Solid State Physics

Phys 446:

Lecture 6

Last week:

(Ch. 3)

Phonons, Einstein and Debye models, QZ1 results

Solid State Physics / Optical

Properties

Today:

Lattice vibrations:
optical properties and Raman scattering

Optical Properties, Raman scattering, Thermal conductivity

Introduction to metals (Ch. 4)

Fall 2007
Lecture 6

Andrei Sirenko, NJIT

Thermal Conductivity
Temperature gradient in a material heat flow from the hotter to the cooler
end.
Heat current density j (amount of heat flowing across unit area per unit time)
is proportional to the temperature gradient (dT/dx):

ju = K

dT
dx

K - thermal conductivity

In metals the heat is carried both by electrons and phonons; electron

Elementary kinetic considerations:

if c is the heat capacity of the single particle, then moving from region
with T+T to a T, particle will give up energy cT

T between the ends of the free path length lx : T = dT l = dT v

x
x
dx
dx
where is the average time between collisions
The net energy flux (n concentration) :

contribution is much larger

ju = n v x

In insulators, there are no mobile electrons heat is transmitted entirely

by phonons

Heat transfer by phonons

phonon gas: in every region of space there are phonons traveling randomly in

kinetic theory of gases

dT
1
dT
c = n v 2 c
dx
3
dx

for phonons, v is constant. nc = C; l=v

all directions, much like the molecules in an ordinary gas

phonon concentration is larger at the hotter end they move to the cooler end
the advantage of using this gas model: can apply familiar concepts of the3

1
dT
ju = Cvl
3
dx

1
K = Cvl
3

- phonon thermal
conductivity
4

Suppose that two phonons of vectors q1 and q2 collide, and produce

a third phonon of vector q3.

Dependence of the thermal conductivity on temperature

Cv dependence on temperature has already been discussed

Momentum conservation: q3 = q1 + q2

Sound velocity v essentially insensitive to temperature

The mean free path l depends strongly on temperature

q3 may lie inside the Brillouin zone, or not. If it's inside

momentum of the system before and after collision is the same.

Three important mechanisms are to be considered:

This is a normal process. It has no effect at all on thermal resistivity,

since it has no effect on the flow of the phonon system as a whole.

(a) collision of a phonon with other phonons

If q3 lies outside the BZ, we reduce it to

equivalent q4 inside the first BZ: q3 = q4 + G

(b) collision of a phonon with imperfections in the crystal

(c) collision of a phonon with the external boundaries of the crystal
The phonon-phonon scattering is due to the anharmonic interaction.
If interatomic forces are purely harmonic no phonon-phonon interaction.
At high temperature atomic displacements are large stronger
anharmonism phonon-phonon collisions become more important
At high T the mean free path l
collision frequency n

The second mechanism - phonon scattering results from defects.

Impurities and defects scatter phonons because they partially
destroy the periodicity of the crystal.
At very low T, both phonon-phonon and phonon-defect collisions become
ineffective:
there are only a few phonons present,
the phonons are long-wavelength ones
not effectively scattered by defects,
which are much smaller in size
In the low-temperature region, the primary
scattering mechanism is the external
boundary of the specimen - so-called
size or geometrical effects.
Becomes effective because the phonon
wavelengths are very long - comparable
to the size of the sample L.
The mean free path here is l ~ L
independent of temperature.

The difference in momentum is transferred

to the center of mass of the lattice.
This type of process is is known as the umklapp process

1/T : number of phonons n T at high T

l 1/n

Momentum conservation: q1 + q2 = q4 + G

highly efficient in changing the momentum of the phonon

responsible for phonon scattering at high temperatures

Anharmonism
So far, lattice vibrations were considered in harmonic
approximation. Some consequences:
Phonons do not interact; no decay
No thermal expansion

low T:
K ~ T3
due to Cv

Elastic constants are independent of pressure and temperature

Heat capacity is constant at high T (T>>D).
Anharmonic terms in potential energy:
high T:
K ~ 1/T
due to l

Thermal conductivity of NaF

(highly purified) 7

U(x) = cx2 gx3 fx4

x - displacement from equilibrium

separation at T = 0

Thermal expansion

Thermal expansion from Phys 103

Calculate average displacement using Boltzmann distribution function:

xe
=
e

U ( x ) k BT

U ( x ) k BT

dx

dx

If anharmonic terms are small, can use Taylor expansion for exponent

x =

gx 4 fx 5 3 1 2 g
x +

+
(k BT )3 2 3g
52
k BT k BT

4
c
=
= 2 k BT

12
cx2 k BT
4c

12
dxe

(k BT )
c

dxe cx

k BT

thermal expansion
Origin of thermal expansion asymmetric potential
9

10

Techniques for probing lattice vibrations

Techniques for probing lattice vibrations

Inelastic X-ray scattering

Neutron scattering
Infrared spectroscopy
Brillouin and Raman scattering

Inelastic X-ray scattering in GaN

k
k0

q k = k0 q

= = =0 =(q)

q = 2k 0 sin = 2n

0
c

sin

Inelastic X-ray scattering

k
k0

q k = k0 q

= = =0 =(q)

q = 2k 0 sin = 2n

0
c

sin

assumed (q) << 0

- true for x-rays:

< 100 meV; 0 ~104 eV

n index of refraction

measuring - 0 and sin one can determine dispersion (q)

main disadvantage difficult to measure - 0 accurately
This difficulty can be overcome by use of neutron scattering
Energy of "thermal" neutrons is comparable with (80 meV for 11
1)

12

Brillouin and Raman spectroscopy

Raman scattering in crystalline solids

Inelastic light scattering mediated by the electronic polarizability of the medium

a material or a molecule scatters irradiant light from a source

Most of the scattered light is at the same wavelength as the laser source
(elastic, or Raileigh scattering)

but a small amount of light is scattered at different wavelengths

(inelastic,

or Raman scattering)

s
Stokes

0
Raileigh

i ~ 5000 , a0 ~ 4-5 phonon >> a0

i Anti-Stokes

Raman scattering in crystalline solids

q0

ki

q 2k
ki
ks

ks
ki

3. Selection rules determined by crystal symmetry

14

Raman scattering in crystalline solids

Raman
scattering

Phonon Energy

ks

only small wavevector (cloze to BZ center) phonons are seen in

the 1st order (single phonon) Raman spectra of bulk crystals

Raman
Scattering
i+ (q)

Analysis of scattered light energy, polarization, relative intensity

provides information on lattice vibrations or other excitations13

Mandelstam-Brillouin
scattering

=i = = s =;

Stokes
Raman
Scattering
i- (q)

1. Energy conservation:

2. Momentum conservation:
4n
ki = k s q 0 q 2 k 0 q

Elastic
(Raileigh)
Scattering

s
AntiStokes

Not every crystal lattice vibration can be probed by Raman

scattering. There are certain Selection rules:

Raman
scattering

G
G G
G
q = k = | ki ks |

Phonon wavevector

15

16

Example of Raman scattering in crystalline solids

3S = 15 modes
3 acoustic modes
12 optical modes; 3 4

2 TO1 + LO1
2 TO2 + LO2
2 TO3 + LO3
2 TO4 + LO4

17

Summary
Phonon thermal conductivity

18

1
K = Cvl
3

Mechanisms of phonon scattering affecting thermal resistivity:

umklapp processes of phonon-phonons collision important at
high T
collision of a phonon with defects and impurities in the crystal
collision of a phonon with the external boundaries of the crystal
important at low T
Anharmonism of potential energy is responsible for such effects as:
phonon-phonon interaction
thermal expansion
Techniques for probing lattice vibrations:
Inelastic X-ray scattering, Neutron scattering,
Infrared spectroscopy, Brillouin and Raman scattering
Electron energy loss spectroscopy
19

Optical Properties of Solids

Dielectric function formalism

Phonon contribution to Dielectric function and
Light interaction with Phonons

(in this Lecture K is a wavevector of light)

20

The interaction of radiation with matter

Materials equations
EM wave

For your references:

G
G
D = ( ) E
G
G 
j = ( ) E

21

The interaction of radiation with matter

Decoupled form of MaxEq.
in vacuum:
Same in material medium
(solid state) [SI]

22

The interaction of radiation with matter

G
G
G
2E
E
E = 2 +
t
t
K-vector of light:
2

[CGS]

If K is real
(no losses)

G
G
G
2E
E
E = 2 +
t G
tG
2

G
2H
H
2 H = 2 +
t
t

EM wave (light)

K 2 0 = 0 0 2 =

K0 =

+i
K 2 = 2 + i = 0 0 2

0 0
0 0

Loss part of K-vector

for nonmagnetic media: = 0

Solution:
Plane EM wave (light)

complex refractive index: n =

23

K = K0

 0
+i
= nK
0 0

( )
+i
= nR + inI = nR + i
0 0
2K0

- absorption coefficient (m-1); E 0 = E0 e

and

I ( z ) = I 0 e 24( )z

The interaction of radiation with matter

Linear spectroscopy

Complex Dielectric Function

i
complex ( ) = + = '+ i ''

ncomplex ( ) = nR + i nI
'real = nR 2 nI 2
''imaginary = 2 nR nI

Light along z-axis:

K
K
K

E ( z , t ) = E0 e it exp(iKz ) = E0 e it exp izK 0
+i

0 0

for >> a, K 0 0
2

(1 nR ) 2 + nI 2
1 n
R=
=
1 + n
(1 + nR ) 2 + nI 2
25

Linear spectroscopy of semiconductors

and
electronic
transitions
dielectrics
phonon

26

Electric field and Displacement vector in a material medium

In general situation:
Ex
G
G
KG

E (r , t ) = E0 exp[i ( Kr t )] = E y
E
z

G G
D =E

xx xy xz xx 0 0

= yx yy yz = 0 yy 0
0 0
zz
zx zy zz


In crystals the number of independent

components decreases according to
the symmetry

xx xy xz Ex
Dx

yx
yy
yz E y
0
y

D
z
zx zy zz Ez

Metal

( ) = 0 [1 + ( )]
27

6 independent
components

In isotropic media:
xx xy xz 0 0

= yx yy yz = 0 0 =
0 0

zx zy zz


28

Dielectric function contributions

Ionic polarizability / Phonon contribution

r ( ) = ( ) / 0 = 1 + Ph ( ) + FC ( ) + E ( )

Evaluate the dielectric constant of an ionic crystal.

Ionic polarizability is related to the motion of ions.

S j2
ph ( ) = 2
TO 2 + i j
j
j

FC ( ) =

p2

Recall the linear chain model we used to describe lattice vibrations:

p2 =

2 + i

Equations of motion
in the presence of
external field:

N FC e 2
core m*

M1

N FC - carrier
concentration

E ( ) =

M2

Pj 2
2
0j

2 + i

d 2u n
dt 2

d 2 u n +1
dt 2

where

e*
2

M 1 (t )
1

E0

+
t = 2C
M1 M 2

u0+ =

e*
2

M 2 (t )

E0

u n = u 0 e i t

Pi = nm e * (u 0 + u 0 )

(nm number of dipoles per unit volume);

where

M 1M 2
M1 + M 2

u n +1 = u 0+ e it

30

r = 1 + el

nm e *2
r 0 = 1 + el +
M R 0t 2

can rewrite

nm e *2
r 0 r
r ( ) = 1 + el +
=

+
r
M R 0t 2 (1 2 t 2 )
1 2 t 2
Note that r(t) . Also, r() = 0 at

nm e *2
r ( ) = 1 + el +
M R 0 (t 2 2 )

1
1

+
M R =
M1 M 2

assume E = E0 e i (qx t )

P = 0E

relative permittivity: r = /0 = 1+ ; = el + i
Get

E external field;

At high frequencies, >> t , the ionic term vanishes:

at = 0,

- transverse optical phonon frequency

at q = 0

The ionic polarization Pi is then

= C (2u n +1 u n + 2 u n ) + e * E

e* - effective charge,

also assume long wavelength, >> a0 q 0

Substitute this solution into equations of motion, solve for u0+ , u0-

u0 =

= C (2u n u n +1 u n 1 ) e * E

29

Get

- reduced mass

l = t

r0
r

Between t and l r() < 0 index of refraction is imaginary:

N ( ) = r = i k ( )
31

wave is reflected
32

Lyddane-Sachs-Teller relation

Physical meaning of l - the frequency of longitudinal optical phonon

D = ( E ) = 0
We had

LO phonons:

TO phonons:

macroscopic field along z :

no field in z direction;
from the symmetry of the
E z
problem:
0 D = 0
E x
z
= 0 E = 0
only if ( ) = 0
x

r 0 r
1 2 t 2

and

l 2 =

r0 2
t
r

combine, get

l 2 2
r ( ) = r 2
t 2

or

r 0 l 2
=
r t 2

If many phonon branches:

r ( ) = r +

( ) =

2
2
LO
j

If phonon decay is included:

2
2
TOj

( ) =

L2 O j

2
TOj

LO

TO

33

Lyddane-Sachs-Teller relation
Raman

Ellipsometry

r 0 l 2
=
r t 2

34

Electronic polarizability of solids

(similar to electronic transitions in atoms )

For an accurate quantitative description, quantum mechanics is needed

But we can get some general ideas with classical approach
Recall our model of atom:
Displaced electronic cloud feels a restoring
force, which is linear (for small displacements)

G
E

A.A. Sirenko, et al., Nature 404, 373 (2000)

A.A. Sirenko, et al., Phys. Rev. Lett. 84, 4625 (2000) and Phys. Rev. Lett. 82, 44500 (1999)
35

For simplicity consider one-dimensional case (r parallel to x)

36

Without an external field:

d 2x
kx = m 2
dt

x(t ) =

Equation for harmonic oscillator. Solution: harmonic vibration

x(t ) = x0 e i0t

0 = k m

with frequency

Equation of motion becomes

(forced oscillator)

eEo e

it

m02 x

=m

x(t ) =

em

02 2

E o e i t =

em

02 2

P=

d 2x
dt 2

get

E (t )

and

e 2 ZN m

02 2

Recall P = 0E and = 0(1+)

NZe 2
1
=
2
0 m (0 2 )
n 2 ( ) =

37

or

= 0 1 +

1
NZe 2

0 m (02 2 )

NZe 2
1

= 1+
0
0 m 02 2

38

n~ = nR + inI
n is complex for nonzero damping:
G
G
 0,
K = nK
and
- complex wavenumber

Now, consider damping force proportional to speed :

Fdamp = m

E (t )

Expect strong response (large x), large susceptibility

large refractive index n at 0

Look for a solution x(t)=x0e-it

get

Dipole moment p = qx, so polarization P = eNZx

(N atoms per unit volume, Z electrons per atom)

Now, have electromagnetic wave with field E(t)=E0e-it

Force F(t)=eE0e-it

em

02

dx
dt

What does it mean?

Equation of motion becomes (damped oscillator):

eEo e it

E = E0 ei ( Kx t ) = E0 ei[ nR +inI ] K0 x it = E0 e nI K0 x ei ( nR K0 x t )

dx
d 2x
m 02 x m
=m 2
dt
dt

or

Again, look for a solution x(t)=x0e-it

get

1
e
x(t ) = E (t ) 2
m
0 2 + i

Therefore
n 2 ( ) =

Same form as before,

just includes damping

NZe 2
= 1+
2

0
0 m 0 2 + i

E = E 0 ei ( nR K0 x t )

where

E 0 = E0 e nI K0 x

Amplitude decays as wave propagates absorption;

results from damping

x
~
E0 = E 0 e 2
~
I E 02 = I 0 e x
and intensity

Then

39

- absorption coefficient (m-1)

40

Reflectivity at normal incidence (in air)

n 1
Field amplitude: r =
n +1

power (intensity):

If n~ = n R + in I then

R = r = rr* =

R= r =

r = r' + ir''

r' = nR2 - nI2 ;

n 2 ( ) =

(n + 1) 2

NZe 2
= 1+
2

0
0 m 0 2 + i

(n R 1) 2 + n I2

e()

(n R + 1) 2 + n I2
Quantum mechanics
gives similar result for
Electronic polarizability:

As we've seen, the dielectric function and refractive index

are generally complex:

We obtained

(n 1) 2

n~ = n R + in I

e2
e ( ) =
m

fj
2
j

2 + i j

Many resonant frequencies j correspond to energy transitions

r'' = 2nRnI

Weighting factors fj called oscillator strengths

nI is called extinction coefficient

(related to transition matrix elements)

41

42

Reflection from metals

Optical properties of conductive solids (metals)

conductivity of a medium :

Have complex refractive index nt:

J = E

Including conductivity in Maxwell's equations in the medium:

B = J +

leads to wave equation:

nR, nI = /2K0 are real

Reflectivity at normal incidence (in air)

E
t

Consider a very good metal: large

(e.g. silver: 6107 -1m-1)

G
G
G
2E
E
2
E = 2 +
t
t

12

n = + i

0
0
2

= nI + i

R = r = rr* =

UV visible

2K0

(n R 1) 2 + n I2
(n R + 1) 2 + n I2

infrared

For

Differs from a "standard" wave equation by the first term in the right part
Still, look for plane wave solution:

E ( r, t ) = E0 e

G G
i K r t

then
43

2K0

= nI >> nR 1

R1

44

Dispersion equation in metals

If we neglect the contribution of bound electrons and also neglect

free electron damping e

The dispersion we got in a model of oscillating electrons:

n 2 ( ) = 1 +

N FC e
1
2

0 m 0 2 + i
2

0 = k m e

Then

k "spring constant"
me electron mass

Introduce

in metal, there are free electrons no restoring force 0 = 0

Still, there may be bound electrons, too.
So

fj
N e2
1
+ 2
n ( ) = 1 + FC 2
0 m + i e j 0 j 2 + i j
2

free electrons

N FC e2
n ( ) = 1
0 m 2
2

Then

N FC e 2
p =
core me

- plasma frequency

core = ( )

p2
n ( ) = 1 2

p2
'( ) = core 1 2

Below p refractive index is complex absorption;

above p

bound electrons
(like in dielectric)

is real, free electron absorption is small

For most metals p lies in the UV range

45

46

Summary
Ionic contribution to dielectric function is related to lattice vibrations
and exhibits dispersion in infrared region, given by
the Lyddane-Sachs-Teller relation:
2
2

Where carrier
concentration
is higher?
Choose between a
and b. Show work

( ) =

2
2
TOj

Electronic polarizability is given by

e ( ) =

fj
e2
1
+ 2
2
2
m + i e
j 0 j + i j
free electrons

b
p =

LO j

N FC e
core me

47

bound electrons

Dielectric function and refractive index are generally complex:

r = r' + ir'' ; n~ = n R + in I ; r' = nR2 - nI2 ; r'' = 2nRnI
absorption coefficient = 2K0nI

nI - extinction coefficient

48

For your references:

22