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.

Lecture Topic Homework Book chapter

1-3 Introduction.
1
The complex refractive index
4-6 Lorentz oscillators.
2
Dispersion and birefringence 1
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 Book: Fox, Optical properties of Solids (Oxford University Press, Second edition 2010)
These notes are to be used in conjunction with the course book. A number of hard copies are
available in the University Library, as well as an ebook that can be accessed online.

Other books that may be useful

• Kittel, Introduction to Solid State Physics (Wiley)
• Burns, Solid State Physics (Academic Press)
• Ibach and Luth, Solid State Physics (Springer-Verlag)

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

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

 Topic 1: Introduction

• Optical coefficients

• Complex dielectric constant

• Complex refractive index

• Introduction to optical materials

Optical coefficients
propagation through
the medium

incident light transmitted light

reflected light

Figure 1.1: Optical coefficients

•  Reflectivity = reflected / incident power

•  Transmissivity = transmitted / incident power
•  T + R =1 if medium is transparent

1
 refraction
Propagation
absorption and luminescence Figure 1.2:
Propagation of
light through a
scattering medium

•  Velocity v= c/n, n is the refractive index

•  I(z) = I0 exp(-αz), α is the absorption coefficient
•  T = (1-R1) exp(-αL) (1-R2)
•  Luminescence : re-emission at lower frequency
•  scattering: elastic- change of direction
inelastic - change of direction and frequency

Luminescence

excited states relaxation •  Luminescence comes

out at lower frequency
than absorption due to
emission
absorption

internal relaxation
•  The energy shift
between absorption
ground state
and luminescence is
Figure 1.3: luminescence mechanisms called the Stokes shift.

2
 Complex optical coefficients
Complex relative dielectric constant: εr = ε1 + iε 2
Complex refractive index: n = n + iκ
Absorption coefficient: α = 4πκ / λ
εr = n2 ; ε1 = n 2 − κ 2 ; ε 2 = 2nκ
1/2
1 " 1/2 %
n= 2
( 2
$ε1 + ε1 + ε 2
2#
) '
&
1/2
1 " 1/2 %
κ= 2
(2
$ −ε1 + ε1 + ε 2
2#
) '
&
2
n −1 (n −1) 2 + κ 2
Reflectivity: R = =
n +1 (n +1) 2 + κ 2

Insulators / semiconductors
UV visible infrared
1.0 • Infrared absorption due
(a)
Al2O3
to phonons
Transmission

• ultraviolet/visible
absorption due to bound
0.0 electrons
0.8 (b) • position of fundamental
absorption edge depends
CdSe on the size of band gap
• transparency region in
0.0 between
0.1 1 10
Wavelength (microns)
Figure 1.4 : transmission spectra of
(a) sapphire (Al2O3) (b) CdSe

3
 Metals
infrared visible UV

1.0
Figure 1.5:
Reflectivity

0.8 Reflectivity spectrum

silver
0.6 of silver
0.4
0.2
0.0
10 1.0 0.1
Wavelength (µm)
• Free electrons in the metal absorb

⇒ High reflectivity up to “plasma frequency” in the UV

Organic materials
UV visible
1.0
Absorption (a.u.)

UV/blue band
0.8 Figure 1.6 : Absorption
0.6 spectrum of polyfluorene
0.4 polyfluorene
(F8)
0.2
0.0
300 400 500 600 700
Wavelength (nm)

•  Strong absorption in UV/visible spectral region due to

electronic transitions
•  Stokes-shifted emission across the visible spectral region

4
 Doped insulators
1.0
sapphire
0.8 Figure 1.7:
Transmission

ruby Transmission spectra

0.6 of sapphire (Al2O3)
yellow/green and ruby (Al2O3: Cr3+)
0.4 band
0.2 blue band

0.0
200 400 600 800 1000
Wavelength (nm)
• Sapphire is transparent for visible wavelengths
• Cr3+ ions doped into sapphire absorb in the blue and yellow/green
spectral regions, hence red colour

Lifting of degeneracies
atom free atom
atom in
in B field
crystal
degenerate
magnetic
levels
crystal Zeeman
field effect
effect

Figure 1.8 : Lifting of degeneracies in the solid state

•  Crystals have directions ⇒ lower symmetry than atoms or molecules

•  new effects due to lower symmetry e.g. lifting of degeneracies

5
E solid free Band formation
atom

Figure 1.9:
Band formation in
the solid state

Interatomic separation

•  Free atoms have sharp absorption and emission lines

•  Solids have broad absorption and emission bands
•  Two types of bands: electronic and vibronic

6
 Topic 2: Dipole oscillators

•  Introduction

•  Lorentz oscillator model

•  Kramers–Kronig relationships

•  Dispersion

•  Optical anisotropy & chirality

Electron oscillators

Figure 2.1: classical model of an atom.

Electrons are bound to the nucleus by springs
which determine the natural frequencies

Bound electrons (insulators, intrinsic semiconductors)

• restoring force for small displacements F = – k x
⇒ natural resonant frequency ω0 = (k/m)1/2
• ω0 lies in the near infrared / visible / UV spectral regions

Free electrons (metals, doped insulators)

• k = 0 ⇒ ω0 = 0

7
 Dipole oscillators Figure 2.2

p(t) t
p(t) = – e x(t)
x(t) P=Np
t
D = ε0 E + P = εrε0 E
x
Light emission
+ • natural oscillations at ω0
π 2π cause radiation at ω0
t=0 t=ω t= ω
0 0 • “Hertzian dipoles”

Refractive index Absorption

• light ≡ AC electric field at ω (≠ω0) • light frequency = ω0
• forced oscillations at ω • resonance phenomenon
• atoms lag on the driving field • atoms absorb energy from
and re-radiate in phase the light beam

Vibrational oscillators
+
Figure 2.3
polar molecule
ε ω0

Molecular physics
IR absorption at resonant frequency of the vibrational modes

Ionic crystals
IR absorption at frequency of optically-active lattice vibrations
i.e. the transverse optic (TO) phonons

8
 Lorentz oscillators
Dielectric constant Refractive index
30 6 Figure 2.4
ε1

4 Lorentz
10

n
oscillator
2
-10 with
ω0 ω0 ω0 = 1014 rad/s
40 4 γ = 5×1012 s-1
εst = 12.1
ε2

γ κ
20 2 ε∞ = 10
0 0
60 100 140 60 100 140
ω (1012 rad/s)
•  absorption at ω0
Ne 2 1 •  γ = 1/τ = damping rate
ε r (ω ) = 1 + χ +
(
ε 0 m0 ω 0 2 − ω 2 − iγω ) •  FWHM = γ,

Example: atomic absorption line

α Lorentzian lineshape
1700 m 1
γ2
α (ω ) = α 0
4Δω 2 + γ 2
0
n 4γΔω
n(ω ) = n0 − Δn
3.95 × 10 5
4Δω 2 + γ 2
n0 ≈ 1
Δω = ω − ω 0

200, 0, 200,
Δν (MHz)

Figure 2.5
•  sodium gas, N = 1×1017 m–3 (low density ⇒ n0 ≈ 1)
•  D2 line at 589.0 nm, hyperfine component with FWHM = 100 MHz

9
 Multiple resonances
Figure 2.6
Refractive index

vibrational electronic
bands resonant frequencies:
transitions
phonons IR
valence electrons vis/UV
core electrons X-ray
1
0
Ne 2 fj
Absorption

ε r (ω ) = 1 + ∑
(
ε 0 m0 j ω 0 j 2 − ω 2 − iγ jω )
0
IR visible UV X-ray • fj = oscillator strength
• classical theory ⇒ fj = 1
1011 1013 1015 1017 • quantum theory ⇒ fj determined
Frequency (Hz) by transition probability

Example: SiO2 glass

SiO2 glass (a) Figure 2.7
Extinction coefficient refractive index

3
real and imaginary
2 part of the refractive
n

index for SiO2 glass

1

1, (b)
Transparency region
10 2, between
phonon frequencies in IR
κ

10 4, and band gap in UV

1012 1013 1014 1015 1016 1017

Frequency (Hz)

10
 Optical fibre losses

http://nobelprize.org/nobel_prizes/physics/laureates/2009/phyadv09.pdf

Kramers–Kronig relationships
2 ω %κ (ω %)
∞
n(ω ) − 1 = P∫ dω %
π 0 ω %2 − ω 2
2
2 ∞ ω % [ n(ω %) − 1]
κ (ω ) = − P dω %
πω ∫0 ω %2 − ω 2
Figure 2.9
•  Refractive index (n) and absorption
Refractive index

4
(κ) are the real and imaginary parts
of the same function: ñ = n+iκ
•  Absorption and refraction are 2
n at 10 µm
related to each other by the
vs band gap
Kramers–Kronig relationships $
0
0 1 2
Band gap wavelength (µm)

11
 UV transmission of glass

(at 546 nm) (at 310 nm)

Add UV absorbers:
•  reduces UV transmission
•  increases refractive index at
visible frequencies

Dispersion Figure 2.10

glass dispersion
Wavelength (nm)
1000 600 400 300 200
IR visible ultraviolet
•  Group velocity
Refractive index, n

1.55 dispersion (GVD)

∝ d2n/d!2
d2n •  GVD determines
1.50 =0
pulse spreading
dλ 2
in optical fibres
•  GVD = 0 near
1.45 SiO2 glass 1300 nm

0.2 0.4 0.6 0.8 1.0 1.2 1.4

Frequency (1015 Hz)

12
 Dispersive prisms

white red Figure 2.11

Dispersion of light by a prism

blue

•  NORMAL dispersion: n increase with frequency

•  ANOMALOUS dispersion: occurs near resonance lines

For Pink Floyd fans …

red red

blue
blue

anomalous dispersion ? normal dispersion

13
 Double refraction (Birefringence)

Double refraction in calcite

optic axis Figure 2.12

Birefringent crystals
such as calcite
109°
e-ray (Iceland Spar)
separate orthogonal
6.2° light polarizations
o-ray
unpolarized into the
light 71° o(rdinary) and
e(xtraordinary) rays

Birefringence (optical anisotropy) : refractive index depends on

the direction of the polarization vector relative to the crystal axes

14
 Optical anisotropy
optic axis optic axis
z z
propagation propagation
direction direction
θ θ
ε ε
y y

(a) o-ray (b) e-ray

Figure 2.13
& Dx # & ε11 0 0 #& E x #
Birefringence caused by $ ! $ !$ !
difference of dielectric constants $ D y ! = ε 0 $ 0 ε 22 0 !$ E y !
(and hence refractive index) $D ! $ 0 0 ε 33 !"$% E z !"
% z" %
along the different crystal axes.

Polarizing beams splitters

Figure 2.14
air gap Glan–Foucault
unpolarized
light " prism
o-ray
" e-ray

optic axis

Critical angle: sin "c = 1/n

Calcite: no = 1.658, "c = 37.1°; ne = 1.486, "c = 42.3°
Hence choose 37.1° ≤ " ≤ 42.3°

15
 Wave plates Figure 2.15

(a) (b)
"
o-ray e-ray
xis
ic a
output "
opt

input
input
polarization
d

2π Half wave plate: !# = $

Δφ = ( no − ne ) d Quarter wave plate: Δφ = π / 2,
λ

Induced birefringence
•  Isotropic materials are non-birefringent
•  Induce birefringence !n with strain or electric field
•  Hence photo-elastic and electro-optic effects
•  Kerr effect (quadratic electro-optic effect) observed in
all materials, including liquids and glass:
Δn = ! K E2 ; K = Kerr constant
•  Hence Kerr cells (see Fig. 11.8)
•  Contrast with linear electro-optic effect (Pockels effect)
observed only in anisotropic crystals (See Fig 11.6)

16
 Chirality
•  Optical properties different for left or right circularly polarized
light due to chirality (helicity) of molecules or crystal
structure
•  Circular dichroism: different absorption for left or right
circular light
•  Optical activity: different refractive index for left or right
circular light.
•  Optical activity causes rotation of linear light: Examples:
dextrose, laevulose (fructose) [latin dexter, laevus]

πd
θ= ( n − nL )
λ R
amino acid

Magneto-optics
•  Induce chirality in non-chiral materials with a magnetic
field
•  magnetic circular dichrosim in absorbing materials
•  Faraday effect in transparent materials: rotation of linear
polarization by magnetic field
$θ = V B d ; V = Verdet coefficient
B

"

input output Figure 2.16

The Faraday effect
d

17
Appendix: Local field corrections
Figure 2.8
P local field ≠ applied field in dense medium
- - - - θ- - -

Lorentz correction:,
++ +
++++ εlocal = ε + P/3ε0 in cubic crystal

ε
Clausius Mossotti relationship
ε r − 1 Nχ a
=
εr + 2 3

18
 Topic 3: Interband absorption

•  Interband transitions: direct and indirect

•  Direct gap materials

•  Optical orientation

•  Indirect gap materials

•  Photodetectors & solar cells

Interband absorption

Energy •  Photon excites electron

upper band from filled valence to
empty conduction band
Ef
•  Fundamental
absorption edge at Eg
Eg !%
•  Process creates an
Ei electron–hole pair
lower band
Figure 3.1

19
 Direct and Indirect absorption
(a)  Direct band gap: Figure 3.2 (b) Indirect band gap
C.B. minimum at k = 0 C.B. minimum at k ≠ 0
E conduction band E

Eg q Eg
!% !%

valence band
k k
0 0
•  kphoton = 2π/λ ~ 107 m–1 negligible compared to B.Z. size π/a ~ 1011 m–1
•  Transitions appear as vertical lines on E – k diagrams
•  Phonon needed to conserve momentum for indirect gap materials
•  Indirect absorption 2nd order process, therefore low probability

Atomic physics of semiconductors

p antibonding Figure 3.3

p conduction band
s antibonding
Eg
s p bonding valence band

s bonding

ATOM MOLECULE CRYSTAL

•  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

20
 GaAs band structure
4
Figure 3.4
2 GaAs
Energy (eV)

Eg !% •  Direct gap at 1.5 eV

0
•  Very important
-2 optoelectronic material
-4
•  Strong absorption for
-6 !% > Eg
L Λ, Γ Δ, X
Wave vector k

fcc lattice Brillouin zone

kz
Symmetry points

Γ 000
X 100
010 L
001 Γ,
K 110 X ky
W
L 111
K
kx

Fig D.5

21
 Four-band model
E Figure 3.5

Electron (e) •  Simplified band

band structure first proposed
by Kane (1957)
Eg •  valid near k = 0
! "

0 k ! Heavy hole transition

Heavy holes (hh)
Δ " Light hole transition
Light holes (lh)
•  Split-off hole
Split-off holes (so) transitions also possible

InAs band edge absorption

1.0
InAs Figure 3.6
α2 (1012 m 2)

0.8 room temperature

InAs is a direct gap
0.6 III–V semiconductor
with Eg = 0.35 eV
0.4
!% < Eg : " = 0
0.2
!% > Eg :
0.0
0.3 0.4 0.5 0.6 " ∝ (!% – Eg)1/2
Energy (eV)

22
 Magneto absorption in germanium
Figure 3.7
45
Transmission (%)

germanium
40 300 K •  direct gap at 0.80 eV
35
B = 3.6 T •  B-Field quantizes motion
30
in direction perpendicular
25 B = 0 to B
20
•  Landau level absorption
15
when
0.78 0.80 0.82 0.84 0.86 !% = Eg + (n+½) !%c
Energy (eV) %c = eB / me
(cyclotron frequency)

Spin injection (optical orientation)

E |M12|2 ∝ MJ
conduction band
⇒  hh transitions three
Eg J = 1/2 times stronger than lh
E1 selection rule
&+ &+ &# &# Δm = ±1 for σ±
hh lh lh hh
0 J = 3/2
#! so so J = 1/2
valence band Figure 3.8
MJ
#3/2 #1/2 +1/2 +3/2
50% spin
N (+1/2) ! N (!1/2)
"= polarization for
N (+1/2) + N (!1/2) σ± excitation

23
 Direct versus indirect absorption
Figure 3.9
Absorption coefficient (m 1)

106
105 •  Direct absorption is
much stronger than
104 indirect absorption
103 GaAs
102 silicon • Silicon has indirect gap
at 1.1 eV
1.0 1.2 1.4 1.6 1.8 2.0
Energy (eV) •  GaAs has direct gap at
1.4 eV

Germanium band structure

4

2 Eg = 0.66eV Figure 3.10

Energy (eV)

direct gap
0
•  Indirect gap
-2 at 0.66 eV

-4 •  Direct gap
at 0.80 eV
-6
L Λ, Γ, Δ, X
Wave vector k

24
 Germanium band edge absorption
10
80 (a) 291 K (b) 300 K germanium
8
'1/2 (m#1/2)

' (105 m#1)

60 phonon ' % (!% # Egdir)1/2
6
absorption

emission
phonon

40 4
20 K Eg
20 2
0 0
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
Energy (eV) Energy (eV)
Figure 3.11
at 300K :
•  indirect absorption: α ∝ (!% – Egind ± !$phonon )2 Egind = 0.66 eV
•  direct absorption: α ∝ (!% – Egdir )1/2 Egdir = 0.80 eV

Silicon absorption
1)
m

E2
(108

2.5
•  Indirect band gap
2.0
Absorption coefficient

E1 at 1.1 eV
1.5
•  Critical points
1.0 (van Hove
Eg silicon
0.5 singularities) at E1
300 K
(3.2 eV) and E2
0 (4.3 eV)
0 2 4 6 8 10
Energy (eV)
Figure 3.12

25
 Silicon band structure
• density of states g(E)
4
∝ 2 g(k) (dE/dk)–1
E1 Eg
0
Energy (eV)

E2 •  Critical points (van

Hove singularities)
-4
whenever dE/dk = 0
-8
•  occurs when
conduction and
-12
valence bands are
L Λ, Γ, Δ, X parallel to each other:
Wave vector k Parallel band effect

Figure 3.13

Absorption spectroscopy Figures 3.14-15

white-light
white-light
source
source
scanning collimation lenses
monochromator sample
reflection in cryostat
detector
collection lenses
sample
entrance slit
transmission
detector spectrograph
valve silicon
diode array # computer
detector
vacuum pump

26
 p-i-n diodes (Appendix E)
E p i n p i n
E

Eg Eg
Figs E.1-2 | eV0 |
li
li
z z
V0 = 0 Reverse bias V0 applied

•  Electric field E = (Vbi – V0) / li li

•  Vbi = built-in voltage ≈ Eg / e p i n

V0
•  V0 is negative in reverse bias z

Photodetectors
Figure 3.16
•  Embed absorbing region within
!% p-n junction to form p-i-n diode
Ipc •  Apply reverse bias V0
(i.e. V0 negative )
p
ε •  Electric field ε = (Vbi – V0) / li
V0 i li
+ - •  Vbi = built-in voltage ≈ Eg / e
n
•  Photons absorbed if !% > Eg
•  Creates electron-hole pairs in
i-region
Examples:
•  photodiodes •  Carriers swept out by ε field
•  solar cells (V0 = 0) into external circuit to generate
photocurrent Ipc

27
 Solar cells (photovoltaics) Figure 3.17

!% pi n

Ipc
R
+ –
V = Ipc R
Ipc maximum
ISC power • Small gap: large ISC , small VOC
• Large gap: small ISC , large VOC
• Single junction: max efficiency ~30%
V • Larger for multi junction
VOC

Solar cell efficiency

28
 Topic 4: Excitons

•  Introduction

•  Wannier excitons

•  Excitonic nonlinearities

•  Frenkel excitons

Excitons Figure 4.1

a h
e

Free (Wannier) Tightly-bound (Frenkel)

radius >> a radius ~ a
small binding energy large binding energy
moves freely through crystal localized on one lattice site

29
 Figure 4.2

Free exciton absorption

•  Hydrogenic series of
n=1 lines satisfying :
α, !% = Eg – RX / n2

n=2 •  enhanced absorption for

!% > Eg
(!% – Eg)1/2
•  only observed when
Photon energy T ≤ ( RX / kB)
Eg

Excitons in bulk GaAs Figs 4.3-4

exciton,
n=1 n=2

1.2 1.2 n=3

294 K
α (106 m 1)
α (106 m 1)

0.8 RX
0.8 21 K
0.4 Eg
0.4 α ∝ (!% 1.425)1/2,
0
1.514 1.520
0
1.42 1.46 1.50 1.54
Photon energy (eV)
Photon energy (eV)
•  ultra pure sample
•  standard purity sample
•  T = 1.2 K
•  T = 21 K – 294 K
•  RX = 4.2 meV

30
 Figure 4.5
Field ionization in GaAs
F ~ 2 RX / e aX
V0 = +1.00 V, Ε ≈ 5 × 105 V / m

Ε, F aX
!%
p
Photocurrent

V0 i Ε li
n ionized if ε > F
T=5K GaAs parameters :
RX ~ 4.2 meV
V0= +1.44 V$ aX ~ 13 nm
Ε≈0 li = 1 µm (typical)
0 F ~ 6 × 105 V / m
1.50 1.51 1.52 Ε ~ 1.5 × 106 V / m
Photon energy (eV) for V0 = 0 !

Figs 4.6 - 7

Nonlinear excitonic absorption

GaAs, 1.2 K
10
8 low density
α (106 m 1)

6 × 1022 m 3
(a) Low density 6 2 × 1023 m 3
Separation » diameter
4
2
0
1.512 1.516 1.520
(b) High density Photon energy (eV)
Separation ≈ diameter
NMott = [ (4/3)πaX3 ]–1
~ 1.1 × 1023 m 3 in GaAs

31
 Figs 4.8 - 9
Frenkel excitons
Alkali halides Organic crystals
3 LiF C16H10 (pyrene)
300 K
α (108 m 1)

Absorption
2 NaCl
Eg
Eg
1
300 K
0
8 10 12 14 3.20 3.30 3.40
Energy (eV) Energy (eV)

Eg(eV) RX (eV)
Also: Rare gas crystals
NaCl 8.8 0.9
(solid Ne, Ar, Kr, Xe)
LiF 13.7 0.9

32
 Topic 5: Luminescence

•  Introduction

•  Photoluminescence

•  Electroluminescence

•  LEDs and lasers

•  Cathodoluminescence

Luminescence
• Luminescence spontaneous emission in solids

• Fluorescence fast luminescence

electric-dipole allowed, τR ~ ns
• Phosphorescence slow luminescence
electric-dipole forbidden, τR ~ µs – ms

• Electroluminescence electrical excitation

• Photoluminescence optical excitation
• Cathodoluminescence cathode ray (e–beam) excitation

33
 Fig. 5.1
Radiative quantum efficiency
inject
electrons
relaxation
ηR = radiative quantum
EXCITED
efficiency
STATE
= radiative transition rate
τNR τR !% total transition rate

GROUND 1
ηR =
STATE 1 + τ R / τ NR
inject holes

•  Radiative transition rate determined by Einstein A-coefficient

•  τR = A–1
•  τΝR determined by phonon population, number of traps etc

Direct gap materials

GaN
conduction band
T = 4 K, Eg = 3.50 eV
E
Luminescence
intensity

Absorption

electrons
Eg !%
holes

k=0 k 3.40 3.50 3.60

valence band Energy (eV)

•  Strong emission at the band gap

•  most III-V and II-VI semiconductors Figs 5.2 – 3
•  linewidth ≥ kBT

34
 Indirect gap materials
conduction band
E

electrons Figure 5.4

phonon
Eg
!%
holes
valence band
k
k=0
•  Low emission probability (2nd order process)
•  Long radiative lifetime ⇒ low radiative quantum efficiency
•  diamond, silicon, germanium, AlAs

Photoluminescence
E E
electrons
conduction
band
Eg
hνL hν Figure 5.5
0
k
valence holes
k=0 band Density of states
•  Excite using laser with photon energy > Eg
•  electrons and holes relax to the bottom of their bands
•  thermal distributions formed according to statistical mechanics
•  emission from Eg to top of carrier distributions

35
 Classical (Boltzmann)Statistics
103 Figure 5.6
PL intensity (a.u.)

GaAs
T = 100 K
102
1.50 1.52 kBT = 8.6 meV
kBT Eg = 1.501 eV
Eg
Fermi’s golden rule
1.49 1.50 1.51 1.52 1.53 Rate ∝ |M|2 ρ(hν)
Energy (eV)

•  Boltzmann statistics: f(E) ∝ exp(–E/kBT) (occupancy factors)

•  I(E) ∝ Density of states × fe(E) fh(E)
•  PL rises sharply at Eg, then decays exponentially. Linewidth ~ kBT

Figs 5.7 – 8
Degeneracy
E Ga0.47In0.53As, TL = 10 K
Photoluminescence (a.u.)

electrons
6nJ/pulse
E Fc

Eg hν 24 ps
250 ps 180 K
EFv
Eg 55 K
holes
Density of states 0.80 0.90 1.00
Energy (eV)

•  Degeneracy observed at high density and low temperatures

•  Emission from Eg to (Eg + EFc +EFv )

36
 Photoluminescence spectroscopy
sample in cryostat Photoluminescence (PL) spectroscopy
• fixed frequency laser, measure spectrum
laser by scanning spectrometer

mirror PL excitation spectroscopy (PLE)

PL collection • detect at peak emission,
lenses vary laser frequency
entrance slit • effectively measures absorption

spectrometer Time-resolved PL spectroscopy

• short pulse laser + fast detector

# • measure lifetimes, relaxation processes

detector computer

Electroluminescence
holes hν ≈ Eg
p-type • Epitaxial growth of high
epitaxial
n-type layers purity light-emitting layers on
electrons substrate crystal
• MBE, MOCVD, LPE ….
substrate

current
• Forward-biassed p-n junction
p • Electrons and holes recombine at the
V0 hν
n junction
• photon energy ~ Eg
Figure 5.10

37
 Lattice matching
substrate materials
SiC sapphire GaAs
InP
hexagonal cubic
direct band gap
6 AlN indirect band gap
Band gap (eV)

4 AlP
GaN GaP AlAs
visible blue
2 spectrum red
GaAs InP fibre
InN InAs optics
0
3 4 5 6
Figure 5.11
Lattice constant (Å)

Figs 5.12 – 3
Junction electroluminescence
depletion
region GaAs, Eg = 1.42 eV
p n
Electroluminescence

Eg electrons
EFv EFc 1 mA
holes 293 K

(a) V0 = 0
1.2 1.4 1.6 1.8
p n Energy (eV)
eV0 hν = Eg •  Emission at Eg
•  Operating voltage ~ Eg / e
(b) V0 ≈ +Eg/e •  Spectral width ~ kBT

38
 Diode lasers Figs 5.14 – 16

l
current
metal contact
hν oxide
R1 R2 p - AlGaAs
i - GaAs
n- GaAs
n - AlGaAs
Gain γν , power ,
Output

substrate
light
Iin output
γth metal contact

Iin •  Mirrors formed by “facets” (i.e. edges) of chip

Ith
•  Emission wavelength ~ hc / Eg
•  Linewidth determined by cavity modes

Figure 5.17
Cathodoluminescence
VACUUM electron •  Focussed spot size ! 100nm
beam •  Primary electrons generate
Primary electrons secondary electrons in
few keV excitation volume
•  Secondary electrons generate
back-scattered
electrons e–h pairs, hence luminescence

penetration excitation
depth (Re) volume
! 1 µm

CRYSTAL cathodoluminescence

•  Commercial use in cathode ray tubes

•  Research tool for investigating nanostructures:
Observe luminescence from electron microscope

39
40
 Topic 6: Quantum confinement
•  Dimensionality
•  Quantum wells
$ Energy levels
$ Optical transitions
$ Quantum confined Stark effect

•  Quantum dots
•  Carbon nanostructures

Fig. 6.1
Dimensionality
Dimensionality /
Confinement
z
3 /0 bulk
y
x
Density of states

quantum
2/1 well
quantum
1/2 wire
quantum
0/3 dot
Eg Energy

41
 Fig. 6.2
Semiconductor quantum wells
AlGaAs GaAs GaAs quantum wells
crystal

substrate
GaAs growth
direction AlGaAs
substrate
z
d b d
C.B. e- C.B.

EgAlGaAs EgGaAs EgGaAs EgAlGaAs

V.B. V.B.
h+
Single quantum well MQW or superlattice
growth •  Molecular beam epitaxy (MBE)
methods •  Metal-organic chemical vapour deposition (MOCVD)

Fig. 6.3
Infinite quantum well
10
E (h 2/8m*d 2)

n=3
•  kn = nπ/d
5 •  En = (!kn)2/2m* = (!2π2/2m*d2) n2
n=2
•  ψn = (2/d)1/2 sin (knz +nπ/2)
n=1
0
z
d/2 0 d/2

•  symmetry about z = 0 ⇒ wave functions have definite parity

•  ψn has (n–1) nodes
•  En depends on m*, hence heavy and light holes split

42
 Figs 6.4–5
Finite quantum well
E y = 0.85 (13.2-x2)½ / x
V0
E2
n=2 8 y = tan(x)
E1 n=1
0 z 4

y
–d 0 d
2 2
0
0 2 4 x
•  Wave functions tunnel into the
barrier Example : GaAs/AlGaAs
•  wave function still identified by V0 = 0.3 eV, d = 10 nm
parity and number of nodes mw*= 0.067me, mb*= 0.092me
•  Confinement energy reduced E1 = 31.5 meV
compared to infinite well c.f. infinite well: E1 = 57 meV
•  graphical solution to find En

Figs 6.6–7

Optical transitions
quantum well
conduction band

!%
n=1 n=2

z valence band

•  Light polarized in x,y plane for normal incidence

•  Parity selection rule: Δn = even number
•  Infinite well selection rule: Δn = 0

43
 Figs 6.8–9
2-D absorption

Absorption coefficient
conduction
band E
3-D

Eg
!% n=3
0 n=2
2-D
kxy n=1
0
valence band 0 5 10
(!%#Eg) in units of (h 2/8d 2µ)
•  Absorption ∝ density of states
•  Density of states constant in 2-D: g2D(E) = m / π!2
•  Thresholds whenever !ω exceeds (Eg + Een+ Ehn)
•  Band edge shifts to (Eg + Ee1+ Ehh1)

Figs 6.10–11
GaAs quantum wells
GaAs/AlAs MQW, d = 7.6 nm GaAs/AlGaAs MQW
d = 10 nm
n=1 n=2 hh lh
Absorption (au)

1.0 10 bulk 4
hh hh
α (105 m 1)

hh lh n=3 n=2
lh lh
0.5 5 2
T=6K n =1 300 K
0.0 0 0
1.6 1.8 2.0 2.2 1.4 1.5 1.6
Photon energy (eV) Photon Energy (eV)
•  Excitonic effects enhanced in quantum wells: strong at room temp
•  Pure 2-D: RX2D = 4 × RX3D
•  Typical GaAs quantum well: RX ~ 10 meV ~ 2.5 × RX (bulk GaAs)
•  Splitting of heavy and light hole transitions

44
 Spin injection in quantum wells
Selection rules
E σ+: Δm = +1,
conduction band σ : Δm = 1
J = 1/2
Eg

&+ &+ &# &#

0
lh lh J = 3/2
hh hh
#! J = 1/2
so so
valence band

3/2, 1/2, +1/2, +3/2,

MJ

Figure 6.12

Quantum confinement Stark effect (1)

Figure 6.13
(a) Ez = 0 (b) Ez = 107 V/m

1800
Energy (meV)

1600 e1
1400 1455.0 1447.9
1438.5
1462.4

–7.4 hh1 9.4

0
–200
–10 0 10 –10 0 10
Position (nm) Position (nm)
•  10 nm GaAs / Al0.3Ga0.7As quantum well in an electric field
•  Eg (GaAs) = 1420 meV

45
 The quantum confined Stark effect (2)
GaAs MQW, d = 9.0 nm, 300 K
pi n MQW
!%
lh1→e1
hh1→e1
hh2→e2
V0 Ez (a) 0 V

Photocurrent (arb. units)

1.5×106 V/m
photocurrent

•  Red shift of excitons

•  Excitons stable to high (b) 10 V
hh1→e2 1.1×107 V/m
fields (c.f. Fig 4.5)
•  Parity selection rule hh2→e1
broken 1.4 1.5 1.6 1.7
•  used to make modulators Energy (eV) Figs 6.14–15

Figure 6.16

Emission spectrum
Zn0.8Cd0.2Se/ZnSe quantum well
Eg = 2.55eV (10K)
d = 2.5 nm
Eg = 2.45eV (300K)
10 K
PL intensity

300 K

•  Emission energy shifted from

Eg to (Eg + Ee1 + Ehh1)
0 •  Tune λ by changing d
2.4 2.5 2.6 2.7 •  Brighter than bulk due to
Energy (eV) improved electron-hole overlap
•  Used in laser diodes and LEDs

46
 Figure 6.17

Intersubband transitions
n-type quantum well
• Need z polarized light
hν n=2 • Parity selection rule: ,
electrons Δn = odd number
n=1

•  Transition energy ~ 0.1 eV (~ 10 µm, infrared)

•  Absorption used for infrared detectors
•  Emission used for infrared lasers (Quantum cascade lasers)

Figure 6.18
Quantum dots

Bulk (3-D)
Density of states

Quantum well (2-D)

Quantum wire (1-D)

z Quantum dot (1-D)

Eg Energy

47
 Quantum dots
Spherical dot
Cuboid dot d

! 2 2 2$
 2π 2 # n x n y n z &
R
E= + +
2m* #" d x2 d y2 d z2 &%
! 2 2$
 2 # Cnl π &
E=
Density of states

2m* #" R2 &%

3-D C10 = 1
C11 = 1.43
C12 = 1.83
0 5 10 C20 = 2
(E Eg) in units of (h 2/8d 2m*) "

Colloidal quantum dots Figure 6.20

(a) CdSe (b)

Absorption (arb. units)

10 K 6 nm CdTe
D 300 K

C 5 nm
B
A 4 nm

1.5 2.0 2.5 3.0 3.5 1.6 1.8 2.0 2.2

Energy (eV) Energy (eV)

•  Found in semiconductor doped glass (Colour glass filters &

stained glass)
•  Available commercially

48
 Self-organized epitaxial dots Figs 6.19, 21

2-D harmonic oscillator levels

m

Energy in unit of !%0

2, 1, 0, 1, 2,
3 ‘d’ shell
InAs 200 nm
2 ‘p’ shell
quantum dot
1 ‘s’ shell
V(r)
0 r
0
GaAs 10 nm
z
h 2π 2 nz2
E≈ + (n + 1)hω0 dz
2m*d z2
a dz ≪ a

InAs quantum dots Figure 6.22

Quantum confined Stark effect
(a) (b) 2.6V
Photocurrent (pA)
PL Intensity (arb. units)

T = 10 K
Bias voltage

Spatially 10 pA
200 nm resolved PL
aperture Single QD

PC
PL Intensity

Far field PL PL
(arb. units)

200 µm ~107 QDs

spot
T = 10 K 0.6V

1.25 1.30 1.35 1.40 1.250 1.255 1.260

Energy (eV) Energy (eV)

49
 Figure 8.20
Carbon nanostructures
graphene nanotube C60 Bucky ball *

* Buckminster fullerene named after

architect R. Buckmintser Fuller

Fig. 8.21
Graphene band structure

Ideal 2-D material

(a) (b) M
4 $' &
K
0 EF

–4 & $ E
Energy (eV)

(c)
–8 $'

–12
!%
ky
–16 & kx
–20 $
& K M &

Taken from Machon, Phys. Rev B 66, 155410 (2002)

50
 Graphene transmission Figure 8.22

100 100

Transmission (%)
(a)
Transmission (%)

(b)
99
98 95
97
graphene, single layer
96 90
95
400 500 600 700 0 1 2 3 4 5
Wavelength (nm) Number of layers

After Nair et al. Science, 320, 1308 (2008).

Nanotube chirality Quantum wire (1-D)

D.O.S.

armchair
(5,5) Eg Energy
chiral
" (7,3)
zig
zag
a2
(9,0)
a1 c
Figure 8.23

chiral vector c = n1 a1 + n2 a2
Metallic if n1−n2 = 3m ; otherwise semiconductor

51
 Nanotube transitions
E E

semiconducting conduction band

nanotube kz emission
valence band

density of states

E E
conduction band
metallic kz EF
nanotube
valence band

density of states Figure 8.24

Semiconducting Nanotube PL spectra

s m SWNT ensemble
E22 E11
3 1.0 (7,5)
Normalized PL intensity (au)
Energy gap (eV)

(8,3)
2 (9,1)

0.0 single
1 1.0
Es11 SWNTs
(9,1)
0 (8,3)
0 1 2 3
Tube diameter (nm) (7,5)
0.0
900 1000 1100 1200
Figure 8.24-5 Wavelength (nm)

52
 Carbon bucky ball: C60

PL (a.u.)

Absorption
(a) (b)

3 S2(u)
Energy (eV)

2 1.2 ns T1(g) 1.6 1.8 2.0 2.2

S1(g)
4 Energy (eV)

(104 cm–1)
Absorption
1 1.8 µs 3
2 S S2 C60
0 S0(g) 1
singlets triplets 1
0
2 3 4 5
Energy (eV)

Figure 8.27

53
54
 Topic 7: Free electrons
•  Free carrier reflectivity

•  Metals

•  Doped semiconductors

•  Plasmons (bulk & surface)

•  Negative refraction

Fig 7.1
Free electron refelctivity
1.0 • Key parameter:
Reflectivity

Plasma frequency ,
0.5 ωp = (Ne2/ε0m0)1/2
• Lightly-damped system,
0.0 εr(ω) = 1 ωp2/ω2,
0 1 2 • R = 100% below ωp
ω / ωp
• transmitting above ωp
Free electron effects observed in: ⇒ ultraviolet transparency
•  metals of metals
•  doped semicondcutors

55
 The Drude model Fig 7.2

!%p
1.0 Aluminium
!%p = 15.8 eV,
0.8
Reflectivity

experimental data σ = 3.6 × 107 Ω–1 m–1

0.6
0.4 γ=0
ωp2
0.2 τ = 8.0 fs ε r (ω ) = 1 −
0.0
ω 2 + iγω
0 5 10 15 20 1/ 2
& Ne 2 #
Energy (eV) ω p = $$ !
ε m !
% 0 0"

• τ = 1/γ = momentum scattering time = m0σ/Ne2, σ = DC conductivity

• Reflectivity < 100% below ωp
• Discrepancies caused by interband absorption transitions

Interband transitions in Aluminium

Transition energy ~ 1.5 eV
• Transitions from filled
16 states below EF to
EF empty states above EF
Energy (eV)

12
• Very high density of
8 states for parallel bands

• “parallel band effect”

4
at the critical points

0 • Hence reflectivity dip

Γ, X W L Γ, K X
at 1.5 eV,
Wave vector k
Fig 7.3

56
 Fig. 7.4, 7.6
Transition metals
E 1.0
4s band 0.8 copper

Reflectivity
optical 0.6
transitions
EF 0.4 !%p

visible
0.2
3d band 0.0
0 2 4 6 8 10 12 14
Density of states Energy (eV)
•  Inner d orbitals form narrow bands below the Fermi energy
•  threshold for optical transitions to outer half-full s band gives a
sharp absorption edge
•  hence characteristic colours of metals, eg copper, gold

Copper band structure Fig 7.5

Electronic configuration: 3d10 4s1

minimum transition energy Integrated density of states

~ 2.2 eV (560 nm)
0 2 4 6 8 10
2 2
Energy (eV)

0 EF 0
Energy (eV)

-2 3d -2
-4 bands -4
-6 copper -6
-8 3d and 4s bands -8
W L Γ, X WK 0 2 4 6
Wave vector k Density of states (states eV 1)

57
 Fig 7.7
Doped semiconductors
n-type InSb at 300 K
100
4.0 × 1024
Reflectivity (%)

80 2.8 × 1024
1.2 × 1024
60
6.2 × 1023
40 3.5 × 1023
20 Plasma frequency ,
0 ωp = (Ne2/ε0εrm*)1/2
10 20 30
Wavelength (µm)

•  Control plasma frequency by varying the doping density

•  Plasma edge in the infrared

Fig 7.8
Free carrier absorption
E
scattering
!k 2
E= process
2me*
Ne 2
!% α free carrier =
EF m * ε 0 ncτω 2

• Transitions from filled states below EF to empty ones above EF

• α ∝ λ2 / τ
• Scattering process required to conserve momentum
• Continuous infrared absorption in doped semiconductors

58
 Fig 7.9

Intervalence band absorption

E

EF "! #$ !!
k
Δ,
hh band

SO band lh band

•  Infrared absorption in p-type semiconductors

Impurity transitions Fig. 7.10

• Impurity levels: En = –(m*/m0)(1/εr2) RH / n2

n conduction band conduction band n

2 donor 2
levels
1 1

n-type
material

valence band valence band

(a) low temperature: (b) high temperature:

infrared absorption band tail below Eg

59
 Donor absorption in n-type silicon
Phosphorous doped Silicon
1.0
Absorption (103 m 1)

2p0
2p± N = 1.2 × 10 20 m–3
3p±
T = 4.2 K
4p±
3p0 5p± me* ~ 0.5 m0
4p0 εr = 12
0 R* ~ 45 meV
32 34 36 38 40 42 44
Photon energy (meV)
*
1 % * me 1
*(
•  simple model: hν = R &1 − 2 # , R = RH
' n $ m0 ε r 2
•  complications due to effective mass anisotropy Fig. 7.11

Plasmons

k
• Quantized plasma waves: i.e. longitudinal
oscillations of the electron plasma at ωp

Fig. 7.12

60
Observation of bulk plasmons
sample Doped semiconductors: !%p ~ 10 meV
!%p Measure by Raman scattering:
!%out = !%in ± n!%p
Ein Eout

Raman scattering rate

!%p plasmon plasmon
emission absorption

Metals: !%p ~ 3–20 eV

observe by electron energy -400 -200 0 200 400
loss spectroscopy : Energy shift (cm 1)
Eout = Ein − n!%p n-type GaAs, T = 300 K
Ein ~ keV N = 1.8 × 10 23 m–3
Figs 7.12-13 !%p = 19 meV (150 cm–1)

Surface plasmons
z
dielectric
dielectric: (d
z=0 x +++ ### +++ ###
k
metal: (m
metal

z •  Surface waves at boundary between

metal and insulator
Ezd (z) •  Plasmonics: propagate energy as
surface plasmons in nano-circuits
0 Ez •  Cannot couple directly to free-space
photons due to wave vector
Ezm (z) mismatch: hence need for couplers
(e.g. gratings)
Figs 7.14 - 15

61
 Surface plasmon polaritons
bulk surface
% %
(a) (b)

% = ck % = ckx /(εd
%p %p
%sp

0 0
0 1 ck /%p 2 0 1 ckx /%p 2

!p
!sp = Hence ωsp = ωp/√2 if εd = 1 (i.e. air)
1+"d
Fig. 7.16

Localized surface plasmons

Gold nanoparticles 6-7nm diameter
1.2!
Absorption (a.u.)!

0.8! Courtesy
MesoGold® M. Sugden
•  pure gold 0.4! T. Richardson
nanoparticles
suspended in 0.0!
300! 500! 700! 900!
water Wavelength (nm)! Fig. 7.17
•  Colloidal gold is not gold coloured !
•  Localized plasma oscillations at surface of metal nanoparticles
•  ωsp ~ ωp/√((d+2) i.e. ωp/√3 for air-metal boundary, but varies
somewhat with size and shape

62
 Negative refraction Figs 7.18 - 19

µr
n=1 n<0
"i "r
II I
ñ = i) n>0
)>0 )=0 perfect lens
)r
n<0 ñ = i)
)=0 )>0
III IV

•  Need both (r and µr to be negative

i.e. region III
•  Not possible in natural materials:
hence need metamaterial metamaterial

63
64
 Topic 8: Phonons
(Chapter 10)
•  Infrared active phonons

•  Reststrahlen

•  Inelastic light scattering

$  Raman scattering

•  Phonon lifetimes

Figs 10.1–2
Lattice absorption
•  Resonant absorption when
ω, k Ω, q photon frequency and wave-
vector match the phonon Ω, q
optical branch •  Only possible for optical
phonons of ionic or polar
Frequency

photon

(partly ionic) crystals

•  Phonon must be transverse:
hence TO phonons involved
acoustic branch •  Resonance occurs in the
0 π infrared ~ 10 – 100 µm
Wave vector (q)
a

65
 TO phonon resonance
ε = ε0eiqz
Figure 10.3
x+ z
x

•  TO phonon modes of ionic crystals: positive and negative ions

move in opposite transverse directions
•  This generates transverse electric field waves
•  Light resonates with these modes when the wave vectors and
frequencies match

Figure 10.4
Reststrahlen
•  100% reflectivity between νTO and νLO
•  Lyddane-Sachs-Teller relationship: νlO / νTO = (εst / ε∞ )1/2

ν TO 2 Example:
ε r (ν ) = ε ∞ + (ε st − ε ∞ ) 2 2
ν TO − ν νTO = 10 THz εst = 12.1
νLO = 11 THz ε∞ = 10

1.0
40
Reflectivity

(a) (b)
20
εr

0
-20
0.0
6 8 10 12 14 6 8 10 12 14
Frequency (THz) Frequency (THz)

66
 Figure 10.5
Infrared reflectivity
1.0
GaAs :
νTO = 273.3 cm–1
Reflectivity

νLO = 297.3 cm–1

InAs GaAs
InAs :
νTO = 218.9 cm–1
0.0 νLO = 243.3 cm–1
200 240 280
Wave number (cm 1) 1 cm–1 = 2.998 × 1010 Hz

•  Reststrahlen band observed between νTO and νLO

•  reflectivity less than 100% due to damping
•  damping caused by anharmonic phonon decay. Typical lifetime ~ 10 ps

Figs 10.6 – 7
Polaritons
•  Polariton = coupled TO phonon polarization wave & photon wave
•  anticrossing of photon and TO phonon modes when ω ~ ΩTO
•  modifies the dispersion of both photons and TO phonons
20 52
ω = v∞ q ω = vst q
ω / 2π (THz)

Energy (meV)

!$LO 48
ΩLO / 2π upper branch
10 44
ΩTO / 2π lower branch 40

0 36
0.0 1.0 2.0 0 1 2 3
Wave vector q (106 m 1) Wave vector (106 m 1)
Calculated: ΩTO / 2π = 10 THz, Raman scattering data on GaP
εst = 12.1, ε∞ = 10

67
 Fig. 10.8
Polarons
•  free electron in a polar solid
produces a local lattice distortion
through the electron-phonon
e coupling αep
•  modifies the effective mass to :
m** = m*(1 – αep/6)–1

•  Polaron effects are small in III-V s (e.g. ~ 1% in GaAs) but increase as

the crystal becomes more ionic.
•  Self-trapping leads to hopping conduction instead of band conduction
•  Organic conductors show strong polaron effects

Fig. 10.9
Inelastic light scattering
• Conservation laws:
,ω1 = ω2 ± Ω ; k1 = k2 ± Q
ω2 , k2
• Stokes scattering:
ω1 , k1 phonon emission (+ sign)
• Anti-Stokes scattering:
Ω,q phonon absorption (– sign)
• Ianti-Stokes / IStokes = exp(–!$/kBT)

•  Raman scattering: scattering from optical phonons

•  Brillouin scattering: scattering from acoustic phonons
•  Qmax = 2k ~ 106 m–1 for back-scattering geometry
∴ can only probe small wave vector phonons
•  Scattering can also be observed from plasmons, magnons etc

68
 Fig. 10.10

Raman scattering arrangement

laser beam computer

sample
in cryostat
reflected entrance slit
laser
scattered
scanning
double
#
spectrometer
light
CCD array
detector

collection
lenses

Fig. 10.11
Raman scattering data
TO LO

•  Raman scattering from TO

GaAs and LO phonons in various
Raman signal (a.u.)

III-V semiconductors using

InP a Nd:YAG laser at 1.06 µm

AlSb •  1cm–1 = 3 × 1010 Hz

= 0.124 meV
300 K GaP

200 300 400

Energy shift (cm 1)

69
 Figs 10.12 – 13
Phonon lifetimes
“Klemens channel” (see Klemens 1966)
Ω2 , q2
ΩTO optical

Frequency (Ω)
Ω1 , q1 branch
ΩTO
Ω3 , q3
2 acoustic
Ω1 , q1 branch
0
π 0 π
Ω3 , q3 a Wave vector (q) a
Ω2 , q2
•  TO phonon can decay into two
•  3 phonon processes
acoustic phonons
caused by anharmonicity
in the crystal •  Lifetime typically ~ 10 ps.

70
 Topic 9: Nonlinear optics
(Chapter 11)
•  Definitions

•  Resonant vs non-resonant nonlinearities

•  Second-order nonlinearities
$ frequency doubling

$ electro-optics

•  third-order nonlinearities

Nonlinear susceptibility
D = ε0 E + P ≡ ε0 εr E
P = ε0 χ(1) E + ε0 χ(2) E2 + ε0 χ(3) E3 + ….
% εr = 1 + χ(1) + χ(2) E + χ(3) E2 + ….

• χ(n) = nth order nonlinear susceptibility,

• χ(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 fields (ie high power lasers)

71
 Nonresonant nonlinear response
P P Figure 11.1
(a) P(t) (b) P(t)

t t
ε, ε,
sine wave
output
t, t,

ε (t), ε (t), distorted output

small amplitude contains terms
large amplitude
sine wave input at 2ω, 3ω etc
sine wave input

•  laser is tuned to the transparency region of crystal

•  far from resonance with any atomic transitions

Resonant nonlinear response

N2
2
A
uν I(z) I – dI
1
N1
Figs. 11.2-3 dz
z
•  laser is tuned to resonance with an atomic transition
•  stimulated emission reduces net absorption rate at high intensity
•  equivalent to “Pauli blocking” of upper state
•  saturable absorption: α(I) = α0 / (1 + I / Is) ; Is = saturation intensity
•  α(I) ≈ α0 – α2 I at small I ; α2 = α0 / Is
•  Δεr ∝ I ∝ E2 ∴third-order nonlinearity

72
 Second order nonlinear effects
Pi(2) = ε0 Σjk χ(2)ijk Ej Ek χ(2) = 0 in centrosymmetric crystals

ω2 ω2
(a) ω1+ω2 (b) ω1 ω2

ω1 ω1 Fig. 11.4

Process Input Ouptut

Frequency mixing ω1, ω2 , , ω1 + ω 2
Frequency doubling ω, ω 2ω,
Down conversion ω1 ω2, ω1 ω2,

Phase matching
χ(2) θ
ω 2ω
kω k2ω

• Phase matching condition: 2kω = k2ω

(conservation of momentum)
⇒ 2× n(ω) ω / c = n(2ω) 2ω / c
⇒ n(ω) = n(2ω)
• not usually possible due to dispersion.
• use a birefringent crystal with optic axis at angle θ :$
1 sin 2 θ cos 2 θ
= +
no (ω ) 2 ne ( 2ω ) 2 no ( 2ω ) 2

73
 Frequency doubling / tripling etc
nonlinear
• use a 2nd order nonlinear crystal crystal
266 nm
2ω, 4ω,
nonlinear
crystal
Nd:YAG laser ω, 2ω, 532 nm
1064 nm

2ω, 3ω,
355 nm
ω,
Figure 11.5 nonlinear
crystal

Electro-optic modulators
y
crossed
45° z polarizer
y' E-O crystal
E x
polarizer output
x'

V
input
• Linear electro-optic (Pockels) effect:
Field-induced birefringence: Δn ∝ rij E
• rij = electro-optic coefficient
≠ 0 for non centro-symmetric crystal
• Consider as χ(2) process with DC field
• Use to make intensity modulators Figure 11.6

74
 Third-order nonlinear processes
ω1
ω
ω2 ω1+ω2+ω3 ω ω
ω
ω3
(a) Four-wave mixing (c) Optical Kerr effect

ω, ω
ω, 3ω, ω ωs
ω, ωs

(b) Frequency tripling (d) Raman effect

Figure 11.7

Kerr cells
crossed crossed
Kerr polarizer Kerr polarizer
medium output medium
polarizer output
polarizer

input E V input

E
laser pulse
• Quadratic electro-optic effect:
Field-induced birefringence: Δn ∝ χ(3) E 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
Figure 11.8

75
 Nonlinear refractive index
Δεr = χ(3) E2
n(I) = n0 + n2 I
Δn = n2 I
⇒ n2 = χ(3) / n02 c ε0

• Third order nonlinear effects found in all materials

including isotropic media e.g. glasses, liquids, gases
• self-phase modulation: Δφ = 2 π Δn L / λ = 2 π n2 I L / λ,

• soliton: balance dispersion

and self-phase modulation
• propagation of high intensity
short pulses along optical fibres
Figure 11.9

Semiconductor nonlinearities
E Figs. 11.10-11 40
GaInAs/InP MQW
α (103 cm 1)

30
20 exciton
Eg 10 300 K
k
0
0.7 0.9 1.1 E (eV)
•  strong Pauli blocking when 8 6700
α(I) = + 2000
1 + I / 290
α (103 cm 1)

!% ~ Eg 6
⇒ saturable absorption 4
•  third order nonlinearity 2
•  excitonic enhancements E = 0.77 eV
0
•  see also Fig. 4.7 10 102 103 104 105
I (W cm 2)

76
 Fig. 11.12
Saturable absorption in quantum dots
Absorbance (units of 10–3)

15

Peak absorbance
10–2
10 3.5 µeV
10–3
5

0 10–4
1.26545 1.26550 1.26555 0.1 1 10 100 1000
Energy (eV) Power (nW)

N2
2
•  Tune laser to QD exciton uν
•  Behaves as saturable two-level atom 1
N1

77