Introduction to Solid State

And Semiconductors

IILM University, Greater Noida

Energy Bands in Solids
• Atom or Molecule is an aggregate of positive ions (immobile on lattice) and negative
free electrons

• The valence electrons are free to move about the whole volume.

• The free electrons move in a completely uniform potential field which is provided by the
lattice ions.

• The motion of electrons in a periodic lattice is characterised by the states of allowed

energy separated by forbidden regions.

• For an isolated atom, the electrons are tightly bound and have discrete, sharp energy
levels.
Energy Bands in Solids
• When atoms are brought together to form a crystal, the valence electrons interact and
constitute a simple system of electrons common to the entire crystal. Therefore all
electrons have to occupy different energy levels, which may be brought about by the
forces exerted by the nuclei of all atoms. As a result of these forces each atomic
energy level splits into large number of closely spaced energy levels. A set of such
closely spaced energy levels is called a band.

• Each energy band has large number of energy levels. The energy levels are filled
according to Pauli Exclusion Principle which states that an energy level can
accommodate only two electrons and each electron can have two possible states (spin
up or spin down)

• The width of this band depends on the degree of overlap of electrons of adjacent
atoms.The amount of splitting is not same for different levels. The levels filled by
valence electrons are distributed to a great extent, while those filled with electrons of
inner shells are distributed only slightly.
Energy Bands in Solids

•
Energy Bands in Solids
Energy Bands in Solids
• Consider Sodium atoms, the ground state configuration of isolated Na atom is
2 2 6 1
1s 2s 2p 3s .
2 2 6 1
• 1s 2s 2p is completely filled while 3s is half filled
• For large atomic distances, the interactions between atoms are negligible and the
energy levels remain un-splitted. With the decrease in interatomic distance, 3s level
splits into bands and with further decrease in distance, 2p level also starts to split. 1s
and 2s levels does not split at all.

• If there are N atoms in a solid, there are N allowed states in each band. Each state can
be occupied by a maximum of two electrons with opposite spin. Thus each band can be
occupied by 2N electrons.
Energy Bands in Solids
Energy Bands in Solids
• VALANCE BAND: In this band large number of free electrons are available. This band is
partially or completely filled. This band is never empty.

• CONDUCTION BAND: The density of electrons in this band is very low. This band is
either empty or partially filled. This band can be empty.

• FORBIDDEN BAND: The separation between valance band and conduction band is
called forbidden band. This band is completely empty.

•
Metals, Semiconductors, Insulators
• On the basis of the forbidden energy band gap, solids are divided into metals,
semiconductors and insulators.

• METALS or CONDUCTORS: In metals, the conduction band and valance band overlaps.
There is no forbidden energy band. A large number of free electrons are available for
electrical conduction. Eg, copper, iron, silver, aluminium.

• SEMICONDUCTORS: In semiconductors, the forbidden band gap is small (less than

1eV). At finite temperature (room temperature) some electrons gain sufficient energy
and jump from valence band to conduction band. When electrons jump to conduction
band they leave hole behind. Eg, Silicone, Germanium, Graphite.

• INSULATORS: In Insulators the forbidden energy band gap is very large (greater than
5eV). The valence electrons are tightly bound to parent atom. Even at finite
temperature the conduction band remains empty. Thus the material does not allow flow
of electric current. Eg, glass,
Metals, Semiconductors, Insulators
Density of States
• The Density of States (DOS) of a system can be defined as the number of states
available to be occupied by electrons per interval of energy E+dE.

• In other words it is number of electron states per unit volume per unit energy

• For a system, high DOS at a specific energy level means that there are many states
available for occupation and zero DOS means that no state can be occupied at that
energy level.

• It is given by expression,

4π 3/2 1/2
D(E) = 3 (2m) E
h
Fermi Dirac Distribution
• The electrons that occupy orbits are described by Fermi Dirac distribution.It
represents the probability of occupation of a state with energy E.

• The Fermi-Dirac distribution applies to fermions, particles with half-integer spin which
must obey the Pauli Exclusion Principle.

• In fields like electronics, one particular factor which is of prime importance is the
conductivity of materials. This characteristic of the material is brought about the
number of electrons which are free within the material to conduct electricity. As per
energy band theory, these are the number of electrons which constitute the conduction
band . Thus in order to have an idea over the conduction mechanism, it is necessary to
know the concentration of the carriers in the conduction band.

1
Mathematically it is given by expression, f(E) =

( kBT )
• E − EF
exp +1
Fermi Dirac Distribution
Fermi Dirac Distribution
Fermi Dirac Distribution
• At T = 0 K, the electrons will have low energy and thus occupy lower energy states. The
highest energy state among these occupied states is referred to as Fermi-level. This
inturn means that no energy states which lie above the Fermi-level are occupied by
electrons. Thus we have a step function defining the Fermi-Dirac distribution function
as shown by the black curve in Figure.

• As the temperature increases, the electrons gain more and more energy due to which
they can even rise to the conduction band. Thus at higher temperatures, one cannot
clearly distinguish between the occupied and the unoccupied states as indicated by
the blue and the red curves shown in Figure.
Fermi Level
• Maximum Possible energy possessed by free electrons at absolute zero.

• Fermi energy is the measure of the energy of the least tightly held electrons within a
solid

• Value of fermi energy is different for different materials.

• Fermi level is that energy level in energy-band-diagram for which the probability of
occupancy becomes half.
Fermi Level
Ec − EF
For conduction band, n = Ncexp[ − ( )]
kBT
EF − Ev
For valence band, p = Nvexp[ − ( )]
kBT

For intrinsic semiconductor, n = p = ni

EF − Ev Ec − EF
Nvexp[ − ( )] = Nc exp[ − ( )]
kBT kBT
Nv 2EF − Ec − Ev
= exp( )
Nc kBT
Fermi Level
Nv 2EF − Ec − Ev
ln =
Nc kBT
kBT Nv Ec + Ev
EF = ln +
2 Nc 2
Ec + Ev
At 0K, EF =
2
Fermi level lies in the middle of the conduction band and valence band.
Intrinsic Semiconductors
• A semiconductor that does not have any kind of impurities is known as intrinsic
semiconductor or pure semiconductor

• It behaves as an insulator at 0K and as a conductor at higher temperatures.

• Eg, Germanium and silicon.

Extrinsic Semiconductors
• A semiconductor which is doped with impurities is called an extrinsic semiconductor.

• Adding suitable amount of impurities to pure semiconductor is called doping.

• Extrinsic semiconductors can be of two types: p-type semiconductors and n-type

semiconductors.

• p-type semiconductors: Adding trivalent impurities (like Al, Ga, In..) to pure
semiconductor creates p-type semiconductor. In this majority charge carriers are
holes.

• n-type semiconductors: Adding pentavalent impurities (like P, As, Sb,..) to pure

semiconductor creates n-type semiconductor. In this majority charge carriers are
electrons.
Extrinsic Semiconductors
Effective Mass
• An electron in a crystal interacts with the lattice potential, hence its response to
external force is different from a free electron.

• An electron in crystal may behave as if it had a mass different from the free electron
mass m . There are crystals in which the effective mass of the carriers is much larger
or much smaller than m .

• Hence the deviation of electrons behavior is taken into account by considering

electrons to have effective mass m*.

1
m* =
• 1 d 2E

ℏ2 dk 2
Carrier Concentration
• The concentration of electrons and holes in a semiconductor can be obtained from density of states in
valence band and conduction band

• Electron concentration in the Conduction band is number of free electrons per unit volume in an energy range
E and E+dE

dn = D(E)f(E)dE

[ ( kBT )] ( )
3/2
Ec − EF 2πmn * kBT
n = Ncexp − ; Nc = 2
h2
• Number of holes per unit volume in an energy range E and E+dE

dp = D(E)(1 − f(E))dE
3/2

[ ( kBT )]
2πmp * kBT
( )
EF − Ev
p = Nvexp − ; Nv = 2
h2
Law of Mass Action
• For a given semiconductor, the product of electron and hole concentrations is a
constant at a given temperature and is equal to square of intrinsic carrier
concentration. This is law of mass action and is valid for both intrinsic and extrinsic
semiconductors.

• For intrinsic semiconductor, n = p = ni

Ec − Ev
Eg
2
np = ni = NcNvexp − = NcNvexp −
kBT kBT

( h2 ) (
3
2πk T
)
3/2
2 B −Eg/kBT
np = ni = 4 mn * mp * e

( h2 )
Eg 3/2
2πkBT
( )
3/4
np = (NcNv) exp −
1/2 −Eg/2kBT
ni = =2 mn * mp * e
2kBT