Band Gap

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Band gap

In solid-state physics, a band gap, also called an energy

gap or band gap, is an energy range in a solid where

no electron states can exist. In graphs of the electronic band

structure of solids, the band gap generally refers to the energy

difference (in electron volts) between the top of the valence

band and the bottom of the conduction and in insulators and

semiconductors. It is the energy required to promote a valence

electron bound to an atom to become a conduction electron,

which is free to move within the crystal lattice and serve as a

charge carrier to conduct electric current. It is closely related to

the HOMO/LUMO gap in chemistry. If the valence band is

completely full and the conduction band is completely empty,

then electrons cannot move in the solid; however, if some

electrons transfer from the valence to the conduction band, then

current can flow (see carrier generation and recombination).


Therefore, the band gap is a major factor determining

the electrical conductivity of a solid. Substances with large band

gaps are generally insulators, those with smaller band gaps

are semiconductors, while conductors either have very small

band gaps or none, because the valence and conduction bands

overlap.
In semiconductor physics

Semiconductor band structure.


Every solid has its own characteristic energy-band structure.

This variation in band structure is responsible for the wide

range of electrical characteristics observed in various materials.

In semiconductors and insulators, electrons are confined to a

number of bands of energy, and forbidden from other regions.

The term "band gap" refers to the energy difference between the

top of the valence band and the bottom of the conduction band.

Electrons are able to jump from one band to another. However,

in order for an electron to jump from a valence band to a

conduction band, it requires a specific minimum amount of

energy for the transition. The required energy differs with

different materials. Electrons can gain enough energy to jump to

the conduction band by absorbing either a phonon (heat) or

a photon (light).

A semiconductor is a material with a small but non-zero band

gap that behaves as an insulator at absolute zero but allows


thermal excitation of electrons into its conduction band at

temperatures that are below its melting point. In contrast, a

material with a large band gap is an insulator. In conductors,

the valence and conduction bands may overlap, so they may not

have a band gap.

The conductivity of intrinsic semiconductors is strongly

dependent on the band gap. The only available charge carriers

for conduction are the electrons that have enough thermal

energy to be excited across the band gap and the electron

holes that are left off when such an excitation occurs.

Band-gap engineering is the process of controlling or altering

the band gap of a material by controlling the composition of

certain semiconductor alloys, such as GaAlAs, InGaAs, and

InAlAs. It is also possible to construct layered materials with

alternating compositions by techniques like molecular-beam


epitaxy. These methods are exploited in the design

of heterojunction bipolar transistors (HBTs), laser diodes and

solar cells.

The distinction between semiconductors and insulators is a

matter of convention. One approach is to think of

semiconductors as a type of insulator with a narrow band gap.

Insulators with a larger band gap, usually greater than 4

eV,[1] are not considered semiconductors and generally do not

exhibit semiconductive behaviour under practical conditions.

Electron mobility also plays a role in determining a material's

informal classification.

The band-gap energy of semiconductors tends to decrease with

increasing temperature. When temperature increases, the

amplitude of atomic vibrations increase, leading to larger

interatomic spacing. The interaction between the


lattice phonons and the free electrons and holes will also affect

the band gap to a smaller extent. The relationship between band

gap energy and temperature can be described by Varshni's

empirical expression (named after Y. P. Varshni),

In a regular semiconductor crystal, the band gap is fixed owing

to continuous energy states. In a quantum dot crystal, the band

gap is size dependent and can be altered to produce a range of

energies between the valence band and conduction band. It is

also known as quantum confinement effect.

Band gaps also depend on pressure. Band gaps can be

either direct or indirect, depending on the electronic band

structure
Photovoltaic cells

The Shockley–Queisser limit gives the maximum possible

efficiency of a single-junction solar cell under un-concentrated

sunlight, as a function of the semiconductor band gap. If the

band gap is too high, most daylight photons cannot be

absorbed; if it is too low, then most photons have much more

energy than necessary to excite electrons across the band gap,


and the rest is wasted. The semiconductors commonly used in

commercial solar cells have band gaps near the peak of this

curve, for example silicon (1.1eV) or CdTe (1.5eV). The

Shockley–Queisser limit has been exceeded experimentally by

combining materials with different band gap energies to

make tandem solar cells.

The optical band gap (see below) determines what portion of the

solar spectrum a photovoltaic cell absorbs. A semiconductor

will not absorb photons of energy less than the band gap; and

the energy of the electron-hole pair produced by a photon is

equal to the bandgap energy. A luminescent solar converter uses

a luminescent medium to down convert photons with energies

above the band gap to photon energies closer to the band gap of

the semiconductor comprising the solar cell.


List of band gaps

Below are band gap values for some selected materials. For a

comprehensive list of band gaps in semiconductors, see List of

semiconductor materials.

Group Material Symbol Band gap (eV) @ 302K

III-V Aluminium nitride AlN 6.0

IV Diamond C 5.5

IV Silicon Si 1.14

IV Germanium Ge 0.67

III–V Gallium nitride GaN 3.4


Group Material Symbol Band gap (eV) @ 302K

III–V Gallium phosphide GaP 2.26

III–V Gallium arsenide GaAs 1.43

IV–V Silicon nitride Si3N4 5

IV–VI Lead sulfide PbS 0.37

IV–VI Silicon dioxide SiO2 9

Copper oxide Cu2O 2.1


Optical versus electronic band gap

In materials with a large exciton binding energy, it is possible

for a photon to have just barely enough energy to create an

exciton (bound electron–hole pair), but not enough energy to

separate the electron and hole (which are electrically attracted

to each other). In this situation, there is a distinction between

"optical bandgap" and "electrical band gap" (or "transport

gap"). The optical bandgap is the threshold for photons to be

absorbed, while the transport gap is the threshold for creating

an electron–hole pair that is not bound together. The optical

bandgap is at a lower energy than the transport gap.

In almost all inorganic semiconductors, such as silicon, gallium

arsenide, etc., there is very little interaction between electrons

and holes (very small exciton binding energy), and therefore the

optical and electronic bandgap are essentially identical, and the


distinction between them is ignored. However, in some systems,

including organic semiconductors and single-walled carbon

nanotubes, the distinction may be significant.

In photonics and phononics

In photonics, band gaps or stop bands are ranges of photon

frequencies where, if tunneling effects are neglected, no photons

can be transmitted through a material. A material exhibiting this

behaviour is known as a photonic crystal. The concept of hyper

uniformity has broadened the range of photonic band gap

materials, beyond photonic crystals. By applying the technique

in super symmetric quantum mechanics, a new class of optical

disordered materials have been suggested, which support band

gaps perfectly equivalent to those of crystals or quasi crystals.

Similar physics applies to phonons in a phononic crystal.

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