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
y Concern with the spectrum of characteristics vibrations of a crystalline

solid.
y Leads to;
y consideration of the conditions for wave propagation in a periodic
y
y
y
y

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 introduces
Th
i t d
us to
t the
th concepts
t off
y forbidden and permitted frequency ranges, and
y electronic spectra of solids

Crystal Dynamics
y

In previous chapters we have assumed that the atoms were at

rest at their equilibrium position. This can not be entirely correct
(against to the HUP); Atoms vibrate about their equilibrium position at
absolute zero.

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

zero point energy.

y The amplitude of the motion increases as the atoms gain more thermal

energy at higher temperatures.

y In this chapter we discuss the nature of atomic motions, sometimes

referred to as lattice vibrations.

y In crystal dynamics we will use the harmonic approximation , amplitude

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

effects occur.

Crystal Dynamics
y 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
a simple
h d used
d to analyse
l
i l harmonic
h
i oscillator.The
ill
Th smallll
amplitude limit is known as harmonic limit.

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

force on each atom is approximately proportional to its displacement

(Hookes Law).

y There are some effects of nonlinearity or anharmonicity for larger

atomic displacements.
displacements

y Anharmonic effects are important for interactions between phonons

and photons.

Crystal Dynamics
y Atomic motions are governed by the forces exerted on atoms

when they are displaced from their equilibrium positions.

y 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
y One of the properties of elasticity is that it takes about twice as

much force to stretch a spring twice as far. That linear

depe de ce o
dependence
of displacement
d sp ace e upo
upon s
stretching
e c g force
o ce is
s ca
called
ed
Hooke's law.

Fspring = k .x
Spring constant k

It takes twice
as much force
t stretch
to
t t ha
spring twice
as far.

2F

Hookes Law

y 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.

y 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.

y The Proportional Limit is the point at which the deformation is no

longer directly proportional to the applied force (Hooke's Law no

l
longer
h ld ) Although
holds).
Alth
h these
th
t
two
points
i t are slightly
li htl different,
diff
t we
will treat them as the same in this course.

SOUND WAVES
waves
are
waves
which propagate
a
y Mechanical
It corresponds
to the
atomic
vibrations
with a longthrough
.
material medium (solid, liquid, or gas) at a wave speed
which depends on the elastic and inertial properties of that
medium.
PresenceThere
of atoms
significance
this wavelength
medium
are has
two no
basic
types ofinwave
motion for
limit,
since
>>a,
so
there
will
no
scattering
due to the
mechanical waves: longitudinal waves and transverse
presence of atoms.
waves.
Longitudinal Waves

Transverse Waves

SOUND WAVES
y Sound waves propagate through solids. This tells us that

wavelike lattice vibrations of wavelength long compared to the

interatomic spacing are possible.
possible The detailed atomic structure
is unimportant for these waves and their propagation is
governed by the macroscopic elastic properties of the crystal.

y We discuss sound waves since they must correspond to the

low frequency, long wavelength limit of the more general lattice

vibrations considered later in this chapter.

y At a given
i
f
frequency
and
d in
i a given
i
di ti in
direction
i a crystal
t l it is
i

possible to transmit three sound waves, differing in their

direction of polarization and in general also in their velocity.

Elastic Waves
y 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
f
d to as elastic
l i waves.

Elastic Wave Propagation (longitudinal) in a bar

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

x+dx

e=

dU
dx

Elastic Waves

y According to Hookes law stress S (force per unit area) is

proportional to the strain e.

S = C.e

C = Young modulus

x+dx

y 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,

( Adx)

2u
= [ S ( x + dx) S ( x) ] A
t 2

Mass x Acceleration

Net Force resulting from stresses

Elastic Waves

y Equation of motion
( Adx)

S = C .e

u
= [ S ( x + dx) S ( x) ] A
t 2
2

[ S ( x + dx) S ( x)] =
( Adx)

2u
2u
=
C
Adx
t 2
x2

S
dx
x

Cancelling common terms of Adx;

2u
2u
=
C
t 2
x 2

u = Ae

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

Which is the wave eqn. with an offered

soln
sol
n and velocity of sound waves ;

i ( kx t )

k = wave number (2/)

= frequency of the wave
A = wave amplitude

= vsk
vs =

C /

Dispersion Relation

y The relation connecting the frequency and wave number is

known as the dispersion relation.

= vs k

At small
At long

Continuum

Discrete

* 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.

Speed of Sound Wave

y 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 p
propagation
p g
in crystalline
y
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

Structure
Type

Nearest
Neighbour
Distance
(A)

Density

(k / 3)
(kg/m

Elastic bulk
modules
Y
(1010 N/m2)

Calculate
d Wave
Speed
(m/s)

Observed
speed of
sound
(m/s)

Sodium

B.C.C

3.71

970

0.52

2320

2250

Copper

F.C.C

2.55

8966

13.4

3880

3830

Aluminum

F.C.C

2.86

2700

7.35

5200

5110

Lead

F.C.C

3.49

11340

4.34

1960

1320

Silicon

Diamond

2 35
2.35

2330

10 1
10.1

6600

9150

Germanium

Diamond

2.44

5360

7.9

3830

5400

NaCl

Rocksalt

2.82

2170

2.5

3400

4730

Solid

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

y A lattice vibrational wave in a crystal is a repetitive and

systematic sequence of atomic displacements of

y longitudinal,
y transverse,
transverse or
y some combination of the two

An equation of motion for any displacement can be

produced
They can be
by
by characterized
means of considering
the restoring forces

A
propagation
velocity,
v
on displaced atoms.
Wavelength
or wavevector
As
a result we can
generate a dispersion relationship
between
frequency
and
wavelength
between angular
A frequency or angular
frequencyor=2
frequency and wavevector.

Lattice vibrations of 1D crystal

Chain of identical atoms
y Atoms interact with a potential V(r) which can be written in
Taylors series.
V (r ) = V (a ) +

V(R)
Repulsive
0

d 2V
2 + ...........
dr r = a

d 2V
K = 2
dr

Attractive
r

This equation looks like as the potential energy

associated of a spring with a spring constant :

r0=4
min

(r a )

r =a

We should relate K with elastic modulus C:

Force = C

(r a )
a

Force = K (r a )

C = Ka

Monoatomic Chain
y The simplest crystal is the one dimensional chain of identical atoms.
y Chain consists of a very large number of identical atoms with identical

masses.

y Atoms are separated by a distance of a.

y Atoms move only in a direction parallel to the chain.
y Only nearest neighbours interact (short-range forces).

Un-2

Un-1

Un

Un+1

Un+2

Monoatomic Chain

y 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
approximation, Newton
Newtons
s equation becomes
..

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

10

Monoatomic Chain

The force on the nth atom;

The force to the right;

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

K (u n u n 1 )

Un

Un+1

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

..

m u n + K ( 2 u 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

y All atoms oscillate with a same amplitude A and frequency .

Then we can offer a solution;

un = A exp i ( kxn0 t )
.

un =

dun
= i A exp i ( kxn0 t )
dt

..
d 2 un
2
2
0

u n = 2 = ( i ) A exp
e p i ( kx
k n t ) u n = 2un
dt

..

0
n

= na

Undisplaced
position

xn = na+un

Displaced
position

11

Equation of motion for nth atom

Monoatomic Chain

..

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

m A e

i kxn0 t

K Ae

i kxn+10 t

2A e

+ Ae

i kxn10 t

i ( kna + ka t )
i ( kna t )
i ( kna ka t )
2 i ( kna t )
m A e
= K Ae
2A e
+ Ae

i ( kna t )
2
m A e
= K

Ae

i ( kna t )

ika

2A e

i ( kna t )

k ( n 1) a

kna

k ( n + 1) a

kna

i kxn0 t

+ Ae

i ( kna t )

ika

)
)

Cancel Common terms

m 2 = K ( eika 2 + e 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 )
ka
m 2 = 4 K sin 2
2
2 =
=

m ax

4K
ka
sin 2
m
2

(1 cos x ) = 2 sin 2

Maximum value of it is 1

4K
ka
sin
m
2

4K
m

12

Monoatomic Chain

y versus k relation;

max = 2

K
m

Vs = / k
B

/a
/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

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

of all atoms leads to the same algebraic eqn.

eqn This shows that our trial
function Un is indeed a solution of the eqn. of motion of n-th atom.

y 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.

y 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.

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

equations N. Lets see whether this is the case;

13

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

u n = 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.
Na = p =

Na 2
2
p
=
Nk =
p
k
a

Monoatomic Chain

What is the physical significance of wave numbers

outside the range of 2/a ?
un

x
a
un

14

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
p
diagram.
g

The point B represents a wave moving to

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

/a 2/a
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
=2
m
Vs = / K

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
K sin
2m =k=k4n/a
a

Bragg reflection
at
2 obtained
n = n2can
= nbe

u a
n

For the
range of k ()
2a whole
= 2d sin90
14243 d = a

15

At the beginning of the chapter,

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

c = Ka

K a2
m

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

2 2
2m = 4 K k a

so

=m
a

sin ka ka

K
Vs = =
a
k
m

Monoatomic Chain

y Since there is only one possible propagation direction

and one polarization direction, the 1D crystal has only

one sound velocity.
y In this calculation we only take nearest neighbor
interaction although this is a good approximation for the
inert gas solids,
inert-gas
solids its not a good assumption for many
solids.
y 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

i still
is
till periodic
i di ffunction
ti off k with
ith period
i d2
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)

16

Chain of two types of atom

y Two different types of atoms of masses M and m are

connected by identical springs of spring constant K;

(n 2)
(n-2)

(n-1)
(n 1)
K

(n)
K

(n+1)

(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

y 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.

y 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.

17

Chain of two types of atom

Un-2

Un-1

Un

Un+1

M
Un+2

Equation of motion for mass M (nth):

mass x acceleration = restoring force
..

M u n = K (un+1 un ) K (un un1 )

= K (un+1 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

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 )
..

18

Chain of two types of atom

For nth atom (M):

..

M u n = K (un+1 2un + un1 )

MAe
MA
2

kna

i
t
2

MAe
2

kna

i
t
2

k ( n +1) a

k ( n 1) a

kna

i
i
t
t
i
t
2
2
2

= K Ae
A
2 Ae
A
+ Ae
A

kna

kna

kna

i
i
i
t i ka
t
t i ka
2

2
e 2 Ae
e 2
= K Ae
+ Ae

Cancel common terms

ka
i
i ka2

M = K e 2 + e 2

ka

2 M = 2 K 1 cos
2

eix + e ix = 2 cos x

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

i
t
2

kna

t i ka
i
2

k ( n 1) a

k ( n2)a

i kna t
i
t
i
t
2
2
2

= K Ae
2 Ae
+ Ae

kna

kna

ka
i kna
t
t i
t i 2 ka
i
i
= K Ae 2 2 Ae 2 e 2 + Ae 2 e 2

Cancel common terms

ka
i

= K 1 2 e 2 + e ika

ka
ka
i
i

2 m = K e 2 2 + e 2

ix
ix
e + e = 2 cos x

2 me

ka
i
2

ka

2 m = 2 K cos
2

19

Chain of two types of atom

2 M = 2 K 1 cos

2 m = K cos

ka

for M

ka

for m

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

y A quadratic equation for 2 can be obtained by cross-

multiplication

Chain of two types of atom

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

4 K 2 cos 2 (
4 K 2 (1 cos 2 (

ka
) = 4 K 2 2 K 2 ( M + m) + 4 Mm
2

kka
)) 2 K 2 (m + M ) + 4 Mm = 0
2

4 2K (

m+M 2
sin 2 (ka / 2)
) + 4 K 2
=0
mM
mM

The two roots are;

m 2 =

x1,2 =

b b 2 4ac
2a

K (m + M )
m + M 2 4sin 2 (ka / 2) 1/ 2
m K [(
)
]
mM
mM
mM

20

Chain of two types of atom

y versus k relation for diatomic chain;

/a

B
C

/a

2/a

N
Normal
l mode
d contains
frequencies
f
i unit
off acells
chain
h iweoffwould
two
t
types
t expect
off atoms.
If the crystal
N
tot find
At A, the two atoms are oscillating in antiphase with their centre of
2N normal modes of vibrations and this is the total number 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 at of
rest;
mass
Misand
m.
at C, M
oscillating
and m is at rest.

Chain of two types of atom

y 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.

21

Chain of two types of atom

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

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

K (m + M )
m + M 2 4sin 2 (ka / 2) 1/ 2
m K [(
)
]
mM
mM
mM

1,2 2 =

12

K (m + M )

m + M 2
4 k 2a2
K

mM
mM mM 4
12

K ( m + M )
mM
2 2
k a
1 1
=

( m + M )2
mM


2

(1 x )
Use Taylor expansion:

12

1 x 2

for smal

K (m + M )

mM
k 2a2
1 1
2
mM

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

Taking -ve root; (min value of acoustical brach)

min acus.2

K ( m + M ) mMk 2 a 2
Kk 2 a 2

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

By substituting these values of in (relative amplitude)

equation
ti
and
d using
i
cos(ka/2)
(k /2) 1
1 ffor k
ka1
1 we fi
find
d th
the
corresponding values of as;

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

OR

M
m

22

Chain of two types of atom

2
min

Substitute

into relative amplitude

ac

K(k 2 a 2 )

2(m + M)

2
min ac

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

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

1/ 2

Optical

w
K
vs = = a

k
2(m + M )

B
C

Acoustical

k
/a

/a

2/a

Chain of two types of atom

2
Substitute max op

2
max

op

into relative amplitude we obtain,

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

2K(m + M)
mM

M
m

Optical

B
C

Acoustical

k
/a

/a

This solution corresponds to point A in

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

2/a

23

Chain of two types of atom

y The other limiting solutions of equation 2 are for ka= ,

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

2
max ac

M + m 2
K (m + M )
4
=
m K

Mm
Mm Mm

=
2
max
=
ac

1/ 2

K ( m + M ) m K ( M m)
Mm

2K
M

(C)

OR

2
min
=
op

2K
2K
m

(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
y The acoustic branch has this name because it gives rise to

long wavelength vibrations - speed of sound.

y 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
th
these
modes
d with
ith electromagnetic
l t
ti radiation
di ti (ie.
(i The
Th oscillating
ill ti
electric fields generated by EM radiation)

24

Transverse optical mode for

diatomic chain

Amplitude of vibration is strongly exaggerated!

Transverse acoustical mode for

diatomic chain

25

What is phonon?
y Consider the regular lattice of atoms in a uniform solid

material.

y There should be energy associated with the vibrations of these

y
y
y
y

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
waves.
And their propagation speed is the speed of sound in the
material.

Phonon

y The vibrational energies of molecules are quantized and

y
y
y

treated as quantum harmonic oscillators.

Quantum harmonic oscillators have equally spaced
energy levels
l
l with
ith separation
ti 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".
phonons .
Like the photons of electromagnetic energy, they obey
Bose-Einstein statistics.

26

PHONONS
Quanta of lattice vibrations
Energies of phonons are
quantized

E phonon =

p phonon =

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

h s

E photon =
~a
a0=10-10m

hc

~10-6m

p photon =

27

Energy of harmonic oscillator

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

1
2

n = n + h

Make a transition to Q.M.

Represents equally spaced

energy levels

Energy, E

h
h
h
h

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 h to the ground state.

1
2

0 = h
A transition from a lower energy level to a higher energy level.

1
1

= n2 + h n1 + h
2
2

= ( n2 n1 ) h = h
1
424
3
unity

absorption of phonon

28

y The converse transition results an emission of phonon

y
y
y
y

with an energy h .
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
10
a
be localized within 10 unit cells.

This wavepacket will represent a fairly localized phonon moving with

group velocity d .

dk

Phonons can be treated as localized particles within some limits.

29

Energy of
phonons

1D crystals

Multiply by h

hk
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.
The prod
They
produce
ce vibrational
ibrational waves.
a es
This motion is increased as the temperature is
raised.
In a solid, the energy associated with this vibration and perhaps also with
gy
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.

30

Therefore, the concept of thermal energy is fundamental to an

understanding many of the basic properties of solids. We would like to
know:

Wh is
What
i the
h value
l off this
hi thermal
h
l 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.

n magnetic materials from magneting ordering.

o cv
vibrations
b o s leads
e ds to
ob
bandd o
of normal
o
mode
ode frequencies
eque c es from
o zero
eo
Atomic
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.

31

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

Energy of oscillator

n = n + h
2

The probability of the oscillator being in this

level as given by the Boltzman factor

exp( n / k BT )

= Pn n
n

n + 2 h exp n + 2 h / k T
B

n=0

(*)

e p n + h / k T
exp
2

n=0

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

z = e h / 2 kBT + e3h / 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

32

Eqn (*) can be written

1 z

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

T 1 e h / kBT
_

= k BT 2

h / 2 kBT
ln (1 e h / kBT )
ln e

T
_
h

x'
= k BT 2
ln (1 e h / kBT )

=
(ln
x
)
T 2k BT T

x
x
h k B h / kBT

2k h k 2T 2 e
1
_
h e h / kBT
= k BT 2 B2 2 + B h / k T = h +
4 k BT
(1 e B ) 2 (1 e h / kBT )

= k BT 2

1
2

= h +

h / k B T

1
2

= h +

h / k B T

gy of phonons.The
p
This is the mean energy
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
b off phonons)
h
) x ((energy off phonon)=(second
h
) (
d tterm iin )
n( ) =

1
e

k BT

The second term in the mean energy is the contribution of

phonons to the energy.

33

k BT

Mean energy of a
harmonic oscillator
as a function of T

1
h
2

low temperature limit

h ff k BT
_

1
2

= h +

k BT

1
2

= h

Zero point energy

Mean energy of a
harmonic oscillator as
a function of T

k BT

1
h
2

x2
+ ..........
2!
h
h
e kBT = 1 +
k BT
_
1
h
= h +
h
2
1+
1
k BT
_
1
= h + k BT
2

ex = 1+ x +
T

high temperature limit

is independent
oscillation
oscillation.

Since exponential term

gets bigger

of

k BT

frequency

of

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.

kBT

34

Heat Capacity C
y Heat capacity C can be found by differentiating the average energy of

phonons of
p
_

d
Cv =
=
dT

hkB

( kBT )

(e

kBT

h
1
h + h
2
e k BT 1

( h )
Cv = k B
2
( k BT )
2

Cv = k B
T

h
=
k

Let

kBT

e
e

e
e

k BT

k BT

Plot of C v as a function of T

Cv = k B
T

( e 1)

where
h

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.

35

Plot of C v as a function of T
Specific heat at constant volume depends on temperature as shown in
figure below. At high temperatures the value of Cv is close to 3R,
where R is the universal gas constant.
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
i known
is
k
as Dulong-Petit
D l
P tit law.
l
Thi law
This
l
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
= 3 Nk B T = 3RT
where N is Avagadros
g
number,, kB is Boltzmann constant and
R is the gas constant. The differentiation wrt temperature
gives;
d
Cv = 3R = 36.021023 (atoms / mole)1.381023 (J / K)
Cv =
dT

Cv = 24.9

J
;1J = 0.2388Cal Cv
( K mole)

Cal
( K mole)

36

Einstein heat capacity of solids

y 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
e T

Cv = kB
2
T e T 1

y 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 nott isolated.They
i l t d Th
are continually
ti
ll exchanging
h
i
th i energy with
their
ith
their surrounding atoms.
y Even this crude model gave the correct limit at high temperatures, a

heat capacity of

3Nk 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 = 3R

In all of these materials

(Pb,Al, Si,and Diamond)
specific
f 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.

37

The Discrepancy of Einstein model

y 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.
y 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;
y the energy of particle can only have special discrete energy
values.
y it cannot increase infinitely from one value to another.
y it has to go up in steps.

38

y These steps can be so small depending on the system that the

energy can be considered as continuous.

y This is the case of classical mechanics.
y 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

y In some cases, each particular energy level can be

associated with more than one different state (or

wavefunction )
y This energy level is said to be degenerate.

y The 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 .

39

There are two sets of waves for solution;

y Running waves
y Standing waves
Running waves:

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

L = Na = p =

Na 2
2
2
pk =
p
=
k =
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.

R ( k ) dk =

running waves

5
L

Standing waves:
0

2
L

3
L

6
L

7
L

L
dk
2

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;

L=

n
2
2 n
n
k =
k =
;k =

L
2
2L

These are the allowed wavenumbers for standing waves; only

positive values are allowed.

k=

2
p
L

for
running waves

k=

for
standing waves

40

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

at a density of S (k )

S (k )dk =
R ( k ) dk =

dk

L
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():

y The number of modes with frequencies and +d will be

g(()d.
y g() can be written in terms of S(k) and R(k).

dR

dn

modes with frequency from to +d corresponds

modes with wavenumber from k to k+dk

41

dn = S (k )dk = g ( )d

dn = R ( k ) dk = g ( ) d ;

g ()

Choose standing waves to obtain

dk
d

g ( ) = S ( k )

Lets remember dispertion relation for 1D monoatomic lattice

2 =

4K
ka
sin 2
m
2

=2

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

g ( ) = S (k )

1
a

g() = S (k)

1
a

1 m1
1
a KK
ka
coska
a
cos

2 2
m

m
1
K cos ( ka / 2 )

sin 2 x + cos 2 x = 1 cos x = 1 sin 2 x

g ( ) = S (k )

K
ka
sin
m
2

m
K

1
ka
1 sin 2
2

4
4

ka
ka
cos = 1 sin 2
2
2
Multibly and divide

Lets remember:

g ( ) = S (k )

g ( ) =

1
a

2
4K 4K
ka

sin
i 2
m
m
2

LN 2 2 1 2 1/ 2
2Na
(max2 )2
a max

True density of states

S (k )dk =

dk

L = Na
4K
ka
2 =
sin 2
m
2
4K
2
max =
m

42

g ( )

g ( ) =

m
K

2N

2
max

2 )

1/ 2

True density of states by

e s of
o above
bove equation
equ o
means

max = 2

K
m

K
m

constant density of states

K
m
goes to zero at this value of .

max = 2 ,

True DOS(density of states) tends to infinity at

since the group velocity d / dk

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
2N
Mean energy of a harmonic
oscillator

2
max

2 )

1/ 2

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.

43

3D DOS
y Lets do it first for 2D
y Then for 3D
3D.
y Consider a crystal in the shape of 2D box with crystal lengths of L.

ky

y
+
L

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
St di waves will
ill be
b off the
th form
f
U = U 0 sin ( k x x ) sin ( k y y )
Assuming the boundary conditions of
Vibration amplitude should vanish at edges of
Vibration
x = 0; y = 0; x = L; y = L
Choosing
p
q
; ky =
kx =
L
L

positive integer

44

ky

y
L
0

kx

Standing wave pattern for

a 2D box

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
of ( L / ) per unit area.
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
L
s ( k ) d k = d 3k = 3 d 3k

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

kz
dk

kx

45

( k ) = Vk is a new density of states defined as the

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:

g ( ) = ( k )

g ( ) d = ( k ) dk

dk
d

Lets find C at low and high temperature by means of

using the expression of g ( ) .

High and Low Temperature Limits

= 3 Nk BT

Each of the 3N lattice

modes of a crystal
containing N atoms

C=

This result is true only if

d
dT

C = 3 Nk B

h
kB

y At low Ts only lattice modes having low frequencies

can be excited from their ground states;

Low frequency

l
long

sound waves

= vs k

vs =

46

vs =

1
dk 1

=
vs
d vs

2
V 2
v
1
g ( ) = s2
2
vs

and

g ( ) =

Vk 2 dk
2 2 d

att low
l
T
Ts

vs depends on the direction and there are two transverse,

one longitudinal acoustic branch:
V2 1
V2 1 2
g ( ) =
g ( ) =
+
2 2 vs3
2 2 vL3 vT3

Velocities of sound in
longitudinal and
transverse direction

h
1
= h + h / kT g ( ) d
1
e
2
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
1)

3
kT
= B x
k BT 3

h
h
x kT
h 3
h

B
0 eh / kT 1 d = 0 e x 1 4 4h dx
kT
d = B 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
4224
3k T
d V2 2 1 121
= V3 k3B + 33 + kB34 4154T 3B at low temperatures
Cv =
30h vL vvLT vT h
dT 15

47

How good is the Debye approximation

at low T?
Cv =

d
2
=
V 2kB
dT 15

1
2 k BT
3 + 3

h
v
v
L
T

The lattice heat capacity of solids thus

varies as T 3 at low temperatures; this is
referred to as the Debye
law.
T3
Figure illustrates the excellent aggrement
of this prediction with experiment for a
non-magnetic insulator.
insulator The heat
capacity vanishes more slowly
than the exponential behaviour of
a single harmonic oscillator
because the vibration spectrum
extends down to zero frequency.

The Debye interpolation scheme

The calculation of g() is a very heavy calculation for 3D, so it
must be calculated numerically.
Debye
D b
obtained
b i d a goodd approximation
i i
to the
h resulting
li
heat
h
capacity by neglecting the dispersion of the acoustic waves, i.e.
assuming

= sk

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.

48

The Debye approximation has two main steps:

1. Approximate the dispersion relation of any branch by a linear

extrapolation of the small k behaviour:
Debye
approximation
to the
dispersion

Einstein
approximation
to the
dispersion

= vk

Debye cut-off frequency D

2. Ensure the correct number of modes by imposing a cut-off
frequency D , above which there are no modes. The cut-off
f
freqency
i chosen
is
h
t make
to
k the
th total
t t l number
b off lattice
l tti modes
d
correct. Since there are 3N lattice vibration modes in a crystal
having N atoms, we choose D so that
D

g ( ) =
V
6

g ( )d = 3 N

V 1 2
( + )
2 2 vL3 vT3
2

V 1 2 D 2
( + ) d = 3N
2 2 vL3 vT3 0
V
1
2
3N
9N
( + )= 3 3= 3
2 2 v L3 vT3
D
D

1
2
+ 3 ) D3 = 3 N
v L3
vT

g ( ) =

9N

3
D

g ( ) /

49

The lattice vibration energy of

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

becomes

E=

1
h
9N D h3
h3
2

+
=
+
(
h
)
d
d
d

h
k
T
h
/
/ kBT

B
1
1

D 0 2
2
e
e
0

9N

3
D 0

and,

9
9N
E = N h D + 3
8
D

h 3 d
e h / k B T 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 = NhD + 3
8
D

C=

dE
dT

dE 9N D h24 eh/ kBT

CD = = 3 2
d
dT D 0 kBT eh/ kBT 1 2

h3d
0 eh / kBT 1

Lets convert this complicated integral into an expression for

the specific heat changing variables to x
x=

h
k BT

d
dx

kT
h

and define the Debye temperature

D =

kT
x
h

hD
kB

50

The Debye prediction for lattice specific heat

4

dE 9N kBT kBT
CD =
=

dT D3 h h
T
= 9NkB

CD

where

D =

h2

2
kBT

D / T

3 /T
D

(e

x 4e x

( e 1)
x

x 4e x
x

1)

dx

dx

h D
kB

Climit
at high and low temperatures?
D

How does

High temperature T D
ex = 1+ x +

X is always small

x4e x

(e
T

1)

x 4 (1 + x)

(1 + x 1)

x2
x3
+
+
2!
3!

x4 (1 + x)
= x2
x2

T
D CD 9 Nk B

3 /T
D

x 2 dx = 3 Nk B

51

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 / 1 5

T
D CD 9 Nk B

3 /T
D

x4e x

(e

1)

dx

We obtain the Debye T 3 law in the form

CD

12 NkB 4 T

5
D

Lattice heat capacity due to Debye interpolation

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

2
D 0 ( e x 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
sc
e e
assumption
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
hD can be used to estimate

the maximum phonon energy in a solid.

Solid
Ar
Na
Cs
Fe
D ( K )

93

158

38

457

Cu

Pb

KCl

343

105

2230

235

52

Anharmonic Effects
y Any real crystal resists compression to a smaller volume than its equilibrium value

more strongly than expansion due to a larger volume.

y This is due to the shape of the interatomic potential curve.

y This is a departure from Hookes law, since harmonic application does not produce

this property.

y 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

y Thermal
Th
l expansion
i is
i an example
l to
t the
th anharmonic
h
i effect.
ff t
y 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.
y 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

53

Phonons are represented by wavenumbers with

If k3 lies outside this range add a suitable multible of

it back within the range of k

to bring

. Then, k3 = k1 + k2 becomes

This phonon is indistinguishable

from a phonon with wavevector k3

where

2
a

k3

n2
= k1 + k2
a

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

Longitudinal
Transverse

3'

a
n =Normal
0 process

a
n Umklapp
0 process

3
2

(due to anharmonic effects)

Phonon3 has k

; Phonon3 has k

and Phonon3=Phonon3

Thermal conduction by phonons

y A flow of heat takes place from a hotter region to a
g
when there is a temperature
p
gradient in a
g
cooler region
solid.
y The most important contribution to thermal conduction
comes from the flow of phonons in an electrically
insulating solid.
y Transport property is an example of thermal conduction.
y Transport property is the process in which the flow of
some quantity occurs.
y Thermal conductivity is a transport coefficient and it
describes the flow.
y The thermal conductivity of a phonon gas in a solid will
be calculated by means of the elementary kinetic theory
of the transport coefficients of gases.

54

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

Mean free path

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
.
_

If P is the energy density E then the flux W is the heat flow per unit area so that

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

_
1
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
Speed is approximately constant.
constant

No
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

55

Temperature dependence of thermal conductivity K

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

1 _
K = l C
3

Approximately equal to
velocity
l it off sound
d and
d 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

y At temperatures much greater then the Debye temperature D the heat capacity is

given by temperature-independent classical result of

C = 3 Nk B
y The rate of collisions of two phonons

phonon density.

y If collisions involving larger number of phonons are important, however, then the

scattering rate will increase more rapidly than this with phonon density.

y At high temperatures the average phonon density is constant and

the total lattice energy

Scattering rate

T;

Then the thermal conductivity of

phonon number

and mean free length

K =

1 _
l C
3

T , so

T 1

T 1.

56

y Experimental results do tend towards this behaviour at high temperatures as

shown in figure (a).

10

10
0

1
T

10-1
5

10 20

T3

10-1

50 100

5 10 20

50 100

T (K )

T (K )

(a)Thermal conductivity of a quartz

crystal

(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 D ,
e D / bT
where b is a number of order unity 2 or 3. Then

l e D / bT

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

such as a factor of T 3 from the heat capacity.

57

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

Specimen diameter

T dependence of K comes from

12 NkB 4 T
CD

5
D

Cv

which obeys

T3

law in this region

Temperature dependence of

Cv dominates.

Size effect
y 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.
ff

y 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;
the thermal conductivity has a T 3 dependence at these temperatures.

y The maximum conductivity between

imperfections.

T 3 and

eD / bT

region is controlled by

y 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.

58