Lecture 8: Topics from Quantum and Semiconductor Physics

• Quantum nature of light

• Energy levels and optical transitions
• Semiconductors
• Energy bands, direct and indirect bandgap
• Doping
• Carrier concentrations at thermal equilibrium
• pn junctions

Reading: Senior 6.2.1, 6.3.1

Keiser 2.1.3, 4.1

Ref: Physics of Optoelectronics, Michael A. Parker, Taylor and Francis Group, 2005
Lasers and Electro-Optics, Christopher Davis, Cambridge, 1996
Fundamentals of Photonics, Saleh and Teich, Wiley, 2007 1
 An overview
• LEDs and laser diodes consist of a
pn junction constructed of
direct- bandgap III-V materials.
• When the pn junction is forward
biased, electrons and holes are
injected into the p and n regions,
respectively.
• The injected minority carriers
recombine either radiatively (a
photon of energy hν is emitted) or The pn junction is
nonradiatively (the known as the active or
recombination energy is recombination region.
dissipated as heat).
2
 Quantum nature of light
•In dealing with the interaction of light and matter, such as the
emission and absorption of light, an electromagnetic wave
description of light is not adequate.
• Quantum theory indicates that optical radiation has particle
and
wave properties.
•The particle nature arises from the observation that light energy is
always emitted or absorbed in discrete units called quanta or
photons. The energy of a photon is determined by its frequency .
• Associated with the particle nature of a photon, there is a
momentum determined by its wavelength , or its wavevector k.
Energy E = h = hc/
For a photon in free space:
Momentum p = E/c = h/c = h/

where h = 6.625 x 10-34 Js is Planck’s constant. 3

 Particle-wave duality of photons

• A photon has energy: E = ħ

Particle nature
• Photon momentum: p = ħk

• Photon wavelength:  = 2/k

Wave nature
• Photon speed: c = /k

where ħ = h/2

4
 Energy levels
• The electrons that are bound within the atoms,
molecules, ions of a medium can occupy only certain
discrete energy levels.
• The medium may be gaseous, liquid, a crystalline or
glassy solid, an insulating material or a semiconductor.
• Electrons can make jumps (transitions) between these
levels.

Electron energy E2

e- E1
5
 Photon-matter interaction processes
• There are three fundamental processes electrons make
transitions between two energy levels upon a photon of energy

E = h12 = E2 – E1

6
Relating fundamental processes to technology
+ - -
h h h
i i i

- + +

Photodiode Light-emitting diode Laser diode

7
 Section of the periodic table relating to semiconductors

II III IV V VI
B C N O
Al Si P S
Zn Ga Ge As Se

Cd In Sn Sb Te

Hg
• The “column” number represents the number of valence
electrons
(e.g. column IV has four valence electrons)
•semiconductors
We will discussand
elemental, binary,
also doped ternary, quaternary
semiconductors. 8
 Elemental semiconductors
• Silicon (Si) and germanium (Ge) are important elemental
semiconductors in column IV (so called Group IV) of the periodic table.

•Nearly all commercial electronic integrated circuits and devices are

fabricated using Si (CMOS).

•Both Si and Ge find widespread use in photonics, principally as

photodetectors (Si for  < 1.1 m, Ge for  < 1.9 m), Si-based
solar cells, CCD cameras and CMOS cameras.

• These materials have traditionally not been used as light emitters

because of their indirect bandgaps.
(Technology note: Silicon and Ge-based Group IV photonics is now a
frontier research field attracting lots of attention. Ge-on-Si light
emission and laser has been recently demonstrated in 2009/10.) 9
 Binary III-V semiconductors

•Compounds formed by combining an element in column III (three

valence electrons), such as aluminum (Al), gallium (Ga) or indium (In),
with an element in column V (five valence electrons), such as
nitrogen (N), phosphorus (P), arsenic (As), or antimony (Sb),
are important semiconductors in photonics (light-emitting diodes,
lasers, detectors) (e.g. gallium arsenide (GaAs), gallium nitride
(GaN)).

N
Al P

Ga As

In Sb 10
 Gallium arsenide (GaAs)

• Silicon represents a prototypical material for electronic

devices.

• Gallium arsenide (GaAs) represents a prototypical direct

bandgap material for optoelectronic components.

• Aluminum and gallium occur in the same column III of

the periodic table.

=> we therefore expect to find compounds in which an

atom of aluminum can replace an atom of gallium.
Such compounds can be designated by AlxGa1-xAs

11
 Ternary III-V semiconductors

• Compounds formed from two elements of column III with one

element from column V (or one from column III with two from column
V) are important ternary semiconductors.

•AlxGa1-xAs is a compound with properties that interpolate between

those of AlAs and GaAs, depending on the compositional mixing
ratio x (the fraction of Ga atoms in GaAs that are replaced by Al
atoms).

•The bandgap energy Eg for this material varies between 1.42 eV for
GaAs and 2.16 eV for AlAs, as x varies between 0 and 1.

• InxGa1-xAs (direct bandgap material) is widely used for photon

sources 12

and detectors in the near-infrared region of the spectrum.

 Quaternary III-V semiconductors
•These compounds are formed by mixing two elements from column
III with two elements from column V (or three from column III with
one from column V).

•Quaternary semiconductors offer more flexibility for fabricating

materials with desired properties than do ternary semiconductors
by virtue of an additional degree of freedom.

• In1-xGaxAs1-yPy, bandgap energy varies between 0.36 eV (InAs)

and
2.26 eV (GaP) as the compositional mixing ratios x and y vary between
0 and 1. In1-xGaxAs1-yPy is used for fabricating light-emitting diodes,
laser diodes, and photodetectors, particularly in the vicinity of the
1550 nm.
 Light-emitting semiconductors
•A desired bandgap energy Eg, (i.e. the radiating wavelength), is
typically created by using III-V compound semiconductors comprised of
several components.
material wavelength range (m) Bandgap energy (eV)

GaxIn1-xP 0.64 – 0.68 1.82 – 1.94

GaAs 0.87 1.42

AlxGa1-xAs 0.65 – 0.87 1.42 – 1.92

1.0 – 1.3 0.95 – 1.24

InxGa1-xAs
0.9 – 1.7 0.73 – 1.35
InxGa1-
*Silicon is not an emitter material, as its holes and electrons do not
xAsyP1-y
recombine directly, making it an inefficient emitter. 14
 Bandgap energy and wavelength
• The energy of a photon of frequency  is

E = h = hc/ = (1239.8 eVnm)/

where h = 6.625 x 10-34 Js is the Plank’s constant.

• The characteristic wavelength associated with the

bandgap energy is

 = hc / Eg

e.g. Eg of GaAs = 1.42 eV,  = 876 nm 15

 Bands as closely spaced energy levels
• When atoms combine to form a solid the sharply
defined energy states that we associate with free atoms
broaden considerably because of the large number of
interactions between an atom and its neighbors.
=> a series of broad energy states, called bands
• The energy states of the outermost electrons of the
atoms constituting the solid broaden and combine to
produce a band of filled energy states called the valence
band.
• Excited energy states of the atoms broaden and
combine to give rise to a series of excited energy bands,
which at absolute zero are empty.
• The lowest, empty energy band is called the conduction
band.
• These two bands are separated by an energy gap, or
band gap.
16
 Energy-band diagram

Conduction band discrete Conduction band discrete

Electron’s energy

Electron’s energy
e- levels
levels
band band
gap Eg gap Eg

discrete holes discrete

Valence band Valence band levels

Tlevels
=0 T>0
• A perfect material containing no impurities is called an intrinsic
material.
• At finite temperatures, electrons are excited from the valence band
to the conduction band, leaving behind “vacancies” or empty
states (holes) in the valence band.
• In an intrinsic material, no energy levels exist within the bandgap.
i.e. one would not expect to find an electron with energy within the
bandgap. 17
 Metal, semiconductor, insulator

• It is the extent of the energy gap that determines

whether a solid is a metal, semiconductor or an insulator.

• Semiconductor --- the energy gap usually extends over

less than about 3 eV (electron-volts).

• Metal --- the upper band is populated with electrons

• Insulators --- have a large energy gap – usually larger

than 3 eV

18
Band diagrams for metals, semiconductors and insulators
Higher lying Higher lying
Conduction band unfilled unfilled
band band

Conduction band
Eg Conduction band

Eg

Valence band Valence band Valence band

insulator metal semiconductor

19
 Simple illustration of a semiconductor crystalline lattice

Using Group IV (Si) as an example

e-
Si

Silicon in column IV requires four extra electrons to fill the

orbital. However, silicon already has four electrons.
=> we therefore expect one silicon atom to covalently bond to four
other silicon atoms
Covalent bonds share valence electrons rather than completely
transferring the electrons to neighboring atoms (as for ionic
bonding).
20
 Thermal excitation
• As the temperature is raised, some electrons in the
valence band gain enough energy from thermal
vibrations of the crystal atoms to be excited to the
conduction band. (thermal excitation)
• For Si this excitation energy must exceed 1.1 eV, which
is the band-gap energy.
• This gives rise to a concentration n of free electrons in
the conduction band, which leaves behind an equal
concentration p of vacancies, or holes, in the valence
band.
Electrons e-
e-
Holes h+ Eg
h+

21
 Holes – the vacancies in the bonding
• The vacancies left behind are “holes” in the bonding.

• Unlike electrons which are real particles, holes are

“quasi” particles --- we cannot isolate a hole in free
space (i.e. we do not have a beam of “holes”)

e- v

An electron beam in free space (e.g. in your old CRT)

h+
There is no “hole
beam”
22
 Holes – the vacancies in the bonding
• But the concept of holes gives a convenient picture to
represent the vacant state in the bonding (in a partially
filled valence band).

• Rather than describing how the many electrons in

the bonding behave, we describe only the
missing few.

• Useful in understanding conductivity due to the valence

electrons in the bonding,

• And the effect of free electrons colliding with such

vacancies in the bonding --- the “recombination” of the
free electrons and the vacancies in the bonding,
releasing energy in the form of photons or heat (causing
lattice vibration) 23
Both free electrons and holes conduct currents
• Both the free electrons and holes are mobile within the
material, so that both can contribute to electrical
conductivity.
• An electron in the valence band can move into a vacant
hole – this action makes the hole move in the opposite
direction to the electron flow.

e-

h+

24
position
 Particle nature of electrons: electron momentum
and effective mass
• When an electric field is applied to a semiconductor
electrons in the conduction band acquire directed
velocities v.
• These velocities are in the opposite direction to the
applied field because the electrons are negatively
charged.
• Each electron moving in a material has
momentum

p = m*v

• The mass m* indicates that this is the effective mass of

an electron moving in the lattice.
• m* is not the same as the free electron mass (electron
mass in free space) because of the wave / particle dual25
lattice (scattering).
character of the electron and its interaction with the
Wave nature of electrons: electron wavelength and
wave vector
• The momentum can be related to the wavelength of the
electron, viewed as a wave given by de Broglie relation

p = m*v = h/

• The “wave vector” k of the electron (think of electron as

plane wave) has magnitude

k = 2/

• We can relate electron momentum p and wave vector k

p = ħk

where ħ = h/2 26
 Electron kinetic energy vs. wave vector
• The moving electron has kinetic energy KE.
• We can relate the electron kinetic energy KE,
momentum p and wave vector k

KE = ½ m*v2 = p2/2m* = ħ2k2/2m* 

k2
from classical
mechanics KE

parabolic

k 27
 Total energy of a conduction electron
• The total energy (potential + kinetic) of a conduction
electron

E = PE + KE

= Eg + ½ m*v2

= Eg + p2/2m*

= Eg + ħ2k2/2m*

• Therefore, the E vs. p plot (or E vs. k plot) has a

parabolic shape. We refer to this energy diagram
as a band diagram.
28
 E vs. k plot for the conduction electron

parabolic

KE
PE = Eg
k
• If the electron receives just enough energy to surmount
the band gap, then it does not have energy to be moving
and the momentum p = 0 (or electron wave vector k =
0)
i.e. the minimum energy of a conduction electron equals
Eg.
29
 Holes can have kinetic energy
• Recall that the holes in the valence band can move =>
can have kinetic energy.
• A plot of the kinetic energy vs. momentum also has a
parabolic shape for the holes

E = p2/2mh
Effective mass
of the hole
• The valence band has a parabolic shape similar to the
conduction band.

• But the effective mass of electrons in the valence

band is
negative indicating a missing electron or a vacancy
=> The valence band parabolic shape has a downward 30
curvature.
 Band diagram with a direct bandgap
E (= ħ) E (=
ħ)

Eg
p (= ħk) p (= ħk)

Temperature = 0 Temperature > 0

• The top of the valence bands is typically taken as the reference level.
• The bottom of the conduction band is located at a higher potential
corresponding to the energy gap.
• For direct bandgap materials (e.g. GaAs), the conduction band
minimum lines up with the valence band maximum. 31
 Discrete distribution in momentum space
• Allowed states have definite energy assignments.
• Now we must consider how the allowed states are
distributed in momentum space (k space).
• This is important in optical transitions as we must
conserve both energy and momentum.
• Consider electrons are waves contained in a crystal of
side L with perfectly reflecting walls (a cubical “box”)
• In quantum mechanics we refer to this as a “square
well” potential with an “infinite barrier” and a width of L.
• The electron wave vector k can have the discrete
values

k = n(/L), where n = 1, 2, 3, …

k = 2/ => 2L =
• These are electron standing waves in a crystal! 32
 Discrete electron wave vector
E (= ħ)

p (= ħk)
/L

• Each value of “k” labels an available electron state in

either the conduction or valence band.
34
 Band diagram with an indirect bandgap
• A material having an indirect bandgap occurs when the
minimum and the maximum do not have the same
value of the wave-vector k (e.g. silicon)
• For both direct and indirect bandgaps, the difference in
energy between the minimum of the conduction band
and the maximum of the valence band gives the
bandgap energy.
E (= ħ) E (= ħ)

Eg Eg
p (= ħk) p (= ħk)

37
Temperature = 0 Temperature > 0
 Doping
• Adding impurity atoms to replace atoms in the host
crystal can affect the electronic and optical properties of
the host material.
• E.g. Doping can be used to control the conductivity
of a host crystal.
• n-type dopants have one extra valence electron than the
material itself.
• E.g. phosphorus (5 valence electrons) is an n-type
dopant for silicon. Not all phosphorous valence
electrons participate in bonding, and the extra valence
electron can freely move about the crystal upon very
small thermal energy.
• p-type dopants have one less electrons in the valence
shell than atoms in the host material.
• E.g. boron (3 valence electrons) is a p-type dopant for
silicon
• Charge neutrality of the material is not altered by the
38
introduction of dopants.
 Doped semiconductors: n-type and p-
type
Using Group IV (Si) as an example

•n-type silicon (doped Si

with Group V
P e-
dopants, phosphorous) e-
P
Electrons as majority
carriers

•p-type silicon (doped

with Group III h+
Si
dopants, boron)
h+ B
Holes as majority
carriers B
39
 Majority and minority carriers

• As the electrical conductivity is proportional to the

carrier concentration, two types of charge carriers
are defined for this material:

1. Majority carriers refer either to electrons in an n-type

material or to holes in a p-type material
2. Minority carriers refer either to holes in an n-type
material or to electrons in a p-type material

The operation of semiconductor devices is essentially

based on the injection and extraction of minority
carriers.
42
Approximated E-k diagrams for Si and GaAs

E E

1.42 eV
1.12 eV
k k

Si GaAs

mc = 1.08 mo mc = 0.067 mo
mv = 0.56 mo mv = 0.52 mo
71
 Built-in electric field
• When the two chunks of material are combined, the
electrons can easily diffuse from the n-type material to the
p-type material; similarly, holes diffuse from “p” to “n”.
This establishes equilibrium for the combined system.

• The diffusing electrons attach themselves to the p-

dopants (ionized acceptors) on the p-side but they leave
behind positively charged cores (ionized donors).

• The separated charges, known as space charges, form a

dipole layer. The direction of the built-in electric field
prevents the diffusion process from indefinitely continuing.

• Electrons on the n-side of the junction would be required

to surmount the energy barrier to reach the p-side by
diffusion =>energy would need to be added to the
electron 73
 Diode equation
• If we neglect recombination in the space charge region
(known as the Shockley ideal diode approximation), we
can consider that each injected electron reaching –xp0
must pass through xn0.
=> the total diode current I at xn0 can be calculated
as the sum of Ip(xn = 0) and –In(xp = 0):

I = Ip(xn =0) – In(xp=0)

= qA[(Dp/Lp) pn + (Dn/Ln) np] (exp(qV/kBT) – 1)

= I0(exp(qV/kBT) – 1)

• This is the diode equation. The bias voltage V can

be 94
positive (forward bias) or negative (reverse bias).
Current-voltage (I-V) curve of an ideal diode

I = I0(exp(qV/kBT) – 1)

+V
-

V
-I0

-V
+

95