Semiconductors, such as Silicon (Si) are made up of individual atoms bonded

together in a regular, periodic structure to form an arrangement whereby each

atom is surrounded by 8 electrons. An individual atom consists of a nucleus
made up of a core of protons (positively charged particles) and neutrons
(particles having no charge) surrounded by electrons. The number of electrons
and protons is equal, such that the atom is overall electrically neutral. The
electrons surrounding each atom in a semiconductor are part of a covalent
bond. A covalent bond consists of two atoms "sharing" a single electron. Each
atom forms 4 covalent bonds with the 4 surrounding atoms. Therefore,
between each atom and its 4 surrounding atoms, 8 electrons are being shared.
The structure of a semiconductor is shown in the figure below.

Energy Bands and Charge Carriers in Semiconductors

Electron and Hole Concentrations at Equilibrium

The F-D distribution function can be used to calculate the electron and hole concentrations in
semiconductors, if the densities of available states in the conduction and valence bands are known.

In equilibrium, the concentration of electrons in the conduction band can be given by

(2.8)
where N(E)dE is the density of available states/cm3 in the energy range dE.

Note: the upper limit of is theoretically not proper, since the conduction band does not extend to infinite
energies; however, since f(E) decreases rapidly with increasing E, the contribution to this integral for
higher energies is negligible.

Using the solution of

that

's wave equation under periodic boundary conditions, it can be shown

(2.9)

Thus, N(E) increases with E, however, f(E) decreases rapidly with E, thus, the product f(E)N(E) decreases
rapidly with E, and very few electrons occupy states far above the conduction band edge, i.e., most
electrons occupy a narrow energy band near the conduction band edge.

Similarly, the probability of finding an empty state in the valence band [1 - f(E)] decreases rapidly
below

, and most holes occupy states near the top of the valence band.

Thus, a mathematical simplification can be made assuming that all available states in the conduction band
can be represented by an effective density of states NC located at the conduction band edge
using Boltzmann approximation.
Thus,

and

(2.10)

where .

Note: as (
) decreases, i.e., the Fermi level moves closer to the conduction band, the electron
concentration increases.

By similar arguments,
(2.11)
where

is the effective density of states located at the valence band edge

Note: the only terms separating the expressions for

and

are the effective masses of electrons (

Charge Carriers in Semiconductors

When an electric field is applied to a metal, negatively charged electrons are accelerated and carry the
resulting current. In a semiconductor the charge is not carried exclusively by electrons. Positively
charged holes also carry charge. These may be viewed either as vacancies in the otherwise filled
valence band, or equivalently as positively charged particles.
Since the Fermi-Dirac distribution is a step function at absolute zero, pure semiconductors will have all
the states in the valence bands filled with electrons and will be insulators at absolute zero. This is
depicted in the E-k diagram below; shaded circles represent filled momentum states and empty circles
unfilled momentum states. In this diagram k, rather than k, has been used to denote that the wave
vector is actually a vector, i.e., a tensor of the first rank, rather than a scalar.

If the band gap is sufficiently small and the temperature is increased from absolute zero, some
electrons may be thermally excited into the conduction band, creating an electron-hole pair. This is as
a result of the smearing out of the Fermi-Dirac distribution at finite temperature. An electron may also
move into the conduction band from the valence band if it absorbs a photon that corresponds to the
energy difference between a filled state and an unfilled state. Any such photon must have an energy
that is greater than or equal to the band gap between the valence band and the conduction band, as in
the diagram below.

Whether thermally or photonically induced, the result is an electron in the conduction band and a
vacant state in the valence band.

If an electric field is now applied to the material, all of the electrons in the solid will feel a force from
the electric field. However, because no two electrons can be in the exact same quantum state, an
electron cannot gain any momentum from the electric field unless there is a vacant momentum state
adjacent to the state being occupied by the electron. In the above schematic, the electron in the

conduction band can gain momentum from the electric field, as can an electron adjacent to the vacant
state left behind in the valence band. In the diagram below, both of these electrons are shown moving
to the right.

The result of this is that the electrons have some net momentum, and so there is an overall movement
of charge. This slight imbalance of positive and negative momentum can be seen in the diagram
below, and it gives rise to an electric current.

The vacant site in the valence band which has moved to the left can be viewed as being a particle
which carries positive electric charge of equal magnitude to the electron charge. This is therefore
a hole. It should be appreciated that these schematics do not represent electrons 'hopping' from site
to site in real space, because the electrons are not localised to specific sites in space. These
schematics are in momentum space. As such, holes should not be thought of as moving through the
semiconductor like dislocations when metals are plastically deformed it suffices to view them simply
as particles which carry positive charge.
The opposite process to the creation of an electron-hole pair is called recombination. This occurs
when an electron drops down in energy from the conduction band to the valence band. Just as the
creation of an electron-hole pair may be induced by a photon, recombination can produce a photon.
This is the principle behind semiconductor optical devices such as light-emitting diodes (LEDs), in
which the photons are light of visible wavelength.

Conduction in Semiconductors
Semiconductor StructureBand Gap

Overview
1. Semiconductors act as insulators at low temperatures and conductors
at higher temperatures.
2. Conduction occurs at higher temperature because the electrons
surrounding the semiconductor atoms can break away from their
covalent bond and move freely about the lattice
3. The conductive property of semiconductors forms the basis for
understanding how we can use these materials in electrical devices.
The bond structure of a semiconductor determines the material properties of a
semiconductor. One key effect are the energy levels which the electrons can occupy and
how they move about the crystal lattice. The electrons in the covalent bond formed
between each of the atoms in the lattice structure are held in place by this bond and
hence they are localized to the region surrounding the atom. These bonded electrons
cannot move or change energy, and thus are not considered "free" and cannot
participate in current flow, absorption, or other physical processes of interest in solar
cells. However, only at absolute zero are all electrons in this "stuck,"
bonded arrangement.At elevated temperatures, especially at the temperatures
where solar cells operate, electrons can gain enough energy to escape from their bonds.
When this happens, the electrons are free to move about the crystal lattice and
participate in conduction. At room temperature, a semiconductor has enough free
electrons to allow it to conduct current. At or close to absolute zero a semiconductor
behaves like an insulator.

When an electron gains enough energy to participate in conduction (is "free"), it is at a

high energy state. When the electron is bound, and thus cannot participate in
conduction, the electron is at a low energy state. Therefore, the presence of the bond
between the two atoms introduces two distinct energy states for the electrons. The
electron cannot attain energy values intermediate to these two levels; it is either at a low
energy position in the bond, or it has gained enough energy to break free and therefore
has a certain minimum energy. This minimum energy is called the "band gap" of a
semiconductor. The number and energy of these free electrons, those electrons
participating in conduction, is basic to the operation of electronic devices.
The space left behind by the electrons allows a covalent bond to move from one electron
to another, thus appearing to be a positive charge moving through the crystal lattice.
This empty space is commonly called a "hole", and is similar to an electron, but with a
positive charge.

Animation showing formation of "free" electrons and holes

when an electron can escape its bond.
The most important parameters of a semiconductor material for solar cell operation are:

the band gap;

the number of free carriers (electrons or holes) available for

conduction; and

the "generation" and recombination of free carriers (electrons or holes)

in response to light shining on the material.

More detail on these properties is given in the following pages.