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Energy-Band Theory

We have seen that every shell is associated with an energy level. An electron orbiting very close
to the nucleus in the first shell is very much tightly bound to the nucleus and possesses only a small
amount of energy. Hence first shell has lowest energy level. Greater the distance of an electron
from the nucleus, the greater is its energy. Hence the energy level of the outer most shell is highest.
Due such high energy, the valence electrons in the outermost shell can be easily extracted out and
hence such electrons take part in chemical reactions and in bonding the atoms together.
The valence electrons possess highest energy level. When such electrons from covalent bonds, due
to the coupling between the valence electrons, the energy levels associated with the valence
electrons merge into each other. This merging forms an energy band.
Similarly the energy levels of various electrons present in the first orbit, second orbit etc. also
merge to form the various energy bands.
So instead of the presence of widely separated energy levels as that of the isolated atoms, the
closely spaced energy levels are present in a solid, which are called energy bands.
Out of all the energy bands three bands are most important to understand the behavior of solids.
These bands are:
Valence band: The energy band formed due to merging of energy levels associated with the
valence electrons is called valence band.
Conduction band: The energy band formed due to merging of energy levels associated with the
free electrons is called conduction band.
- Under normal condition, the conduction band is empty and once energy is imparted, the
valence electrons jump from valence band to conduction band.
- While jumping from valence band to conduction band the electrons have to cross an energy
Forbidden band: The energy gap which separating the conduction band and the valence band is
called forbidden band or forbidden gap.
Note: - The energy imparted to the electrons must be greater than the energy associated with the
forbidden gap,, to extract the electrons from valence band and transfer t them to conduction band.
The energy associated to forbidden band is denoted as EG.
- The electrons cannot exit in the forbidden gap.
The representation of the energy bands in a solid is called Energy Band Diagram.

Fig. 1: Energy band diagram

The electrons in the various orbits revolving the nucleus occupy the various bands including fully
or partly occupied valence band. The conduction band which is normally empty carries the
electrons which get drifted from the valence band. These electrons present in the conduction band
are free electrons and they drift about in the space between the atoms.
For any given types of material the forbidden energy gap may be large, small or nonexistent. The
classification of materials as insulators, conductors and semiconductor is mainly dependent on the
width of the forbidden energy gap.

Conductors: A metal which is very good carrier of electricity is called conductor. As we

know, materials having large number of free electrons can conduct very easily. In fact, in
the metals like copper, aluminum there is no forbidden gap between valence band and
conduction band. The two bands overlap. Hence even at room temperature, a large
number of electrons are available for conduction. So without any additional energy, such
metals contain a large number of free electrons and hence called good conductors.

Fig. 2: Energy band diagram of conductor

Insulators: A very poor conductor of electricity is termed as insulator. In case of such
insulating material there existing a large for bidden gap in between the conduction band
and the valence band. Practically it is impossible for an electron to jump from the valence
band to the conduction band. Hence such materials cannot conduct and called insulators.
The forbidden gap is very wide, approximately of about 7 eV is present in insulators. For
diamond, which is an insulator the forbidden gap is about 6 eV. Such materials may
conduct only at very high temperatures or if they are subjected to high voltage. Such a
conduction is rare is called breakdown of insulator.

Fig. 3: Energy band diagram of insulator

Semiconductors: A metal having a conductivity which is between conductor and insulator
is called semiconductor. The forbidden gap in such material is very narrow as shown
below. The forbidden gap is about 1 eV. In such materials the energy provided by the heat
at room temperature is sufficient to lift the electrons from the valence band to the
conduction band. Therefore at room temperature, semiconductors are capable of
conduction. But at 0 0K or absolute zero (-273 0C), all the electrons of semiconductor
materials find themselves blocked in the valence band. Hence at 0 0K, the semiconductor
materials behave as perfect insulators. In case of semiconductors, forbidden gap energy
depends on the temperature. For silicon and germanium, this energy is given by,

EG = 1.21 3.6 x 10 -4 x T eV (for silicon)

EG = 0.785 2.23 x 10 -4 x T eV( for Germanium)
Where T = absolute temperature in 0K.

The energy band diagram for semiconductor is:

Fig 4: Energy band diagram for semiconductor