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Energy vs. crystal momentum for a semiconductor with an
indirect band gap, showing that an electron cannot shift
from the lowest-energy state in the conduction band (green)
to the highest-energy state in the valence band (red) without
a change in momentum. Here, almost all of the energy
comes from a photon (vertical arrow), while almost all of
the momentum comes from a phonon (horizontal arrow).
Direct and indirect band gaps
From Wikipedia, the free encyclopedia
In semiconductor physics, the band gap of a semiconductor is always one of two types, a direct band gap or an
indirect band gap. The minimal-energy state in the conduction band and the maximal-energy state in the valence
band are each characterized by a certain crystal momentum (k-vector) in the Brillouin zone. If the k-vectors are the
same, it is called a "direct gap". If they are different, it is called an "indirect gap". The band gap is called "direct" if
the momentum of electrons and holes is the same in both the conduction band and the valence band; an electron
can directly emit a photon. In an "indirect" gap, a photon cannot be emitted because the electron must pass through
an intermediate state and transfer momentum to the crystal lattice.
Contents
1 Implications for radiative recombination
2 Implications for light absorption
2.1 Formulae for absorption
3 Other aspects
4 References
5 External links
Implications for radiative
recombination
See also: Radiative recombination
Interactions among electrons, holes, phonons,
photons, and other particles are required to satisfy
conservation of energy and crystal momentum (i.e.,
conservation of total k-vector). A photon with an
energy near a semiconductor band gap has almost
zero momentum. One important process is called
radiative recombination, where an electron in the conduction band annihilates a hole in the valence band, releasing
the excess energy as a photon. This is possible in a direct band gap semiconductor if the electron has a k-vector
near the conduction band minima (the hole will share the same k-vector), but not possible in an indirect band gap
semiconductor, as photons cannot carry crystal momentum, and thus conservation of crystal momentum would be
violated. For radiative recombination to occur in an indirect band gap material, the process must also involve the
absorption or emission of a phonon, where the phonon momentum equals the difference between the electron and
hole momentum. (It can also, instead, involve a crystallographic defect, which performs essentially the same role.)
The involvement of the phonon makes this process much less likely to occur in a given span of time, which is why
radiative recombination is far slower in indirect band gap materials than direct band gap ones. This is why
light-emitting and laser diodes are almost always made of direct band gap materials, and not indirect band gap ones
like silicon.
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Energy vs. crystal momentum for a semiconductor with a
direct band gap, showing that an electron can shift from the
lowest-energy state in the conduction band (green) to the
highest-energy state in the valence band (red) without a
change in crystal momentum. Depicted is a transition in
which a photon excites an electron from the valence band to
the conduction band.
The fact that radiative recombination is slow in indirect band gap materials also means that, under most
circumstances, radiative recombinations will be a small proportion of total recombinations, with most
recombinations being non-radiative, taking place at point defects or at grain boundaries. However, if the excited
electrons are prevented from reaching these recombination places, they have no choice but to eventually fall back
into the valence band by radiative recombination. This can be done by creating a dislocation loop in the material. At
the edge of the loop, the planes above and beneath the "dislocation disk" are pulled apart, creating a negative
pressure, which raises the energy of the conduction band substantially, with the result that the electrons cannot pass
this edge. Provided that the area directly above the dislocation loop is defect-free (no non-radiative recombination
possible), the electrons will fall back into the valence shell by radiative recombination, thus emitting light. This is the
principle on which "DELEDs" (Dislocation Engineered LEDs) are based.
Implications for light absorption
The exact reverse of radiative recombination is light
absorption. For the same reason as above, light
with a photon energy close to the band gap can
penetrate much farther before being absorbed in an
indirect band gap material than a direct band gap
one (at least insofar as the light absorption is due to
exciting electrons across the band gap).
This fact is very important for photovoltaics (solar
cells). Silicon is the most common solar-cell
material, despite the fact that it is indirect-gap and
therefore does not absorb light very well. Silicon
solar cells are typically hundreds of micrometres
thick; if it was much thinner, much of the light
(particularly in the infrared) would simply pass
through. On the other hand, thin-film solar cells are
made of direct band gap materials (such as CdTe,
CIGS or CZTS), which absorb the light in a much
thinner region, and consequently can be made with
a very thin active layer (often less than 1
micrometre thick).
The absorption spectrum of an indirect band gap
material usually depends more on temperature than that of a direct material, because at low temperatures there are
fewer phonons, and therefore it is less likely that a photon and phonon can be simultaneously absorbed to create an
indirect transition. For example, silicon is opaque to visible light at room temperature, but transparent to red light at
liquid helium temperatures, because red photons can only be absorbed in an indirect transition.
Formulae for absorption
A common and simple method for determining whether a band gap is direct or indirect uses absorption
spectroscopy. By plotting certain powers of the absorption coefficient against photon energy, one can normally tell
both what value the band gap has, and whether or not it is direct.
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For a direct band gap, the absorption coefficient is related to light frequency according to the following
formula:
[1][2]
, with
where:
is the absorption coefficient, a function of light frequency
is light frequency
is Planck's constant ( is the energy of a photon with frequency )
is reduced Planck's constant ( )
is the band gap energy
is a certain frequency-independent constant, with formula above
, where and are the effective masses of the electron and hole, respectively (
is called a "reduced mass")
is the elementary charge
is the (real) index of refraction
is the vacuum permittivity
is a "matrix element", with units of length and typical value the same order of magnitude as the lattice
constant.
This formula is valid only for light with photon energy larger, but not too much larger, than the band gap (more
specifically, this formula assumes the bands are approximately parabolic), and ignores all other sources of
absorption other than the band-to-band absorption in question, as well as the electrical attraction between the
newly created electron and hole (see exciton). It is also invalid in the case that the direct transition is forbidden, or in
the case that many of the valence band states are empty or conduction band states are full.
[3]
On the other hand, for an indirect band gap, the formula is:
[3]
where:
is the energy of the phonon that assists in the transition
is Boltzmann's constant
is the thermodynamic temperature
(This formula involves the same approximations mentioned above.)
Therefore, if a plot of versus forms a straight line, it can normally be inferred that there is a direct band gap,
measurable by extrapolating the straight line to the axis. On the other hand, if a plot of versus
forms a straight line, it can normally be inferred that there is an indirect band gap, measurable by extrapolating the
straight line to the axis (assuming ).
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Other aspects
In some materials with an indirect gap, the value of the gap is negative. The top of the valence band is higher than
the bottom of the conduction band in energy. Such materials are known as semimetals.
References
1. ^ Optoelectronics, by E. Rosencher, 2002, equation (7.25).
2. ^ Pankove has the same equation, but with an apparently different prefactor . However, in the Pankove
version, the units / dimensional analysis appears not to work out.
3. ^
a

b
J.I. Pankove, Optical Processes in Semiconductors. Dover, 1971.
External links
B. Van Zeghbroeck's Principles of Semiconductor Devices (http://ece-
www.colorado.edu/~bart/book/book/chapter4/ch4_6.htm) at Electrical and Computer Engineering
Department of University of Colorado at Boulder
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Categories: Electronic band structures Optoelectronics
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