Electrical Properties of

Material
EECE 315

Muhammed Zubair Rahman

Lecturer
Department of Electrical, Electronic and Communication
Engineering (EECE)
Military Institute of Science and Technology,
Dhaka, Bangladesh
Class – 22&23
Band Theory of Solids
Preliminary Talks

Postulates of Bohr’s Model of an Atom

• In an atom, electrons (negatively charged) revolve around the positively

charged nucleus in a definite circular path called orbits or shells.

• Each orbit or shell has a fixed energy and these circular orbits are known
as orbital shells.

• The energy levels are represented by an integer (n=1, 2, 3…) known as the
quantum number. This range of quantum number starts from nucleus side
with n=1 having the lowest energy level. The orbits n=1, 2, 3, 4… are
assigned as K, L, M, N…. shells and when an electron attains the lowest
energy level, it is said to be in the ground state.

• The electrons in an atom move from a lower energy level to a higher

energy level by gaining the required energy and an electron moves from a
higher energy level to lower energy level by losing energy.
Preliminary Talks
Aufbau Principle

• It states that electrons are filled into atomic orbitals in the increasing
order of orbital energy level. According to the Aufbau principle, the
available atomic orbitals with the lowest energy levels are occupied
before those with higher energy levels.
• The order in which the energy of orbitals increases can be determined
with the help of the (n+l) rule, where the sum of the principal and
azimuthal quantum numbers determines the energy level of the orbital.
• The order in which the orbitals are filled with electrons is: 1s, 2s, 2p, 3s,
3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, and so on.

Pauli Exclusion Principle

• The Pauli exclusion principle states that in a single atom, no two electrons
will have an identical set or the same quantum numbers.
• The two electrons that are present in the same orbital must have opposite
spins, or they should be antiparallel.
Preliminary Talks

de Broglie Wavelength

Scientist de Broglie reasoned that matter also could show wave-

particle duality, just like light, since light can behave both as a
wave (it can be diffracted and it has a wavelength) and as a
particle (it contains packets of energy hν). He also reasoned that
matter would follow the same equation for wavelength as light,
namely,

λ=h/p
Where p is the linear momentum
Preliminary Talks
Schrodinger Wave Equation

• The Schrodinger wave equation is a mathematical expression describing

the energy and position of the electron in space and time, taking into
account the matter wave nature of the electron inside an atom.
• It is based on three considerations. They are:
❖ Classical plane wave equation
❖ Broglie’s hypothesis of matter-wave
❖ Conservation of energy

• The Schrodinger equation gives us a detailed account of the form of

the wave functions or probability waves that control the motion of
some smaller particles.
• The equation also describes how these waves are influenced by
external factors.
• Moreover, the equation makes use of the energy conservation
concept that offers details about the behavior of an electron that is
attached to the nucleus.
Band theory from molecular orbital

Psi MO is the summation of number of different atomic orbitals in the

molecule but multiplied by respective co-efficient.
MOLECULAR ORBITAL THEORY OF BONDING

• We’re interested to know the physics when two hydrogen

atoms approach each other to form the hydrogen molecule.

• Let us examine the energy levels of the H–H system as a

function of the interatomic distance R. When the atoms are
infinitely separated, each atom has its own set of energy levels,
labeled 1s, 2s, 2p, etc. The electron energy in each atom is
−13.6 eV with respect to the “free” state. The energy of the
two isolated hydrogen atoms is twice −13.6 eV.

• As the atoms approach closer, the electrons interact both with

each other and with the other nuclei. The new energy is
actually lower than twice −13.6 eV, which means that the H2
formation is energetically favorable.
Molecular Orbital Formation

Molecular Orbita0l (ψ)

depends on the interaction
of individual atomic
wavefunctions and is
symmetric
regarded as an electron considerable magnitude
wavefunction within the between the nuclei
molecule.

asymmetric
a node
Two ways: between the nuclei
both same direction (+)
or
opposite direction (-)
Molecular Orbital Formation
The resulting electron probability distributions

Figure 4.2
• Since ψσ* has a node, it holds a higher energy than the ψσ orbital and therefore
a different energy quantum number, which means that the Pauli exclusion
principle is no longer violated.
• ∣ψσ ∣2 has an appreciable electron concentration between the two nuclei, the
electrostatic PE, and hence the total energy for the wavefunction ψσ , will be
lower than that for ψσ* , as well as those for the individual atomic wavefunctions.
Molecular Orbital Formation

• The two energies, Eσ and Eσ* ,

are widely different, with Eσ
below E1s and Eσ* above E1s.
• As R decreases and the two
H atoms get closer, the energy
of the ψσ orbital state passes
through a minimum at R = a.
• Each orbital state can hold two
electrons with spins paired, and
within the two hydrogen atoms,
there is exactly two electrons.

Figure 4.3:
(a) Energy of ψσ and ψσ* vs. the
interatomic separation R.
(b) Schematic diagram showing the changes in the electron energy as two isolated H
atoms, far left and far right, come together to form a hydrogen molecule.
Molecular Orbital Formation
• When two atoms are brought together, the two identical atomic wavefunctions
combine in two ways to generate two different molecular orbitals, each with a
different energy. Effectively, then, an atomic energy level, such as E1s , splits
into two, Eσ and Eσ* .
The splitting is due to the interaction (or overlap) between the atomic orbitals.

• If these electrons enter the ψσ orbital and pair their spins, then this new
configuration is energetically more favorable than two isolated H atoms.
It corresponds to the hydrogen molecule H2 .

• The energy difference between that of the two isolated H atoms and the Eσ
minimum energy at R = a is the bonding energy or stabilization energy.
• When the two electrons in the H2 molecule occupy the ψσ orbital, their
probability distribution (and hence, the negative charge distribution) is such
that the negative PE, arising from the attractions of these two electrons to the
two protons, is stronger in magnitude than the positive PE, arising from
electron–electron repulsions and proton–proton repulsions and the kinetic
energy of the two electrons.
Therefore, the H2 molecule is energetically stable.
Molecular Orbital Formation

We’ve two MOs, one Bonding MO and another Antibonding MO. Bonding MO is
the result of constructing interference (build up the electron density of electron
between the nuclei causing most favorable Columbic attracting force with the
positively charged nuclei) of the wave functions of the atomic orbitals and
Antibonding is the vice-versa.
Molecular Orbital Formation

Energy destabilization = 17.2 eV

Energy stabilization = 4 eV

Thus, the Bonding MO is the most favorable and stable zone

for electrons to reside and form molecule.
Molecular Orbital Formation

This is the plot of molecular orbital wavefunction along internuclear axis.

Bonding MO Antibonding MO
• Constructive Interference • Destructive Interference
• Increases e density between • Nodal Plane between nuclei
nuclei • Higher energy
• Lower energy
Molecular Orbital Formation

• Now, the 1s orbital has paired

electrons and is full.

• The 1s atomic energy level will

again split into two levels, Eσ and
Eσ* , associated with the
molecular orbitals ψσ and ψσ*.

• However, in the He–He system,

there are four electrons, so two
occupy the ψσ orbital state and Figure 4.5 (in S.O. Kasap, 4ED): Two
two go to the ψσ* orbital state. He atoms have four electrons.
Consequently, the system energy is When He atoms come together,
not lowered by bringing the two two of the electrons enter the Eσ
He atoms closer. level and two the Eσ* level, so the
overall energy is greater than two
isolated He atoms
Molecular Orbital Formation

• From the He–He example, we can conclude that, as a general rule, the overlap
of full atomic orbital states does not lead to bonding.
• In fact, full orbitals repel each other, because any overlap results in an increase
in the system energy.
• To form a bond between two atoms, it essentially needs an overlap of half-
occupied orbitals, as in the H2 molecule.
Molecular Orbital Formation
Bond
Order
• Bond Order = 0.5*(Nb –Na)
• It corresponds to the number of possible bonds that can take place to form a
molecule.
• Nb = number of Bonding Electron
• Na = number of Electron present at Antibonding Orbital
• If Nb > Na , then the molecule is said be stable. However, if Nb ≤ Na,
then the molecule is considered to be unstable.
• For instance:
• H2 molecule, Bond Order = 0.5*(2 - 0) = 1 ; stable
• 2He molecule, Bond Order = 0.5*(2 - 2) = 0 ; unstable

Can the BO be fractions? If it is, than what does it signify???

Molecular Orbital Formation

• When we bring three hydrogen atoms (labeled A, B, and C) together, we

generate three separate molecular orbital states, ψa , ψb , and ψc , from
three ψ1s atomic states.

• Each molecular orbital must be either symmetric or antisymmetric with

respect to center atom B. The reason is that the molecule A–B–C in which
A, B, and C are identical atoms, is symmetric with respect to B.

• Thus, each wavefunction must be either symmetric or antisymmetric, that

it must have even or odd parity.
The orbitals that satisfy even and odd requirements are:

where, ψ1s (A), ψ1s (B), and ψ1s (C) are the 1s atomic wavefunctions centered
around the atoms A, B, and C, respectively.
 Molecular Orbital Formation
Decreasing
Stability

• Since ψa , ψb , and ψc are different, their energies Ea , Eb , and Ec must be

different. Consequently, the 1s energy level splits into three separate levels,
corresponding to the energies of ψa , ψb , and ψc.
• The number of nodes increases while the stability decreases. The configuration
with the lowest number of nodes is most stable (or lowest in energy).
Molecular Orbital Formation

• Thus, ψa has the lowest energy Ea , ψb

has the next higher energy Eb , and ψc
has the highest energy Ec.

• There are three electrons in the 3H

system. The first two pair their spins and
enter orbital ψa at energy Ea , and the
third enters orbital ψb at energy Eb.

• In comparison, we notice that although

H2 and H3 both have two electrons in
the lowest energy level, H3 also has an
extra electron at the higher energy level
(Eb ), which tends to increase the net
energy of the atom. Thus, the H3
molecule is much less stable than the H2
molecule.
Molecular Orbital Formation

• Consider the formation of a solid of N number of Li

(lithium) atoms from infinity and bring them together to
form the Li metal.
• Lithium has the electronic configuration 1s2 2s1 , which is
somewhat like the hydrogen atom, since the K shell is
closed and the third electron is alone in the 2s orbital.
• Based on our previous discussions, we assume that the
atomic energy levels will split into N separate energy levels.
• Since the 1s electrons will stay close to their parent nuclei,
we will not consider them during formation of the solid.
• As N atoms are brought together to form the solid, the
energy level at E2s splits into N finely separated energy
levels. The maximum width of the energy splitting depends
on the closest interatomic distance a in the solid.
Molecular Orbital Formation

• Consequently, there are N separate energy levels, each of which can take
two electrons with opposite spins. The N electrons fill all the levels up to and
including the level at N/2.
• Therefore, the band is half full. Half filled simply means half the states in the
band are filled from the bottom up.
Molecular Orbital Formation

• We can get an idea of the separation of energy levels in the 2s band by noting
that the maximum separation, ET − EB, between the top and bottom of the
band is on the order of 10 eV, but there are some 10^23 atoms, giving rise to
1023 energy levels between EB and ET. Thus, the energy levels are finely
separated, forming, for all practical purposes, a continuum of energy levels.
• The 2p energy level, as well as the higher levels at 3s and so on, also split into
finely separated energy levels.
• In fact, some of these energy levels overlap the 2s band; hence, they provide
further energy levels and “extend” the 2s band into higher energy levels which
shows how energy bands in metals are often represented.
• We therefore have a band of energies that stretches from the bottom of the 2s
band all the way to the vacuum level.
Molecular Orbital Formation
Figure 4.9 (S.O. Kasap, 4ED) As Li
atoms are brought together from
infinity, the atomic orbitals overlap
and give rise to bands (Schematic only.
) 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.

Figure 4.10 (S.O. Kasap, 4ED) In a

metal, the various energy bands
overlap to give a single energy band
that is only partially full of electrons.
There are states with energies up to
the vacuum level, where the
electron is free.
Molecular Orbital Formation

• The separation between the filled

states and the empty states is called
the Fermi energy and is denoted by
EF.

• At a temperature of absolute zero, or

nearly so, the thermal energy is
insufficient to excite the electrons to
higher energy levels, so all the
electrons pair their spins and fill each
energy level from EB up to an energy
level EFO that we call the Fermi level Figure 4.11 (S.O. Kasap, 4ED) Typical
at 0 K electron energy band diagram for a
metal. All the valence electrons are
• The band formed by the empty 2p in an energy band, which they only
shell as the conduction band. partially fill. The top of the band is
the vacuum level, where the electron
is free from the solid (PE = 0).
Band structure of Solids

The energy spectrum gradually changes

as atoms are assembled to form the solid
Properties of Electron in a Band
Properties of Electron in a Band
Properties of Electron in a Band
• The electrons below the b′ energy level do not contribute to conduction and are
excluded from further consideration. Notice that electrons above the b′ level are
only moving right and their momenta are not canceled.

• Thus, the conductivity is determined by the electrons in the energy range from
b’ to a’ about the Fermi level.

• Further, as the energy change from a to a′ is orders of magnitude smaller than

EFO, we can summarize that conduction occurs by the drift of electrons at the
Fermi level.
Properties of Electron in a Band
• The application of the electric field bends
the energy band, because the electrostatic
PE of the electron is −eV(x) where V(x) is
the voltage at position x.

• However, V(x) changes linearly from 0 to V,

by virtue of dV∕dx = −Ex .

• Since E = −eV(x) adds to the energy of the

electron, the energy band must bend to
account for the additional electrostatic
energy.

• Since only the electrons near EFO

contribute to electrical conduction, we can
represent this by drifting the electrons at
EFO down the potential hill.