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Lattice Dynamics-1

Prof.P. Ravindran,

Department of Physics, Central University of Tamil

Nadu, India

http://folk.uio.no/ravi/CMP2013

What is phonon?

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 that

material.

Phonon

treated as quantum harmonic oscillators.

Quantum harmonic oscillators have equally spaced energy

levels with separation ΔE = 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.

Lattice Dynamics

crystalline solid.

Leads to;

– understanding 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.

Lattice Vibrations Phonons

• Mechanical waves are waves which propagate through a material medium

at a wave speed which depends on the elastic and inertial properties of that

medium.

• There are two basic types of wave motion for mechanical waves:

longitudinal waves and transverse waves.

Longitudinal Waves

Transverse Waves

limit, since λ>>a, so there will no scattering due to the

presence of atoms.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

5

Crystal Dynamics

their equilibrium position. This can not be entirely; 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.

lattice vibrations.

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

effects occur.

Crystal Dynamics

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.

force on each atom is approximately proportional to its displacement

(Hooke’s Law).

atomic displacements.

and photons.

Crystal Dynamics

atoms when they are displaced from their equilibrium

positions.

wavefunctions and energies of the electrons within the

crystal. Fortunately many important properties of the

atomic motions can be deduced without doing these

calculations.

PHONONS PHOTONS

• Quanta of lattice vibrations • Quanta of electromagnetic

• Energies of phonons are

radiation

quantized • Energies of photons are

quantized as well

h s hc

E phonon E photon

~a0=10-10m

~10-6m

h

p phonon h

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.

Energy, E

• Represents equally spaced energy

levels

Energy levels of atoms

vibrating at a single

frequency ω

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

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

unity

absorption of phonon

The converse transition results an emission of phonon

with an energy .

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 principle.

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 be localized within 10 unit cells. 10a

with group velocity d .

dk

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.

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 1g mole by one Kelvin.

Hooke's Law

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

linear dependence of displacement upon stretching force is

called Hooke's law.

It takes twice

Fspring k .x

as much force

to stretch a

spring twice

Spring constant k

F as far.

2F

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Hooke’s 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.

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.

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

longer holds).

SOUND WAVES

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.

low frequency, long wavelength limit of the more general

lattice vibrations considered later.

possible to transmit three sound waves, differing in their

direction of polarization and in general also in their velocity.

Elastic Waves

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.

U(x) and strain ‘e’ is defined as the x x+dx

dU

e

dx

Elastic Waves

proportional to the strain e.

S C.e

A

C = Young modulus x x+dx

segment of length dx as shown above. Using Newton’s second law,

we can write for the motion of this segment,

2u

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

t

Elastic Waves

Equation of motion S C.e

2u du

( Adx) 2 S ( x dx) S ( x) A e

dx

t u

S C.

S x

S ( x dx) S ( x) dx S 2u

x x

C. 2

x

2u 2u

( Adx) 2 C 2 Adx Cancelling common terms of Adx;

t x

2u 2u

2 C 2 Which is the wave eqn. with an offered

t x sol’n and velocity of sound waves ;

i ( kx t )

u Ae – ω = frequency of the wave

vs C/

– A = wave amplitude

Dispersion Relation

The relation connecting the frequency and wave number is

known as the dispersion relation.

vs k

• At small λ k → ∞ (scattering occurs)

ω Continuum • At long λ k → 0 (no scattering)

• When k increases velocity decreases.

Discrete As k increases further, the scattering

becomes greater since the strength of

k scattering increases as the wavelength

0

decreases, and the velocity decreases

even further.

* Slope of the curve gives

the velocity of the wave.

Speed of Sound Wave

of density ρ is

VL ρ = Mass density

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

Nearest Elastic bulk Calculate Observed

Density

Structure Neighbour modules d Wave speed of

Solid ρ Speed sound

Type Distance Y

(A°) (kg/m3) (m/s) (m/s)

(1010 N/m2)

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 2330 10.1 6600 9150

Germanium Diamond 2.44 5360 7.9 3830 5400

NaCl Rocksalt 2.82 2170 2.5 3400 4730

•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.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Sound Wave Speed

systematic sequence of atomic displacements of

– longitudinal,

– transverse, or

– some combination of the two

• An equation of motion for any displacement can be produced by means

of considering the restoring forces on displaced atoms.

• They can be characterized by

– A propagation velocity, v

– Wavelength λ or wave vector

– A frequency or angular frequency ω=2π

• As a result we can generate a dispersion relationship between

frequency and wavelength or between angular frequency and

wavevector.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

To illustrate the procedure for treating the interatomic potential in

the harmonic approximation, consider just two neighboring atoms.

Assume that they interact with a known potential V(r).

Expand V(r) in a Taylor’s series in displacements about the

equilibrium separation, keeping only up through quadratic

terms in the displacements:

V(R)

Repulsive This potential energy is the same as

that associated with a spring with

0 a spring constant:

Attractive d 2V

K 2

r R dr r a

Force K (r a)

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Normal Modes of Vibration

One dimensional model # 1: The Monatomic

Chain

nearest-neighbor, “Hooke’s Law” type forces (F = - kx)

between the atoms.

This is equivalent to a force-spring model, with masses m &

spring constants K.

Monoatomic Chain

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).

a a a a a a

Monoatomic Chain

a a

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, Then, the Newton’s 2nd Law

equation of motion becomes:

..

m u n K (un1 2un un1 )

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Monoatomic Chain

The force on the nth atom; a a

K (un1 un )

•The force to the left;

K (un un1 )

Un-1 Un Un+1

..

m u n K (2u n u n1 u n1 ) 0

Eqn’s of motion of all atoms are of this form, only the value of

‘n’ varies

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Assume that all atoms oscillate with the same amplitude A &

the same frequency ω. Assume harmonic solutions for the

displacements un of the form:

0 .

n

dt

..

d 2 un

u n 2 i 2 A exp i kxn0 t u n 2un

..

2

dt

Undisplaced Position Displaced Position

xn0 na xn na un

• Put all of this into the equation of motion:

..

Equation of motion for n th atom

Monoatomic Chain

..

mu n K (un1 2un un1 )

i kxn0 t

i kxn10 t 2 A ei kx t A eikx n1 t

0 0

2 n

m A e K Ae

k ( n 1) a kna k ( n 1) a

kna

2

m A e

i kna t

K Ae i kna ka t

2A e

i kna t

Ae

i kna ka t

2

m A e

i kna t

K Ae i kna t

e

ika

2A e

i kna t

Ae

i kna t

e

ika

Cancel Common terms

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Monoatomic Chain

eix eix 2cos x

m 2 K eika 2 eika eika eika 2cos ka

m 2 K 2cos ka 2

2 K (1 cos ka) 1 cos x 2 sin 2

x

2 2 ka 2

m 4 K sin

2

4K ka

2 sin 2

m 2 Maximum value of it is 1

4K ka

sin

m 2

4K

max

m

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Mathematical Manipulation finally gives:

Solution to the Normal

Mode Eigenvalue Problem

for the monatomic chain.

• The maximum allowed frequency is:

chain, the only allowed vibrational frequencies ω must be related to

the wavenumber k = (2π/λ) or the wavelength λ in this way.

• This result is often called the “Phonon Dispersion Relation” for

the chain, even though these are classical lattice vibrations &

there are no (quantum mechanical) phonons in the classical theory.

Monoatomic Chain

ω versus k relation;

K

max 2

m

Vs / k

C B A

k

–л / a 0 л /a 2 л /a

0

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 2π/a.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

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 nth atom.

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 ω given by above eqn. and oscillates

independently of the other modes.

As we already said, these are called the Normal Modes of the system. They are a

collective property of the system as a whole & not a property of any of the individual

atoms. Each mode represented by ω(k) oscillates independently of the other

modes. Also, it can be shown that the number of modes is the same as the original

number of equations N. Proof of this follows.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

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

must satisfy the periodic boundary condition

un uN 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 2π/a of k, there are N allowed values of k.

Na 2 2

Na p Nk p

p k a

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Monoatomic Chain

What is the physical significance of wave numbers outside

the range of 2π/a?

Un

a

Un

Monoatomic Chain

This value of k corresponds to the

2a;k 2 k

maximum frequency; alternate atoms

a oscillate in antiphase and the waves at

this value of k are standing waves.

White line :

4 7a 7a k 2 8 1.14

4 7a 7a a

4

Green line :

3 7a 7a k 2 6 0.85

3 7a 7a a un

3

x

un a

ω-k relation

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

• What is the physical significance of wave numbers k outside of the

First Brillouin Zone [-(π/a) k (π/a)]?

• At the Brillouin Zone edge:

• This k value corresponds to the maximum frequency. A detailed analysis

of the displacements shows that, in that mode, every atom is oscillating

π radians out of phase with it’s 2 nearest neighbors. That is, a wave at

this value of k is A STANDING WAVE.

Black

k = π/a

or

= 2a

Green:

k = (0.85)π/a

or x

= 2.35 a

Monoatomic Chain

•The points A and C both have same w 2

K

m

frequency and same atomic displacements Vs / K

dispersion diagram. -π/a 0 π/a 2π/a k

ω-k relation (dispertion diagram)

•The point B has the same frequency and

displacement with that of the points A and C •The points A and C are exactly

with a difference. equivalent; adding any multiple of

2π/a to k does not change the

•The point B represents a wave moving to the frequency and its group velocity, so

right since its group velocity (dω/dk)>0. point A has no physical significance.

un •k=±π/a has special significance

x

•θ=90o

Bragg reflection can be obtained at

k= ±nπ/a

un

a

m 4K sin

2 2 ka n n2 n 2n

2 x

k

For the whole range of k (λ)

a

2a 2d sin90 d a

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I 1

At the beginning stated that, in

the long wavelength limit, the

c Ka K a2

velocity of sound waves has been

derived as m

Vs c

Using elastic properties, let’s see m

a

whether the dispersion relation

leads to the same equation in the

long λ limit.

If λ is very long; ka 1 so sin ka ka

k 2a 2

Vs

K

m 4K

2 a

k

4 m

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

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 ω is

still periodic function of k with period 2π/a

• Group velocity vanishes at k=(±)π/a

• There are still N distinct normal modes

• Furthermore the motion at long wavelengths corresponds to

sound waves with a velocity given by (velocity formula)

(k ): Dispersion relation

dk

1st Brillouin zone : k

a a

Frequency, w

2

a 0 a a

Wavevector, k

First Brillouin zone

Briefly look in more detail at the group velocity, vg.

The dispersion relation is: 4K ka

sin

m 2

So, the group velocity is:

vg (dω/dk) = a(K/m)½cos(½ka)

vg = 0 at the BZ edge [k = (π/a)]

– This tells us that a wave with λ corresponding to a zone edge

wavenumber k = (π/a) will not propagate.

That is, it must be a standing wave!

– At the BZ edge, the displacements have the form (for site n):

Un= Uoeinka = Uo ei(nπ/a) = Uo(-1)n

Group Velocity, vg in the 1st BZ

At the 1st BZ Edge,

4K ka

The dispersion relation is: sin vg = 0

m 2• This means that a wave

with λ corresponding to a

vg (dω/dk) = a(K/m)½cos(½ka) zone edge wavenumber

k = (π/a) Will Not

Propagate!

• That is, it must be a

Standing Wave!

1st BZ Edge

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Group velocity

v g d dK or v g grad K K

K 1

2 | sin( ka ) |

m 2

K 1 - Beats

vg a cos( ka )

m 2

The velocity of energy propagation in the medium

This is zero at the edge of the zone Standing wave

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

The Monatomic Chain

k = (/a) = (2/); = 2a

k 0;

Acoustic branch

n 0 exp(it )exp(inka), vg

K 1

a cos( ka )

m 2

-k 0 : Long wavelength or continuum limit

K

vg a a0 : Velocity of sound in a crystal

m

Acoustic branch

Frequency, w

Speed of sound

K

- k : Edge of first Brillouin zone

a

vg 0

exp( ika )

n 0 exp( inka ) Brillouin zone

0 Wavevector, k a

Standing wave

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

by identical springs of spring constant K;

(n-2) (n-1) (n) (n+1) (n+2)

K K K K

M M m M a)

m

b)

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

Chain of two types of atom

is a poor approximation in ionic crystals because there is a long

range interaction between the ions.

types of atoms which move in opposite directions.

One for mass m.

Chain of two types of atom

M M m M

m

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

Chain of two types of atom

m M

M m M

Un-2

α : complex number which determines the relative amplitude and phase of the

vibrational wave.

..

Chain of two types of atom

For nth atom (M):

..

M u n K (un1 2un un1 )

k n 1 a k n 1 a

kna

i

t i

t kna

i

t i t

2 MAe 2

K Ae

2 Ae 2 Ae

2 2

kna

i

t kna

i

t i ka

kna

i

t

kna

i t i ka

2 MAe 2

K Ae 2 e 2 2 Ae 2 Ae 2 e 2

Cancel common terms

i

ka

i

ka

M K e 2 e

2 2 2 eix e ix 2 cos x

ka

2 M 2 K 1 cos

2

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

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

..

mu n1 K (un 2un1 un2 )

k n 1 a k n 1 a k n 2a

i

t i kna t i

t i t

A 2 me

K Ae 2 2 Ae

Ae

2 2 2

kna

i

t i ka i kna

t

kna

i

t i ka

kna

i t i 2 ka

2 mAe 2

e 2

K Ae 2 2 Ae 2 e 2 Ae 2 e 2

Cancel common terms

i

ka

i

ka

ika

me

2

K 1 2 e e

2 2

ka

i

ka

i

ka

m 2 K cos

2

m K e 2 e

2 2 2

2

eix e ix 2 cos x

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

ka

M 2 K 1 cos

2

for M

2

ka

m K cos

2

2 for m

2

function of k. α can be found as

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

2K m

2

2 K cos(ka / 2)

multiplication

Chain of two types of atom

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

2K m

2

2 K cos(ka / 2)

ka

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

2 2

2

ka

4 K 2 (1 cos 2 ( )) 2 K 2 (m M ) 4 Mm 0

2

m M sin 2

(ka / 2)

2K (

4

) 4 K

2 2

0

mM mM

b b 2 4ac

The two roots are; x1,2

2a

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

2

K [( ) ]

mM mM mM

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

ω versus k relation for diatomic chain;

w

A

B

C

modes of vibrations and this is the total number of atoms and hence the

total number of equations of motion for mass M and m.

• Normal mode frequencies of a chain of two types of atoms.

• At A, the two atoms are oscillating in antiphase with their centre of

mass at rest;

• at B, the lighter mass m is oscillating and M is at rest;

• at C, M is oscillating and m is at rest.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

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

dispersion relation is said to have two branches;

Optical Branch

A Upper branch is due to the

B +ve sign of the root.

C

Acoustical Branch

Lower branch is due to the

-ve sign of the root.

–л/a 0 л/a 2л/a k

2 π /a = 2 π /(unit cell length).

• This result remains valid for a chain of containing an

arbitrary number of atoms per unit cell.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

Let’s examine the limiting solutions at 0, A, B and C.

In long wavelength region (ka«1); sin(ka/2)≈ ka/2 in ω-k.

K ( m M ) m M 4sin 2

(ka / 2) 1/ 2

1,2

2

K [( )

2

]

mM mM mM

K m M

12

m M 4 k a

2 2 2

2

K

mM mM mM 4

K m M

12

mM

1 1 k a

2 2

mM m M 2

Use Taylor expansion:1 x 1 x 2 for small x

12

K m M mM 2 2

2

1 1 k a

2(m M )

2

mM

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

Taking +ve root; sinka«1 (max value of optical branch)

2K m M

max opt 2

mM

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

K m M mMk 2 a 2 Kk 2 a 2

min acus.2 2

mM 2(m M ) 2(m M )

equation and using cos(ka/2) ≈1 for ka«1 we find the

corresponding values of α as;

2K 2 M 1

M

OR

m

2 K cos(ka / 2)

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

2

Substitute min ac into relative amplitude α

K(k a ) 2 2 2K 2 M

2

1

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

min ac

the neighbourhood of point 0 in the graph; the two types

of atoms oscillate with same amplitude and phase, and the

velocity of sound is

w

1/ 2

A w K

vs a

Optical

B

C k 2( m M )

Acoustical

k

–π/a 0 π/a 2π/a

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Chain of two types of atom

Substitute maxop

2

into relative amplitude we obtain,

2K(m M) 2K 2 M

M

2

max op

mM 2 K cos(ka / 2) m

w

A

Optical

B This solution corresponds to point A

C in dispersion graph. This value of α

shows that the two atoms oscillate in

Acoustical antiphase with their center of mass at

k rest.

–π/a 0 π/a 2π/a

Chain of two types of atom

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

1/ 2

K (m M ) M m 4

2

2

max ac K

Mm Mm Mm

K (m M ) K ( M m)

Mm

2K 2K

OR min

2 2

max ac

(C) (B)

M op

m

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

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

The Diatomic Chain Solution:

( = 2a)

Optic Modes Near the BZ edge [q = (π/a)]

(Optic Branch) (Assuming m > M)

The Optic Mode becomes:

(ω+)2 2K/M

Gap The Acoustic Mode becomes:

(ω-)2 2K/m

So, at the BZ edge, the vibrations of

wavelength = 2a for the 2 modes

qa behave as if there were 2 uncoupled

masses m & M , vibrating

Acoustic Modes independently with identical springs

(Acoustic Branch)

of constant K.

Acoustic/Optical Branches

long wavelength vibrations - speed of sound.

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)

Acoustic & Optic Branches

it’s results for the vibrational normal modes ω contain

considerable qualitative physics that carries over to the observed

vibrational frequencies for many real materials.

So, much of the physics contained in the diatomic chain

results can teach us something about the physics contained in

the normal modes of many real materials.

In particular, ALL MATERIALS with 2 atoms per unit cell are

observed to have two very different kinds of vibrational normal

modes. These are called The Acoustic Branch & The

Optic Branch

The Acoustic Branch

This branch received it’s name because it contains long

wavelength vibrations of the form ω = vsk, where vs is the

velocity of sound. Thus, at long wavelengths, it’s ω vs. k

relationship is identical to that for ordinary acoustic (sound)

waves in a medium like air.

The Optic Branch

This branch is always at much higher vibrational frequencies than the

acoustic branch. So, in real materials, a probe at optical frequencies is

needed to excite these modes.

Historically, the term “Optic” came from how these modes were

discovered. Consider an ionic crystal in which atom 1 has a positive

charge & atom 2 has a negative charge. As we’ve seen, in those modes,

these atoms are moving in opposite directions. (So, each unit cell contains

an oscillating dipole.) These modes can be excited with optical frequency

range electromagnetic radiation.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Transverse optical mode for

diatomic chain

A Longitudinal Optic Mode

Transverse acoustical mode for

diatomic chain

Acoustic vs. Optic Phonons

Which has lower energy? Why?

Optic Mode

Acoustic Mode

Less Compression of Springs

hence higher energy.

Phonon Dispersion and Scattering

Act like spring Vibration

many solids

Transverse vs. Longitudinal polarization

Three modes of wave vectors for one atom per unit cell

One longitudinal mode Two transverse modes

Dispersion Relation for Real Crystal

- Number of branches

If there are q atoms in the primitive cell, there are 3q

branches to the dispersion relation

2 transverse acoustic (TA)

3q - 3 optical branches : q - 1 longitudinal optical (LO)

2q - 2 transverse optical (TO)

Frequency gap

The group velocity of phonons in the optical branches is small

contribute little to the thermal conduction

At low temperatures : TA are dominant contributors to the heat

conduction

At high temperatures : LA are dominant contributors to the heat

conduction

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Diatomic Basis: Experimental Results 77

The optical modes generally have frequencies near = 1013 1/s, which is in the infrared part

of the electromagnetic spectrum. Thus, when IR radiation is incident upon such a lattice it

should be strongly absorbed in this band of frequencies.

incident upon a very thin NaCl film.

Note the sharp minimum in transmission

(maximum in absorption) at a wavelength of

about 61 10-4 cm. This corresponds to a

frequency = 4.9 1012 1/s.

Phonon scattering

Phonon-phonon scattering

and semiconductor

scattering event is different from that after the event

1 2 3 or 1 2 3 : energy conservation

k1 k2 k3 or k1 k2 k3 : crystal momentum

conservation

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Umklapp(or U) process : Outside the 1st brillouin zone

k k G

k1 k2 k3 G or k1 G k2 k3

kz kz

k1

k1

k2

a a a a

kx kx

k3

k2 k3

k1 k2

G

N process U process

N-process vs. U-process

N - process U - process

Conservation

Momentum Net momentum not

Conserved

Conservation conserved

Thermal

Not dominant Dominant

conductivity

Distributing the

role resistance to heat flow

phonon energy

Phonon scattering: Temperature dependence

Above room temperature U 1/ : Positive constants

A, B :

Scattering rate of the U-

U ( A B 2 )T process

1

U T

T

Below room temperature

1 1

Cv

p K T e / k BT

1 2

Cv T , Cv T

At high temperature

specific heat does not change Thermal conductivity of

silicon

significantly

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Phonon scattering – 4 phonon & defect

2 1 1 3

1 3 2 4

4 3 2 4

four U : Negligible

Phonon – defect scattering

Elastic scattering

Independent of temperature

Defendant on the phonon wavelength

ph-d 4

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Phonon scattering- phonon-electron

Dominant at high temperature

Eac Ee negligible

and electron (Joule heating)

+ : phonon absorption

(i : initial state f : final

- : phonon emission

state)

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Phonon scattering- Raman scattering

Phonon and photon inelastic scattering

neutronscattering, and Brillouin scattering

i: incident photon

s: scattered photon

ph: phonon

Energy of

1D crystals phonons

k Multiply by

k

Crystal momentum

•They can be created and destroyed during collisions .

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 magnetic 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

oscillator and hence of a lattice

mode of angular frequency ω Energy of

at temperature T oscillator

1

The probability of the oscillator n n

being in this level as given by the 2

Boltzman factor exp( n / kBT )

1 1

_ n exp n / k BT

Pn n n 0 2 2 (*)

_

1

n

exp n / k BT

n 0 2

1

z exp[(n ) ]

n 0 2 k BT

/ 2 k BT / 2 k BT / 2 k BT

z e e 3 e 5 .....

/ 2 k BT / k BT / k BT

z e (1 e e 2 .....

/ 2 k BT / k BT 1

z e (1 e )

Eqn (*) can be written

_

1 z 2

k BT 2

k BT (ln z )

z T T

_

2 e / 2 k BT

k BT ln

T 1 e / kBT

/ 2 k BT

_

k BT 2 ln e ln 1 e / k BT

T

ln 1 e

_

/ k BT

k BT

2

x'

T 2 k B

T T (ln x)

x x

k B / k BT

_ 2k k 2T 2 e 1 e / k BT

k BT 2 B2 2 B / k T

4 k BT 1 e B

2 1 e / k BT

_

1

/ k BT

2 e 1

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

_

1

/ k BT

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 0ºK atoms vibrate in the crystal and have zero-point

energy. This is the minimum energy of the system.

The avarage number of phonons with a particular frequecy ω is

given by Bose-Einstein distribution as

_

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

1

n( )

e kBT

1

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

1

2

T

k BT

_

1 Since exponential term gets

bigger

2 e kBT 1

_

1

Zero point energy

2

k BT Mean energy of a

harmonic oscillator as a

function of T

2

x

1 kBT e x 1 x ..........

2!

2

T e k BT

1

k BT

high temperature limit

_

1

2

• is independent of frequency of oscillation. 1 1

k BT

•This is the classical limit because the energy

_

steps are now small compared with the 1

energy of the harmonic oscillator. kBT

2

•So that = kBTis the thermal energy of the

classical 1D harmonic oscillator.

_

kB T

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Heat Capacity C

Heat capacity C can be found by differentiating the average

energy of phonons of

_

1

2 e kBT 1

kB

e kBT

kBT

2 2

d

kBT

e

Cv Cv k B

e kBT

2 2 2

dT kBT

1 e kBT

1

2

eT

Cv k B

Let

T e T 1

2

k

Plot of Cv as a function of T

2

eT

Cv k B

where

T e T 1

2

k

low T’s and tends to classical value at

kB high temperatures.

Area=

The features are common to all

quantum systems; the energy tends to the

2 zero-point-energy at low T’s and to the

classical value of Boltzmann constant at

T high T’s.

kB

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 Cv 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 the figure it is seen that Cv is equal to

3R at high temperatures regardless of

3R 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

T, K 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 energy per atom, regarded as a 3D

oscillator, is 3kT, and consequently the energy per mole is

= 3NkBT 3RT

where N is Avagadro’s 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)

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

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

e T

Cv k B

T

e

2

T

1

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

energy of the oscillators are taken quantum mechanically.

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

not isolated.They are continuslly exchanging their energy with their

surrounding atoms.

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

capacity of 3NkB 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

In all of these materials (Pb,Al,

cal Si,and Diamond) specific heat

6

Kmol approaches constant value

asymptotically at high T’s. But

at low T’s, the specific heat

decreases towards zero which

T is in a complete contradiction

with the above classical result.

Cv 3R

kB

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

The Discrepancy of Einstein model

to zero at absolute zero, but the temperature dependence

near T=0 did not agree with experiment.

frequencies in a solid this discrepancy can be accounted

using one dimensional model of monoatomic lattice

Having studied the structural arrangements of atoms in solids,

we now turn to properties of solids that arise from collective

vibrations of the atoms about their equilibrium positions.

A. Heat Capacity—Einstein Model (1907)

E1 K U

m

12 mv x2 12 mv y2 12 mv z2 12 k x x 2 12 k y y 2 12 k z z 2

ky

kx

equilibrium each quadratic term in the E has an average energy 12 k BT , so:

E1 6(12 k BT ) 3k BT

Classical Heat Capacity

E 3Nk BT

Total energy per mole: 3N Ak BT 3RT

n n

Heat capacity at constant

d E

volume per mole is: CV 3R 25 molJ K

dT n V

by most solids at high T ( > 300 K). But by the middle of the

19th century it was clear that CV 0 as T 0 for solids.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Einstein Uses Planck’s Work

energies En n n 0, 1, 2, ...

oscillators, all with same , and use Planck’s equation for energy levels

f ( En )

classical physics

(probability of oscillator

being in level n) e

n 0

En / kT

(Boltzmann factor)

Average total n

E e En / kT

energy of solid: E U 3 N f ( En ) En 3 N n 0

n 0

e

n 0

En / kT

Some Nifty Summing

n e n / kT

Using Planck’s equation: U 3N n 0 Now let x

kT

e

n 0

n / kT

d nx d x

ne e e

nx n

Which can dx n 0 dx n 0

U 3 N be rewritten: U 3N 3N

n 0

e

e

n 0

nx

e

n 0

nx

n 0

x n

e

1 ex

Now we can use 1

xn

for x 1 To give: x n

x

the infinite sum: n 0 1 x n 0 1 e x

e 1

d ex

x

dx e 1 3N 3N

So we obtain: U 3N

ex e x 1 e / kT 1

x

e 1

At last…the Heat Capacity!

d U d 3N A

Using our previous definition: CV / kT

dT n V dT e 1

CV

3 N A e / kT 3R e

kT 2

2

kT

/ kT

e 1 e 1

Differentiating: / kT 2 / kT 2

E

an “Einstein temperature”: k

CV (T )

3R e

E 2

T

E /T

e

So we obtain the prediction:

E /T 2

1

Limiting Behavior of CV(T)

E

1 (T )

1

3R E 2

3RT

E

T

1 1

High T limit:

CV

T E 2

T

3R e E 2 E /T

3R e

E E 2

Low T limit: 1 CV (T ) T E / T

T

e E /T 2 T

3R

These predictions are qualitatively correct: CV

3R for large T and CV 0 as T 0:

CV

T/E

But Let’s Take a Closer Look:

High T behavior:

Reasonable

agreement with

experiment

Low T behavior:

CV 0 too quickly

as T 0 !

B. The Debye Model (1912)

Despite its success in reproducing the approach of CV 0 as T 0, the

Einstein model is clearly deficient at very low T. What might be wrong with

the assumptions it makes?

Details of the Debye Model

Pieter Debye succeeded Einstein as professor of physics in Zürich, and soon

developed a more sophisticated (but still approximate) treatment of atomic

vibrations in solids.

Debye’s model of a solid:

• 3N normal modes (patterns) of oscillations

• Spectrum of frequencies from = 0 to max

• Treat solid as continuous elastic medium (ignore details of atomic structure)

max

because each mode of oscillation

contributes a frequency-dependent CV (T )

N ( ) C

0

E ( , T ) d

heat capacity and we now have to

integrate over all :

# of oscillators per Einstein function

unit for one oscillator

C. The Continuous Elastic Solid

We can describe a propagating vibration of amplitude u along a rod of

material with Young’s modulus E and density with the wave equation:

2u E 2u

for wave propagation along the x-direction

t 2

x 2

2u 2 u

2

E So the wave speed is independent of

v we find that v wavelength for an elastic medium!

t 2

x 2

v

2f 2 kv dispersion relation of

the solid, and here it is

linear (no dispersion!)

d

group velocity vg k

dk

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Dispersion Relations: Theory vs.

Experiment

In a 3-D atomic lattice we

expect to observe 3 different

branches of the dispersion

relation, since there are two

mutually perpendicular

transverse wave patterns in

addition to the longitudinal

pattern we have considered.

the reciprocal lattice the

shape of the dispersion

relation is different. But

note the resemblance to the

simple 1-D result we found.

Density of States

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.

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.

states per unit energy interval, and so that the number

of states between and d will be ( )d .

There are two sets of waves for solution;

Running waves

Standing waves

Running waves:

k

4 2 0 2 4 6

L L L L 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 Length of

p k Na L the 1D

chain

density of R k between k and k+dk.

L

running waves R k dk dk

2

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Standing waves: 5 4 3

L L L

6

k L 2

0 2 3 L

L L L 7 0

L 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 for for

k p k p

L running waves L standing waves

These allowed k’s are uniformly distributed between k and

k+dk at a density of S (k )

L

S (k )dk dk DOS of standing wave

L

R k dk dk DOS of running wave

2

•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 .

E. Counting Modes and Finding N()

A vibrational mode is a vibration of a given wave vector k (and thus ),

frequency , and energy

E . How many modes

are found in the

interval between (, E, k ) and ( d , E dE , k dk ) ?

# modes dN N ()d N ( E)dE N (k )d k 3

able to calculate N() and evaluate CV in the Debye model.

First step: simplify problem by using periodic boundary conditions for the

linear chain of atoms:

s+N-1 We assume atoms s

L = Na and s+N have the

same displacement—

s the lattice has periodic

behavior, where N is

s+1 very large.

x = sa x = (s+N)a

s+2

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

First: finding N(k)

Since atoms s and s+N have the same displacement, we can write:

allowed k values: kNa 2n k n 1, 2, 3, ...

Na

k n the density of modes

allowed solutions (k values) is: Na Na in k-space is uniform

# of modes 1 Na L

Thus, in 1-D:

interval of k space k 2 2

Next: finding N()

Now for a 3-D lattice we can apply periodic boundary N3c

conditions to a sample of N1 x N2 x N3 atoms:

N2b

# of modes N a N 2b N 3c V N1a

1 3 N (k )

volume of k space 2 2 2 8

that we can write the dN N ( )d N (k )d k 3 d k 3

in k-space by using a

“volume” element made up

d k ( surface area) dk

3

dS dk

thickness dk:

N() at last!

Rewriting the differential V

3

dN N ( )d dS dk

number of modes in an interval: 8

V dk V 1

8 3 d 8 3

We get the result: N ( ) dS dS

k

A very similar result holds for N(E) using constant energy surfaces for the

density of electron states in a periodic lattice!

This equation gives the prescription for calculating the density of modes

N() if we know the dispersion relation (k).

We can now set up the Debye’s calculation of the heat capacity of a solid.

The density of states per unit frequency range

g():

g()d.

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

dn S (k )dk g ()d

;

dn R (k )dk g ()d

dk

g () S (k )

d

Let’s remember dispertion relation for 1D monoatomic lattice

4K 2 ka K ka

2

sin 2 sin

m 2 m 2

1

g () S (k ) K ka

d 2a K ka a cos

cos m 2

dk 2 m 2

1 m 1

K ka

a cos a K ka

m 2 cos

2

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

1 m 1

g () S (k )

a K cos ka / 2

cos 1 sin

2 2

1 m 1 4 Multibly and divide

g () S (k )

a K ka 4

1 sin 2 Let’s remember:

2

L

S (k )dk dk

1 2

g () S (k )

a 4 K 4 K 2 ka L Na

sin

2 4K 2 ka

m m

2

sin

m 2

2 1

g ( )

2L

Na

N

2

max

2 1/ 2

a max

2

2

max

2

4K

m

True density of states

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

g ( )

g ( )

2N

2

max

2 1/ 2

N m

True density of states by

K means of above equation

K K

max 2

m m

K

True DOS(density of states) tends to infinity at max 2 ,

m

since the group velocity d / dk goes to zero at this value of .

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

1

/ kT g d

0

2 e 1

Mean energy of a

2N

2

max

2 1/ 2 for 1D

harmonic oscillator

running waves.

results with experiment.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

3D DOS

Let’s do it first for 2D

Then for 3D.

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

L.

y ky

+ -

L L

L

- +

+ -

0 x kx

L

box

•Let’s 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

•Vibration amplitude should vanish at edges of

x 0; y 0; x L; y L

Choosing positive integer

p q

kx ; ky

L L

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

y ky

+ -

L L

L - +

+ -

0 x kx

L

Standing wave pattern for Configuration in k-space

a 2D box

•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 of

per unit area. L / 2

• This result can be extended to 3D.

L

Octant of the crystal:

kx,ky,kz(all have positive values)

L

3

L 3 V 3

s k d k d k 3 d k

3

L

1

kz L / 4 k 2 dk

8

V 1

s k d k 3 4 k 2 dk

3

dk

8

2

Vk

ky k d 3

k 2 dk

2

k s

Vk 2

kx S k 2

2

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

2

• k Vk is a new density of states defined as the number

2 2

dk

g d k dk g k

d

the expression of g .

High and Low Temperature Limits

Each of the 3N lattice d

3NkBT modes of a crystal C C 3NkB

containing N atoms dT

This result is true only if T=

kB

w can be excited from their ground states;

Low frequency long

sound waves

0 k

vs k vs

a k

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

1 k

dk 1 Vk 2 dk

vs and g 2

k vs d vs 2 d

2

V 2

g vs 1

at low T’s

2 2 vs

vs depends on the direction and there are two transverse, one longitudinal acoustic

branch:

V2 1 V2 1 2

g g 2 3

3

2 vs

2 3

2 vL vT

Velocities of sound in

longitudinal and transverse

direction

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

1

/ kT g d Zero point energy= z

0

2 e 1

1 1 2

V

2

3 3 d

2

0

2 e / kT

1 2

vL vT

V 1 2

3

z 2 3 3 / kT d x

2 vL vT 0 e 1

k BT

3

B 3

k T

k BT

x

x

3

k BT

0 e / kT 1 d 0 e x 1 dx

k BT

d dx

V 1 2 k BT

4 4

z 3 2 3 3 4 3 3

2 vL kvBTT x 15

e

0

d

/ kT

1

dx3 e

0

x

1

at low temperatures

d V 1 2 4 3

4 15

2

d 2 1 2 kBT

3 k B 4T

3 P.Ravindran,

Cv V kB 3 3

2

3

dT 30 vL vT dT 15

PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

vL vT

How good is the Debye approximation at low T?

d 1 2 k T

3

2

Cv V 2 kB 3 3 B

dT 15 vL vT

varies as T 3 at low temperatures; this

is referred to as the Debye T 3 law.

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 harmonic

oscillator because the vibration

spectrum extends down to zero

frequency.

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

The Debye interpolation scheme

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. Debye’s

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 Debye

approximation approximation

to the to the vk

dispersion dispersion

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

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 3 N

0

V 1 2

2 V 1 2 D 2

2 2 vL3 vT3 0

g ( ) ( 3 3) ( ) d 3N

2 vL vT

2

V 1 2 3N 9N

V 1

2

) D3 3 N ( 3 3) 3 3 3

6 2

( 3

vL vT3 2 vL vT

2

D D

9N

g ( ) 2

g ( ) / 2

3

D

The lattice vibration energy of

1

E ( / kBT )g ( )d

0

2 e 1

becomes

D

9N 1 9 N D

3 D

3

E 3 0 ( 2 e / kBT 1) d D3 0 2 d 0 e / kBT 1d

2

D

and, D

9 9N 3d

E N D 3

8 D e

0

/ k BT

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.

dE

The heat capacity is C

dT

D

D

d 3

dE 9 N 4 e / k BT

2

9 9N

E N D 3 CD 3 d

8 D 0

e / k BT 1 dT D 0

kBT e / kBT 1

2 2

the specific heat changing variables to x

d kT

kT

x x

k BT dx

D

D

kB

The Debye prediction for lattice specific heat

D / T

4

dE 9 N kBT kBT 2

x4e x

CD 3 2 dx

dT D e 1

2

kBT 0

x

3 /T

T D

x 4e x

CD 9 Nk B dx

e 1

2

D 0

x

D

where D

kB

How does CD limit at high and low temperatures?

High temperature T = D

x2 x3

X is always small e 1 x

x

2! 3!

x 4e x x 4 (1 x)

x 4 (1 x)

x 2

e 1

2 2 2

x

1 x 1 x

3 /T

T D

T = D CD 9 NkB

D

0

x 2 dx 3Nk B

How does CD limit at high and low temperatures?

the integral is then a known integral of 4 4 /15 .

3 /T

T D

x 4e x

T D CD 9 Nk B

< dx

e 1

2

D 0

x

3

12 NkB 4 T

CD

5

D

Lattice heat capacity due to Debye interpolation

scheme

Figure shows the heat

capacity between the two limits of C

high and low T as predicted by the 3 Nk B T

Debye interpolation formula. 1

3 D / T

T x 4e x

CD 9 Nk B dx

D e 1

x 2

0

limits the Debye formula gives quite a good

representation of the heat capacity of most solids, even 1 T / D

though the actual phonon-density of states curve may Lattice heat capacity of a solid as

differ appreciably from the Debye assumption. predicted by the Debye interpolation

scheme

D 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 D for

various solids is given in table. Debye energy D can be used to estimate

the maximum phonon energy in a solid.

Solid Ar Na Cs Fe Cu Pb C KCl

D ( K ) 93 158 38 457 343 105 2230 235

F. The Debye Model Calculation

We know that we need to evaluate an upper limit for the heat capacity integral:

max

CV (T )

N ( ) C

0

E ( , T ) d

If the dispersion relation is known, the upper limit will be the maximum value.

But Debye made several simple assumptions, consistent with a uniform, isotropic,

elastic solid:

• continuous, elastic solid: = vgk

• max given by the value that gives the correct number of modes per polarization

(N)

N() in the Debye Model

d V 1 V

3

First we can evaluate vg N ( ) dS dS

the density of modes: dk 8 vg 8 vg

3

directions in k-space are the same, so

2

the constant surface is a sphere of k dS 4 k

radius k, and the integral reduces to:

V 2

V

Giving: N ( ) 3 4k 2 3 2 for one polarization

8 vg 2 vg

Next we need to find the upper limit for the integral over the allowed range of

frequencies.

max in the Debye Model

max

Since there are N atoms in the solid, there are N unique

modes of vibration for each polarization. This requires:

0

N ( )d N

max

Vmax

1/ 3

6 N

3

V 2

2 3

Giving: d 2 3 N

2

max vg D

2 vg 0 6 vg V

The Debye cutoff frequency

Now the pieces are in place to evaluate the heat capacity using the Debye

model! Remember that there are three polarizations, so you should add a factor

of 3 in the expression for CV. If you follow the instructions in the problem, you

should obtain:

T D 4 z

z e dz

CV (T ) 9 Nk B

D

0

(e z 1) 2

expression in the limits of low T

(T << D) and high T (T >> D).

Debye Model:

Theory vs. Expt.

Better agreement

than Einstein

model at low T

Universal behavior

for all solids!

Debye temperature

is related to

“stiffness” of solid,

as expected

Debye Model

at low T:

Theory vs.

Expt.

Quite impressive

agreement with

predicted CV T3

dependence for Ar!

(noble gas solid)

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 Hooke’s 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.

r a

2

d 2V

V (r ) V (a ) 2 ....................

2 dr r a

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 3 , k3

1 , k1

After collision another phonon is produced

2 , k2

phonon2 3 1 2 and k3 k1 k2

3 1 2 conservation of energy

k3 k1 k2 conservation of momentum

Phonons are represented by wavenumbers with

k

a a

2

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

it back within the range of k . Then, k3 k1 k2 becomes

a a

This phonon is indistinguishable from a phonon n2

with wavevector

k3 k3 k1 k2

a

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

Longitudinal 3 3' 3

1 1 2

Transverse 2

k k

0 0

a a a a

n 0 Normal process n 0 Umklapp process

(due to anharmonic effects)

Phonon3 has k ; Phonon3 has k and Phonon3=Phonon3’

a a

P.Ravindran, PHY075- Condensed Matter Physics, Spring 2013 : Lattice Dynamics I

Thermal conduction by phonons

region when there is a temperature gradient in a solid.

The most important contribution to thermal conduction

comes from the flow of phonons in an electrically insulating

solid.

Transport property is an example of thermal conduction.

Transport property is the process in which the flow of some

quantity occurs.

Thermal conductivity is a transport coefficient and it describes

the flow.

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.

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

Angular average

3 dz

Constant average speed for

Mean free path

molecules

In the simplest case where P is the number density of particles the transport

_

coefficient obtained from above eqn. is the diffusion 1

D coefficient

l

3

.

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

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 Works well for a phonon gas

3

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

•Both the number density and energy •Average velocity and kinetic energy per

density is greater at the hot end. particle are greater at the hot end, but

the number density is greater at the cold

•Heat flow is primarily due to phonon

end, and the energy density is uniform

flow with phonons being created at the

due to the uniform pressure.

hot end and destroyed at the cold end

•Heat flow is solely by transfer of kinetic

energy from one particle to another in

collisions which is a minor effect in

hot cold phonon case.

hot cold

Temperature dependence of thermal

conductivity K

1 _

K l C Approximately equal to velocity

of sound and so temperature

Vanishes exponentially at low

3 independent.

T’s and tends to classical value

at high T’s k B

?

•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 3NkB

The rate of collisions of two phonons phonon density.

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

the total lattice energy T; phonon number T , so

Scattering rate T and mean free length T 1

_

1

Then the thermal conductivity of K l C T 1 .

3

Experimental results do tend towards this behaviour at

high temperatures as shown in figure (a).

10

10

0

0

1

T

10-1

10-1 T3

5 10 20 50 100

T (K )

2 5 10 20 50 100

(a)Thermal conductivity of a T (K )

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 k / a . So

3

The energy of relevant phonons is thus not sharply defined but their

number is expected to vary roughly as

e D / bT when T D ,

where b is a number of order unity 2 or 3. Then

l eD / bT

This exponential factor dominates any low power of T in thermal

conductivity,

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

Conduction at low temperatures

l for phonon-phonon collisions becomes very long at low T’s and eventually

exceeds the size of the solid, because

exponentially as

eD / bT

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

l Specimen diameter

3

12 NkB T 4

CD

5

D

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.

dislocations, grain boundaries and impurities, then these will also scatter

phonons. At the very lowest T’s 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.

D / bT

The maximum conductivity between T

3

and e 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.

Crystal Dynamics

atoms when they are displaced from their equilibrium

positions.

wavefunctions and energies of the electrons within the

crystal. Fortunately many important properties of the

atomic motions can be deduced without doing these

calculations.

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