Examples where phonons are important

Energy loss is problem for solar cells

 Indirect semiconductors
Describe differences.

Low energy transition can only be excited if phonons present

Real Phonon Spectra Might Look Slightly Different
Why?

We made several simplifications:

•Interactions beyond nearest neighbors are
not included
•Assumed harmonic potential
•Ignored electron-phonon coupling
 Predict for Diamond
along one direction (try 001)
http://exciting-code.org/phonon-properties-in-diamond-structure-crystals

Longitudinal Optical

Transversal Optical
degenerate
1 1 1
( , , )
(0,0,0) 4 4 4
Longitudinal Acoustic

fcc lattice with basis

Transversal Acoustic
degenerate P=2
2x3=6 branches
expected
 Can you guess what this is?
What makes this look quite different?
How could we measure this?
All measurements before from neutrons.
 Neutron Diffraction for Phonons

Neutrons were discovered in 1932 and their wave

properties was shown in 1936.

E = p2/2m p = h/λ
E=Energy λ=Wavelength
p=Momentum
mn=Mass of neutron = 1.67x10-27kg

λ ~1A°
Energy E~0.08 eV. This energy is of the same order
of magnitude as the thermal energy kT at room
temperature, 0.025 eV, and for this reason they are
good at probing phonons.
 Diffraction Methods

Diffraction

X-ray Neutron Electron

The physical basis for the diffraction of electron and

neutron beams is the same as that for the diffraction of X-
rays, the only difference is the mechanism of scattering.
 Neutron Diffraction
• Neutron has no electrical charge. Interaction is with atomic
nuclei (strong force, short range)

• Neutron-matter interaction is weak (mean free path ~1 cm)

• Although uncharged, neutron has an intrinsic magnetic

moment, so it will interact strongly with atoms and ions in
the crystal which also have magnetic moments.
• Neutrons are more useful than X-rays for determining the
crystal structures of solids containing light (low atomic
number) elements.

• Neutron sources in the world are limited so neutron

diffraction is a very special tool.
 Oak Ridge, Tennessee
Start with negatively charged hydrogen ions (1 proton and 2 electrons), produced by
an ion source. Ions injected into a linear accelerator.
The ions pass through a foil, which strips off the electrons, converting it to a proton.
The high-energy protons strike a target of liquid mercury, where spallation occurs.
The spalled neutrons are guided through beam lines.
Very expensive and involved experiments
(construction of Oak Ridge neutron source was ~ $1 billion)

Table top alternatives ?

Yes, infrared absorption and

inelastic light scattering (Raman and Brillouin)

However only q~0 accessible (atomic

scattering factors decrease as q2 for light).
See ch. 7 of http://www.slideshare.net/dasepbux/wave-
diffraction-53527785

Lonely scientist in the reactor hall

 Phonon spectroscopy =
Conditions for: in elastic scattering
Constraints:
Conservation laws of
Momentum Energy

In all interactions involving phonons, energy must be

conserved and crystal momentum must be conserved to within
a reciprocal lattice vector.
 Magnetic Applications of Neutron Diffraction
Establishing magnetic structure of materials
– Neutrons carry magnetic moments and their scattering
is affected by magnetic moments of atoms

Example: Mn
Magnetism of MnO
Mn2+ ions
face-centered cube
O2- ions
in the centers of all edges O
and in the body center

What crystal structure?

What happens to the unit

cell when you add the
magnetic structure?
 Magnetic Super-Structures
(cubic symmetry)

a a
Anti-Ferromagnetic=FM in one plane
Ferromagnetic (FM)=has a spontaneous but antiparallel in next plane, M=0
magnetization whose direction can be Magnetic and charge have the different
changed with a magnetic field unit cells. Magnetic unit cell doubles
Magnetic and charge have the same unit cell nuclear unit cell.
 Compare the a can c lattice
parameters to the non-magnetic
version in the case of MnO.
Mn

cnon-
magnetic
O

anon-magnetic
XRD of MnO (from Kittel)
What do you expect to happen?
Chemical unit
cell (FCC)
(all odd or
even h,k,l)

Magnetic
unit cell

15
Like Telescope Time, Beamtime is Competitive

Ranking scheme:
1. Must do
2. High Priority
3 pages to describe why 3. Medium Priority
your work is important, 4. Low priority
what you expect to learn, 5. Don’t do
how you will do it and
why you can’t do it
anywhere else!

Due ~ 1 year before the

work is done!

Cutoff
 If You Do Get Time
Magnetism experts

XAS expert

I = Installation/Maintanence
me

You might get three days to do all of your experiments for the year!
Heat Capacity Revisited
(now with phonons)
 Revisiting Heat Capacity

• Dustin will discuss a summary of heat capacity

next time, so let me skip to the focus of today
• Drude (spring-like) -> constant heat capacity
• Sommerfield: linear T dependence

At low T quantum phenomena are

important and must be taken into account.
Specific heat tends to classical value at
high temperatures.
 Lattice Vibrational Contribution 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.
The magnetic ordering in magnetic materials.
 Thermal Energy & Heat Capacity
Quantum Model

According to Quantum Mechanics if a particle is constrained;

• the energy of particle can only have special discrete energy
values.
• it cannot increase infinitely from one value to another.
• it has to go up in steps.
 Treating Phonons like QM Oscillator
Einstein Model = Heat capacity C can be found by
differentiating the QM average phonon energy

   Pn n
The energy of a harmonic n
Energy of a single
oscillator and hence of a oscillator
lattice mode of angular
frequency  at temperature T  1
n   n   
What happens to  as the temperature increases?  2
The probability of the
oscillator being in this level as
given by the Boltzman factor
exp( n / kBT )
 Average energy

 1   1 
_  Pn n _   n    exp    n    / k BT 
 2   2 
 n
  n 0 
P n

  1 
exp    n    / k BT 
n
n 0   2 

1 
Partition function z   exp[(n  ) ]  What is dz/dT?
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  .....
z  e  / 2 k BT
(1  e   / k BT 1
)  Will need soon
According to the Binomial expansion for x«1 where
 h / k BT
xe

1

n 0
x 
n

1 x
 
 1   1 
Can be written as: _  

n 
2


 exp


 

n 
2


 / k T
B 

  n 0 
_
1 z    1 
  k BT 2  k BT 2 (ln z )  exp 
  n    / k T
B 
z T T n 0   2 
_
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

 T 2 k T   T 
B
 x'
(ln x) 
  k B   / k BT  x x
_  2k  k 2T 2 e  1 e  / k BT
  k BT  2 2 
2 B B
 
 4 k BT 1  e   / k BT
  2 1  e  / k BT

 
_
1 
Finally, the     / k BT
result is 2 e 1
 _
1 
    / k BT
2 e 1

This is the Mean Phonon Energy. The first term in the above equation
is the zero-point energy. As mentioned before even at 0ºK atoms vibrate
in the crystal.
The number of phonons is given by the Bose-Einstein distribution as
kBT

1
f ( )  
1
 e kBT
1
2
T _
(number of phonons) x (energy of phonon) = (second term in  )

The second term in the mean energy is the phonon contribution to the
thermal energy.
 Heat Capacity C (Einstein Model)
• Heat capacity C can be found by differentiating the
average phonon energy
_
1 
    
2 e kBT  1
 kB 

  e k BT


 k BT   
2 2
d
k BT
e
Cv   Cv  k B
   kBT 
 
 2 2  2
dT
e k BT
1 e kBT
1

 
2
 eT
Let  Cv  k B   

 T  e T 1

2
k
  
2 


eT
Cv  k B   

 T  e T 1
 where
2

Specific heat in this approximation

vanishes exponentially at low T and
tends to classical value at high
Cv
temperatures.
kB These features are common to all
 quantum systems; the energy tends to
Area = the zero-point-energy at low T and to
2 the classical value of the Boltzmann
T constant at high T.

kB The difference between classical and Einstein
models comes from zero point energy.
 Einstein Model Fails at Low Temp
• 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. Why?
• Taking into account the actual distribution of vibration
frequencies in a solid this discrepancy can be accounted for
CV of Diamond
Einstein was aware that getting
the frequency of the actual
oscillations would be different.
He proposed this theory
because it was a simple
demonstration that QM
could solve the specific heat
problem.
Finding the 3d density of states D(E) for Photons
2 Good analogy for low temp phonons. Why?
k
g (k ) 
 2

)dk  gg(E)
g (kg(k) ( E )dE
g(k) g(E) dE
g (k )  g ( E )
dk
Number of States N=gV (for Photons)
How about for Ng   
V2 1
Ng   
V2  1 2 
 3
2  3
2 vs
2 3
2  vL vT 
Phonons?

Factor of 3 from one

longitudinal and 2 transverse
 Debye approximation has two main steps
1. Approx. dispersion relation of any branch by a linear extrapolation
2. Ensure 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
Einstein Debye  D
 D so that:
approximation to approximation  g ( )d  3N
0 
the dispersion to the dispersion V 1 2 D 2
( 3  3 )   d  3N
2 vL vT 0
2
V 1 2
  vk 6 2
( 3

vL vT 3
)D3  3 N
V 1 2 3N 9N
(  )  3 
2 2 vL3 vT3 D3 D3

9N
g ( )  2 g ( ) /  2
D3
 Einstein Debye
Accordingly, the Debye spectrum may be written as

9 N 2
 3 for   D
g ( )    D
0   D
 for
Actual
Notes:
The Debye spectrum is only an idealization of the actual situation obtaining in a
solid; it may be compared with a typical spectrum.
While for low-frequency modes (the so called acoustical modes) the Debye
approximation is reasonably valid, there are serious discrepancies in the case
of high-frequency modes ( the optical modes).
For “averaged” quantities, such as the specific heat, the finer details of the
spectrum are not very important.
Though not as common, the longitudinal and the transverse modes of the solid
should have their own cut-off frequencies, D,L and D,T say, rather than
D. Accordingly, we should have:
having a common cut-off at
 D ,L  D ,T
 d
2
 2 d
 V 2 2cL3  N and  2 2cT3  2 N
 Debye Lattice Energy and Heat Capacity

1  g ( ) 
9N
2
The lattice vibration energy of E   (    / kBT )g ( )d
2 e 1 D3
0

D
9N 1  9 N  D
 3 D
 3 
becomes E 3 0 ( 2   e  / kBT  1) d  D3  0 2 d  0 e  / kBT  1d 
2

D  
D
9 9N  3d
and, 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.
D 2
 4 e  / k BT  d kT
dE 9 N x 
CD   3
dT D  kBT  e  / kBT  1
2 2
d k BT
kT
dx
0  x define the Debye
3  /T temperature
 T  D
x e 4 x
D
CD  9 Nk B    dx D 
 D  e  1
x 2 kB
0
How does C D limit at high and low temperatures?
High temperature T >> D
x2 x3 3  /T
e  1 x 
x
   T  D
x 4e x
2! 3! CD  9 Nk B    dx
 D  e  1
x 2
0
4 x
xe x (1  x)
4
x (1  x) ~ 2
4
  x 
x
 e  1 1  x  1
2 2 2 is small
x x
k BT
3  /T
 T  D

T >>  D  CD  9 Nk B 

 D
 
0
x 2 dx  3Nk B
Low temperature T << D
For low temperature the upper limit of the integral is ~infinite; the
integral is then a known integral of 4 4 /15 .
3  /T
 T  D
x 4e x
T <<  D  CD  9 NkB    dx
 e  1
2
 D x
D
0

We obtain the Debye T 3 law in the form D 

3
kB
12 Nk B 4  T 
CD   
5 
 D
 How good is the Debye approximation at low T?
d  1 2   k BT 
 3
1   2
 V  kB  3  3  
       g   d Cv  2

0
2 e  / kT
1  dT 15  L
v vT   

The lattice heat capacity of solids varies

as T 3at low temperatures; Debye law.

Excellent agreement for

non-magnetic insulators!

Motivation for Debye: The exact calculation of DOS is difficult for 3D.
Debye obtained a good approximation to the heat capacity by neglecting
the dispersion of the acoustic waves, i.e. assuming   s k
for arbitrary wavenumber.
In a 1D crystal, Debye’s approximation gives the correct answer in both
the high and low temperature limits.
This approximation is still widely used today.
 Lattice heat capacity due to Debye scheme
3 D / T
 T  x 4e x
CD  9 Nk B    dx
 D  e  1
x 2
0 C
3 Nk B T
Debye formula gives quite a good 1

representation of the heat capacity of most

solids, even though the actual phonon- Lattice heat capacity of a solid as
predicted by the Debye interpolation
density of states curve may differ scheme

appreciably from the Debye assumption. T / D

1

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 . 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
 Summary: Debye Specific Heat
1
For T>>D c  3 Nk
V
Same as a classical non-interacting gas

4  T  4 3
For T<<D cT  
1
3 Nk  
V 5 
Quantum effects important

The assumptions of Debye theory are:

• the crystal is harmonic
• elastic waves in the crystal are non-dispersive
• the crystal is isotropic (no directional dependence)
• there is a high-frequency cut-off determined by the number of
degrees of freedom
 Comparing Phonon and Electron
contributions to heat capacity (for metals)
Phonon contribution Electron contribution

d 2  1 2   k BT 
3
𝜋2𝑘𝐵 𝑇
Cv   V  kB  3  3  
2
 Cv=
dT 15  L
v vT   2 𝑇𝐹
T > Debye temp

• If each unit cell contributes one or two electrons, then

the ratio is about kBT/EF (small for most metals)
• Thus, electrons do not contribute much to room
temperature heat capacity (significant at low temp)
 Class Discussion
Experimentally, the specific heat of EuO at very
low temperatures is proportional to T3/2.

• Is EuO a metal or an insulator? Why?

• Any idea what type of elementary excitation this
behavior results from? (you may not know)

• What was the temperature dependence in metals?

• Remember what materials Debye was good for?
• Magnons with an energy dependence of k2
 How good is the Debye approximation at low T?
d  1 2   k BT 
3
2
Cv   V  kB  3  3  
2

dT 15  L
v vT   

The lattice heat capacity of solids thus

varies as T 3 at low temperatures; this is
3
referred to as the Debye T law.
Figure illustrates the excellent
agreement 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.
 Reminder: 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
At low T’s only lattice modes having low frequencies can be
excited from their ground states;

 Low frequency long 

sound waves

  vs k vs 
k k
0 
a
Calculating Specific Heat Capacity

1  
      / kT   g   d Zero point energy =  z
0
2 e 1 


1   V  1 2  
2
       2  3  3  d x
0
2 e  / kT
 1  2  vL vT 
k BT
 V  1 2   

3
   z  2  3  3      / kT d  k BT
 2  vL vT   0  e
  1   x
 
 k BT  3
3
k BT

3    x kT d  dx
V  1 2   k BT   4  
4

  z  2  3  3 
2  vL vT  3
15
e 
0
/ kT
1
d  
0
e 1
x
B
dx


 k BT 
4 
 3
x3
e 
0
/ kT
1
d  3 0 e x  1dx
 4 15

d  1 2   kBT 
3
2
Cv   V  kB  3  3  
2
 at low temperatures
dT 15  L
v vT   
 Example
Calculate the temperature at which the photon
energy density in a solid will exceed the phonon
energy density in the same solid, if the solid has
a Debye temperature of 300K, a phonon velocity
of 400,000 cm/s and an index of refraction of
n=2
and assuming the solid does not melt.

Should we consider the high or low temperature regime?

Heat capacity of the free electron gas
• From the diagram of n(E,T) the change in the distribution of
electrons can be resembled into triangles of height ½ g(EF) and
a base of 2kBT so the area gives that ½ g(EF)kBT electrons
increased their energy by kBT.

 The difference in thermal energy

from the value at T=0°K

1
E (T )  E (0) ~ g ( EF )(k BT ) 2
2
• Differentiating with respect to T gives the heat
capacity at constant volume,
E
Cv   g ( EF )k B 2T
T g (E) 
V
(2 m ) 3/ 2 1/ 2
E
E E
2 2 3

2 F F
V V
N  EF g ( EF )  0  0 2 2 E dE 
3/ 2 1/ 2 3/ 2
N g ( E ) dE (2m) (2mE )
3 2
3 3 F
3
3 N 3N
g ( EF )  
2 EF 2k B TF

3N 3 T 
Cv  g ( EF )k B T 
2
k B 2T Cv  NkB  
2k B TF 2  TF 
Heat capacity of
Free electron gas
 The energy of diffraction methods

X-Ray Neutron Electron

λ = 1A° λ = 1A° λ = 2A°

E ~ 104 eV E ~ 0.08 eV E ~ 150 eV

interact with electron interact with nuclei interact with electron

Penetrating Highly Penetrating Less Penetrating

~ Bulk Measurement Bulk Measurement Surface Sensitive

if sample is thin (<100s nm)
 kBT

 Mean energy of a
harmonic oscillator
1 as a function of T

2
T

Low Temperature Limit

  kBT
_
1 
     Since exponential term
2 gets bigger
e kBT  1
_
1
   Zero Point Energy
2
 kBT Mean energy of a
 harmonic oscillator
as a function of T
1
 x2
2 e  1  x   ..........
x

2!
T 

High Temperature Limit e  1k BT

k BT
 << kBT _
1
   

2 
 is assumed independent of frequency of 1 1
k BT
oscillation by the Einstein method. _
1
    k BT
This is the classical limit because the energy 2
steps are now small compared with the energy
of the harmonic oscillator. _
Notice that  is the thermal energy of the   kBT
classical 1D harmonic oscillator.
 When k is not small, DOS bigger
Total energy determination tricky
Gradient goes to zero at edges of Brillouin Zone

Like electronic density of

states, there will be a van
Hove singularity in the
phonon density of states.
 Another View of the Low Temperature Limit
At low T’s only lattice modes having low frequencies can be
excited from their ground states, since the Bose-Einstein function
falls to zero for small values of 

Low frequency
sound waves

at low T   vs k vs 
k
 k
0
a
 2 
V 2 
Vk 2 dk
g    2 g     vs  1
2 d 2 2 vs
 k 1 dk 1
vs      vs depends on the direction
k  vs d  vs
V2 1 V2  1 2 
g     g    2  3
 3
2 vs
2 3
2  vL vT 