Lecture 11a Band Theory of Solids

FEE3201 Physical Electronics A
Band theory of solids
Mwema
University of Nairobi
September 2023
WM (UoN) Band theory of solids 09/01 1 / 81

The hydrogen molecule
In determining the energy band structure, three methods are usually

applied


applied
The tight binding or linear combination of atomic orbitals (LCAO)
method


applied
method
Begins with the atomic orbitals and combines these into itinerant
wavefunctions or molecular orbitals


applied
method
The nearly-free electron (NFE) method


applied
method
Begins with wavefunctions of completely free electrons which are then
perturbed with pseudopotentials at the ion cores e.g. Krönig-Penney
model


applied
method
model
!
The k !
p method


applied
method
model
!
The k !
p method
!
begins with high-symmetry points in the k -space and uses
perturbation theory to compute the curvature around these points


applied
method
model
!
The k !
p method
!
begins with high-symmetry points in the k -space and uses
perturbation theory to compute the curvature around these points
Our discussion will be con…ned to the LCAO method

Each atom in a system of isolated hydrogen atoms has its own set of
energy levels En and associated atomic orbitals ψn

Each electron therefore has the same energy equal to the ionisation
energy, Ei ' 13, 6 eV of the hydrogen atom

The total energy of a system of two hydrogen atoms in isolation is
then 2Ei ' 27, 2 eV

then 2Ei ' 27, 2 eV
When two hydrogen atoms are at a separation distance r , electrons in
the two atoms interact with each other and the two nuclei

then 2Ei ' 27, 2 eV
When two hydrogen atoms are at a separation distance r , electrons in
the two atoms interact with each other and the two nuclei
The e¤ective wavefunction of the system will therefore have a
di¤erent potential energy term from that of the monatomic system

Let ψσ be a molecular orbital that depends on the interaction

between individual atomic wavefunctions or atomic orbitals

Let ψσ be a molecular orbital that depends on the interaction

between individual atomic wavefunctions or atomic orbitals
We will regard ψσ as the wavefunction of an electron in the hydrogen
molecule

Identical sets of the ψ1s atomic orbitals are not allowed within the
molecule because of

molecule because of
Pauli’s exclusion principle

molecule because of
Overlap in the ψ1s orbitals as the two atoms come close together in
the molecule

molecule because of
the molecule
When the two atomic wavefunctions interact, they may do so either

molecule because of
the molecule
In phase
ψσ = ψ1s (rA ) + ψ1s (rB )

molecule because of
the molecule
In phase
ψσ = ψ1s (rA ) + ψ1s (rB )
In anti-phase
ψσ = ψ1s (rA ) ψ1s (rB )

An illustration of the bonding and anti-bonding orbital formation in a

diatomic molecule
e- e-
+ +
atoms in isolation
Ψ1s(rB)
Ψ1s(rA)
+ + r
8
A B
e- + + e-
bonding molecular orbital
Ψσ=Ψ1s(rA)+Ψ1s(rB)
+ + r
a
A B
antibonding molecular orbital

Ψσ*=Ψ1s(rA)-Ψ1s(rB)
B
+
+ r
A
Bonding and antibonding molecular orbitals in a hydrogen molecule

The two molecular orbitals arising from the interaction of the two
atomic orbitals are by convention labeled ψσ and ψσ

Generation of ψσ and ψσ from the atomic orbitals is a linear
combination of atomic orbitals (LCAO)

We note that ψσ is symmetric w.r.t. the centre of the internuclear
distance while ψσ is anti-symmetric

We note that ψσ is symmetric w.r.t. the centre of the internuclear
distance while ψσ is anti-symmetric
Therefore, ψσ exhibits a node at the centre of the internuclear
separation

Recall that the energy associated with a given wavefunction increases

with the number of its internal nodes


Hence the energy associated with ψσ will be higher than that
associated ψσ


associated ψσ
We note that jψσ j2 will be signi…cant between the two nuclei meaning
that it will be more likely to …nd an electron here


associated ψσ
We note that jψσ j2 will be signi…cant between the two nuclei meaning
that it will be more likely to …nd an electron here
The total energy associated with ψσ is hence lower than that
associated with the individual atomic orbitals

The potential energy function in the H-H system has a positive

potential energy contribution from


Electron-electron repulsion as the atoms come close together


Proton-proton repulsion from the same cause


Proton-proton repulsion from the same cause
Potential energy contributions from attraction between the electrons
and the nuclei will lower the overall potential energy

The energy Eσ and Eσ associated with the two molecular orbitals ψσ

and ψσ resp. are widely separated in the H-H system

The energy Eσ and Eσ associated with the two molecular orbitals ψσ

and ψσ resp. are widely separated in the H-H system
If we denote the energy associated with the ψ1s as E1s , then
Eσ > E1s
and
Eσ < E1s

We can illustrate the energy pro…le in the H-H system as

E
Eσ*(r)
ψσ∗
Eσ(r) ψ1s
E1s
0
bonding
energy
Eσ ψσ
r
a isolated atoms
Energy level splitting as interatomic separation is reduced

Each orbital state can hold up to two electrons with paired spins

The di¤erence between E1s and Eσ is the bond energy of the H-H
system

system
The formation of ψσ and ψσ from the two ψ1s atomic orbitals can be
regarded as the splitting of E1s into the two levels Eσ and Eσ as
Eσ*
E1s E1s
∆E=bonding energy
Eσ
A simpli…ed energy diagram for a two-atom hydrogen system

system
The formation of ψσ and ψσ from the two ψ1s atomic orbitals can be
regarded as the splitting of E1s into the two levels Eσ and Eσ as
Eσ*
E1s E1s
∆E=bonding energy
Eσ
A simpli…ed energy diagram for a two-atom hydrogen system

Energy level splitting is due to interaction between the atomic orbitals

In the case of the helium atom, the 1s orbital is complete with the
energy level already split into Eσ and Eσ

If two helium atoms were to come together to form a He-He system,
two electrons would occupy the ψσ orbital

If two helium atoms were to come together to form a He-He system,
two electrons would occupy the ψσ orbital
The other two must then occupy the ψσ orbital which does not
favour a lowered overall system energy

QM theory shows that Eσ associated with ψσ shifts to a higher

energy above E1s than Eσ does below E1s


We conclude therefore that overlapping complete orbitals does not
favour bond formation


We conclude therefore that overlapping complete orbitals does not
favour bond formation
Bonding must therefore require overlap between partially …lled orbitals

The tri-hydrogen molecule
Suppose three hydrogen atoms were to form a triatomic hydrogen

molecule H-H-H


molecule H-H-H
We let these atoms be labeled A, B, C, but not because we can
distinguish between them!


molecule H-H-H
We let these atoms be labeled A, B, C, but not because we can
distinguish between them!
We label the three molecular orbitals arising from the overlapping
atomic orbitals of the three atoms as ψA , ψB , ψC respectively

Thus, the molecular orbitals will be of the form

symmetric
+ + + r
a C
A B
antisymmetric
B C
+ +
+ r
A
symmetric
B
+
+ + r
A C
Composite molecular orbitals for a H3 molecule

This is justi…ed because, with A, B, C identical


The molecule A-B-C must be symmetric w.r.t. atom B


Each wavefunction must have either an odd or even parity


Each wavefunction must have either an odd or even parity
The three molecular orbitals must then satisfy
ψ1 = ψ1s ,A + ψ1s ,B + ψ1s ,C
ψ2 = ψ1s ,A ψ1s ,C
ψ3 = ψ1s ,A ψ1s ,B + ψ1s ,C

The energies E1 , E2 , E3 associated with ψ1 , ψ2 , ψ3 are solutions of

Schrödinger’s equation for the three-atom system with the
appropriate potential energy term


The E1 , E2 , E3 are di¤erent since their associated wavefunctions are
di¤erent


The E1 , E2 , E3 are di¤erent since their associated wavefunctions are
di¤erent
The 1s energy level is hence seen to split into three sublevels to form
three molecular energy sublevels

Since the energy of a wavefunction increases with the number of

internal nodes, i.e., excluding the end nodes, ψ3 has the highest
associated energy while ψ1 has the lowest


We can thus order the energy levels as,
E1 < E2 < E3


E1 < E2 < E3
In the H3 molecule, two electrons will pair their spins and occupy the
E1 sublevel


E1 < E2 < E3
E1 sublevel
The third electron must then occupy the sublevel with the next higher
energy, i.e., E2


E1 < E2 < E3
E1 sublevel
energy, i.e., E2
A H3 molecule can be expected to have a higher overall energy than
the H2 molecule


E1 < E2 < E3
E1 sublevel
energy, i.e., E2
A H3 molecule can be expected to have a higher overall energy than
the H2 molecule
This molecule will therefore be less stable than the H2 molecule

The lithium crystal
We now consider a linear crystal of lithium with N atoms

The lithium crystal

Lithium has the electronic con…guration, 1s2 2s1

The lithium crystal

Like in the hydrogen system, we expect an N-fold splitting in each of
the atomic energy levels for the atoms in the crystal

The lithium crystal

The 1s level being close to the nucleus can be expected to be
essentially una¤ected by the interatomic interactions

The lithium crystal

The 1s level being close to the nucleus can be expected to be
essentially una¤ected by the interatomic interactions
Thus, the two 1s electrons will remain bound to their parent nuclei

The lithium crystal
For the N-atom system, there are N electrons in the ψ2s orbitals with
associated energy E2s in the isolated atoms

The lithium crystal
When N is large, E2s will split into N closely separated levels when
the crystal is formed

The lithium crystal
The maximum width of the energy split will depend on how close the
atoms can come together in the crystal, i.e., the equilibrium lattice
constant a

The lithium crystal
The maximum width of the energy split will depend on how close the
atoms can come together in the crystal, i.e., the equilibrium lattice
constant a
An interatomic separation larger than a will lead to a lower density of
energy splitting

The lithium crystal
The interactions between the N, ψ2s atomic orbitals will therefore

spread the energy sublevels between a lowest level Ebottom and a
highest level Etop as determined by a

The lithium crystal

i.e., the separation between Ebottom and Etop is determined by the
interatomic separation of the nearest neighbours in the crystal

The lithium crystal

Each energy level Ei , i = 1, 2, . . . , N is associated with a molecular
orbital ψi representing a particular combination of the N, ψ2s atomic
orbitals

The lithium crystal

Each energy level Ei , i = 1, 2, . . . , N is associated with a molecular
orbital ψi representing a particular combination of the N, ψ2s atomic
orbitals
We note that N wavefunctions can be combined in N di¤erent ways

since each wavefunction can add either in phase or in anti-phase

The lithium crystal
In the H-H-H hydrogen system, we saw that

The lithium crystal

The molecular orbital ψ1 with the lowest associated energy resulted
from an in-phase atomic wavefunction linear combination

The lithium crystal

The molecular orbital ψ3 with the highest associated energy resulted
atomic wavefunction linear combination in alternate phase

The lithium crystal

The molecular orbital ψ3 with the highest associated energy resulted
atomic wavefunction linear combination in alternate phase
We therefore anticipate that for the N-atom system, the molecular
orbitals with the lowest and highest associated energies will
correspond to similar combinations

The lithium crystal
Wavefunction combination in alternate phase will maximise the

number of inner nodes in the resultant wavefunction

The lithium crystal

We can therefore associate ψ1 and ψN with the energies Ebottom and
Etop resp.

The lithium crystal

We can therefore associate ψ1 and ψN with the energies Ebottom and
Etop resp.
The rest of the combinations will have associated energies lying
between these two extremes with associated energies ordered in terms
of the number of internal nodes

The lithium crystal
Lithium crystallises in the BCC crystal structure with a density of

0, 542 gcm 1 and relative atomic mass of 6, 941 gmol 1

The lithium crystal

Hence, the atom concentration in the lithium crystal is
ρNA 6, 022 1023 mol 1 0, 542 gcm 1

n = =
MLi 6, 941 gmol 1
= 4, 7 1022 cm 3

The lithium crystal

Hence, the atom concentration in the lithium crystal is
ρNA 6, 022 1023 mol 1 0, 542 gcm 1

n = =
MLi 6, 941 gmol 1
= 4, 7 1022 cm 3
In a 1 cm3 crystal, N = 4, 7 1022

The lithium crystal
Hence, the sublevels with Etop Ebottom ' 10 eV in Li, will be

separated by
10 eV
∆E = ' 2 10 22 eV
4, 7 1022

The lithium crystal

separated by
10 eV
∆E = ' 2 10 22 eV
4, 7 1022
The energy separation ∆E is therefore so small that the discrete
energy levels between Ebottom and Etop essentially form a continuous
band

The lithium crystal

separated by
10 eV
∆E = ' 2 10 22 eV
4, 7 1022
The energy separation ∆E is therefore so small that the discrete
energy levels between Ebottom and Etop essentially form a continuous
band
This band of energies is loosely described as the 2s band

The lithium crystal
Due to the 2-spin degeneracy of each level, the N, 2s electrons will

occupy all the energy levels from Ebottom to EN /2 , in the lithium
crystal and the band is therefore half-full

The lithium crystal

Note, EN = Etop

The lithium crystal

Note, EN = Etop
However, the sublevels are not equally separated between the bottom
and top of the band

The lithium crystal

Note, EN = Etop
However, the sublevels are not equally separated between the bottom
and top of the band
Hence, as a consequence, the band will not be …lled up to the
mid-band level, EN /2

The lithium crystal
An N-way splitting in each of the other atomic energy levels , i.e., 2p,
3s, 3p, . . . may have some of the sublevels overlapping with the 2s
levels

The lithium crystal
levels
This e¤ectively extends the width of the 2s band into higher energy
levels

The lithium crystal
levels
levels
For the 3d, 4s, etc., the energy levels will be above the vacuum level
in Li

The lithium crystal
levels
levels
For the 3d, 4s, etc., the energy levels will be above the vacuum level
in Li
An electron will therefore be free before acquiring energy associated
with these levels

The lithium crystal
At 0 K , thermal energy is insu¢ cient to excite electrons into higher

energy levels

The lithium crystal

energy levels
Electrons are hence spin paired and occupy levels from Ebottom up to
an energy level Ef 0

The lithium crystal

energy levels
Electrons are hence spin paired and occupy levels from Ebottom up to
an energy level Ef 0
Ef 0 is called the Fermi energy at 0 K

The lithium crystal
We can illustrate the 0 K energy band diagram of the lithium crystal

as
E
vacuum level 0 (7,2eV)
qΦm empty levels
Ef0 -2.5eV (4,7eV)
Ef0 filled levels
Ebottom -7.2eV (0)
Energy band diagram for Li

Signi…cance of the Fermi level
The Fermi-level is measured w.r.t. to the bottom of the band


In Li, Ef 0 is 4, 7 eV above the bottom of the band


At 0 K , the probability that an electron with energy E < Ef 0 will be
found in the population is unity


At 0 K , the probability that an electron with energy E < Ef 0 will be
found in the population is unity
The workfunction qΦm of a material is the energy required to excite

an electron at the Fermi level to the vacuum state

Electron behaviour within an energy band of a metal
crystal
Electrons in the 2s energy band of Li are the loosely bound valence

electrons

crystal

electrons
These become free in the crystal during the metallic bond formation
due to the quasi-continuous energy band

crystal

electrons
The 3-DEG (free or conduction electrons) of the metallic bond

consists of the 2s electrons in Li

crystal

electrons

No electron in the electron gas can be associated with a particular
atom however

crystal

electrons

No electron in the electron gas can be associated with a particular
atom however
Hence, these electrons move freely throughout the crystal

crystal
Wavefunctions of the conduction electrons are propagating uniform

plane waves

crystal

plane waves
These are solutions of Schrödinger’s equation for a free particle

crystal

plane waves
In the direction of propagation, each electron can thus be represented
by a wavevector
! 2π
k =b r
λ

crystal

plane waves
by a wavevector
! 2π
k =b r
λ
b
r is a unit vector in the direction of propagation

crystal

plane waves
by a wavevector
! 2π
k =b r
λ
b
r is a unit vector in the direction of propagation
The wave momentum is then given by
! !
p =}k

crystal
Electrons in the electron cloud are essentially free and their energy is
therefore entirely translational kinetic

crystal
Electron energy in the band increases with electron momentum as
1 ! ! p2
p p = = }2 k 2
2mn 2mn

crystal
1 ! ! p2
p p = = }2 k 2
2mn 2mn
Hence, energy of a free electron is parabolic in p

crystal
1 ! ! p2
p p = = }2 k 2
2mn 2mn

The average momentum of the electrons in the band is zero under
thermal equilibrium conditions

crystal
1 ! ! p2
p p = = }2 k 2
2mn 2mn

Electrons are in random thermal motion

crystal
1 ! ! p2
p p = = }2 k 2
2mn 2mn

Electrons are in random thermal motion
For every electron with momentum !
p in the cloud, there is another
with momentum ! p

crystal
!
Suppose an electric …eld E = b
x Ex is applied in the crystal

crystal
!
The …eld exerts an electrostatic force on each electron in the cloud
given by
( q ) (b
x Ex ) = b x q Ex

crystal
!
given by
( q ) (b
x Ex ) = b x q Ex
An electron moving in the x-direction will be decelerated and lose

momentum

crystal
!
given by
( q ) (b
x Ex ) = b x q Ex
An electron moving in the x-direction will be decelerated and lose

momentum
A corresponding electron moving in the x-direction will be
accelerated and gain momentum

crystal
In the Li crystal, loss or gain of momentum is relatively easy because

crystal

The energy sublevels within the band have an in…nitesimally small
separation ∆E hence, the band is essentially continuous

crystal

Energy bands above the Fermi level are available since the sublevels in
the band are occupied only from Ebottom to Ef

crystal

Energy bands above the Fermi level are available since the sublevels in
the band are occupied only from Ebottom to Ef
Thus, under the in‡uence of the applied electric …eld, the whole
distribution of electrons shifts in the x-direction

crystal
The forces randomising electron motion in the crystal come from

crystal

Electron interactions with lattice vibrations (phonons)

crystal

Electron interactions with other crystal defects

crystal

Vacancies

crystal

Vacancies
Impurities, etc.

crystal
In a perfect crystal, the only scattering mechanism will be interactions

with the lattice vibrations

crystal

Lattice vibrations have typically low energy but considerable
momentum

crystal

momentum
Hence, for an electron to be scattered by lattice vibrations,

crystal

momentum
Energy levels of roughly the same energy must be available while
allowing the scattered electron to change its momentum signi…cantly

crystal

momentum
Energy levels of roughly the same energy must be available while
allowing the scattered electron to change its momentum signi…cantly
An electron with energy close to Ef will ‡ip its momentum in the
opposite direction after a scattering event

crystal
The net momentum in the x-direction is non-zero

crystal

This constitutes net charge ‡ow or a net current in the x-direction

crystal

Conventional electric current is in the direction of ‡ow of positively
charged particles

crystal

Conventional electric current is in the direction of ‡ow of positively
charged particles
Only electrons with energies in a small range ∆E about Ef will

participate in conduction however

crystal
For typical currents in metals, ∆E 10 6 eV while Ef lies between 1

and 10 eV in most metals

crystal

An electron moving in an applied electric …eld gains an electrostatic
potential energy
Ue (x ) = qΦ (x )
where Φ (x ) is the electric potential at x in the crystal

crystal

An electron moving in an applied electric …eld gains an electrostatic
potential energy
Ue (x ) = qΦ (x )
where Φ (x ) is the electric potential at x in the crystal
If the applied electric …eld is of uniform intensity, Φ (x ) varies linearly
from 0 to Φ (x ) at x, since
dΦ
Ex =
dx

crystal
Ue (x ) adds to the electron energy

crystal

Hence, the band edges must bend to re‡ect this excess electrostatic
potential energy

crystal

Hence, the band edges must bend to re‡ect this excess electrostatic
potential energy
Since only electrons with energy close to Ef participate in charge
transport, the electrons can be visualised as rolling down a potential
hill

crystal
An illustration of band bending in a metal crystal under an applied
electric …eld
Etop
Etop-qV
empty levels
Ef
filled levels Ebottom
Ebottom-qV
WM (UoN) Band edge bending dueof solids
Band theory to applied electric …eld 09/01 42 / 81
crystal
The electrons move with a high average thermal velocity
vth ' 106 ms 1

crystal
The electrons move with a high average thermal velocity
vth ' 106 ms 1
The drift velocity due to the …eld is however small, 10 2 -

10 1 ms 1 in typical current ‡ows

crystal
If the metal is irradiated with a photon source of su¢ cient photon

energy, an electron will be excited to the vacuum level and hence
emitted

crystal
If the metal is irradiated with a photon source of su¢ cient photon

energy, an electron will be excited to the vacuum level and hence
emitted
The longest wavelength of radiation that will cause photoemission is
such that
hc }ω
= = Φm
qλ q

crystal
Electrons can gain energy from thermal sources as well

crystal

Heat increases the amplitude of lattice vibrations and heat capacity of
metals therefore consists of

crystal

A component of energy absorbed by lattice vibrations

crystal

A component of energy absorbed by the conduction electrons

crystal

The dominant mechanism in‡uencing heat capacity of a metal is

crystal


Lattice vibration absorption at moderate temperatures

crystal


Lattice vibration absorption at moderate temperatures
Electronic absorption at low temperatures

Covalently bonded semiconductors
Silicon with the electronic con…guration 1s2 2s2 2p6 3s2 3p2 , is an
important group IV semiconductor

The inner shells n = 1, 2 are complete or closed

Hence, do not participate in interatomic interactions during
crystallisation

Hence, do not participate in interatomic interactions during
crystallisation
The covalent bond in a silicon crystal involves the 3s and 3p electrons

When …ve Si atoms interact, the 3s and 3p subshells, interact and

form of four molecular orbitals, ψ3s , ψ3px , ψ3py , ψ3pz , directed
toward the corners of a tetrahedron


The molecular orbitals combine to form hybrid orbitals in an sp3
hybridisation process


One s and three p orbitals are involved in sp3 hybridisation


Each sp3 hybrid orbital (ψh ) in Si has one electron


Each sp3 hybrid orbital (ψh ) in Si has one electron
Four Si atoms hence overlap their hybrid orbitals to form a covalent
bond with one other Si atom

The hybrid orbitals can arise in two ways


In phase interaction


i.e., both hybrid orbitals positive or negative, interact to form a
bonding orbital ψB with associated energy EB


Anti-phase interaction


i.e., one orbital positive the other negative, interact to form an
antibonding orbital ψA with associated energy EA > EB


i.e., one orbital positive the other negative, interact to form an
antibonding orbital ψA with associated energy EA > EB
Each Si-Si bond then corresponds to two spin-paired electrons in the

bonding orbital

Silicon crystallises in the diamond crystal structure with a density
2, 33 gcm 3

2, 33 gcm 3
As we have seen this structure can be visualised as an FCC structure
with a basis of two atoms

2, 33 gcm 3
The relative atomic mass of silicon is 28, 085 gmol 1

2, 33 gcm 3
Hence, the atom density in a silicon crystal is given by
ρNA 2, 33 gcm 3 6, 022 1023 mol 1
n= = ' 5, 0 1022 cm 3
MSi 28, 085 gmol 1

2, 33 gcm 3
ρNA 2, 33 gcm 3 6, 022 1023 mol 1
n= = ' 5, 0 1022 cm 3
MSi 28, 085 gmol 1
Thus, in a 1 cm3 crystal, N ' 5 1022 atoms and as many ψB
orbitals

2, 33 gcm 3
ρNA 2, 33 gcm 3 6, 022 1023 mol 1
n= = ' 5, 0 1022 cm 3
MSi 28, 085 gmol 1
orbitals
Interactions of the ψB orbitals lead to splitting of the EB energy level
into N closely separated sublevels

2, 33 gcm 3
ρNA 2, 33 gcm 3 6, 022 1023 mol 1
n= = ' 5, 0 1022 cm 3
MSi 28, 085 gmol 1
orbitals
These sublevels form the valence band of the silicon crystal which will
be essentially full at 0 K ,

2, 33 gcm 3
ρNA 2, 33 gcm 3 6, 022 1023 mol 1
n= = ' 5, 0 1022 cm 3
MSi 28, 085 gmol 1
orbitals
These sublevels form the valence band of the silicon crystal which will
be essentially full at 0 K ,
i.e., most of the valence electrons in the crystal will have one of the
energies allowed in this band
The band of N closely separated sublevels of the EA level arising from

the interactions among the ψA orbitals forms the conduction band


This band is essentially empty at 0 K


i.e., none of the valence electrons in the crystal has energy
corresponding to allowed energy in this band


The valence and conduction bands are each bounded by a minimum
and maximum energy level due to the N-way combinations of the
bonding and antibonding orbitals


We label the top edge of the valence band as EV and the bottom
edge of the conduction band as EC


We label the top edge of the valence band as EV and the bottom
edge of the conduction band as EC
The valence and conduction bands are separated by an energy gap of

width Eg where no allowed energy levels exist

We illustrate the energy band structure of a Si crystal as
4N states
0 electrons }conduction band
6N states
energy, E
2N 3p electrons
Eg
energy gap
2N states
2N 3s electrons
4N states
4N electrons }valence band
inner shell atomic

energy levels unaffected
ro interatomic separation, r
crystal lattice
constant
The silicon energy band structure

The electronic states in the bands extend throughout the crystal


Because these states result from the N, ψB and N, ψA overlapping
orbitals


Because these states result from the N, ψB and N, ψA overlapping
orbitals
There are N ways in which these orbitals can interact to generate N,
ψVB and N, ψCB distinct wavefunctions in the valence and
conduction bands resp.

The ψVB orbitals of the valence band are not centred around any
particular atom

particular atom
i.e., a particular electron in the valence band cannot be associated with
any one given bond or site in the crystal

particular atom
At temperatures above 0 K , it is possible that lattice vibrations may
transfer su¢ cient energy to valence band electrons and excite them to
higher allowed energies in the conduction band

particular atom
Since the conduction band is essentially empty, there is a high
number of available states

particular atom
Since the conduction band is essentially empty, there is a high
number of available states
Hence the excited valence band electrons are essentially free as in a
metal crystal and can participate in electrical conduction

For every electron in the conduction band, there will be a missing

electron in the valence band


Hence, an unoccupied state and therefore available


Empty valence band states are known as holes


Holes will participate in electrical conduction in the sense that when
an electron in the valence band occupies such an empty state, it
leaves its original state unoccupied


Holes will participate in electrical conduction in the sense that when
an electron in the valence band occupies such an empty state, it
leaves its original state unoccupied
Holes will therefore move in the opposite direction to the movement
of electrons, i.e., will behave like positively charged electrons

Electronic con…guration of important group IV elements
Si: [Ne]3s2 3p2

Ge: [Ar]3d10 4s2 4p2
Sn: [Ar]3d10 4s2 4p6 5s2 5p2

Si: [Ne]3s2 3p2

Ge: [Ar]3d10 4s2 4p2
Sn: [Ar]3d10 4s2 4p6 5s2 5p2
Other important semiconductors are the group III-V compounds such

as GaAs, GaP, GaN, InAs, InP, AlGaAs, etc.

Si: [Ne]3s2 3p2

Ge: [Ar]3d10 4s2 4p2
Sn: [Ar]3d10 4s2 4p6 5s2 5p2
Other important semiconductors are the group III-V compounds such

as GaAs, GaP, GaN, InAs, InP, AlGaAs, etc.
We will however restrict our discussion to the elemental
semiconductor Si

The Krönig-Penny model of solid crystals
A direct solution of Schrödinger’s equation for a multi-atom system is

very di¢ cult if not impossible and approximate techniques must be
resorted to


resorted to
Each atom in the crystal creates a local potential well at the lattice
site which attracts electrons


resorted to
Each atom in the crystal creates a local potential well at the lattice
site which attracts electrons
The potential energy of the electron depends on its distance from the
nucleus of the atom

We consider a hydrogen-like silicon atom and assume the screening

e¤ect of the core electrons can be ignored


From electrostatics, the potential energy of interaction of the single
outermost electron between an outer electron of charge q and the
nucleus of charge +qZ is given by
q2 Z
U (r ) =
4πer


From electrostatics, the potential energy of interaction of the single
outermost electron between an outer electron of charge q and the
nucleus of charge +qZ is given by
q2 Z
U (r ) =
4πer
Where U (0) = ∞, U (∞) = 0 and r is the distance of the electron
from the nucleus

Consider a linear Si crystal consisting of an in…nite chain of atoms

positioned periodically along the oriented in the x-axis to re‡ect the
position of the atoms within the real crystal

Consider a linear Si crystal consisting of an in…nite chain of atoms

positioned periodically along the oriented in the x-axis to re‡ect the
position of the atoms within the real crystal
The atom-generated periodic potential wells can then be
mathematically expressed as
U (x + a + b ) = U (x )
where a + b is the interatomic separation in the x-direction

Bloch’s theorem
The crystal wavefunction must satisfy the time-independent

Schrödinger equation when x + a + b is substituted for x in ψ (x ) to
re‡ect the periodicity

Bloch’s theorem

This is achieved if the wavefunction satis…es Bloch’s theorem stated
as:

Bloch’s theorem

This is achieved if the wavefunction satis…es Bloch’s theorem stated
as:
If U (x ) is periodic such that U (x + a + b ) = U (x ) then
ψ (x + a + b ) = ψ (x ) exp fjk (a + b )g

Bloch’s theorem
Alternatively, Bloch’s theorem can be stated as:

Bloch’s theorem
Alternatively, Bloch’s theorem can be stated as:
If U (x ) is periodic such that U (x + a + b ) = U (x ) then
ψ (x ) = uk (x ) exp (jkx )
where
uk ( x + a + b ) = uk ( x )

Bloch’s theorem
The two statements are equivalent since,
ψ (x + a + b ) = uk (x + a + b ) exp fjk (x + a + b )g
= uk (x ) exp (jkx ) exp fjk (a + b )g
= ψ (x ) exp fjk (a + b )g

Bloch’s theorem
The two statements are equivalent since,
ψ (x + a + b ) = uk (x + a + b ) exp fjk (x + a + b )g
= uk (x ) exp (jkx ) exp fjk (a + b )g
= ψ (x ) exp fjk (a + b )g
U (x ) is a complicated function of interatomic separation in real

crystals

The Krönig-Penny model idealises U (x ) as a periodic sequence of
rectangular potential wells while preserving the essential features of
the lattice

the lattice
Potential energy between the atoms is taken as U0 and that in the
wells as U1 as illustrated below
U(x)
-b 0 a
0 x
U0
Region I
Region II
U1
The Krönig-Penney model of the periodic crystal potential

the lattice
Potential energy between the atoms is taken as U0 and that in the
wells as U1 as illustrated below
U(x)
-b 0 a
0 x
U0
Region I
Region II
U1
The Krönig-Penney model of the periodic crystal potential

We can therefore write,
U ( x ) = U0 , b x 0
= U1 , 0 x a
We consider an essentially free electron with total energy E between

U0 and U1


U0 and U1
With U (x ) = U1 and E > U1 in region I , 0 x a, relevant
Schrödinger equation is
}2 d 2
= ψ (x ) + (E U1 ) ψ ( x ) = 0
2m dx 2


U0 and U1
}2 d 2
= ψ (x ) + (E U1 ) ψ ( x ) = 0
2m dx 2
This has a general solution
ψI (x ) = A1 exp (j βx ) + A2 exp ( j βx )


U0 and U1
}2 d 2
= ψ (x ) + (E U1 ) ψ ( x ) = 0
2m dx 2
This has a general solution
ψI (x ) = A1 exp (j βx ) + A2 exp ( j βx )
Where r
2m (E U1 )
β=
}2
and real

With U (x ) = U0 and E < U0 in region II , b x 0, the relevant

}2 d 2
ψ (x ) + (E U0 ) ψ ( x ) = 0
2m dx 2


}2 d 2
ψ (x ) + (E U0 ) ψ ( x ) = 0
2m dx 2
This has a general solution of the form,
ψII (x ) = B1 exp (αx ) + B2 exp ( αx )


}2 d 2
ψ (x ) + (E U0 ) ψ ( x ) = 0
2m dx 2
This has a general solution of the form,
ψII (x ) = B1 exp (αx ) + B2 exp ( αx )
Where r
2m (U0 E)
α=
}2
and real

The periodic nature of the crystal lattice suggests that we require

these wavefunctions satisfy Bloch’s theorem
ψk (x ) = uk (x ) exp (jkx )
where uk (x ) is periodic with a spatial period a + b



Hence,
uk (x + n (a + b )) = uk (x )



Hence,
uk (x + n (a + b )) = uk (x )
And
ψI (x + n (a + b )) = ψI (x ) exp fjkn (a + b )g
ψII (x + n (a + b )) = ψII (x ) exp fjkn (a + b )g

At x = 0 and x = a, we require ψ (x ) and d ψ (x ) /dx be continuous

(the boundary conditions from postulate 3)


Continuity of ψ (x ) and d ψ (x ) /dx at x = 0 hence requires that,
ψII (0) = ψI (0)
d ψII (x ) d ψI (x )
j x =0 = j x =0
dx dx


Continuity of ψ (x ) and d ψ (x ) /dx at x = 0 hence requires that,
ψII (0) = ψI (0)
j x =0 = j x =0
dx dx
Hence,
A1 + A2 B1 B2 = 0
j β f A1 A2 g α f B1 B2 g = 0

Continuity of ψ (x ) and d ψ (x ) /dx at x = a requires
ψII (a) = ψI (a)
j x =a = j x =a
dx dx

ψII (a) = ψI (a)
j x =a = j x =a
dx dx
Using Bloch’s theorem at x = a, we can write,
ψI (a) = ψI ( b ) exp fjk (a + b )g

ψII (a) = ψI (a)
j x =a = j x =a
dx dx
Using Bloch’s theorem at x = a, we can write,
ψI (a) = ψI ( b ) exp fjk (a + b )g
Hence,
h i
e jk (a +b ) A1 e j βb
+ A2 e j βb B1 e αa B2 e αa
=0
h i
j βe jk (a +b ) A1 e j βb
A2 e j βb α B1 e αa B2 e αa
=0

We can expressed these equations in matrix form as

2 32 3
1 1 1 1 A
6 jβ j β α α 7 6 A2 7
6 76 7
4 e jk (a +b ) e j βb e jk (a +b ) e j βb e αa e αa 5 4 B1 5 = 0
j βe jk ( a + b ) e j βb j βe jk ( a + b ) e j βb αe αa αe αa B2

We can expressed these equations in matrix form as

2 32 3
1 1 1 1 A
6 jβ j β α α 7 6 A2 7
6 76 7
4 e jk (a +b ) e j βb e jk (a +b ) e j βb e αa e αa 5 4 B1 5 = 0
j βe jk ( a + b ) e j βb j βe jk ( a + b ) e j βb αe αa αe αa B2
For a non-trivial solution for A1 , A2 , B1 , B2 , the determinant of this

matrix must vanish

Invoking this requirement yields,
α2 β2
sinh αa sin βb + cosh αa cos βb = cos (k (a + b )) = P (E )
2αβ

α2 β2
2αβ
P (E ) is a function of the total energy E alone through the

parameters α and β

α2 β2
2αβ

Since k must be real, simultaneous solution of this transcendental
equation imposes constraints on the allowable values P (E ) can have

α2 β2
2αβ

That is, P (E ) must be bounded such that
1 P (E ) 1

α2 β2
2αβ

That is, P (E ) must be bounded such that
1 P (E ) 1
This means that the allowed values of E are restricted

A plot of P (E ) in the momentum space (k-space) is of the form

P(E)
forbidden bands
allowed bands
1
k
-1
Allowed and forbidden energy bands due to the periodic lattice

potential

The corresponding plot of E (k ) in momentum space if of the form

E(k) 1st Brillouin Zone
Forbidden energy
band
Allowed band
Forbidden energy
band
k
−2π/(a+b) −π/(a+b) π/(a+b) 2π/(a+b)
E (k ) in the extended scheme

Because of the periodicity of the crystal lattice, periodicity of the

k-space or reciprocal lattice has period 2π/ (a + b )


E (k ) extends from k = ∞ to k = ∞ with a period 2π/ (a + b )
but values of E (k ) can be restricted to the interval
[ π/ (a + b ) , π/ (a + b )) w.n.l.o.g.


[ π/ (a + b ) , π/ (a + b )) w.n.l.o.g.
This is called the …rst Brillouin zone


[ π/ (a + b ) , π/ (a + b )) w.n.l.o.g.
This is called the …rst Brillouin zone
A of E (k ) for k values in the …rst Brillouin zone is the reduced
scheme

A plot of E (k ) in the reduced scheme is shown below

E(k)
energy curves in higher-order
Brillouin zones collapsed to the 1st zone
1st Brillouin Zone
Forbidden energy band
Allowed band
Forbidden energy band
k
−2π/(a+b) −π/(a+b) π/(a+b) 2π/(a+b)
Allowed energy plot in k-space

Consider a …ctitious 1-D crystal of length L bent such that x = 0 and

x = L coincide


x = L coincide
Applying the Born-von Karman boundary conditions then yields,
ψ (x + N (a + b )) = ψ (x )


x = L coincide
Applying the Born-von Karman boundary conditions then yields,
ψ (x + N (a + b )) = ψ (x )
Hence,
ψ (x + N (a + b )) = A exp fjk (x + N (a + b ))g

= ψ (x ) exp fjkN (a + b )g

This requires that,

exp fjkN (a + b )g = 1

This requires that,

Or
2πn N
k= , n = 0, 1, 2, . . . ,
N (a + b ) 2

This requires that,

Or
2πn N
k= , n = 0, 1, 2, . . . ,
N (a + b ) 2
N is the number of unit cells in the crystal or the number of atoms in
the one-dimensional crystal

The …rst Brillouin zone therefore lies in the range

π π
k<
a+b a+b


π π
k<
a+b a+b
and
N N
n 1
2 2


π π
k<
a+b a+b
and
N N
n 1
2 2
Hence, there are therefore N wavenumbers in the …rst Brillouin zone
corresponding to the number of unit cells


π π
k<
a+b a+b
and
N N
n 1
2 2
There is an allowed energy value in each band for each wavenumber


π π
k<
a+b a+b
and
N N
n 1
2 2
There is an allowed energy value in each band for each wavenumber

Each band can contain a maximum of 2N electrons, considering the
electron spin (Pauli’s exclusion principle)

E¤ective mass of an electron in a solid
An electron with energy near the Fermi level can gain energy from an
applied electric …eld and be excited to higher energy levels

We have already seen this when discussing the Drude-Sommerfeld
model of conduction in solids

The external force on the electron arising from an applied electric
!
…eld E = b x Ex is given by
Fext = q Ex

The external force on the electron arising from an applied electric
!
…eld E = b x Ex is given by
Fext = q Ex
According to Newton’s second law of motion, a completely free

electron is accelerated in the x-direction with an acceleration
Fext
a=
mn

In a solid however, an electron also experiences a local force Fi due to

interactions with the lattice in a perfect crystal

In a solid however, an electron also experiences a local force Fi due to

interactions with the lattice in a perfect crystal
The potential energy of the electron hence varies with position within
the crystal

Mass is interpreted as the inertial resistance of an object to

acceleration per unit applied force


For a force Fext applied to a free electron, the acceleration of the
electron is
Fext
afree =
mn


electron is
Fext
afree =
mn
When this force is applied to an electron in a crystal, the acceleration
will be
Fext + Fi
axtal =
mn


electron is
Fext
afree =
mn
When this force is applied to an electron in a crystal, the acceleration
will be
Fext + Fi
axtal =
mn
Fi is to be understood to be the total internal force acting on an
electron due to the crystal defects we have already encountered

The external force hence sees the electron as having a mass mn

di¤erent from the rest mass mn such that
Fext
axtal =
mn

The external force hence sees the electron as having a mass mn

di¤erent from the rest mass mn such that
Fext
axtal =
mn
Since atoms are arranged periodically in the crystal, Fi and the

electron potential energy in the crystal vary with position in a periodic
way

In a …lled band, Newton’s second law of motion is applicable as long

as the electron mass is modi…ed to a mass mn appropriate in the
given crystal

In a …lled band, Newton’s second law of motion is applicable as long

as the electron mass is modi…ed to a mass mn appropriate in the
given crystal
mn is hence an e¤ective mass of the electron in the crystal and
depends on the properties of the particular band in which the electron
resides

Lecture 11a Band Theory of Solids

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FEE3201 Physical Electronics A

Band theory of solids

WM (UoN) Band theory of solids 09/01 1 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

WM (UoN) Band theory of solids 09/01 2 / 81

In determining the energy band structure, three methods are usually

Our discussion will be con…ned to the LCAO method

WM (UoN) Band theory of solids 09/01 2 / 81

WM (UoN) Band theory of solids 09/01 3 / 81

WM (UoN) Band theory of solids 09/01 3 / 81

WM (UoN) Band theory of solids 09/01 3 / 81

WM (UoN) Band theory of solids 09/01 3 / 81

WM (UoN) Band theory of solids 09/01 3 / 81

Let ψσ be a molecular orbital that depends on the interaction

WM (UoN) Band theory of solids 09/01 4 / 81

Let ψσ be a molecular orbital that depends on the interaction

WM (UoN) Band theory of solids 09/01 4 / 81

WM (UoN) Band theory of solids 09/01 5 / 81

WM (UoN) Band theory of solids 09/01 5 / 81

WM (UoN) Band theory of solids 09/01 5 / 81

WM (UoN) Band theory of solids 09/01 5 / 81

WM (UoN) Band theory of solids 09/01 5 / 81

WM (UoN) Band theory of solids 09/01 5 / 81

An illustration of the bonding and anti-bonding orbital formation in a

bonding molecular orbital

antibonding molecular orbital

Bonding and antibonding molecular orbitals in a hydrogen molecule

WM (UoN) Band theory of solids 09/01 7 / 81

WM (UoN) Band theory of solids 09/01 7 / 81

WM (UoN) Band theory of solids 09/01 7 / 81

WM (UoN) Band theory of solids 09/01 7 / 81

Recall that the energy associated with a given wavefunction increases

WM (UoN) Band theory of solids 09/01 8 / 81

Recall that the energy associated with a given wavefunction increases

WM (UoN) Band theory of solids 09/01 8 / 81

Recall that the energy associated with a given wavefunction increases

WM (UoN) Band theory of solids 09/01 8 / 81

Recall that the energy associated with a given wavefunction increases

WM (UoN) Band theory of solids 09/01 8 / 81

The potential energy function in the H-H system has a positive

WM (UoN) Band theory of solids 09/01 9 / 81

The potential energy function in the H-H system has a positive

WM (UoN) Band theory of solids 09/01 9 / 81

The potential energy function in the H-H system has a positive

WM (UoN) Band theory of solids 09/01 9 / 81

The potential energy function in the H-H system has a positive

WM (UoN) Band theory of solids 09/01 9 / 81