ENGINEERING PHYSICS II (SUBJECT CODE: 303192102)

Dr. Mudra Jadav, Assistant Professor

Applied Sciences and Humanities (ASH), PIET, Parul University
 CHAPTER
Band Theory and Semiconductors
 Classification of solid Materials
• Solid materials can be classified into
three categories based on their
electronic structure and properties:
1. Conductors
2. Semiconductors
3. Insulators

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 Concept of Valence band, Conduction band and Band gap

• Valence band that contains energy

levels of valence electrons which
remain in the outermost orbit.

• Conduction band that contains energy

levels of free electrons (conduction
electrons)

• Band gap is the gap between the top

of the valence band and the bottom
of the conduction band which does
not contain any energy levels
(forbidden region).
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 Formation of Energy band in Solid (Qualitative Explanation)

• When atom is single, electrons in discrete orbits

will occupy discrete energy levels.
• Spreading of single energy level into two when
atoms containing single electrons are very close.
 Formation of Energy band in Solid (Qualitative Explanation)

• If there are N no. of such atoms very close to each other, then energy level n=1 will
spread out into N levels.
 Formation of Energy band in Solid (Qualitative Explanation)

• Similarly, if electrons are filled up to 3rd orbit in an

atom and when such atoms are brought close to
each other, then first n=3 level will spread out
because of interaction of outermost electrons.

• If the interatomic distance further decreases,

electrons of level n=2 will start interaction and
thus n=2 level will spread out.

• If the interatomic distance further decreases, then

electrons of level n=1 will also start interacting and
the level n=1 will also spread out at very small
interatomic distance.
 Formation of Energy band in Solid (Qualitative Explanation)
• When a collection of atoms is considered, the
permissible energy levels spread out into bands due to
interaction between atoms and electrons.
• As the interatomic distance is decreased, the discrete
levels broaden out into bands, eventually the bands
overlap at a point called cross over point.
• As the interatomic distance is further decreased, a split
occurs between the upper band and the lower band.
At the equilibrium spacing, the two bands are widely
separated.
• The upper and lower bands are called conduction and
valence band respectively.
• The gap between the two band is known as forbidden
energy gap (Eg).
• For diamond, Eg ≈ 6 eV at 300 K, it is a good insulator.
• For silicon, Eg ≈ 1 eV, it is a semiconductor.
 Brief Introduction: Free Electron Gas theory (classical)
• Free Electron theory of Metals (Drude-Lorentz’s classical Theory):
• Drude (in 1900) postulated that the metals consists of positive ion cores with the valence electrons
moving freely among these cores. The electrons are bound to move within the metal due to electro
static attraction between positive ion cores and the electrons. The potential field of these cores is
assumed to be constant or zero through out the metal.
• Successes:
• The free electrons in a metal move in random direction and do not constitute a current until an
electric field is applied across the metal which accelerate the electrons in a particular direction. For
this steady state current, magnitude of current is proportional to the voltage applied (at constant
temp.), as in Ohm’s law.
• This theory explained high electrical and thermal conductivities of metals.
• Failures:
• Temperature dependent resistivity could not be explained.
• Heat capacity and Paramagnetic susceptibility could not be explained.
 Brief Introduction: Sommerfeld’s Quantum theory of free electrons
• Sommerfeld’s Quantum Theory of free electrons:
• Sommerfeld treated the problem quantum mechanically using Fermi-Dirac statistics.
(in classical theory Maxwell-Boltzmann statistics considered)
• Consider an electron, which is bound to move in a one-dimensional box of crystal of length L. The
electron is prevented from leaving the crystal by the presence of a large potential energy barrier at
its surfaces (for simplicity V → ∞).
• We have
∞ ∞
• V(x) = 0 for 0 < x < L
• V(x) = ∞ for x ≤ 0 and x ≥ L
• Schrodinger’s wave equation is
V(x)

x
• Since V=0 inside the box
0 L
 Brief Introduction: Sommerfeld’s Quantum theory of free electrons
• The general solution of this equation is

• Where A and B are constants and can be determined from the

boundary conditions.
• K is wave vector, magnitude of which is given by,

• From Boundary conditions,

Where n = 1, 2, 3….
The energy levels and
• The allowed energy values are given by
corresponding wave functions
are shown in figure.
 Fermi Energy
• Each energy level (principle quantum number, n) can accommodate two electrons with magnetic spin
quantum number (ms), corresponding to values +½ and -½.
• If there are 7 electrons, it requires four energy levels n= 1, 2, 3, 4. The fourth level would contain the
last unpaired electron. That means n<4 would be occupied while n>4 would be empty.
• The topmost filled energy level at 0K is known as the Fermi level and the energy corresponding to
this level is called the Fermi energy (EF).
• For temp. greater than 0K, the Fermi level may not be the
topmost filled level since some electrons are thermally excited
to upper levels.
• The probability that a particular quantum state of energy E is
occupied at a temp. T is given by Fermi function,

• For temp. greater than 0K, the Fermi level may be defined as
the level where the probability of occupation is 1/2. At E=EF,
f(EF) = ½.
 Density of States
• The density of states g(E), is the total number of available energy states per unit volume in the
small energy range E to (E+dE).
• Consider a system of N free electrons, the occupied states may be represented by points inside a
sphere in the k-space. The energy corresponding to the surface of the sphere is Fermi energy (EF). Let
KF be the wave vector from the origin of the k-space to the surface of the sphere.
• Electron which lie on the same spherical shell of radius kF will have the same energy, Fermi energy
given by,
(1)
• Total number of energy states will be,

(2)

• The factor 2 appears because for each n, there are two

allowed values of ms, +1/2 and -1/2.
 Density of States
• Assume that the number of states are equal to the number of electrons (N). From Eq. (2)

(3)
• This shows that the value of kF depends on the concentration of electrons, N/V and independent of
mass of electron.
• From Eq. (1) and (3),
(4)
EF depends on both the electron concentration and mass.
• The total number of electrons is given by, from Eq. (1) and (2)

(5)
• Total number of electrons, Where D(E) Number of states in the small energy
range E to (E+dE) in the total volume V.

• Substitute value from Eq. (5)

 Density of States
• Expressing the integral in an indefinite form,

D(E) 1
g(E) =
V
 Introduction to Band theory
• Free Electron theory could not explained various properties of solids. For example why
certain solids have a large number of free electrons (i.e. metals) and certain others have
hardly any free electrons (i.e. insulators).
• The failure of free electron model is due to the oversimplified assumption that potential of
of ion cores experienced by conduction electrons is constant or zero.
• In the Band theory, ion cores are considered at rest and a potential experienced by an
electron in a crystal is assumed to be periodic with period equal to the lattice constant (a),
for one dimensional case.
 Kronig-Penny Model
• A simple one-dimensional model of periodic potential is
considered as shown in fig., free electron is travelling in
this periodic potential, square wells with period of (a+b).
• At the bottom of the well i.e. for 0<x<a the electron is
assumed to be in the vicinity of a ion core and the
potential energy is taken as zero. Whereas outside a well,
for –b<x<0, the potential energy is assumed to be V0.
• The Schrodinger equation for the two regions are,

• Where

• The wave function must be in the form of Bloch function where

 Kronig-Penny Model
• The general solution to these equations are,

• The Boundary conditions says that wave function ψ and its derivative 𝑑ψ 𝑑𝑥 and so 𝑢 and 𝑑𝑢 𝑑𝑥
must be continuous at x=0 and at boundaries x= a and –b.
• Applying Boundary conditions and assuming that V0 tends to infinity and b approaches zero, but the
product V0b remains finite, (potential barrier would infinitely thin), we can get
This is the condition which must be
satisfied for the solutions to the wave
• Where equation to exist.

• P is a measure of area V0b of the potential barrier. Thus increasing P has the physical meaning of
binding an electron more strongly to a particular potential well.
 Kronig-Penny Model
• From the equation, left hand side is plotted with 𝛼𝑎.
• The vertical axis lying between -1 and +1 are indicated by the horizontal lines, represents the values
acceptable to the left hand side.
• Conclusions are
(1) The energy spectrum of the electrons
consists of alternate regions of
allowed energy bands (solid lines on
abscissa) and forbidden energy bands
(broken lines).
(2) The width of the allowed energy
bands increases with 𝛼𝑎 or the
energy.
(3) The width of a particular allowed
energy band decreases with increase
in the binding energy of the electrons.
 Kronig-Penny Model
4. As P→∞, the allowed energy bands are compressed into energy levels and a line spectrum is
resulted. In such case,

Eq. has solution only if

so,

This equation gives energy levels of a particle in a constant potential box of atomic dimensions.
Physically, for large P, the tunnelling through the barrier becomes difficult.
5. As P→0, from equation

We get

so, which is applicable to completely free electrons for which all the
energies are allowed. Physically, electrons become free and free electron model becomes
applicable.
 E-K Diagram (Energy vs. Wave-vector Relationship)

• From Eq. and

E
total energy (E) of the electron versus the wave vector
(k) can be plotted as below.

𝑛𝜋
• For 𝑘 = ,
R.H.S of this equation becomes ±1 and
𝑎
hence the discontinuities in the E versus k graph occur
𝑛𝜋
at 𝑘 = , n= ±1, ±2, ±3……..
𝑎
• The electron has allowed energy values in the region
𝜋 𝜋
from 𝑘 = − to + . The zone is called the first
𝑎 𝑎
Brillouin zone.
• Then there is a break in the energy values called the
forbidden region (band).
 E-K Diagram (Energy vs. Wave-vector Relationship)

• Then another allowed zone of energy values in the

𝜋 2𝜋 𝜋
region extending from 𝑘 = − to − and 𝑘 = +
𝑎 𝑎 𝑎
2𝜋
to + . It is called second Brillouin zone.
𝑎
• In similar way, other higher order Brillouin zones can be
defined.

• The E-k curve in the reduced zone scheme is shown in

figure. It is obtained by reducing the contents of the
other zones so as to correspond to the first Brillouin
𝜋 𝜋
zone, i.e. to the region 𝑘 = − to + .
𝑎 𝑎
 Effective Mass of Electron

• Mass of electron under the influence of

periodic potential in a material is called
Effective Mass.

• When electron is moving through a crystal, it

experiences internal forces due to positive Effective Mass
ions and other electrons present. Hence, the of Electron
original mass of electron seems to change
and it is called effective mass of electron.

• Effective mass can be positive or it can be

negative also.
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 Effective Mass of Electron
• When effective mass is negative (after the point of inflection,
k0), electrons behave as a positively charged particles like
holes.

• Velocity decreases after point of inflection (when k>k0), thus

acceleration is negative i.e. opposite to the applied force
implying a negative mass.

• This means that in this region of k-space the lattice exerts

such a large retarding force on the electron that it overcomes
the applied force and produces a negative acceleration.
 Distinction between Metals, Insulators and Semiconductors
• Consider an energy band which is filled with electrons up to a certain level k1.
• The effective number of free electrons in the energy band are given by,

Conclusions:
(1) The effective number of free electrons in a completely filled band is zero. This is because dE/dk
vanishes at the top of the band
(2) The effective number of free electrons attains a maximum when the band is filled up to the point
of inflection.

• It follows that a solid having a partially filled energy band has

more free electrons and so act as conductor.
• A solid having certain number of energy bands completely
filled and all other bands completely empty, will act as an
insulator.
Direct and Indirect band gap materials
Direct Band Gap Materials
Indirect band gap materials
Examples of Direct and Indirect band gap materials
Application of Direct and Indirect band gap materials
Density of States in Semiconductor
Density of States in Semiconductor
Continue
Energy dependence on density of state
Charge Carrier Concentration
Concentration of Electrons in Conduction band
Concentration of Electrons in Conduction band
Cont….
Concentration of Electrons in Conduction band
Cont….
Concentration of Electrons in Conduction band
Cont….
 Concentration of holes in Valence band

(for holes)

P
(1 - )
Concentration of holes in Valence band
Cont….
Concentration of holes in Valence band
Cont….
Concentration of holes in Valence band
Cont….
 Intrinsic Semiconductor

T = 0K At any ordinary temperature, T

• Each silicon atom has four valence electrons and can form four covalent bonds with four
neighbouring silicon atoms. At T=0K, no electron is free to cause conduction.
• As temp. increases above 0K, some of the electrons acquire sufficient thermal energy to break
covalent bond and become free. These electrons move randomly in the crystal, referred as
conduction electrons. Each escaped electron leaves behind an empty space called a hole, which also
act as current carrier.
 Intrinsic Semiconductor

T = 0K At any ordinary temperature, T

• An electron-hole pair is generated. In intrinsic semiconductor the electrons in the conduction band
are always equal to the holes in the valence band (ni = pi).
• The electrons move when the conduction band is nearly empty, and holes move when the valence
band is nearly full. Thus electrons move mainly under the applied electric field while holes move
under the combined effect of the applied electric field and the ionic field of the lattice. Thus the
properties such as effective mass, mobility etc. of a hole are quite different from the corresponding
properties of electrons. E.g. a hole has larger effective mass and lower mobility than the
corresponding properties of electrons.
 Extrinsic Semiconductor: N-type
• When a pentavalent impurity
(donor) atom such as phosphorus,
arsenic or antimony, is introduced
into silicon, four of its five valence
electrons form covalent bonds
with the neighbouring four silicon
atoms while the fifth valence
electron remains loosely bound to
its nucleus.
• The energy level corresponding to the fifth valence electron lies in the band gap just below the
conduction band edge. It is called donor level.
• The electrons in the donor level can be easily transferred to the conduction band, leaving behind
positively charged immobile impurity ions.
• The electron concentration is quite large as compared to hole concentration in n-type
semiconductor, but their product always remains constant (n0p0 = nipi = ni2).
 Extrinsic Semiconductor: P-type
• When a trivalent impurity (acceptor)
atom i.e. boron, aluminium, gallium or
indium, is introduced into silicon, it
forms three covalent bonds with the
neighbouring three silicon atoms, while
the fourth bond is not completed due to
the deficiency of one electron. The
incomplete bond is shown by a broken
line, and the small circle presents
electron deficiency (hole).
• The trivalent impurity atom has a tendency to accept one electron from the neighbouring silicon atom.
• The energy level corresponding to the hole is located just above the valence band and is called acceptor
level. An electron can be easily transferred from the valence band to the acceptor level (energy provided
through thermal agitation).
• The negatively charged impurity atom remains immobile and does not contribute to conduction.
• The concentration of holes is large compared to electrons but their product will be same (n0p0=nipi=ni2).
Position of Fermi Level in Semiconductors
 Position of Fermi Level in Intrinsic Semiconductor

• Substitute eq. (2) and (3) in (1),

F ……(2)

F ……(3)

• Fermi level is equal to the intrinsic level, EF=Ei, ……(4)

 Position of Fermi Level in Intrinsic Semiconductor
Cont….
• From and, , Eq (4) can be written as,

• At T=0K,
• The Fermi level lies in the middle of the
conduction band and valence band.

• This is also true at all other temperatures provided that mn=mp.

• In general, mp>mn and Fermi level is raised slightly as T exceeds 0K. For practical
purposes, increase (so small) in Fermi level can be neglected.
Position of Fermi Level in Extrinsic Semiconductor

0
Position of Fermi Level in Extrinsic Semiconductor
Cont….

0
 Position of Fermi Level in Extrinsic Semiconductor
Cont….
0

0 0

For N-type Semiconductor For P-type Semiconductor

 Position of Fermi Level in Semiconductors

0 0

0 0

0 0
 P-N Junction
• The p-type region has excess holes and n-
type region has excess electrons which are
free to move at ordinary temperatures.
• At junction, due to the gradient of
concentration of carriers, some of the
electrons of the n-region diffuse into the p-
region where they recombine with an equal
number of holes.
• Similarly, some holes diffuse from p-side to
n-side and recombine with an equal number
of electrons. Such flow of carriers constitute
diffusion current.
• Due to such recombination, positive charges
are developed in the n-region and negative
charges are developed in the p-region near
the junction, are called uncovered charges.
 P-N Junction
Cont….

• Due to the presence of these charges, a negative potential built up in the p-region and a
positive potential is built up in the n-region near the junction. It is called built-in-potential
(VB).
• The corresponding electric field is called the barrier field and is directed from n-side to p-
side. It opposes further diffusion of carriers across the junction.
• The region in which the barrier field exists is depleted of carriers and is known as depletion
region. Its thickness is of the order of 10-6 m.
• The p-region always contains some electrons and n-region always contains some holes as
the minority carriers. The presence of electric field helps the minority carriers to cross over
the junction and hence produces a current known as the drift current.
• The drift current is always equal and opposite to the diffusion current and there is no steady
state movement of charges across the junction.
 P-N Junction
Cont….
• The energy of an electron in the n-region is less than that of an electron in the p-
region. The difference in electron energies in the two regions is known as the
barrier energy, EB = eVB. This energy is required by an electron to move from n-side
to p-side. An equal amount of energy is also required by a hole to cross the
depletion layer in opposite direction.
p n
 Biased P-N Junction
• Forward Bias:
• When the positive terminal of a battery is
connected to the p-side and the negative
terminal to the n-side, the junction is said to be
forward biased.
• In forward bias, the electrostatic potential
barrier of junction decreases to the value VB-V.
Thus applied force opposes the built-in field,
the electric field within the junction decreases.
The majority carriers move more towards the
junction. So, junction width reduces. The
energy bands separation decreases to e(VB-V).
• As V exceeds VB, the effect of barrier potential
is completely eliminated and the p-n junction Forward Bias Reverse Bias
allows flow of current offering little resistance.
 Biased P-N Junction
• Reverse Bias:
• When the positive terminal of a battery is connected
to the n-region and the negative terminal to the p-
region, the junction is said to be reverse biased.
• In reverse bias, the applied voltage is in the same
direction as the intrinsic electrostatic potential barrier Symbolic representation of P-N junction in
case of (a) Forward bias (b) Reverse bias
and hence increases the height of the potential barrier
VB+V. This increases the built-in field which forces the
majority carriers to move further away from the
junction, therefore widening the depletion layer. The
energy bands separation decreases to e(VB-V).
• A small reverse saturation current flows in the
direction of applied voltage due to movement of
minority carriers which are generated due to thermal
effects. This current increases with temperature. I-V characteristic of P-N Junction
 Application of P-N junction diode

• A p-n junction diode allows current to pass only when

it is forward biased. This property is used to rectify
alternating voltages and the circuit used for this
purpose is called a rectifier.
• When the voltage at A is positive, the diode is forward
biased and it conducts. When A is negative, the diode
is reverse-biased and it does not conduct. The reverse
saturation current of a diode is negligible and can be
considered equal to zero for practical purposes.
• If an alternating voltage is applied across a diode in
series with a load, a pulsating voltage will appear
across the load only during the half cycles of the ac
input during which the diode is forward biased.
Ohmic Junction
Continue

I-V Characteristics
Schottky Junction
Continue

I-V Characteristics
 References

1. Solid State Physics, R. K. Puri and V. K. Babbar

2. Engineering Physics, H. K. Malik and A. K. Singh
www.paruluniversity.ac.in