Review of Optical Properties of Materials

Review of optics

Absorption in semiconductors: qualitative discussion

Derivation of Optical Absorption Coefficient in Direct

Semiconductors
 Photons
• When dealing with events on the atomic scale, it is often
best to regard light as composed of quasi- particles
PHOTONS
Photons are Quanta of light
Electromagnetic radiation is quantized
& occurs in finite "bundles" of energy 
Photons
– The energy of a single photon in terms of its frequency , or
wavelength  is,
Eph = h = (hc)/
Maxwell – Electromagnetic Waves
 Light as an Electromagnetic Wave
• Light as an electromagnetic wave is characterized
by a combination of a time-varying electric field
(E) & magnetic field (H) propagating through
space.
• Maxwell’s equations give the result that both E &
H satisfy the same wave equation:

1  2
  E, H   2  2   E, H 
2

c  t 
Changes in the fields propagate
through space with speed c.
 Speed of Light, c
• Frequency of oscillation, of the fields and their
wavelength, o in vacuum are related by;
– c = o
• In any other medium the speed, v is given by;
– v= c/n = 
• n = refractive index of the medium
•  = wavelength in the medium
• And, n   r  r
• r = relative magnetic permeability of the medium
• r = relative electric permittivity of the medium

The speed of light in a medium is related to the

electric and magnetic properties of the medium,
and the speed of light can be expressed as
 Electromagnetic Spectrum
Shorter wavelength

Larger
Photon
Energy (eV)

Longer wavelength
 Interaction Between Light & Bulk Material
Many different possible processes can occur!

Scattering
3c “Semi-transparent”
material 1- Refraction
Incident light 2- Transmission
4 3a – Specular reflection
1
3b – Total internal
reflection
3a
3b 3c – Diffused reflection
4 Dispersion –where
2 different colors bend
differently
 Refraction, Reflection and Dispersion

Light when it High n

travels in a Small n
medium can be
absorbed and
reemitted by every n1 = refractive index of
atom in its path. material 1
n2 = refractive index of
Determined by refractive index; n
material 2
 Total Internal Reflection
Transmitted
(refracted) light
kt
t n2 Evanescent wave
n 1 > n2
ki i i kr c c i > c
TIR
Incident Reflected
light light
(a) (b ) (c)

Light wave travelling in a more dense medium strikes a less dense medium. Depending on
the incidence angle with respect to  c, which is determined by the ratio of the refractive
indices, the wave may be transmitted (refracted) or reflected. (a) i < c (b)  i = c (c) i
>  c and total internal reflection (TIR).

© 1999 S.O. Kasap, Optoelectronics (Prentice Hall)

 Mechanism and Application of TIR
Optical fibre for
communication

What sort of materials do

you think are suitable for
fibre optics cables?
 Review of optical processes

Energy levels are everything in quantum mechanics.

Excited level

 E = h

Energy
Ground level

The atom is vibrating The atom is at least partially in

at frequency, . an excited state.
 Review of optical processes
Before After

Spontaneous
emission

Absorption

Stimulated
emission
• Recall: Semiconductor Bandgaps Eg are
usually in the range: 0 < Eg < 3 eV
(up to 6 eV if diamond is included)
• Also, at equilibrium, at temperature T = 0, the valence
band is full & the conduction band is empty.
• Now, consider what happens if electromagnetic
radiation (“light”) is shined on the material.
• In the photon representation of this radiation
If hν  Eg, some
electrons can be promoted to the conduction band
leaving some holes in the valence band.
• Consider various types of spectra associated with this process:
• Absorption:
– Looks at the number of absorbed photons (intensity) vs. photon frequency ω
• Reflection:
– Looks at the number of reflected photons (intensity) vs. photon frequency ω
• Transmission:
– Looks at the number of transmitted photons (intensity) vs. photon frequency ω
• Emission:
– Looks at the number of emitted photons (intensity) vs. photon frequency ω
• Each of these types of spectra are
rich, complicated, & varied!
• Understanding such spectra gives
huge amounts of information
about electronic energy bands, vibrational properties, defects,
 Appearance of insulator, metal and
semiconductor
 Appearance in terms of color depends on the interaction between the
light with the electronics configuration of the material.
 Normally,
 High resistivity material: insulator  transparent
 High conductivity material: metals  metallic luster and opaque
 Semiconductors  colored, opaque or transparent, color
depending on the band gap of the material
 For semiconductors the energy band diagram can explain the
appearance of the material in terms of luster and color.
Question: Why is Silicon Black and
Shiny?
Answer.
 Need to know, the energy gap of Si
 Egap = 1.2eV
 Need to know visible light photon energy
 Evis ~ 1.8 – 3.1eV
 Evis is larger than Silicon Egap
 All visible light will be absorbed
 Silicon appears black
 Why is Si shiny?
 Significant photon absorption occurs in silicon, because there are
a significant number of electrons in the conduction band. These
electrons are delocalized. They scatter photons.
Colors of Semiconductors
Evis= 1.8eV 3.1eV

I B G Y O R

•If Photon Energy, Evis > Egap  Photons will be absorbed

•If Photon Energy, Evis < Egap  Photons will be transmitted
•If Photon Energy is in the range of Egap ;
•Those with higher energy than Egap will be absorbed.
•We see the color of the light being transmitted
•If all colors are transmitted = White
Why is glass transparent?
 Glass is an insulator (huge band gap)
 The electrons find it hard to jump across a big energy gap:
Egap >> 5eV
 Egap >> E visible spectrum ~ 3.1- 1.8eV
 All colored photons are transmitted, no absorption, hence light transmission –
transparent.
 Defined transmission and absorption by Lambert’s law:
 I = Io exp (- l)
 I = incident beam
 Io = transmitted beam
  = total linear absorption coefficient (m-1)
  = takes into account the loss of intensity from both scattering centers
and absorption centers.
  = approaching zero for pure insulator.
 What happens during
photon absorption process?
Photon interacts with the lattice
Photon interacts with defects
Photon interacts with valance electrons
Absorption – an important phenomenon in describing
optical properties of semiconductors

 Light, being a form of electromagnetic radiation,

interacts with the electronic structure of atoms of a
material.
 The initial interaction is one of absorption; that is,
the electrons of atoms on the surface of a material
will absorb the energy of the colliding photons of
light and move to the higher-energy states.
 The degree of absorption depends, among other
things, on the number of free electrons capable of
receiving this photon energy.
Absorption Process of Semiconductors

 The interaction process is a characteristic of a photon and depends

on the energy of the photon
 Low-energy photons interact principally by ionization or
excitation of the outer orbitals in solids’ atoms.
 Light of low-energy photons (< 10 eV) is represented by infrared
(IR), visible light, and ultraviolet (UV) in the electromagnetic
spectrum.
 High-energy protons (> 104 eV) such as x-rays (and gamma rays)
scatter mainly elastically and are used for structure determination
 The minimum photon energy required to excite and/or ionize the
component atoms of a solid is called the absorption edge or
threshold.
 Absorption Process of Semiconductors

Wavelength (m)
Vis
UV IR
Absorption coefficient (), cm-1

Important region:

Eg ~ vis

Photon energy (eV)

Absorption spectrum of a semiconductor.
 Valance-Conduction Absorption

Process requires the

lowest E of photon to
initiate electron
Conduction band,
jumping (excitation)
EC
• EC-EV = h
• EC-EV = Egap
• If h > Egap then h Ephoton
transition happens Egap
•Electrons in the
conduction band and
excited.
Valance band, EV
Absorption
 Types  Direct and Indirect photon absorption
 For all absorption process there must be:
 Conservation of energy
 Conservation of momentum or the wavevector

 The production of e-h pairs is very important for

various electronics devices especially the
photovoltaic and photodetectors devices.
 The absorbed light can be transformed to current
in these devices
 Direct Band Gap
E

Direct Conservation of E
vertical
h = EC(min) - Ev (max) = Egap
transition

K (wave number)
h
Momentum of Conservation of wavevector
photon is
negligible Kvmax + photon = kc
Interband absorption in indirect gap semiconductors

Indirect-gap semiconductor: highest occupied and lowest unoccupied state have k≠0

Direct transitions possible for k0

 strong direct interband absorption
occurs at E > Egap

Egap Other possibility: momentum and

energy can be conserved by photon
absorption and simultaneous absorption or
emission of a phonon:

Indirect transitions possible with

‘assistance of a phonon’

Shown here are optically induced transitions

Egap - during phonon emission
a phonon is generated in the process
- during phonon absorption
a phonon is generated in the process
Excitons

Excitons are combined electron-hole states:

A free electron and a free hole (empty electronic state in the valence band)
exert Coulomb force on each other:

hydrogen-like bound states possible: excitonic states

n=3
E
n=2 Eb is the exciton
n=1
binding energy =
h
Coulomb
force energy released upon
e exciton formation, or
Eb
energy required for
k exciton breakup

Wave functions of electron and hole look similar to free electron and free hole
Note: exciton can move through crystal, i.e. not bound to specific atom!
Excitonic absorption

Light can excite an electron from the valence band and generate an exciton
at energies slightly below the bandgap
 see absorption at Ephot = Egap – Eb (absorption slightly below Egap)

Eb

Exciton binding energy on the order of a few meV

Thermal energy at room temperature: kT ~ 25 meV
 exciton rapidly dissociates at room temperature
 absorption lines broaden / disappear for higher temperatures
Optical transitions related to dopant atoms

Ga: 3 valence electrons

Si: 4 valence electrons
As: 5 valence electrons
Donor levels

Substitute Si atom with As atom (impurity atom in the Si lattice):

weakly bound extra valence electron

Low T

Low T: donors neutral, electron weakly bound

low energy light can excite donor electron in to conduciton band

Binding energy Ed similar to kT at room temperature (‘RT’):

At room temperature the bound electron is quickly released
 impurity mostly ionized at RT : Arsenic is a donor in Si RT

At RT such transitions are typically too broad to observe

Acceptor levels

Substitute Si atom with Ga atom : empty electronic state just above the Si
valence band: at finite temperature, Si valence electron may fill acceptor level
 location of unoccupied valence state (hole) can orbit the charged Ga dopant

‘hole’ =
available
electron
state

Binding energy Ea similar to kT at room temperature (‘RT’):

At room temperature the hole can leave the dopant,
producing a ‘free charge’
Infrared absorption due to dopants

Dopant binding energies low: donor level related absorptions invisible at RT,
but observable at low temperatures
Example: direct valence band → acceptor level absorption in boron doped Si

Transition at ~40 meV  absorption at 30 m : infrared

Dopant related transitions

Possible dopant related transitions:

Typically visible at low T, but not clearly observable at RT

Free carrier absorption

At RT, predominant dopant related absorption is free carrier absorption

in which a photon excites an electron into a higher lying state
Example: p-type semiconductors: filled states in the conduction band:
optical transitions possible at Ephot < Egap !

Free electrons:
absorption typically indirect
phonon-assisted transition

Free holes can make direct transitions

from the heavy-hole band
to the light-hole band
 holes cause stronger free carrier
absorption than electrons
Free carrier absorption

Free electron absorption can be described by the Drude model

Dopant levels in semiconductors range from ~1014 - 1018 /cm3
which is ~108 – 104 lower than free electron densities in metals
Plasma frequency of doped semiconductors 104 - 103 lower than of metals: IR

At frequencies above plasma frequency, εr is complex and  is described by

 p2  p2  p2 
 r ' ( )  1  2 ,  r " ( )  3  3
  

  p2   2
 ( )   " ( )  
c c 2
c 2p

Electron FCA up for lower energies

Free hole absorption less well defined
 Derivation of Optical Absorption
Coefficient in Direct Semiconductors

Chuang Ch. 9
 Outline of derivation
•Absorption Coefficient:  (  )
I ( , z )  Io ( , z )e  (  ) z

•Examples: lasers, solar cells, etc.

•Time-dependent perturbation
poly-Si Solar Cells
•Fermi’s Golden rule
•Direct-gap net absorption rate
•Absorption Coefficient & Simplifications
 Fermi’s Golden Rule

2 ' 2
Wi f  Hfi ( (Ef  Ei   )   (Ef  Ei   ))


Ef Ei
 

Ei Ef

Absorption Emission
 Direct-Gap Net Absorption Rate
Ec E
2 2π
Rvc   H 'cv δ(Εc  Εv   )fv 1  fc 
2

V kv kc 

Assumptions:
k kv = kc = k
Undoped, low excitation
Ev
fv = 1, fc = 0
2k 2
Ev   2 2π
 
2
2mh* Rabs H 'cv δ(Εc  Εv   )
V k 
2k 2
Ec  E g 
2me*
 Absorption Coefficient
Rabs (no. of photons absorbed per second per unit volume)
 ( ) 
P /  (no. of injected photons per second per unit area)

 2 2π

2
 H 'cv δ(Εc  Εv   )
(nr c o Ao / 2) V k 
2 2


•How to find H’cv? H 'cv   ψ H' (r )ψ v d r
*
c
3

2

H (r , t ) 
1
2mo
  
pˆ  eA  V (r )

 eAo
H ' (r )   eˆ  pˆ
2mo Momentum matrix element

πe 2 2  2
 (  )  
nr c o mo  V k
2
eˆ  pcv δ(Εc  Εv   )
 More Practical Form
πe 2  2 V 2k 2
k V 2 3 δ(Eg  2m   )  k 
2 3
 (  )n c m 2 e  pcv
ˆ
r o o   r


πe 2  2 2 2k 2
 eˆ  pcv   2 3 g 2mr
   3
δ(E  )d k
nr c o mo 
2

•Using E-k (dispersion) relationship:

 3/2
πe 2  1  2mr 
 k 
2
 2 2  2 
1/ 2
 (  )  eˆ  pcv δ(Eg   k   )d  k
nr c o mo 
2

3/2
1  2mr 
NJ ( k )  k
2 2   2 
πe 2  2 mo E g  1 
 (  )  eˆ  pcv NJ (   Eg ) p 
2
  1
nr c o mo 
2 cv
2  me 
 Conclusions
Absorption Coefficient at 5K
•Example: InSb
•Eg = 0.17eV
•Different for 2D,1D,0D
•Density of States

•Not 100% accurate

•Parabolic band
approximation
•nr depends on
Yu, Cardona: p. 260 wavelength
Red: calculation at 300K •Exciton absorption
below bandgap