowest Ts the dominant phonon wavelength becomes so long that these
imperfections are not effective scatterers, so;
3
the thermal conductivity has a T dependence at these temperatures.
D / bT
3
The maximum conductivity between T
and
region is controlled by
imperfections.

For an impure or polycrystalline specimen the maximum can be broad and low
[figure (a) on pg 59], whereas for a carefully prepared single crystal, as illustrated in
figure(b) on pg 59, the maximum is quite sharp and conductivity reaches a very high
value, of the order that of the metallic copper in which the conductivity is
predominantly due to conduction electrons.