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Energy Band Model: Metals & Semiconductors

The energy band model describes how the atomic orbitals of atoms in solids overlap to form molecular orbitals that spread over the entire crystal lattice, creating energy bands. In metals, the valence band overlaps with a higher empty band, allowing electrons to move freely and conduct electricity. In semiconductors, the small band gap can be bridged by thermal excitation, increasing conductivity with temperature. Intrinsic semiconductors have a small inherent band gap, while extrinsic semiconductors are doped with additional elements to donate electrons (n-type) or accept electrons (p-type). Insulators have a large band gap that cannot be crossed by thermal excitation, resulting in very low conductivity.

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61 views2 pages

Energy Band Model: Metals & Semiconductors

The energy band model describes how the atomic orbitals of atoms in solids overlap to form molecular orbitals that spread over the entire crystal lattice, creating energy bands. In metals, the valence band overlaps with a higher empty band, allowing electrons to move freely and conduct electricity. In semiconductors, the small band gap can be bridged by thermal excitation, increasing conductivity with temperature. Intrinsic semiconductors have a small inherent band gap, while extrinsic semiconductors are doped with additional elements to donate electrons (n-type) or accept electrons (p-type). Insulators have a large band gap that cannot be crossed by thermal excitation, resulting in very low conductivity.

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shahalam sarder
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The Energy Band Model -Metal, Semiconductor, Insulator-

Band formation:
The energy band model can be explained using the molecular orbital theory. Solids are
regarded as aggregations of an almost infinite number of atoms.
The linear combination and overlap of N atomic orbitals in a solid leads to N molecular
orbitals, which are closely spaced in energy and spread over the whole crystal (energy band).
An almost continuous band of energy levels is formed. The molecular orbitals are not allowed
to have the same energy (Hund´s rule).
The 1s-band is separated (not for all solids, the band may also overlap) from the 2s-band by a
band gap. I a band gap no molecular orbital occur. The width of a band gap depends on the
energy-difference of the atomic orbitals and the strength of interactions between the crystal
atoms. A band consists of countable number of near-continuum energy levels. There is only a
narrow spread of orbital energies.

Fermi level
The highest occupied orbital at T = 0K is called the Fermi level.

Densities of states
The density of states (DOS) is defined as the quantity of energy levels in an energy range
divided by the range’s width. It is not uniform across a band. The energy levels may be more
closely or less closely.

Conductivity of metals:
In metals the valence band overlap with the next higher band (e.g. for alkaline earth metals) or
a not fully occupied band exists (e.g. for alkaline metals). Electrons can travel in unoccupied
energy levels. There is a decrease of electrical conductivity with increasing temperature.
Increasing vibration of atoms with increasing temperature leads to an increasing number of
collisions between electrons and atoms.

Conductivity of semiconductors:
The electrical conductivity increases with increasing temperature.

Intrinsic semiconductors (band gap 1-3 eV):


The band gap between the empty conduction band and the full valence band is so small that
electrons can populate the empty upper band by slight thermal excitation. The absence of
electrons in the valence band introduces positive charges.

Extrinsic semiconductors (impurity semiconductors):


They are intentionally doped with impurities. The doping is substitutional, the dopant atom
takes the place of the host atom.

n-type semiconductors: Host material doped with an element with more valence electrons than
the host element. The doping material supply electrons to the conduction band. The filled
donor band is commonly near the empty conduction band. (electron conduction)

p-type semiconductors: Host material doped with an element with less valence electrons than
the host element. Doping atoms form an empty acceptor band lying above the full valence
band of the host material. Electron of the host material occupy this band Æelectron gaps in
host material are formed. Conductivity because of migration of positive holes in the valence
band (hole conduction).
Conductivity of insulators:
The valence band is completely filled, while the conduction band is empty. The band gap is
higher than 3 eV (e.g. NaCl: 7 eV, Diamond: 5,5 eV). A thermal excitation of electrons in the
conducting band is difficult or not possible.

Literature:
Shriver and Atkins: Inorganic Chemistry; fourth edition
Riedel: Anorganische Chemie; 6. Auflage

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