Band Theory of solids:

In simple MO theory, the atomic orbitals on two atoms come together to form
bonding and anti-bonding orbitals.

• If we bring three atoms together we will have a bonding orbital, an anti-

bonding orbital, and a nonbonding orbital. Nonbonding orbital is an orbital that
neither increases nor decreases the net bonding in the molecule. So, three
atomic orbitals result in three molecular orbitals.

• Now if it is extended to ‘n’ atomic orbitals, there must be ‘n’ molecular orbitals
produced. If n is even there will be n/2 bonding and n/2 anti-bonding orbitals. If n
is uneven, there will be a non-bonding orbital.

• If the n is so large (like Avogadro number) then there will be huge number of
bonding and anti-bonding orbitals.
• These orbitals will be so close together in energy that they begin to blur (and
appear to be continuous) and create bands of bonding and anti-bonding
orbitals, as follows:
• All of the MOs are delocalized over all of the atoms in the solid, the highest
filled band of MOs is called the valence band; the lowest unfilled band is
called the conduction band.

• Valence Band
• The energy band involving the energy levels of valence electrons is known
as the valence band.

• It is the highest occupied energy band.

• When compared with insulators, the band gap in semiconductors is smaller.

• It allows the electrons in the valence band to jump into the conduction band
on receiving any external energy.

• The energy separation between the top of the valence band and the bottom
of the conduction band is called the band gap.
Conduction Band
 It is the lowest, unoccupied band that includes the energy levels of
positive (holes) or negative (free electrons) charge carriers.

 It has conducting electrons resulting in the flow of current.

 The conduction band possess a high energy level and is generally empty.

 The conduction band in semiconductors accepts the electrons from the

valence band.
The electronic band structure is an energy diagram to describe the conductivity of
conductors, insulators, and semiconductors.
The diagram consists of two energy bands (valence and conduction band) and the
band gap.
 Semiconductors

Semiconductors are materials which

have a conductivity between
conductors (generally metals) and
non-conductors or insulators (such as
silicon
ceramics).

Semiconductors can be compounds,

such as gallium arsenide, or pure
elements, such as germanium or
silicon.

germanium
 Semiconductors
• A semiconductor is a solid with a filled valence and an
empty conduction band, with small band gap, as shown
in the Figure.

In case of semiconductors, the valence band is

completely filled and conduction band is empty at 0 0K.
But the forbidden gap is about 1ev.

• There is a small thermal population of the conduction

band at normal temperature (some electrons from
valence band get excited into conduction band with the
energy of room temperature), hence a small
conductivity.
• Increase in temperature increases conductivity
further. (In metals, increase in temperature reduces
conductivity).
Example: Silicon
Example: Silicon
• It has a band gap of only 1.12 eV, due to poor overlap of the sp3 hybrids of
the larger Si atoms.
In the group 4 elements, the band gap decreases in magnitude for the larger atoms as
orbital overlap becomes weaker. C (5.47 eV) is insulator, Si (1.12 eV) &Ge (0.66
eV) show semi-conductivity, while Sn (0 eV) shows high conductivity as a metal.
Doped semi-conductors (Role of doping on band structures)
When a pure semi-conductor like Silicon is doped with a penta-valent elements like
Phosphorus, Arsenic, Antimony etc. it becomes electron rich (as per octet rule) and is
called n-doped semiconductor.
Similarly, when doped with trivalent elements like Boron, Aluminum, Indium etc. it
becomes electron deficient (or hole rich) and is called p-doped semiconductor.

• In such a doping, new energy levels (or bands) are formed between the valence band
and conduction band by the doped elements. A donor level corresponding to n-
doping (close to conduction band) & and an acceptor level corresponding to p-
doping (close to valence band) are formed.
• These intermediate energy levels facilitate easy electron jump, in steps, from valence
band to conduction band, because less energy is required as compared to direct jump
from valence band to conduction band.
• The doped semiconductors therefore show higher conductivity.
Applications of Semiconductors
 Temperature sensors are made with semiconductor devices.  They
are used in 3D printing machines
 Used in microchips and self-driving cars
 Used in calculators, solar plates, computers and other electronic
devices.
 The physical and chemical properties of semiconductors make them
capable of designing technological wonders like microchips,
transistors, LEDs, solar cells, etc
 The microprocessor used for controlling the operation of space
vehicles, trains, robots, etc., is made up of transistors and other
controlling devices, which are manufactured by semiconductor
materials.