1

Chapter Five Phonons II. Thermal Properties

Phonons : dominate thermal properties of materials and affect the
electrical transports of conductors by scatterings of electrons
Phonon generations : How are phonons created or excited in a crystal?
External perturbations vibrations or sound transducer
Scattering of particles energy transferred into lattice vibrations
Thermal (K
B
T) excited at any finite temperature (T0K)
Thermal phonons : consider a system with energy level E
n
E
n
E
n-3
E
n-1
Probability of occupancy
at temperature T
Boltzmann factor
|
|
.
|

\
|

T k
E
exp ) P(E
B
n
n
2
Excitation level amplitude (n) w/. energy
, k mode
r
( )
( )
( )
( ) T k

x where
sx exp
sx exp
dx
d


T k
1/2) (s
exp
T k
1/2) (s
exp s

T k
E
exp

T k
E
exp s
E P
E P s
n
B
s
s
s
B
s
B
s
B
s
s
B
s
s
s
s
s
h
h
h
=

=
|
|
.
|

\
|
+

|
|
.
|

\
|
+

=
|
|
.
|

\
|

|
|
.
|

\
|

= =

Planck distribution of < n(, T) >

average # of phonons excited
per mode at
1
T k

exp
1
T) , n(
B

(

=
h

2
1
n h
|
.
|

\
|
+
Average of phonons
3
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0


<

n
(

,

T
)

>
x
-1
= k
B
T / h
High T ( k
B
T >> h )
< n(, T) > ~
Low T ( k
B
T < h )
< n(, T) > ~
1
T k

exp

) D( d
) n( ) D( d
n U
B
i
mode
i
i

|
|
.
|

\
|
=
=
=

h
h
h
h
Thermal energy
thermal equilibrium
density of modes
h
T k
B
|
.
|

\
|

h
T k
exp
B
4
Density of states (modes) : uniform in k-space
1D D(k)density of states = number of states per unit k at k
D(k)dk number of states from k to k+dk
A linear chain of length L carries N+1 particles with separation a.
Boundary condition : u
0
(t)=0 and u
N
(t)=0 fixed points
s=0
s=N
L
1) - (N
... ,
L
4
,
L
3
,
L
2
,
L

No motion at all.

L
a sN
.
|
\
|
u
s
(t)=u exp[-i
k,p
t] sin(ska) where k=
Why is there no N/L for allowed k? u
s
(t) =0
( ) s sin sin =
|
L

k =
One mode for each interval

>

=
a

k for 0
a

k for

L
D(k)
The number of modes per unit range of k
5
Unbounded medium but w/. periodic solution over the distance L
Periodic boundary conditions u(sa)=u(sa+L) for a large system
u
s
(t)=u exp[ i(ska-
k,p
t) ] where k=
... ,
L
6
,
L
4
,
L
2
, 0
L
2
k = One mode for each interval
otherwise 0
a

k
a

for
2
L
D(k)
=
=
The number of modes per unit range of k
d
d
dk
D(k) 2 D(k)dk 2 )d D(
k of for 2 and dk
2
L
D(k)dk
= =
=
The number of modes per unit frequency range
g
v
2D(k)
/dk d
2D(k)
d
dk
D(k) 2 ) D( = = =
Singularity at v
g
=0, determined by (k)
Dispersion relation
6
One dimensional monatomic lattice
( )
2 2
max
2
max



C
M

N

2
ka
cos
2
a
M
4C
Na/2 2
/dk d
2D(k)
) D(
2
ka
sin
M
4C

=
|
.
|

\
|
= =
|
.
|

\
|
=
D()

k
D(k)
L/2
-/a
/a
0
(N/)(M/C)
1/2
(4C/M)
1/2
0
Total number of modes
)d D( )d D( N
a
2
2
L
dk D(k) N
M
4C
0

0
/a
/a
max

= = = = =

7
In two dimensions :
periodic boundary condition, N
2
primitive cells within a square of side L
exp[ i(k
x
x+k
y
y) ] = exp[ i( k
x
(x+L) + k
y
(y+L) ) ]
whence k
x
, k
y
=
... ,
L
6
,
L
4
,
L
2
, 0
2
2
2
y x
4
L
L
2
k k
1
=
|
.
|

\
|
=

One mode per unit area in k-space
Number of modes with wavevector from k to k+dk in k-space
dk k 2
4
L
dk dk
k k
1
D(k)dk
2
2
y x
y x
= =
The number of modes per unit frequency range
g
2
v
1
k 2
4
A
/dk d
D(k)
) D( = =
g
2
3
v
1
k 4
8
V
/dk d
D(k)
) D( = =
In three dimensions :
8
D()d = D(k)d
3
k
complicated ! -- must map out dispersion relation and count all
k-values with each frequency
for each polarization
Continuum waves : = v
g
k depending only on amplitude of k
d
v

2
V

v
d
v

2
V

dk k 4
8
V

k d D(k) d ) D(
3
g
2
2
g
2
g
2
2
3
3
=
|
|
.
|

\
|
=
=
=
k
X
k
y
k
The number of modes per unit frequency range for each polarization
3
g
2
2
v

2
V
) D( =
a quadratic dependence !
9
Quadratic at low

D
Peaks at high
-- cutoff of
max
in
different k direction
N primitive cells in the crystal,
A total number of acoustic phonon mode is N for each polarization
3 / 1
2
g
D
D
3 / 1
3
g
2
D
V
N 6
v

k
V
N v 6

|
|
.
|

\
|
= =
|
|
.
|

\
|
=
Cutoff frequency
Cutoff wavevector
10
Thermal energy
|
|
|
|
|
.
|

\
|

|
|
.
|

\
|
=
=

1
T k

exp

v 2
V
d
) n( ) D( d U
B
3
g
2
2

0
D
h
h
h
each polarization
There are three polarizations : 2 transverse + 1 longitudinal
( ) T k

x where
1 x exp
x
dx
T k
v 2
3V

1
T k

exp

d
v 2
3V
U
B
x
0
4
B
3
g
2
B

0
3
g
2
3
D
3
D
h
h
h
h
h
=
|
|
.
|

\
|

|
.
|

\
|
=
|
|
|
|
|
.
|

\
|

|
|
.
|

\
|
=

11
Defining the Debye temperature
D
3 / 1
2
B
g
3 / 1
3
g
2
B B
D
D
V
N 6
k
v
V
N v 6
k k

|
|
.
|

\
|
=
|
|
.
|

\
|
= =
h
h h
( )

1 x exp
x
dx
T
T 9Nk U
3
D
/T
0
3
D
B
|
|
.
|

\
|

|
|
.
|

\
|

=

Peter Debye, 1884-1966
1936 Nobel prize winner
in chemistry
Therefore x
D
= h
D
/k
B
T=
D
/T
The total phonon energy
In classical model : equipartition theorem (0.5k
B
T for each excitation mode)
3 translational + 3 vibrational modes : six degrees of freedom
U = N 6 (0.5k
B
T) = 3 N k
B
T for N atoms in the crystal
C
v
= 3Nk
B
Dulong and Petit Law
12
( )
( )
( ) ( )
( )

1 e
e x
dx
T
9Nk

1 T /k exp
T /k exp
d
T
1
k v 2
3V

1 T /k exp

d
T v 2
3V
T
U
C
D
D
D
x
0
2
x
x 4
3
D
B
2
B
B
4

0
2
B
3
g
2

0
B
3
3
g
2
V
V

|
|
.
|

\
|

|
.
|

\
|

|
|
.
|

\
|

|
|
.
|

\
|
=
(
(

|
|
.
|

\
|
=

=
h
h h h
h
h
( )
3
D
3
D
x
x
0
T 3
1
x
3
1

1 e
x
dx
3
D
|
.
|

\
|

=
|
|
.
|

\
|

x=
D
/T <<1
At T >>
D
, U 3Nk
B
T
C
V
3Nk
B
( )
( )
( ) ( )
2
B
B
2
B
B
V
V
B
1 T /k exp
T /k exp
T k

Nk 3
T
U
C

1 T /k exp
3N
n N 3 U

|
|
.
|

\
|
=

= =
h
h h
h
h
h
Einstein model
( )
( )
3
D
3
D
2
x
x
x
0
T 3
1
x
3
1

1 e
e x
dx
4
D
|
.
|

\
|

13
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0.0
0.2
0.4
0.6
0.8
1.0


C
V


(
3
N
k
B
)
x
-1
= k
B
T / h
high T C
V
3Nk
B
low T C
V
3Nk
B
(h/k
B
T)
2
e
-
h/kT
Einstein model
classical model
Einstein model (1907) : N identical oscillators of frequency
At high T, C
V
3Nk
B
same as the Dulong and Petit value
At low T, C
V
3Nk
B
(h/k
B
T)
2
exp(-h/k
B
T)
( )
( ) ( )
2
B
B
2
B
B V
1 T /k exp
T /k exp
T k

Nk 3 C

|
|
.
|

\
|
=
h
h h
14
T/
D
C

(
c
a
l
/
m
o
l
e
-
K
)
Diamond,
Experimental data red points
Einsteins model blue curve
w/.
D
=1320K
Ann. Physik 22, 180 (1907)
If Plancks theory of radiation has hit upon the heart of the matter, then
we must also expect to find contradictions between the present kinetic
molecular theory and practical experience in other area of heat theory,
contradiction can be removed in the same way.
Einstein theory shows correct trends with temperature.
For simple harmonic oscillator of spring constant C and mass M, .
M
C
=
15
C

(
c
a
l
/
m
o
l
e
-
K
)
T (K)
Ag
Einsteins model
At low T, there are systematic deviations between data and Einstein model.
Einstein realized that the oscillations of a solid where complex,
far from single frequency.
Key point is that however low the temperature, there are always
some modes with low enough frequencies to be excited.
By Walther Nernst
Einstein model : At low T, C
V
3Nk
B
(h/k
B
T)
2
exp(-h/kBT)
Experimental data show T
3
dependence of C
V
instead
16
Debye and Einstein models
C

(
J
/
m
o
l
e
-
K
)
T/
D
Red points :
Experimental data of Ag

D
=225K
In the Einstein model, C decreases too rapidly at low temperatures.
Debye model gives correct T
3
dependence of C at low T.
17
Debye T
3
model
Assume continuum elastic phonon mode only up to some cutoff frequency
D

, , 0
,
v 2
V
) D(
D
D
3
g
2
2

>

=
Number of phonon mode for each polarization is equal to N

v 2
V
d ) D( d N
D D

0
3
g
2
2

0

= =
B
D
D
3 / 1
2
g
D
D
3 / 1
3
g
2
D
k

V
N 6
v

k
V
N v 6

h
=
|
|
.
|

\
|
= =
|
|
.
|

\
|
=
Debye frequency
Debye wavevector
Debye temperature

D
0

k
D
v
g
k
18

D
,
D
depend on v
g
, n, ~ v
g
n
1/3
High for stiff, light materials
105 165 225 343 428

D
(K)
Pb Au Ag Cu
Al
material
Kittel : Table 1 in ch.5 (P.116)

1 e
x
dx
T k
v 2
3V
U
x
x
0
4
B
3
g
2
3
D
|
|
.
|

\
|

|
.
|

\
|
=

h
h
( )

1 e
e x
dx
T
9Nk C
D
x
0
2
x
x 4
3
D
B V


|
|
.
|

\
|

=
At very low temperature, T<<
D,
x
D
=
D
/T
15

1 e
x
dx
4
x
0
3
=
|
|
.
|

\
|

T
234Nk
5
T Nk 12
C and
5
T Nk 3
U
3
D
B
3
D
3
B
4
V
3
D
4
B
4
|
|
.
|

\
|

Debye T
3
approximation
19
T
3
observed in most insulators for T<0.1
D
solid Ar w/.
D
=92K
Why T
3
at low temperatures ?
Only long wave length acoustic modes are thermally excited.
These modes can be treated as an elastic continuum.
The energy of short wavelength modes is too high for them to
be populated significantly at low temperatures.
20
C
V
/
T

(
J
o
u
l
e

M
o
l
e
-
1
K
-
2
)
T
2
(K
2
)
KCl
Cu
Phys. Rev. 91, 1354
(1953)
Low Temperature
Solid State Physics
(1963)
21
Other simple idea to understand T
3
dependence :
Total phonon mode :
D
(or k k
D
= )
k
D
k
T
k
x
k
y
Excited phonon mode
k
B
T/h (or k /v
g
= = k
T
)
Others are frozen out
Fraction excited at T :
of the total volume in k-space
T
v
k
g
B
h
D
g
B

v
k
h
3
D
3
D
T

T
k
k
|
|
.
|

\
|
=
|
|
.
|

\
|
Thermal wavevector
Each mode has energy k
B
T
U ~
C
V
~ T
3
B
T
2Nk 1
|
T k
T
N 3
B
3
D
|
|
.
|

\
|

3
D .
|
\
|

|
too small but correct T
3
dependence
22
General result for D() : the number of states per unit frequency

|
.
|

\
|
=
shell
3
3
k d
2
L
)d D(
dS

: an element of area on the surface in K space of selected

constant frequency .

= dk dS k d

shell
3

+d
dk

d dk
k
=

g

k

v
d
dS

d
dS dk dS =

d
v
dS
2
L
)d D(
g

|
.
|

\
|
=
k
x
k
y
k
z
dS
w
( )

=
g

3
v
dS
2
V
) D(
23
Lattice vibrations : mode (k, )
k is in BZ, discrete
(k) dispersion relation
D( ) density of states
E( ) = (n+1/2) h
Phonons : number n energy = h
crystal momentum hk
1 e
1
n
T /k
B

=
h
Thermal properties (equilibrium)
) n( ) D( d U h

=
thermal energy
heat capacity
dT
dU
C
V
=
24
Transport properties (non-equilibrium)
Conduction of sound and heat through the crystal
vibration energy
Ultrasonic attenuation Thermal conduction
excite single phonon mode
measure decay of amplitude
apply temperature gradient
measure heat current by phonons
Phonon thermal conductivity
Apply temperature gradient T determine heat current density j
U
T
H
T
L
T
j
U
dx
dT
j
U
=
the energy transmitted
across unit area per unit time
The flux of the thermal energy
: thermal conductivity coefficient
25
In solids, heat is transported
by phonon and free electrons.
For metals, it is electronic
contribution that dominates
the thermal conductivity.
This does not mean that
insulators are necessarily
poor thermal conductors.
26
Propagations of phonons
No interaction/scattering
Ballistic
In harmonic approximation in perfect, infinite crystal,
Expect no scattering phonon modes are uncoupled,
independent plane waves and standing waves
dk
d
v v
g
= =
Diffusion Phonons scatter, random walk through crystal
Phonons scatter in real crystals.
Scattering processes :
boundary scattering
defect scattering
phonon-phonon scattering
dk
d
v v
g
= <<
27
The flux of thermal energy is based on that
the process of thermal energy transfer is a random process.
ie. the energy diffuses through the crystal, suffering frequent collisions.
dx
dT
T J
T J
U
U
=

across the whole sample

Ballistic :
local
Diffusive :
For diffusion, thermal conductivity is defined by
phonon properties
scattering
crystal quality (size, defect)
temperature
( ) T
j

U

v
j
U
[Watt/m
2
], [(Watt/m
2
)/(K/m)] = [Watt/m/K]
28
Kinetic theory of gases:
consider phonons as gases contained in a crystal volume
calculate diffusion in the presence of temperature gradient
T
H
T
L
T
j
U
Ficks law
dx
dT
dT
dn
dx
dn
=
n
x
n : concentration of molecules
C : heat capacity per unit volume = nc
v
g
: phonon velocity
l : phonon mean free path =v
g

dx
dT
c v n
3
1
dx
dT
c v n j
2 2
x U
= =
v
dx
dT
dx
dT
T
x x
= = l
l
g
Cv
3
1
=
dx
dT
Cv
3
1
dx
dT
c nv
3
1
j
g
2
g U
l = =
29
From anharmonic terms in binding potential
U
x
x
o
The general shape applies for
any type of binding
( ) ( ) ( ) ... x x
x
U
6
1
x x
x
U
2
1
x x
x
U
) U(x U(x)
3
o
x
3
3
2
o
x
2
2
o
x
o
o o
o
+

+ =
( ) ( ) ... x x
x
U
6
1
x x
x
U
2
1
) U(x - U(x) U(x)
3
o
x
3
3
2
o
x
2
2
o
o o
+

= =
Reset the equilibrium, let displacement x-x
o
x
harmonic term
anharmonic term
... fx gx cx U(x)
4 3 2
=
30
Thermal expansion thermal energy causes fluctuation of x from x
o
anharmonic term gives the net change of <x>

=
]
T k
fx gx cx
exp[ dx
]
T k
fx gx cx
exp[ dx x
]
T k
U(x)
exp[ dx
]
T k
U(x)
exp[ dx x
x
B
4 3 2
B
4 3 2
B
B
|
|
.
|

\
|
+ +
|
|
.
|

\
|

|
|
.
|

\
|
+
|
|
.
|

\
|
=
|
|
.
|

\
|

T k
fx
T k
gx
1
T k
cx
exp
T k
fx
T k
gx
exp
T k
cx
exp
T k
fx gx cx
exp
B
4
B
3
B
2
B
4
B
3
B
2
B
4 3 2
+ + + + =
! 3
x
! 2
x
x 1
3 2
x
e
T k
4C
3g
x
B
2
=
linear dependence of T
high T limit
Coefficient of linear expansion
31
Phonon-phonon scattering
phonon displaces atom which changes the force constant C (anharmonic terms)
scatter other phonons
three phonon process
Normal processes : all ks are in BZ
1st BZ in
k-space
1
k
2
k
3
k
3 2 1
k k k = +
crystal momentum is conserved
Umklapp processes : k
3
is outside BZ
1st BZ in
k-space
1
k
2
k
*
3
k
3
k
G
*
2 1
3
k k k = +
*
3
3
k G k = +
G k k k
3 2 1
+ = +
crystal momentum is not conserved
Folding over
R. Peierls, Ann. Physik 3, 1055 (1929)
outside BZ
32
U-processes occur at high temperatures : require large k (ie. large )
How large ?
D B D
D
D
k
2
1
~
2
1
~ E

2
1
~
k
2
1
~ k
h
k
x
k
y
k
z
Debye sphere
kk
D
Phonon-phonon scattering : rate
-1
# of phonons involved
U-process :
-1
N
U
~ exp(-
D
/2T) (phonons w/. large k only)
at intermediate temperatures
At very low temperatures, phonons are populated at low k mode
U process can not occur
33
Phonon mean
free path l
( )
T (K)
Log-log plot
Exponential
Slope -1
Very low T ,
l=v
g
=constant
Intermediate T ,
l=v
g
(1/T)exp(1/T)
dominated by U process
High T ,
l=v
g
T
-1
(number of phonons)
-1
No distinction between
N and U processes
34
Log-log plot of (T)
Below 5K, enriched Ge
74
shows
T
3
dependence of
due to boundary scattering
At low temperatures, l L
(samples size)
Phonon propagation ~ ballistic
=(1/3)v
g
lC
V
~ v
g
LC
V
C
V
T
3
Debye
At intermediate temperatures,
=(1/3)v
g
lC
V
=(1/3)v
g
2
C
V
/T
B V
D
e ~
3Nk constant C = =
/T
D
e ~
U-processes
35
Thermal conductivity of LiF crystal bar w/. different cross sectional areas

(
W
a
t
t

m
-
1
K
-
1
)
Data show
1. Below 10K, T
3
2. As temperature increases, increases
and reaches a maximum around 18K.
3. Above 18K, decreases w/. increasing
temperature and follows that exp(1/T).
4. Cross sectional area influences
below 20K. Bigger area crystal has,
larger it has.
T(K)
36
Impurity scatterings
Defect scatterings
break periodicity Other effects
Log-log plot
Slope -1
Exponential
Slope 3

(Watt/m/K)
T (K)
37
Cu
Experimental results
Phys. Rev. 155, 619 (1967)
Phys. Rev. B7, 2393 (1967)
Solid line Numerical calculation
based on experimental data (k)
Dashed line -- Numerical fit w/.

D
= 4.5 10
13
rad./sec

D
= 344K
38
Summary of part (I)
Solids are defined by their capacity to be solid
to resist shear stress
A crystal is truly solid (as opposed to a glass which is just a
slow liquid)
Crystalline order is defined by the regular positions of the nuclei
crystal structure = lattice + basis
Lattice and reciprocal lattice
Diffraction and experimental studies
Brillouin zone
Crystal binding
Type of binding
Elastic constants and elastic waves
39
Summary of part (I)
Vibrations of atoms
Harmonic approximation
Quantization of vibrations
phonons act like particles
-- can be created or destroyed by inelastic scatterings
Thermal properties
Fundamental law of probabilities
Planck distribution for phonons
Heat capacity : C
Low T, C T
3
and High T, C ~ constant
Thermal conductivity :
maximum as function of T