ES2B3 Electronic Materials

MODULE STRUCTURE

This part of the course consists of 5 lectures (Week 15-19) and a

laboratory (Hall effect)
Lecture 1:
Lecture 2:
Lecture 3:
Lecture 4:
Lecture 5:

A bit of Quantum theory

Semiconductors
Magnetic Electronic materials
Optical Electronic materials
Electronic materials in an Electrical field

Recommended text for the course:

Copies in the library

Warning, the latest issues are priced at 150+
Older issues MUCH cheaper!

ES2B3 Electronic Materials

Well worth a read:

ES2B3 Electronic Materials

A good reference:

ES2B3 Electronic Materials

Well worth a read:

ES2B3 Electronic Materials

ES2B3 Electronic Materials

Lecture 1: A bit of Quantum theory

ES2B3 Electronic Materials

A Sense of Scale

Quantum Mechanics

ES2B3 Electronic Materials

To describe things that are very

small requires quantum
mechanics.
The Heisenberg uncertainty
principle:
The more precisely we know the
position of an object, the worse we
know its momentum.

To describe anything as small as an

atom requires the use of
quantum mechanics.
To understand electronic materials Heisenberg in 1925, at the age of 24
we need to think at the atomic
level!

ES2B3 Electronic Materials

Relativity
To describe things moving very fast
requires the theory of relativity.
Special Relativity
We cannot catch up with light.
Mass is a form of energy.

E = m c2
General Relativity
GR encompasses gravity and
describes the expanding universe
and black holes.

Not needed for the course, but

needs mentioning!
Einstein in 1905, at the age of 26

ES2B3 Electronic Materials

Schrdinger
light and particles are both waves
and particles
Want to think of particles or
systems (e.g. a lump of
silicon!) in terms of waves
Talk about probability
functions
Schrdingers theory allows us to
start to do this!
Wont go into Schrdinger in this
course in any detail!

Schrodingers atom

Dispensed with the concept of the

particle
Focussed on the wave-like
properties of matter
Picture has electron standing waves
as orbits
Actually in 3-D
2-D pictures shown here

ES2B3 Electronic Materials

Our present theory of particle physics:

The Standard Model

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This is a grand intellectual

achievement of the second
half of the 20th Century

The theory is based on

relativistic quantum field
theory (QFT).
The first QFT was the quantum
theory of electricity and
magnetism.
Way, way beyond the scope of
this course!
Feynman ca. 1960

ES2B3 Electronic Materials

Heisenbergs uncertainty principle:

The more precisely the position is
determined, the less precisely the
momentum is known in this instant,
and vice versa.
--Heisenberg, uncertainty paper,
1927
1
xp x
2
(Uncertainty in position times uncertainty in momentum is
greater than or equal to a constant)

ES2B3 Electronic Materials

Heisenberg Uncertainty Principle: Example

Consider an electron in the lowest-energy state of a hydrogen atom; its position is
known to an accuracy of about 0.05 nm (the radius of the atom). What is the
minimum range of its possible momenta? Velocity?

Solution:
xp

Heisenbergs uncertainty principle (with = h/2p).

p /x

= 1.0510-34 Js.

= 2.110-24 Js/m

= 2.110-24 kg-m/s
v= p/me
= 2.3106 m/s

me = 0.9110-30 kg.

ES2B3 Electronic Materials

Uncertainty Principle Implications

The uncertainty principle explains why (negative) electrons in
atoms dont simply fall into the (positive) nucleus: If the
electron were confined too close to the nucleus (small x), it
would have a large p, and therefore a very large average
kinetic energy ( (p)2/2m).

The uncertainty principle does not say everything is

uncertain. Rather, it tells us very exactly where the limits of
certainty lie when we make measurements of quantum
systems.

Bohrs Atomic Model

Niels Bohr proposed an

atomic model that suggested
that electrons orbit the
nucleus, much like the Earth
revolving around the Sun.
These orbitals (the path by
which the electrons orbit the
nucleus) had fixed distances
and fixed energies.
The orbitals closest to the
nucleus have the lowest
energy, and the orbitals
furthest away from the
nucleus have the greatest
energy (like a SPRING)

ES2B3 Electronic Materials

Bohrs Electron Shells and

Principal Quantum Numbers

ES2B3 Electronic Materials

Bohr assigned his quantized electron orbits, which he called shells, a

number, n. This number is known as the principal quantum number. As
the number grew larger, the shell got further and further away from the
nucleus.
Bohr also stated that:
The energy of each shells grew as n grew larger.
Each shell can hold a maximum of 2n2 electrons
As we try to determine where the electrons in an atom are, we should
fill the shells from the innermost shell (n=1) to the outermost shell
(n=4) (most of the time, although it can equal 5, 6, 7, 8, etc.)
Any atom with its electrons in their lowest energy levels is said to be in its
ground state

ES2B3 Electronic Materials

Orbital occupancy for the first 10 elements, H through Ne.

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Using the Periodic Table to Fill Subshells

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Valance Shells, Energy, Ground states and Excited States

A valance shell is the outermost occupied shell of an atom. Valence
electrons are, therefore, the electrons occupying that shell.
This valence electron determines the chemical and electrical
characteristics of the element
Core electrons are the electrons in the filled inner (core) shells.
The energy of the atom increases as n increases, and as the shells are
not completely filled.
The ground state refers to the configuration of electrons in an atom
that results in the lowest possible energy.
An excited state refers to when an electron jumps to a higher energy
shell even though the lower energy shells are not completely filled.

ES2B3 Electronic Materials

Another Way of Looking

at the Hydrogen
Spectrum:
Electrons dropping from
one level to another give
out light with the energy
of each photon equal to
the difference in the
electronic energy levels

ES2B3 Electronic Materials

What happens when we look at a solid? - Lithium (3

electrons)
Single atom has 2 electrons in 1s, and 1 in 2s
Know Lithium is a metallic solid
Think of a solid; it will have N electrons (Lots:~1023) in N 2s
orbitals
As the atoms are brought together, the energy levels split into
N levels finely separated
This is a consequence of the Pauli exclusion principle
Maximum energy spread between the energy levels when the
atoms are spaced at an inter-atomic distance, a
These N energy levels form an energy band

ES2B3 Electronic Materials

ET

EB

solid(N)

2p

E2p

FULL EMPTY

Electron Energy in the

System of N Li Atoms

System of N Li Atoms

2s

solid(1)
1s
a
Solid

E2s

SYSTEM
N Li Atoms
N Electrons
N Orbitals
2N States

E1s

Interatomic
Separation (R)

Isolated Atoms

Fig. 4.8: The formation of a 2s-energy band from the 2s-orbitals

when N Li atoms come together to form the Li solid. The are N
2s-electrons but 2N states in the band. The 2s-band therefore is
only half full. The atomic 1s orbital is close to the Li nucleus and
remains undisturbed in the solid. Thus each Li atom has a closed
K-shell (full 1s orbital).
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

We call this the 2s energy band

1s band is, of course full!
Because N is so big, then we think of the band as a
continuum
About 10eV between the top and bottom of the band
Other levels also split, and some overlap the 2s energy
band (fig. 4.9)
This forms a band that stretches from the bottom of the 2s
level up to the vacuum (free electron) level
The higher levels (3d, 4s etc) have energies above the
vacuum level, so arent occupied

Free electron
E = 0 (Vacuum Level)

FULL EMPTY

Electron energy

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E3s
E2p
E2s
E1s
R=a

The Solid

R=

Interatomic
Separation (R)

Isolated Atoms

Fig. 4.9: As solid atoms are brought together from infinity, the
atomic orbitals overlap and give rise to bands. Outer orbitals overlap
first. The 3s orbitals give rise to the 3s band, 2p orbitals to the 2p
band and so on. The various bands overlap to produce a single band
in which the energy is nearly continuous.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

At absolute zero, electrons fill all the lower levels, from EB

up to EFO, the Fermi Level
Need to know what reference you use for the energy levels
Fermi level measured relative to the bottom of the band,
and called the Fermi energy, 4.7eV for Li
Energy needed to promote an electron from the Fermi level
to the vacuum level is the Work Function () of the metal
Above 0K, electrons are excited above the Fermi level by
heat
Electrons arent bonded to a specific atom, and occupy a
gas or sea around the atoms
Means that the electrons are represented by a travelling,
not a localised wave-function
Each electron has a wave-vector, k, and its momentum is
k

ES2B3 Electronic Materials

Electron outside
the metal

Electron Energy

Vacuum
Level
Electron inside
the metal
E

EB

7.2 eV

-2.5 eV

4.7 eV

-7.2 eV

Empty levels

F0

EF0

Levels occupied
by electrons

Fig. 4.11: Typical electron energy band diagram for a metal All
the valence electrons are in an energy band which they only
partially fill. The top of the band is the vacuum level where the
electron is free from the solid (PE = 0).
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

If we think of a sea of electrons, then all of their energy

is kinetic
Energy of an electron increases with its momentum, p, as
p2/2me
Electrons take on all momentum values until their energy
reaches EFO
Average momentum is zero, and there is no net current
As Temperature increases, must consider what happens to
the distribution of electrons throughout the energy levels,
leads to the idea of the Fermi-Dirac function Fig. 4.26

ES2B3 Electronic Materials

T2 > T1
T=0
EF
T1

1
/
2

f(E)

Fig. 4.26: The Fermi-Dirac function, f(E), describes the

statistics of electrons in a solid. The electrons interact with
each other and the environment so that they obey the Pauili
Exclusion Principle.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

Semiconductors
(What youve all been waiting for!)
Si has 14 electrons
The electrons in Si atoms strongly interact
when atoms brought close, so Si is a solid
Ground levels full
Only need to consider 3s and 3p levels

ES2B3 Electronic Materials

Each Si-Si bond has 2 paired electrons.

Gives an energy band called the valence band (VB)

This is full
Also have an energy band with an energy gap, Eg above
the valence band, and is called the conduction band
So we have a CB and a VB across the whole solid

ES2B3 Electronic Materials

Electron energy

CB

Ec
Thermal
excitation

Eg

Ev
VB

Fig. 4.18: Energy band diagram of a semiconductor. CB is the

conduction band and VB is the valence band. At 0 K, the VB is full
with all the valence electrons.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

Density of states in an energy band

Following the same ideas we used for Li, we know there are
lots of levels in a band (~1023)
Single atom has a fixed number of nearest neighbours and
many distant neighbours
Define the density of states g(E) such that g(E)dE is the
number of states (wavefunctions) in the energy interval E to
E+dE per unit volume of the sample.
The number of states per unit volume up to some energy E
is:
E

S v E g E dE
0

ES2B3 Electronic Materials

Intrinsic semiconductors
Intrinsic means perfect i.e. with no impurities
Si has a diamond structure, and will vibrate at temperatures
above 0K
Thermal vibrations can rupture bonds producing free
electrons and holes
Extrinsic Si has impurities added Adding As effectively adds electrons to give n-type
Adding B accepts electrons to give p-type

(a)

hyb orbitals
Valence
electron

ES2B3 Electronic Materials

Si ion core (+4e)

Si crystal in 2-D

Electron energy

Ec+

Conduction Band (CB)

Empty of electrons at 0 K.

Ec

Bandgap = Eg

Ev
Valence Band (VB)
Full of electrons at 0 K.

(b)

(c)

Fig. 5.1: (a) A simplified two dimensional illustration of a Si atom with

four hybrid orbitals, hyb. Each orbital has one electron. (b) A simplified
two dimensional view of a region of the Si crystal showing covalent
bonds. (c) The energy band diagram at absolute zero of temperature.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

Electrons in the CB can be treated If free,

though must use an effective mass, me
Figure 5.3 shows the creation of an
electron-hole pair by a photon
Figure 5.4 shows the creation of an
electron-hole pair by a thermal vibration

ES2B3 Electronic Materials

Electron energy
Ec+
CB
Ec
h > Eg

FREE e

Eg

Ev

HOLE

hole

VB
0

(a)

(b)

Fig. 5.3: (a) A photon with an energy greater than Eg can

excite an electron from the VB to the CB. (b) When a
photon breaks a Si-Si bond, a free electron and a hole in the
Si-Si bond is created.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca

ES2B3 Electronic Materials

End of lecture 1

ES2B3 Electronic Materials

Heisenburgs Uncertainty Principle

For an electron trapped in an infinite well, there is an uncertainty of a in its
position, from x = 0 to x = a.

The momentum is

p x k

Taking the product of the uncertainties

2p
xp x a
h
a

Generally, -Heisenbergs Uncertainty Principle

xp x

V(x)

ES2B3 Electronic Materials

Electron

V=

V=0

V=
x

0
a
Energy levels in the well (x) sin(npx/a) Probability density |(x)|2
4

Energy of electron

E4

n=4
3

E3
E2
E1
0

x=0

n=3
2

n=2
n=1

1
x=a

a0

Fig. 3.15: Electron in a one-dimensional infinite PE well. The energy

of the electron is quantized. Possible wavefunctions and the
probability distributions for the electron are shown.
From Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( McGraw-Hill, 2002)
http://Materials.Usask.Ca