PHY475

OPTICAL PROPERTIES OF SOLIDS

Prof. Mark Fox















AUTUMN SEMESTER
PHY475: OPTICAL PROPERTIES OF SOLIDS
Prof. Mark Fox
Autumn Semester (10 credits)

Course aims and outcomes
Understand the classical theory of light propagation in solid state dielectric materials;
Understand the quantum theory of absorption and emission in solids;
Appreciate the importance of excitonic effects in solids;
Understand the origin of nonlinear optical effects in crystals.
The outcome of the course will be that the student will be familiarised with the optical phenomena
that occur in a wide range of solid state materials, based on an understanding of both the classical
and quantum theories of how light interacts with dielectric materials.

Assessment
Homework: 15% (3 problem sheets), Exam: 85% (any 3 questions from 5)

Course Book
Fox, Optical properties of Solids (Oxford University Press, Second edition 2010)

Also useful
Kittel, Introduction to Solid State Physics (7
th
Edition, Wiley, 1996)
Burns, Solid State Physics (Academic Press, 1985)
Ibach and Luth, Solid State Physics (2
nd
Edition, Springer-Verlag, 1995)

Lecture Topic Homework Book chapter
1-3 Introduction.
The complex refractive index

1
4-6 Lorentz oscillators.
Dispersion and birefringence

1
2
7-8 Interband absorption 3
9-10 Excitons 2 4
11-12 Interband Luminescence 5
13-14 Quantum confinement 6, 8.5
15-16 Metals. Doped semiconductors 3 7
17-18 Phonons 10
19-20 Nonlinear optics 11

Course www page: http://www.mark-fox.staff.shef.ac.uk/PHY475/

1
Topic 1: Introduction
Optical coeIIicients
Complex dielectric constant
Complex reIractive index
Introduction to optical materials
Optical coeIIicients
Figure 1.1: Optical coefficients
incident light
reflected light
transmitted light
propagation through
the medium
ReIlectivity reIlected / incident power
Transmissivity transmitted / incident power
T R 1 iI medium is transparent
2
Propagation
refraction
absorption and luminescence
scattering
Figure 1.2:
Propagation of
light through a
medium
Velocity v c/n, n is the refractive index
I(z) I
0
exp(-z), is the absorption coefficient
T (1-R
1
) exp(-L) (1-R
2
)
Luminescence : re-emission at lower Irequency
scattering: elastic- change oI direction
inelastic - change oI direction and Irequency
Luminescence
Figure 1.3: luminescence mechanisms
a
b
s
o
r
p
t
i
o
n
e
m
i
s
s
i
o
n
relaxation
ground state
excited states
Luminescence comes
out at lower Irequency
than absorption due to
internal relaxation
The energy shiIt
between absorption
and luminescence is
called the Stokes shift.
3
Complex optical coeIIicients
! "
! "
! "
! "
! "
" " "
! "
!#"
!#"
" "
! ! "
!#"
!#"
" "
! ! "
$%&'()* ,)(-./0) 1/)()2.,/2 2%34.-3.5 /
$%&'()* ,)6,-2./0) /31)*5 /
784%,'./%3 2%)66/2/)3.5 9 #
: : "
!
"
!
"
;)6()2./0/.<5
!
!
" "
" " "
"
"
#

# $
# $
#
# # #
# $ $
# $ $

! "
! "
" " "
" "
! !
! !
"
" "

$
#
$ $ $
Insulators / semiconductors
Figure 1.4 : transmission spectra of
(a) sapphire (Al
2
O
3
) (b) CdSe
Al
2
O
3
CdSe
Wavelength (microns)
0.0
1.0
0.1 1 10
0.0
0.8
T
r
a
n
s
m
i
s
s
i
o
n
inIrared UV visible
(a)
(b)
InIrared absorption due
to phonons
ultraviolet/visible
absorption due to bound
electrons
position oI Iundamental
absorption edge depends
on the size oI band gap
transparency region in
between
4
Metals
10 1.0 0.1
0.0
0.2
0.4
0.6
0.8
1.0
Wavelength (m)
R
e
I
l
e
c
t
i
v
i
t
y
inIrared visible UV
silver
Free electrons in the metal absorb
High reIlectivity up to 'plasma Irequency in the UV
Figure 1.5:
ReIlectivity spectrum
oI silver
Organic materials
Figure 1.6 : Absorption
spectrum oI polyIluorene
Strong absorption in UV/visible spectral region due to
electronic transitions
Stokes-shiIted emission across the visible spectral region
300 400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
A
b
s
o
r
p
t
i
o
n

(
a
.
u
.
)
Wavelength (nm)
polyfluorene
(F8)
UV/blue band
UV visible
5
Doped insulators
200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
ruby
sapphire
Wavelength (nm)
T
r
a
n
s
m
i
s
s
i
o
n
yellow/green
band
blue band
Figure 1.7:
Transmission spectra
oI sapphire (Al
2
O
3
)
and ruby (Al
2
O
3
: Cr
3
)
Sapphire is transparent Ior visible wavelengths
Cr
3
ions doped into sapphire absorb in the blue and yellow/green
spectral regions, hence red colour
LiIting oI degeneracies
free atom
degenerate
magnetic
levels
atom in
B field
atom
in
crystal
crystal
field
effect
Zeeman
effect
Figure 1.8 : LiIting oI degeneracies in the solid state
Crystals have directions lower symmetry than atoms or molecules
new eIIects due to lower symmetry e.g. liIting oI degeneracies
6
Band Iormation
E
Interatomic separation
solid
free
atom
Figure 1.9:
Band Iormation in
the solid state
Free atoms have sharp absorption and emission lines
Solids have broad absorption and emission bands
Two types oI bands: electronic and vibronic
7
Topic 2: Dipole oscillators
Introduction
Lorentz oscillator model
KramersKronig relationships
Dispersion
Optical anisotropy & chirality
Electron oscillators
Figure 2.1: classical model oI an atom.
Electrons are bound to the nucleus by springs
which determine the natural Irequencies
Bound electrons (insulators, intrinsic semiconductors)
restoring Iorce Ior small displacements F k x
natural resonant Irequency
0
(k/m)
1/2

0
lies in the near inIrared / visible / UV spectral regions
Free electrons (metals, doped insulators)
k 0
0
0
8
Dipole oscillators
p(t) e x(t)
P N p
D =
0
E + P =
r

E
p(t)
t
+
t 0 t

t
x(t)
x
Refractive index
light AC electric Iield at (
0
)
Iorced oscillations at
atoms lag on the driving Iield
and re-radiate in phase
Light emission
natural oscillations at
0
cause radiation at
0
'Hertzian dipoles
Absorption
light Irequency
0
resonance phenomenon
atoms absorb energy Irom
the light beam
Figure 2.2
Vibrational oscillators
Figure 2.3
polar molecule
+

Molecular physics
IR absorption at resonant Irequency oI the vibrational modes
Ionic crystals
IR absorption at Irequency oI optically-active lattice vibrations
i.e. the transverse optic (TO) phonons

0
9
Lorentz oscillators
Dielectric constant ReIractive index
Figure 2.4
Lorentz
oscillator
with
e
0
100 THz
5 THz
c
st
12.1
c

10
1 THz 10
12
Hz
-10
10
30
c
1
60 100 140
0
20
40
c
2
e (THz)

e
0
2
4
6
n
60 100 140
0
2
4
k
e
0
( ) e e e
c
_ e c
i
1
1 ) (
2 2
0
0 0
2
r

+ + =
m
Ne
absorption at e
0
= 1/t damping rate
FWHM
Example: atomic absorption line
Figure 2.5
sodium gas, N 110
17
m
3
(low density n
0
~ 1)
D
2
line at 589.0 nm, hyperIine component with FWHM 100 MHz
n
0
~ 1
200 0 200
Av (MHz)
n
o
0
1700 m
1
3.95 10
5
2
0 2 2
0 2 2
0
2
( )
4
4
( )
4
n n n

o e o
e
e
e
e
e e e
=
A +
A
= + A
A +
A =
Lorentzian lineshape
10
Multiple resonances
Figure 2.6
resonant Irequencies:
phonons IR
valence electrons vis/UV
core electrons X-ray
0
1
R
e
I
r
a
c
t
i
v
e

i
n
d
e
x
A
b
s
o
r
p
t
i
o
n
10
11
10
13
10
15
10
17
Frequency (Hz)
0
vibrational
bands
electronic
transitions
IR visible UV X-ray
- f
j
oscillator strength
- classical theory f
j
1
- quantum theory f
j
determined
by transition probability
( )

+ =
j
j j
j
r
i
f
m
Ne
e e e
c
e c
2 2
0
0 0
2
1 ) (
Example: SiO
2
glass
10
12
10
13
10
14
10
15
10
16
10
17
10
4
10
2
1
E
x
t
i
n
c
t
i
o
n

c
o
e
f
f
i
c
i
e
n
t
k
Frequency (Hz)
(b)
1
2
3
r
e
f
r
a
c
t
i
v
e

i
n
d
e
x
n
(a)
SiO
2
glass Figure 2.7
real and imaginary
part oI the reIractive
index Ior SiO
2
glass
Transparency region
between
phonon Irequencies in IR
and band gap in UV
11
Optical Iibre losses
http://nobelprize.org/nobelprizes/physics/laureates/2009/phyadv09.pdI
KramersKronig relationships
| |
2 2
0
2
2 2
0
2 ( )
( ) 1 P d
( ) 1
2
( ) P d
n
n
e k e
e e
t e e
e e
k e e
te e e

' '
' =
'
' '
' =
'
}
}
0 1 2
0
2
4
R
e
I
r
a
c
t
i
v
e

i
n
d
e
x
Band gap wavelength (!m)
ReIractive index (n) and absorption
(k) are the real and imaginary parts
oI the same Iunction: nik
Absorption and reIraction are
related to each other by the
KramersKronig relationships
n at 10 m
vs band gap
Figure 2.9
12
UV transmission oI glass
Add UV absorbers:
reduces UV transmission
increases reIractive index at
visible Irequencies
(at 310 nm) (at 546 nm)
Dispersion
Figure 2.10
glass dispersion
0.2 0.4 0.6 0.8 1.0 1.2 1.4
1.45
1.50
1.55
R
e
I
r
a
c
t
i
v
e

i
n
d
e
x
,

n
Frequency (10
15
Hz)
1000 600 400 300 200
Wavelength (nm)
SiO
2
glass
2
2
d
0
d
n

visible ultraviolet IR
Group velocity
dispersion (GVD)
d
2
n/d
2
GVD determines
pulse spreading
in optical Iibres
GVD 0 near
1300 nm
13
Dispersive prisms
blue
red white
Figure 2.11
Dispersion oI light by a prism
NORMAL dispersion: n increase with Irequency
ANOMALOUS dispersion: occurs near resonance lines
For Pink Floyd Ians .
normal dispersion anomalous dispersion ?
red
red
blue
blue
14
Double reIraction (BireIringence)
Double reIraction in calcite
Figure 2.12
BireIringent crystals
such as calcite
(Iceland Spar)
separate orthogonal
light polarizations
into the
o(rdinary) and
e(xtraordinary) rays
109
71
6.2
e-ray
o-ray
unpolarized
light
optic axis
Birefringence (optical anisotropy) : reIractive index depends on
the direction oI the polarization vector relative to the crystal axes
15
Optical anisotropy
u
y
z
optic axis
propagation
direction
(b) e-ray
c
u
y
z
optic axis
propagation
direction
(a) o-ray
c
Figure 2.13
BireIringence caused by
diIIerence oI dielectric constants
(and hence reIractive index)
along the diIIerent crystal axes.
|
|
|
.
|

\
|
|
|
|
.
|

\
|
=
|
|
|
.
|

\
|
z
y
x
z
y
x
E
E
E
D
D
D
33
22
11
0
0 0
0 0
0 0
c
c
c
c
Polarizing beams splitters
e-ray
o-ray
unpolarized
light

air gap
optic axis

Critical angle: sin

c
1/n
Calcite: n
o
1.658,
c
37.1; n
e
1.486,
c
42.3
Hence choose 37.1 42.3
Figure 2.14
GlanFoucault
prism
16
Wave plates
(b) (a)

o
p
t
i
c

a
x
i
s
d
input
output

o
p
t
i
c
a
x
i
s
o-ray e-ray
input
polarization
( )
o e
2
n n d
t
|

A =
HalI wave plate: !
Quarter wave plate: A| = t / 2
Figure 2.15
Induced bireIringence
Isotropic materials are non-bireIringent
Induce bireIringence n with strain or electric field
Hence photo-elastic and electro-optic eIIects
Kerr effect (quadratic electro-optic eIIect) observed in
all materials, including liquids and glass:
n K
2
; K Kerr constant
Hence Kerr cells (see Fig. 11.8)
Contrast with linear electro-optic eIIect (Pockels eIIect)
observed only in anisotropic crystals (See Fig 11.6)
17
Chirality

R L
d
n n

Optical properties diIIerent Ior leIt or right circularly polarized
light due to chirality (helicity) oI molecules or crystal structure
Circular dichroism: diIIerent absorption Ior leIt or right
circular light
Optical activity: diIIerent reIractive index Ior leIt or right
circular light.
Optical activity causes rotation oI linear light: Examples:
dextrose, laevulose (Iructose) |latin dexter, laevus|
amino acid
Magneto-optics
Induce chirality in non-chiral materials with a magnetic Iield
magnetic circular dichrosim in absorbing materials
Faraday effect in transparent materials: rotation oI linear
polarization by magnetic Iield
V B d ; V Verdet coeIIicient

d
input output
B
Figure 2.16
The Faraday eIIect
18
Appendix: Local Iield corrections
Figure 2.8
local Iield applied Iield in dense medium
+
+ +
+
+
+
+
-
- -
- -
-
-
P

Lorentz correction:

local
P/3
0
in cubic crystal
Clausius Mossotti relationship
3 2
1
r
r a
N

19
Topic 3: Interband absorption
Interband transitions: direct and indirect
Direct gap materials
Optical orientation
Indirect gap materials
Photodetectors & solar cells
Interband absorption
E
I
E
i
E
g
upper band
lower band
Energy
Photon excites electron
Irom Iilled valence to
empty conduction band
Fundamental
absorption edge at E
g
Process creates an
electronhole pair
Figure 3.1
20
Direct and Indirect absorption
q
valence band
conduction band
(a) Direct band gap:
C.B. minimum at k 0
(b) Indirect band gap
C.B. minimum at k 0
k
E
k
E
0 0
E
g
E
g
k
photon
2 ~ 10
7
m
1
negligible compared to B.Z. size /a ~ 10
11
m
1
Transitions appear as vertical lines on E k diagrams
Phonon needed to conserve momentum Ior indirect gap materials
Indirect absorption 2
nd
order process, thereIore low probability
Figure 3.2

Atomic physics oI semiconductors
s
p
s bonding
s antibonding
p bonding
p antibonding
ATOM MOLECULE CRYSTAL
E
g
valence band
conduction band
Figure 3.3
Four valence electrons per atom: Group IV (C, Si, Ge),
III-V compounds (GaAs, InAs, InSb, GaN ..)
II-VI compounds (ZnS, ZnSe, CdSe, HgTe, .. )
V.B. C.B. is p s, hence allowed transition
21
GaAs band structure
Figure 3.4
Direct gap at 1.5 eV
Very important
optoelectronic material
Strong absorption Ior
~ E
g
-6
-4
-2
0
2
4
E
n
e
r
g
y

(
e
V
)
X L
E
g

GaAs
Wave vector k

Icc lattice Brillouin zone

X
L
K
W
k
z
k
x
k
y
Symmetry points
000
X 100
010
001
K 110
L 111
Fig D.5
22
Four-band model
k
E
Electron (e)
band
Heavy holes (hh)
Light holes (lh)
Split-oII holes (so)
E
g
0

Figure 3.5
SimpliIied band
structure Iirst proposed
by Kane (1957)
valid near k 0
Heavy hole transition
Light hole transition
Split-oII hole
transitions also possible
InAs band edge absorption
Figure 3.6
InAs is a direct gap
IIIV semiconductor
with E
g
0.35 eV
E
g
: " #
~ E
g
:
E
g
)
1/2
0.3 0.4 0.5 0.6
0.0
0.2
0.4
0.6
0.8
1.0
Energy (eV)

2
(
1
0
1
2
m

)
InAs
room temperature
23
Magneto absorption in germanium
Figure 3.7
direct gap at 0.80 eV
B-Field quantizes motion
in direction perpendicular
to B
Landau level absorption
when
E
g
(n)
c

c
eB / m
e
(cyclotron Irequency)
0.78 0.80 0.82 0.84 0.86
15
20
25
30
35
40
45
Energy (eV)
T
r
a
n
s
m
i
s
s
i
o
n

(

)
germanium
300 K
B 3.6 T
B 0
Spin injection (optical orientation)
E
M
J
J 3/2
J 1/2
J 1/2
!"# $"# %$"# %!"#
valence band
conduction band

0
E
g

hh hh lh lh
so so
Figure 3.8
,M
12
,
2
M
J
hh transitions three
times stronger than lh
! "#$% ! "#$%
! "#$% ! "#$%
! !
! !
%
&
% %
50 spin
polarization Ior

excitation
E1 selection rule
m 1 Ior

24
Direct versus indirect absorption
1.0 1.2 1.4 1.6 1.8 2.0
10
2
10
3
10
4
10
5
10
6
Energy (eV)
A
b
s
o
r
p
t
i
o
n

c
o
e
I
I
i
c
i
e
n
t

(
m

)
GaAs
silicon
Figure 3.9
Direct absorption is
much stronger than
indirect absorption
Silicon has indirect gap
at 1.1 eV
GaAs has direct gap at
1.4 eV
Germanium band structure
Figure 3.10
-6
-4
-2
0
2
4
E
n
e
r
g
y

(
e
V
)
Wave vector k
E
g
0.66eV
direct gap
L X
Indirect gap
at 0.66 eV
Direct gap
at 0.80 eV
25
Germanium band edge absorption
Figure 3.11
indirect absorption: ( E
g
ind
+
phonon
)
2
direct absorption: ( E
g
dir
)
1/2
at 300K :
E
g
ind
0.66 eV
E
g
dir
0.80 eV
0.6 0.7 0.8 0.9
0
20
40
60
80

!
"
#
$
m

!
"
#
%
Energy (eV)
p
h
o
n
o
n
a
b
s
o
r
p
t
i
o
n
291 K
20 K
phonon
emission
(a) (b)
0.6 0.7 0.8 0.9
0
2
4
6
8
10

$
!
'
(
m

!
%
Energy (eV)
$ E
g
dir
%
!"#
E
g
300 K germanium
Silicon absorption
0 2 4 6 8 10
0
0.5
1.0
1.5
2.0
2.5
Energy (eV)
A
b
s
o
r
p
t
i
o
n

c
o
e
I
I
i
c
i
e
n
t

(
1
0
8
m

)
silicon
300 K
E
g
E
1
E
2
Figure 3.12
Indirect band gap
at 1.1 eV
Critical points
(van Hove
singularities) at E
1
(3.2 eV) and E
2
(4.3 eV)
26
Silicon band structure
Figure 3.13
-12
-8
-4
0
4
Wave vector k
E
n
e
r
g
y

(
e
V
)
X L
E
1
E
2
E
g
density oI states g(E)
2 g(k) (dE/dk)
1
Critical points (van
Hove singularities)
whenever dE/dk 0
occurs when
conduction and
valence bands are
parallel to each other:
'Parallel band eIIect
Absorption spectroscopy Figures 3.14-15
sample
white-light
source
scanning
monochromator
transmission
detector
reIlection
detector
vacuum pump
valve
sample
in cryostat
collection lenses
spectrograph
entrance slit
computer

collimation lenses
white-light
source
silicon
diode array
detector
27
p-i-n diodes (Appendix E)
p i n
l
i
E
g
V
0
0
z
E
Reverse bias V
0
applied
p i n
l
i
E
g
, eV
0
,
z
E
i
l
i
V
0
z
p n
Electric Iield (V
bi
V
0
) / l
i
V
bi
built-in voltage E
g
/ e
V
0
is negative in reverse bias
Figs E.1-2
Photodetectors
Figure 3.16
Embed absorbing region within
p-n junction to Iorm p-i-n diode
Apply reverse bias V
0
(i.e. V
0
negative )
Electric Iield (V
bi
V
0
) / l
i
V
bi
built-in voltage E
g
/ e
Photons absorbed iI ~ E
g
Creates electron-hole pairs in
i-region
Carriers swept out by Iield
into external circuit to generate
photocurrent I
pc
V
0
I
pc
p
i
n

+ -

l
i
Examples:
photodiodes
solar cells (V
0
0)
28
Solar cells (photovoltaics) Figure 3.17
V I
pc
R
I
pc
p i n

R
I
SC
V
OC
V
maximum
power
I
pc
Small gap: large I
SC
, small V
OC
Large gap: small I
SC
, large V
OC
Single junction: max eIIiciency ~30
Larger Ior multi junction
Solar cell eIIiciency
29
Topic 4: Excitons
Introduction
Wannier excitons
Excitonic nonlinearities
Frenkel excitons
Excitons
Figure 4.1
Free (Wannier)
radius ~~ a
small binding energy
moves Ireely through crystal
Tightly-bound (Frenkel)
radius ~ a
large binding energy
localized on one lattice site
e
h
h
e
a
30
Free exciton absorption
Figure 4.2
E
g
o
Photon energy
n 1
n 2
( E
g
)
1/2
Hydrogenic series oI
lines satisIying :
E
g
R
X
/ n
2
enhanced absorption Ior
~ E
g
only observed when
T s ( R
X
/ k
B
)
Excitons in bulk GaAs
Figs 4.3-4
o
(
1
0
6
m

1
)
0.4
0.8
1.2
Photon energy (eV)
1.514 1.520
0
E
g
n 1 n 2
n 3
o ( 1.425)
1/2
1.42 1.46 1.50 1.54
0
0.4
0.8
1.2
o
(
1
0
6
m

1
)
Photon energy (eV)
exciton
21 K
294 K
standard purity sample
T 21 K 294 K
ultra pure sample
T 1.2 K
R
X
4.2 meV
R
X
31
Field ionization in GaAs
Figure 4.5
1.50 1.51 1.52
Photon energy (eV)
P
h
o
t
o
c
u
r
r
e
n
t
T 5 K
V
0
1.44 V
~ 0
V
0
1.00 V, ~ 5 10
5
V / m
0
GaAs parameters :
R
X
~ 4.2 meV
a
X
~ 13 nm
l
i
1 m (typical)
F ~ 6 10
5
V / m
~ 1.5 10
6
V / m
Ior V
0
0 !
F
a
X
F ~ 2 R
X
/ e a
X
ionized iI c ~ F

p
i
n
V
0
l
i

Nonlinear excitonic absorption

Figs 4.6 - 7
(a) Low density
Separation diameter
(b) High density
Separation ~ diameter
1.512 1.516 1.520
0
2
4
6
8
10
Photon energy (eV)
o
(
1
0
6
m

1
)
low density
6 10
22
m
3
2 10
23
m
3
GaAs, 1.2 K
N
Mott
| (4/3)ta
X
3
|
1
~ 1.1 10
23
m
3
in GaAs
32
Frenkel excitons
8 10 12 14
0
1
2
3

(
1
0
8
m

)
Energy (eV)
E
g
(eV) R
X
(eV)
NaCl 8.8 0.9
LiF 13.7 0.9
E
g
E
g
LiF
NaCl
300 K
Figs 4.8 - 9
300 K
3.20 3.30 3.40
A
b
s
o
r
p
t
i
o
n
C
16
H
10
(pyrene)
Energy (eV)
Alkali halides Organic crystals
Also: Rare gas crystals
(solid Ne, Ar, Kr, Xe)
33
Topic 5: Luminescence
Introduction
Photoluminescence
Electroluminescence
LEDs and lasers
Cathodoluminescence
Luminescence
Luminescence spontaneous emission in solids
Fluorescence Iast luminescence
electric-dipole allowed,
R
~ ns
Phosphorescence slow luminescence
electric-dipole Iorbidden,
R
~ s ms
Electroluminescence electrical excitation
Photoluminescence optical excitation
Cathodoluminescence cathode ray (ebeam) excitation
34
Radiative quantum eIIiciency

inject
electrons
inject holes
relaxation

NR

R
GROUND
STATE
EXCITED
STATE
Fig. 5.1
Radiative transition rate determined by Einstein A-coeIIicient

R
= A
1

R
determined by phonon population, number oI traps etc
NR R
R
/ 1
1

R
radiative quantum
eIIiciency
radiative transition rate
total transition rate
Direct gap materials

electrons
holes
conduction band
valence band
E
g
E
k
k 0
GaN
T 4 K, E
g
3.50 eV
3.40 3.50 3.60
L
u
m
i
n
e
s
c
e
n
c
e

i
n
t
e
n
s
i
t
y

Energy (eV)
A
b
s
o
r
p
t
i
o
n
Strong emission at the band gap
most III-V and II-VI semiconductors
linewidth k
B
T
Figs 5.2 3
35
Indirect gap materials
Figure 5.4

electrons
holes
conduction band
valence band
E
g
E
k
phonon
k 0
Low emission probability (2nd order process)
Long radiative liIetime low radiative quantum eIIiciency
diamond, silicon, germanium, AlAs
Photoluminescence
h
electrons
holes
conduction
band
valence
band
E
g
E
k
k 0
0
h
L
Density oI states
E
Excite using laser with photon energy ~ E
g
electrons and holes relax to the bottom oI their bands
thermal distributions Iormed according to statistical mechanics
emission Irom E
g
to top oI carrier distributions
Figure 5.5
36
Classical (Boltzmann)Statistics
Figure 5.6
GaAs
T 100 K
k
B
T 8.6 meV
E
g
1.501 eV
1.49 1.50 1.51 1.52 1.53
1.50 1.52
10
2
10
3
P
L

i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
E
g
k
B
T
Boltzmann statistics: f(E) exp(E/k
B
T) (occupancy factors)
I(E) Density oI states f
e
(E) f
h
(E)
PL rises sharply at E
g
, then decays exponentially. Linewidth ~ k
B
T
Fermi`s golden rule
Rate ,M,
2
(h)
Degeneracy
electrons
holes
Density oI states
E
c
F
E
v
F
E
g
E
h
0.80 0.90 1.00
P
h
o
t
o
l
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Ga
0.47
In
0.53
As, T
L
10 K
24 ps
180 K
250 ps
55 K
Energy (eV)
E
g
6nJ/pulse
Figs 5.7 8
Degeneracy observed at high density and low temperatures
Emission Irom E
g
to (E
g
E
F
c
E
F
v
)
37
Photoluminescence spectroscopy
sample in cryostat
collection
lenses
laser
PL
entrance slit
computer
detector
spectrometer

mirror
Photoluminescence (PL) spectroscopy
Iixed Irequency laser, measure spectrum
by scanning spectrometer
PL excitation spectroscopy (PLE)
detect at peak emission,
vary laser Irequency
eIIectively measures absorption
Time-resolved PL spectroscopy
short pulse laser Iast detector
measure liIetimes, relaxation processes
Electroluminescence
p
n
h E
g
current
V
0
p-type
n-type
substrate
epitaxial
layers
holes
electrons
h
Forward-biassed p-n junction
Electrons and holes recombine at the
junction
photon energy ~ E
g
Epitaxial growth oI high
purity light-emitting layers on
substrate crystal
MBE, MOCVD, LPE ..
Figure 5.10
38
Lattice matching
3 4 5 6
0
2
4
6
B
a
n
d

g
a
p

(
e
V
)
Lattice constant ()
AlN
GaN
InN
InAs
AlAs
InP
AlP
GaP
SiC
GaAs
GaAs
InP
blue
red
substrate materials
direct band gap
indirect band gap
sapphire
visible spectrum
Iibre optics
hexagonal
cubic
Figure 5.11
Junction electroluminescence
(a) V
0
0
p n
E
g
holes
electrons
depletion
region
(b) V
0
E
g
/e
p n
h E
g
eV
0
E
F
c E
F
v
1.2 1.4 1.6 1.8
GaAs, E
g
1.42 eV
Energy (eV)
E
l
e
c
t
r
o
l
u
m
i
n
e
s
c
e
n
c
e
1 mA
293 K
Emission at E
g
Operating voltage ~ E
g
/ e
Spectral width ~ k
B
T
Figs 5.12 3
39
Diode lasers
h
R
1
R
2
l
G
a
i
n

I
in
I
th

th
O
u
t
p
u
t
p
o
w
e
r
I
in
p - AlGaAs
i - GaAs
n - AlGaAs
light
output
metal contact
oxide
current
metal contact
n- GaAs
substrate
Mirrors Iormed by 'Iacets (i.e. edges) oI chip
Emission wavelength ~ hc / E
g
Linewidth determined by cavity modes
Figs 5.14 16
Cathodoluminescence
back-scattered
electrons
excitation
volume
penetration
depth (R
e
)
1 m
electron
beam
VACUUM
CRYSTAL
cathodoluminescence
Commercial use in cathode ray tubes
Research tool Ior investigating nanostructures:
Observe luminescence Irom electron microscope
Focussed spot size 100nm
Primary electrons generate
secondary electrons in
excitation volume
Secondary electrons generate
eh pairs, hence luminescence
Primary electrons
Iew keV
Figure 5.17
!"
41
Topic 6: Quantum conIinement
Dimensionality
Quantum wells
Energy levels
Optical transitions
Quantum conIined Stark eIIect
Quantum dots
Carbon nanostructures
Dimensionality
z
x
y
bulk
quantum
well
quantum
wire
quantum
dot
Energy
D
e
n
s
i
t
y

o
I

s
t
a
t
e
s
E
g
Dimensionality /
ConIinement
3 /0
2 / 1
1 / 2
0 / 3
Fig. 6.1
42
Semiconductor quantum wells
d
GaAs quantum wells
C.B.
V.B.
b
AlGaAs
s
u
b
s
t
r
a
t
e
d
AlGaAs
z
e
-
h

crystal
growth
direction
C.B.
V.B.
E
g
GaAs
E
g
AlGaAs
GaAs
substrate
GaAs
Single quantum well
MQW or superlattice
Fig. 6.2
E
g
GaAs
E
g
AlGaAs
Molecular beam epitaxy (MBE)
Metal-organic chemical vapour deposition (MOCVD)
growth
methods
InIinite quantum well
Fig. 6.3
0
5
10
0 d2 d2
n 1
n 2
n 3
z
E
(
h
2
/
8
m
*
d

)
k
n
n/d
E
n
(k
n
)
2
/2m* (
2

2
/2m*d
2
) n
2

n
(2/d)
1/2
sin (k
n
z n/2)
symmetry about z 0 wave Iunctions have deIinite parity

n
has (n1) nodes
E
n
depends on m*, hence heavy and light holes split
43
Finite quantum well
Figs 6.45
0
4
8
0 2 4
x
y
y tan(x)
y 0.85 (13.2x
2
)

/ x
V
0
E
2
E
1
0
E
n 1
n 2
d
2
z
0 d
2

Wave Iunctions tunnel into the

barrier
wave Iunction still identiIied by
parity and number oI nodes
ConIinement energy reduced
compared to inIinite well
graphical solution to Iind E
n
Example : GaAs/AlGaAs
V
0
0.3 eV, d 10 nm
m
w
* 0.067m
e
, m
b
* 0.092m
e
E
1
31.5 meV
c.I. inIinite well: E
1
57 meV
Optical transitions
Figs 6.67
quantum well

z
n 2 n 1
conduction band
valence band
Light polarized in x,y plane Ior normal incidence
Parity selection rule: n even number
InIinite well selection rule: n 0
44
2-D absorption
0
E
g
E

k
xy
conduction
band
valence band
0
Figs 6.89
Absorption density oI states
Density oI states constant in 2-D: g
2D
(E) m / t
2
Thresholds whenever qe exceeds (E
g
E
en
E
hn
)
Band edge shiIts to (E
g
E
e1
E
hh1
)
0 5 10
(E
g
) in units oI (h
2
/8d
2
!)
A
b
s
o
r
p
t
i
o
n

c
o
e
I
I
i
c
i
e
n
t
3-D
2-D
n 1
n 2
n 3
GaAs quantum wells
GaAs/AlGaAs MQW
d 10 nm
1.4 1.5 1.6
0
5
10
Photon Energy (eV)
o
(
1
0
5
m

1
)
0
2
4
bulk
n 1
n 2
hh
lh
300 K
Figs 6.1011
GaAs/AlAs MQW, d 7.6 nm
Photon energy (eV)
1.6 1.8 2.0 2.2
A
b
s
o
r
p
t
i
o
n

(
a
u
)
0.0
0.5
1.0
hh
lh
hh
lh
n 1 n 2
n 3
hh
lh
T 6 K
Excitonic eIIects enhanced in quantum wells: strong at room temp
Pure 2-D: R
X
2D
4 R
X
3D
Typical GaAs quantum well: R
X
~ 10 meV ~ 2.5 R
X
(bulk GaAs)
Splitting oI heavy and light hole transitions
45
Spin injection in quantum wells
E
M
J
J 3/2
J 1/2
J 1/2
1/2 3/2 +3/2 +1/2
valence band
conduction band

0
E
g

hh hh
lh lh
so so
Figure 6.12
Selection rules
o
+
: Am = +1
o

: Am = 1
Quantum conIinement Stark eIIect (1)
0 10 10
Position (nm)
0 10 10
200
0
1400
1600
1800
E
n
e
r
g
y

(
m
e
V
)
Position (nm)
(a)
z
0 (b)
z
10
7
V/m
1455.0
1447.9
7.4
9.4
1
4
6
2
.
4
1
4
3
8
.
5
e1
hh1
10 nm GaAs / Al
0.3
Ga
0.7
As quantum well in an electric Iield
E
g
(GaAs) 1420 meV
Figure 6.13
46
The quantum conIined Stark eIIect (2)
MQW
pi n

z
V
0
photocurrent
Energy (eV)
1.4 1.5 1.6 1.7
P
h
o
t
o
c
u
r
r
e
n
t

(
a
r
b
.

u
n
i
t
s
)
(b) 10 V
1.110
7
V/m
(a) 0 V
1.510
6
V/m
hh1e2
hh2e1
hh2e2
lh1e1
hh1e1
GaAs MQW, d 9.0 nm, 300 K
Figs 6.1415
Red shiIt oI excitons
Excitons stable to high
Iields (c.I. Fig 4.5)
Parity selection rule
broken
used to make modulators
Emission spectrum
Figure 6.16
2.4 2.5 2.6 2.7
0
Energy (eV)
P
L


i
n
t
e
n
s
i
t
y
300 K
10 K
Zn
0.8
Cd
0.2
Se/ZnSe quantum well
d 2.5 nm
E
g
2.55eV (10K)
E
g
2.45eV (300K)
Emission energy shiIted Irom
E
g
to (E
g
E
e1
E
hh1
)
Tune by changing d
Brighter than bulk due to
improved electron-hole overlap
Used in laser diodes and LEDs
47
Intersubband transitions
Figure 6.17
n 1
n 2
electrons
h
n-type quantum well
Transition energy ~ 0.1 eV (~ 10 m, inIrared)
Absorption used Ior inIrared detectors
Emission used Ior inIrared lasers (Quantum cascade lasers)
Need z polarized light
Parity selection rule:
n odd number
Quantum dots
z
Energy
D
e
n
s
i
t
y

o
I

s
t
a
t
e
s
E
g
Bulk (3-D)
Quantum well (2-D)
Quantum wire (1-D)
Quantum dot (1-D)
Figure 6.18
48
Quantum dots
2
2 2 2 2
* 2 2 2
2
y
x z
x y z
n
n n
E
m d d d
t
| |
| = + +
|
\ .

(EE
g
) in units oI (h
2
/8d
2
m
*
)
D
e
n
s
i
t
y

o
I

s
t
a
t
e
s
3-D
0
5 10
d Cuboid dot
Spherical dot
R
2 2 2
* 2
2
nl
C
E
m R
t
| |
=
|
|
\ .

C
10
1
C
11
1.43
C
12
1.83
C
20
2

Colloidal quantum dots

1.5 2.0 2.5 3.0 3.5
A
b
s
o
r
p
t
i
o
n

(
a
r
b
.

u
n
i
t
s
)
Energy (eV)
CdSe
10 K
D
C
B
A
(a)
1.6 1.8 2.0 2.2
Energy (eV)
6 nm
5 nm
4 nm
CdTe
300 K
(b)
Found in semiconductor doped glass (Colour glass Iilters &
stained glass)
Available commercially
Figure 6.20
49
SelI-organized epitaxial dots
InAs
quantum dot
200 nm
10 nm GaAs
m

0
1
2
3
E
n
e
r
g
y

i
n

u
n
i
t

o
I

!
0
r
V(r)
s` shell
p` shell
d` shell
2-D harmonic oscillator levels
d
z
a
z
a
d
z
2 2 2
0
* 2
( 1)
2
z
z
n
E n
m d

Figs 6.19, 21
InAs quantum dots
Figure 6.22
1.25 1.30 1.35 1.40
200 m
spot
200 nm
aperture
Spatially
resolved PL
Single QD
Far Iield PL
~10
7
QDs
T 10 K
P
L

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Energy (eV)
(a)
1.250 1.255 1.260
P
h
o
t
o
c
u
r
r
e
n
t

(
p
A
)
Energy (eV)
PC
PL
10 pA
0.6V
P
L

I
n
t
e
n
s
i
t
y
(
a
r
b
.

u
n
i
t
s
)
2.6V
B
i
a
s

v
o
l
t
a
g
e
(b)
T 10 K
Quantum conIined Stark eIIect
50
Carbon nanostructures
graphene nanotube C
60
Bucky ball *
* Buckminster Iullerene named aIter
architect R. Buckmintser Fuller
Figure 8.20
Fig. 8.21
Taken Irom Machon, Phys. Rev B 66, 155410 (2002)
(a) (b)
k
y
E

K
(c)

k
x
E
F

K M
20
16
12
8
4
0
4
E
n
e
r
g
y

(
e
V
)

Graphene band structure

Ideal 2-D material
51
Figure 8.22
Graphene transmission
AIter Nair et al. Science, 320, 1308 (2008).
0 1 2 3 4 5
90
95
100
T
r
a
n
s
m
i
s
s
i
o
n

(

)
Number oI layers
(b)
400 500 600 700
95
96
97
98
99
100
T
r
a
n
s
m
i
s
s
i
o
n

(

)
Wavelength (nm)
(a)
graphene, single layer
a
1
a
2
armchair
z
i
g
z
a
g
(5,5)
(9,0)
(7,3)

c
h
ir
a
l
Figure 8.23
Nanotube chirality
chiral vector c n
1
a
1
n
2
a
2
Metallic iI n
1
n
2
3m ; otherwise semiconductor
c
Energy
D
.
O
.
S
.
E
g
Quantum wire (1-D)
52
Figure 8.24
E E
density oI states
k
z
conduction band
valence band
semiconducting
nanotube
E E
k
z
conduction band
valence band
density oI states
metallic
nanotube
E
F
Nanotube transitions
emission
Figure 8.24-5
0 1 2 3
0
1
2
3
E
n
e
r
g
y

g
a
p

(
e
V
)
Tube diameter (nm)
E
11
m
E
11
s
E
22
s
900 1000 1100 1200
0.0
1.0
N
o
r
m
a
l
i
z
e
d

P
L

i
n
t
e
n
s
i
t
y

(
a
u
)
Wavelength (nm)
0.0
1.0
(9,1)
single
SWNTs
(7,5)
(8,3)
SWNT ensemble
(9,1)
(8,3)
(7,5)
Semiconducting Nanotube PL spectra
53
Figure 8.27
0
1
2
3
E
n
e
r
g
y

(
e
V
)
singlets triplets
S
0
(g)
S
1
(g)
S
2
(u)
T
1
(g)
1.2 ns
1.8 s
(a) (b)
Energy (eV)
2 3 4 5
0
1
2
3
4
A
b
s
o
r
p
t
i
o
n
(
1
0
4
c
m

1
)
1.6 1.8 2.0 2.2
A
b
s
o
r
p
t
i
o
n

Energy (eV)
P
L

(
a
.
u
.
)
S
1
S
2
C
60
Carbon bucky ball: C
60
!"
55
Topic 7: Free electrons
Free carrier reIlectivity
Metals
Doped semiconductors
Plasmons (bulk & surIace)
Negative reIraction
Free electron reIelctivity
Fig 7.1
/
p
R
e
f
l
e
c
t
i
v
i
t
y
0 1 2
0.0
0.5
1.0
Free electron eIIects observed in:
metals
doped semicondcutors
Key parameter:
Plasma frequency

p
(Ne
2
/
0
m
0
)
1/2
Lightly-damped system

r
() 1
p

R 100 below
p
transmitting above
p
ultraviolet transparency
of metals
56
The Drude model
Fig 7.2
( )
2 / 1
0 0
2
p
2
2
p
r

i
1
|
|
.
|

\
|
=
+
=
m
Ne
c
e
e e
e
e c
- t 1/ momentum scattering time m
0
o/Ne
2
, o DC conductivity
- ReIlectivity 100 below e
p
- Discrepancies caused by interband absorption transitions
0 5 10 15 20
0.0
0.2
0.4
0.6
0.8
1.0
Energy (eV)
R
e
I
l
e
c
t
i
v
i
t
y
experimental data
t 8.0 Is
0

p
Aluminium

p
15.8 eV,
o 3.6 10
7
O
1
m
1
Interband transitions in Aluminium
Fig 7.3
- Transitions Irom Iilled
states below E
F
to
empty states above E
F
- Very high density oI
states Ior parallel bands
- 'parallel band eIIect
at the critical points
- Hence reIlectivity dip
at 1.5 eV
Transition energy ~ 1.5 eV
E
n
e
r
g
y

(
e
V
)
I X W L I K X
0
4
8
12
16
Wave vector k
E
F
57
Transition metals
Density oI states
E
3d band
4s band
E
F
optical
transitions
0 2 4 6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
copper
Energy (eV)
R
e
I
l
e
c
t
i
v
i
t
y

p
v
i
s
i
b
l
e
Fig. 7.4, 7.6
Inner d orbitals Iorm narrow bands below the Fermi energy
threshold Ior optical transitions to outer halI-Iull s band gives a
sharp absorption edge
hence characteristic colours oI metals, eg copper, gold
Copper band structure
W L X W K
-8
-6
-4
-2
0
2
E
n
e
r
g
y

(
e
V
)
0 2 4 6
E
n
e
r
g
y

(
e
V
)
Density oI states (states eV

)
0 2 4 6 8 10
-8
-6
-4
-2
0
2
Integrated density oI states
Wave vector k
E
F
copper
3d and 4s bands
3d
bands
minimum transition energy
~ 2.2 eV (560 nm)
Fig 7.5
Electronic conIiguration: 3d
10
4s
1
58
Doped semiconductors
10 20 30
0
20
40
60
80
100
Wavelength (m)
R
e
I
l
e
c
t
i
v
i
t
y

(

)
4.0 10
24
2.8 10
24
1.2 10
24
6.2 10
23
3.5 10
23
n-type InSb at 300 K
Plasma frequency
e
p
(Ne
2
/c
0
c
r
m*)
1/2
Control plasma Irequency by varying the doping density
Plasma edge in the inIrared
Fig 7.7
Free carrier absorption
k
E
E
F
scattering
process

E
k
2
2m
e
*
- Transitions Irom Iilled states below E
F
to empty ones above E
F
- o
2
/ t
- Scattering process required to conserve momentum
- Continuous inIrared absorption in doped semiconductors
2
0
2
carrier Iree
* te c
o
nc m
Ne
=
Fig 7.8
59
Intervalence band absorption
k
E
E
F

hh band
lh band
SO band

InIrared absorption in p-type semiconductors

Fig 7.9
Impurity transitions
Fig. 7.10
conduction band
valence band
1
2
n
donor
levels
conduction band
valence band
1
2
n
(a) low temperature:
inIrared absorption
(b) high temperature:
band tail below E
g
Impurity levels: E
n
(m*/m
0
)(1/
r
2
) R
H
/ n
2
n-type
material
60
Donor absorption in n-type silicon
32 34 36 38 40 42 44
0
1.0
Photon energy (meV)
A
b
s
o
r
p
t
i
o
n

(
1
0
3

m

1
)
2p
0
4p
0
3p
0
2p
+
3p
+
4p
+
5p
+
Phosphorous doped Silicon
H
2
r
0
*
e *
2
*
1
,
n
1
1 R
m
m
R R h
c
v =
|
.
|

\
|
=
Fig. 7.11
N 1.2 10
20
m
3
T 4.2 K
m
e
* ~ 0.5 m
0
c
r
12
R* ~ 45 meV
simple model:
complications due to eIIective mass anisotropy
k
Plasmons
- Quantized plasma waves: i.e. longitudinal
oscillations oI the electron plasma at e
p
Fig. 7.12
61
Observation oI bulk plasmons
-400 -200 0 200 400
Energy shiIt (cm

)
plasmon
absorption
plasmon
emission
R
a
m
a
n

s
c
a
t
t
e
r
i
n
g

r
a
t
e
Metals:
p
~ 320 eV
observe by electron energy
loss spectroscopy :
E
out
E
in
n
p
E
in
~ keV
Doped semiconductors:
p
~ 10 meV
Measure by Raman scattering:

out

in
n
p
n-type GaAs, T 300 K
N 1.8 10
23
m
3

p
19 meV (150 cm
1
)
E
in
E
out

p
sample

p
Figs 7.12-13
SurIace plasmons
0
z
dielectric:
d
x
metal:
m
z 0
z
k

z
(z)
d

z
(z)
m
SurIace waves at boundary between
metal and insulator
Plasmonics: propagate energy as
surIace plasmons in nano-circuits
Cannot couple directly to Iree-space
photons due to wave vector
mismatch: hence need Ior couplers
(e.g. gratings)
!!! !!!
metal
dielectric
Figs 7.14 - 15
62
SurIace plasmon polaritons
0 1 2 0 1 2 ck !
p
ck
x
!
p

p

p
0 0

= ck
(a) (b)

sp
ck
x
!
d
bulk
surIace
!
"!
#
$%

" Hence
sp

p
/2 iI
d
1 (i.e. air)
Fig. 7.16
Localized surIace plasmons
300 500 700 900
0.0
0.4
0.8
1.2
A
b
s
o
r
p
t
i
o
n

(
a
.
u
.
)
Wavelength (nm)
Gold nanoparticles 6-7nm diameter
Courtesy
M. Sugden
T. Richardson
Colloidal gold is not gold coloured !
Localized plasma oscillations at surIace oI metal nanoparticles

sp
~
p
/(
d
2) i.e.
p
/3 Ior air-metal boundary, but varies
somewhat with size and shape
MesoGold
pure gold
nanoparticles
suspended in
water
Fig. 7.17
63
Negative reIraction

r
!
r
n " 0
0
n $ 0
0
= i
" 0
I II
III IV
= i
" 0

i

r
n $ 0 n % 1
perIect lens
metamaterial
Need both
r
and !
r
to be negative
i.e. region III
Not possible in natural materials:
hence need metamaterial
Figs 7.18 - 19
!"
65
Topic 8: Phonons
(Chapter 10)
InIrared active phonons
Reststrahlen
Inelastic light scattering
Raman scattering
Phonon liIetimes
Lattice absorption
Figs 10.12
, k , q
Wave vector (q)
F
r
e
q
u
e
n
c
y
acoustic branch
optical branch

a
0
p
h
o
t
o
n
Resonant absorption when
photon Irequency and wave-
vector match the phonon , q
Only possible Ior optical
phonons oI ionic or polar
(partly ionic) crystals
Phonon must be transverse:
hence TO phonons involved
Resonance occurs in the
infrared ~ 10 100 m
66
TO phonon resonance
=
0
e
iqz
x

z
Figure 10.3
TO phonon modes oI ionic crystals: positive and negative ions
move in opposite transverse directions
This generates transverse electric Iield waves
Light resonates with these modes when the wave vectors and
Irequencies match
Reststrahlen
6 8 10 12 14
-20
0
20
40
(a)

r

Frequency (THz)
6 8 10 12 14
0.0
1.0
(b)
Frequency (THz)
R
e
I
l
e
c
t
i
v
i
t
y
Figure 10.4
2 2
2
) ( ) (

TO
TO
st r
Example:

TO
10 THz
st
12.1

LO
11 THz

10
100 reIlectivity between
TO
and
LO
Lyddane-Sachs-Teller relationship:
lO
/
TO
(
st
/

)
1/2
67
InIrared reIlectivity
200 240 280
0.0
1.0
GaAs InAs
R
e
I
l
e
c
t
i
v
i
t
y
Wave number (cm
1
)
Figure 10.5
Reststrahlen band observed between v
TO
and v
LO
reIlectivity less than 100 due to damping
damping caused by anharmonic phonon decay. Typical liIetime ~ 10 ps
GaAs :
v
TO
273.3 cm
1
v
LO
297.3 cm
1
InAs :
v
TO
218.9 cm
1
v
LO
243.3 cm
1
1 cm
1
2.998 10
10
Hz
Polaritons
0.0 1.0 2.0
0
10
20
Wave vector q (10
6
m
1
)
e

/
2
t



(
T
H
z
)
O
TO
/ 2t
O
LO
/ 2t
e v
st
q e v

q
Figs 10.6 7
Raman scattering data on GaP

LO
lower branch
upper branch
0 1 2 3
36
40
44
48
52
E
n
e
r
g
y

(
m
e
V
)
Wave vector (10
6
m
1
)
Calculated: v
TO
10 THz,
c
st
12.1, c

10
Polariton coupled TO phonon polarization wave & photon wave
anticrossing oI photon and TO phonon modes when v ~ v
TO
modiIies the dispersion oI both photons and TO phonons
68
Polarons
Fig. 10.8
e

Iree electron in a polar solid

produces a local lattice distortion
through the electron-phonon
coupling o
ep
modiIies the eIIective mass to :
m** m*(1 o
ep
/6)
1
Polaron eIIects are small in III-V`s (e.g. ~ 1 in GaAs) but increase as
the crystal becomes more ionic.
SelI-trapping leads to hopping conduction instead oI band conduction
Organic conductors show strong polaron eIIects
Inelastic light scattering
Fig. 10.9
e
1
, k
1
e
2
, k
2
O , q
- Conservation laws:
e
1
= e
2
O ; k
1
k
2
+ Q
- Stokes scattering:
phonon emission ( sign)
- Anti-Stokes scattering:
phonon absorption ( sign)
- I
anti-Stokes
/ I
Stokes
exp(/k
B
T)
Raman scattering: scattering Irom optical phonons
Brillouin scattering: scattering Irom acoustic phonons
Q
max
2k ~ 10
6
m
1
Ior back-scattering geometry
can only probe small wave vector phonons
Scattering can also be observed Irom plasmons, magnons etc
69
Raman scattering arrangement
Fig. 10.10
sample
in cryostat
collection
lenses
laser beam
reIlected
laser
scattered
light
CCD array
detector
scanning
double
spectrometer
entrance slit
computer

Raman scattering data

Fig. 10.11
200 300 400
GaP
AlSb
InP
GaAs
300 K
R
a
m
a
n

s
i
g
n
a
l

(
a
.
u
.
)
Energy shiIt (cm
1
)
Raman scattering Irom TO
and LO phonons in various
III-V semiconductors using
a Nd:YAG laser at 1.06 m
1cm
1
3 10
10
Hz
0.124 meV
TO LO
70
Phonon liIetimes

, q
1

, q
2

, q
3

, q
1

, q
2

, q
3
Figs 10.12 13
3 phonon processes
caused by anharmonicity
in the crystal
Wave vector (q)
F
r
e
q
u
e
n
c
y

(

)
acoustic
branch
optical
branch
0

a

TO

TO
2
0

a
TO phonon can decay into two
acoustic phonons
LiIetime typically ~ 10 ps.
71
Topic 9: Nonlinear optics
(Chapter 11)
DeIinitions
Resonant vs non-resonant nonlinearities
Second-order nonlinearities
Irequency doubling
electro-optics
third-order nonlinearities
Nonlinear susceptibility
D =
0
E P
0

r
E
P
0

(1)
E
0

(2)
E
2

0

(3)
E
3
..

r
1
(1)

(2)
E
(3)
E
2
..

(n)
n
th
order nonlinear susceptibility

(2)
0 in materials with inversion symmetry (centrosymmetric)
ie: all isotropic materials (gases, liquids, glasses)
some crystals (eg NaCl)
optical properties depend on the light intensity
needs large electric Iields (ie high power lasers)
72
Nonresonant nonlinear response
P

(t)
t
t
P(t)
P

(t)
t
t
P(t) (a)
(b)
Figure 11.1
distorted output
contains terms
at 2, 3 etc
small amplitude
sine wave input
large amplitude
sine wave input
sine wave
output
laser is tuned to the transparency region oI crystal
Iar Irom resonance with any atomic transitions
Resonant nonlinear response
Figs. 11.2-3
N
2
N
1
2
1
u

A
z
dz
I(z) I dI
laser is tuned to resonance with an atomic transition
stimulated emission reduces net absorption rate at high intensity
equivalent to 'Pauli blocking oI upper state
saturable absorption: (I)
0
/ (1 I / I
s
) ; I
s
saturation intensity
(I)
0

2
I at small I ;
2

0
/ I
s

r
I E
2
third-order nonlinearity
73
Second order nonlinear eIIects
e
2
e
1
e
1
+e
2
Process Input Ouptut
Frequency mixing e
1
, e
2
e
1
+ e
2
Frequency doubling e, e 2e
Down conversion e
1
e
2
, e
1
e
2
e
2
e
1
e
1
e
2
(b)
Fig. 11.4
(a)
P
i
(2)
c
0
E
jk
_
(2)
ijk
E
j
E
k
_
(2)
0 in centrosymmetric crystals
Phase matching
- Phase matching condition: 2k
e
k
2e
(conservation oI momentum)
2 n(e) e / c n(2e) 2e / c
n(e) n(2e)
- not usually possible due to dispersion.
- use a bireIringent crystal with optic axis at angle u :
k
e
2e
_
(2)
e
k
2e
2
o
2
2
e
2
2
o
) 2 (
cos
) 2 (
sin
) (
1
e
u
e
u
e n n n
+ =
u
74
2e
Frequency doubling / tripling etc
Figure 11.5
Nd:YAG laser
1064 nm
nonlinear
crystal
532 nm
355 nm
266 nm
2e
4e
e
e
2e
3e
nonlinear
crystal
nonlinear
crystal
- use a 2
nd
order nonlinear crystal
Electro-optic modulators
z
x
y
x'
y'
45

polarizer
crossed
polarizer
E-O crystal
V
input
output
Linear electro-optic (Pockels) effect:
Field-induced birefringence: An r
ij

r
ij
= electro-optic coefficient
= 0 for non centro-symmetric crystal
Consider as _
(2)
process with DC field
Use to make intensity modulators
Figure 11.6
75
Third-order nonlinear processes
Figure 11.7
(b) Frequency tripling
e
e
e
3e
(c) Optical Kerr eIIect
e
e
e
e
(a) Four-wave mixing
e
1
e
2
e
3
e
1
+e
2
+e
3
(d) Raman eIIect
e
e
e
s
e
s
Kerr cells

polarizer
crossed
polarizer
Kerr
medium
input
output
V
polarizer
crossed
polarizer Kerr
medium
input
output
laser pulse

Figure 11.8
Quadratic electro-optic effect:
Field-induced birefringence: An _
(3)

2
Occurs even in isotropic materials (eg glass, liquids)
DC Kerr effect: rotate polarization with DC field
Optical Kerr effect: induce birefringence with light pulse
76
Nonlinear reIractive index
Figure 11.9
Ac
r
_
(3)
E
2
An n
2
I
n
2
_
(3)
/ n
0
2
c c
0
n(I) n
0
n
2
I
- Third order nonlinear eIIects Iound in all materials
including isotropic media e.g. glasses, liquids, gases
- selI-phase modulation: A| 2 t An L / 2 t n
2
I L /
- soliton: balance dispersion
and selI-phase modulation
- propagation oI high intensity
short pulses along optical Iibres
Semiconductor nonlinearities
Figs. 11.10-11
k
E
E
g
10 10
2
10
3
10
4
10
5
0
2
4
6
8
o
(
1
0
3
c
m

1
)
I (W cm
2
)
o( )
/
I
I
=
+
+
6700
1 290
2000
E 0.77 eV
0.7 0.9 1.1
0
10
20
30
40
o
(
1
0
3
c
m

1
)
E (eV)
GaInAs/InP MQW
exciton
300 K
strong Pauli blocking when
~ E
g
saturable absorption
third order nonlinearity
excitonic enhancements
see also Fig. 4.7
77
Saturable absorption in quantum dots
Fig. 11.12
0.1 1 10 100 1000
10
4
10
3
10
2
Power (nW)
P
e
a
k

a
b
s
o
r
b
a
n
c
e
1.26545 1.26550 1.26555
0
5
10
15
Energy (eV)
A
b
s
o
r
b
a
n
c
e

(
u
n
i
t
s

o
I

1
0

3
)
3.5 eV
Tune laser to QD exciton
Behaves as saturable two-level atom
N
2
N
1
2
1
u