Solid state physics

Dr. \Fatemah F Alharbi

8th lecture
Phys 371 T, 4 Credit

Thermal properties of solids

10/10/2022
 Thermal properties
yj of solids

• Phonon is vibration of atoms in a crystal. Phonons play a major role in many of physical
properties of solids, including a material's thermal and electrical conductivities. Hence the
study of phonons is an important part of solid-state physics.
 Comparison of Phonons
yj & Photons

PHOTONS PHONONS
• Quantized normal modes • Quantized normal modes
of electromagnetic waves. of lattice vibrations.
The energies & momenta The energies &
of photons are quantized: momenta of phonons
are quantized:
Ephoton  Ephonon hvs
 
hc
pphoton pphonon
 
h h
Photon Wavelength: λphoton ≈ Phonon Wavelength: λphonon ≈
10-6 m (visible) a ≈ 10-10 m
 Thermal Energy &y jLattice Vibrations

• As is discussed in detail in any solid state physics course, the atoms in a crystalline solid
vibrate with small amplitude about their equilibrium positions.

This motion produces vibrational waves.

• The amplitude of this vibrational motion increases as the temperature increases.
• In a solid, the energy associated with these vibrations is called the Thermal Energy
• Most importantly, the thermal energy plays a fundamental role in
determining the many properties of solids.
• Examples: Thermodynamic Properties of solid
Knowledge of how the thermal energy changes with temperature gives an understanding of
heat energy necessary to raise the temperature of the material.
• An important, measureable property of a solid is it’s Specific Heat or Heat Capacity
 Lattice Vibrational Contribution
yj to the Heat Capacity

• The Thermal Energy is the dominant contribution to the heat capacity in most
solids. In non-magnetic insulators, it is the only contribution.

• Some other contributions:

-Conduction Electrons in metals & semiconductors.

-Magnetic ordering in magnetic materials.

 Classical Theory of Heat
y j Capacity of Solids

• Each atom is bound to its site by a harmonic force. When heated, atoms
vibrate at low amplitude around their equilibrium sites like a coupled set of
harmonic oscillators.
• By the Equipartition Theorem, the classical thermal average energy for a
1D oscillator is kT. Therefore, the average energy per atom, regarded as a 3D
oscillator, is 3kT. So, the energy per mole is:
E = 3RT
R is the gas constant. The heat capacity per mole is thus given by
Cv =(dE/dT)V . This clearly gives:
CV 
3R
 Thermal Energyy &
j Heat Capacity

• The following makes use of the Canonical Ensemble

• We’ve already seen that the Quantized Energy solution to
1D oscillator is:
‫ شريدنير‬the Schrodinger Equation for a single

 n
 1 
 n   n = 0,1,2,3,..
2
ħ
• If the oscillator interacts with a heat reservoir at absolute temperature T,
the probability Pn of it being in level n is proportional to:

exp( n / k BT )
 Quantized Energy ofy ja Single Oscillator:

 1  n = 0,1,2,3,..
   n  
n
2
ħ
• The probability of the oscillator being in level n has the form:

Pn  exp( n / k BT )
• In the Canonical Ensemble, the average energy of the harmonic
oscillator & therefore of a lattice normal mode of angular
frequency ω at temperature T is:
_

 n P 
n n
 Quantized Energy ofy ja Single Oscillator:

_
1  (1)
  e  / k BT

 2  1
This is the Thermal Average Phonon Energy. (One oscillator)

• The first term in the above equation is called “The Zero-Point Energy”.
• It’s physical interpretation is that, even at T= 0K the atoms vibrate in the crystal
& have a zero-point energy.
• The Zero Point Energy is the minimum energy of the system.
 Thermal Averagey jPhonon Energy

_1 
  e  / kBT (1)
2  1

• The denominator of second term in (1) is often written:

1
n(  )  (2)
e kB T
1

• Equation (2) is interpreted as the thermal average number of
phonons n(ω) at temperature T & frequency ω.
• In modern terminology, (2) is called The Bose-Einstein
Distribution or The Planck Distribution.
 Einstein’s Model of Heat
yj Capacity of Solids
• The Einstein Model was the first application of quantum theory to
solids. He made the (absurd & unphysical) assumption the each of 3N
vibrational modes of a solid of N atoms has the same frequency, so that
the whole solid has a heat capacity 3N times, the heat capacity of one
mode:

2 e T

Cv    
e
B
T  
3NkB 
k T
1
 3R
2
Einstein's
y j Model
 Einstein's
y j Model

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

3R = 6 cal/K per mole; they require 6 calories per mole to raise their
temperature 1K.
This agreement between observation and classical theory breaks 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

T

Cv 
kB
 Einstein Model for Lattice
yj Vibrations in a Solid
Cv vs T for Diamond
Einstein, Annalen der Physik 22 (4), 180 (1907)

Points:
Experiment
Curve:
Einstein Model For diamond the
Prediction Einstein Temperature
TE = 1320 K
 Einstein Model for Lattice
yj Vibrations in a Solid
• The Einstein model correctly gives a specific heat tending to zero at
absolute zero, but the temperature dependence near T= 0 does not agree
with experiment.
• However, a model which takes into account the actual distribution of vibration
frequencies in a solid is needed in order to understand the observed
temperature dependence of Cv at low temperatures:

CV = AT3
A= constant
 Debye Model Vibrational
yj Heat Capacity

Brief Discussion
• In general, the thermal average vibrational energy of a solid has the form:
  
1   g d 
  0
  e  / kT
1 
2 
• The term in parenthesis is the mean thermal energy for one
mode as before: _ 1 
  e /k T B

 2  1
• The function g() is called the density of modes.
• Formally, it is the number of modes between  & d
• Its form depends on the details of the (k).
 Debye Model Vibrational
yj Heat Capacity

  
1   g d 
  0
  e  / kT
1 
2 
• The Debye  Model assumes that every (k) is an acoustic mode (like
ordinary sound waves) with

• It can be shown that this results in a density of modes g() which

has the form:

Or g(ω)dω  Cω2dω
C = constant
 Lattice heat capacityy in
j the Debye Model
3 D / T
 T  x 4e x
CD     dx
The figure shows the heat capacity between the limits e
B 2
9Nk  0
x
1
 D 
of high & low T predicted by the Debye model. C

Because it is exact in both high & low T limits, the D
3Nk BT
1
Debye formula gives quite a good representation of
the heat capacity of most solids, even though the D
actual phonon-density of states curve may differ Lattice heat capacity of a
solid as predicted by the
appreciably from the Debye assumption. Debye interpolation scheme
D
1
T / D

•The Debye frequency ωD & the Debye temperature ΘD scale with the velocity of sound in the solid.
So solids with low densities and large elastic moduli have high values of ΘD for various solids in the
table. The Debye energy ħωD is an estimate of 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

Debye Model of the Vibrational
y j Heat Capacity of Solids
 Debye Model Density
yj
of States g(ω) &
an Example of an actual Density of States