Carrier generation and recombination

In the solid-state physics of semiconductors, carrier generation and carrier recombination are
processes by which mobile charge carriers (electrons and electron holes) are created and eliminated.
Carrier generation and recombination processes are fundamental to the operation of many
optoelectronic semiconductor devices, such as photodiodes, light-emitting diodes and laser diodes. They
are also critical to a full analysis of p-n junction devices such as bipolar junction transistors and p-n
junction diodes.

The electron–hole pair is the fundamental unit of generation and recombination in inorganic
semiconductors, corresponding to an electron transitioning between the valence band and the
conduction band where generation of electron is a transition from the valence band to the conduction
band and recombination leads to a reverse transition.

Contents
Overview
Relation between generation and recombination
Carrier generation
Recombination mechanisms
Radiative recombination
Band-to-band radiative recombination
Stimulated emission
Non-radiative recombination
Shockley–Read–Hall (SRH)
Types of traps
Electron traps vs. hole traps
Shallow traps vs. deep traps
SRH Model
Auger recombination
Surface recombination
Langevin recombination
References
Further reading
External links

Overview
Like other solids, semiconductor materials have an electronic band structure determined by the crystal
properties of the material. Energy distribution among electrons is described by the Fermi level and the
temperature of the electrons. At absolute zero temperature, all of the electrons have energy below the
Fermi level; but at non-zero temperatures the
energy levels are filled following a Boltzmann
distribution.

In undoped semiconductors the Fermi level

lies in the middle of a forbidden band or band
gap between two allowed bands called the
valence band and the conduction band. The
valence band, immediately below the
forbidden band, is normally very nearly
completely occupied. The conduction band,
above the Fermi level, is normally nearly
completely empty. Because the valence band is
so nearly full, its electrons are not mobile, and
cannot flow as electric current.

However, if an electron in the valence band

acquires enough energy to reach the
conduction band (as a result of interaction Electronic band structure of a semiconductor material.
with other electrons, holes, photons, or the
vibrating crystal lattice itself), it can flow freely
among the nearly empty conduction band energy states. Furthermore, it will also leave behind a hole that
can flow as current exactly like a physical charged particle.

Carrier generation describes processes by which electrons gain energy and move from the valence
band to the conduction band, producing two mobile carriers; while recombination describes processes
by which a conduction band electron loses energy and re-occupies the energy state of an electron hole in
the valence band.

These processes must conserve both quantized energy and crystal momentum, and the vibrating lattice
plays a large role in conserving momentum as, in collisions, photons can transfer very little momentum
in relation to their energy.

Relation between generation and recombination

Recombination and generation are always happening in semiconductors, both optically and thermally.
As predicted by thermodynamics, a material at thermal equilibrium will have generation and
recombination rates that are balanced so that the net charge carrier density remains constant. The
resulting probability of occupation of energy states in each energy band is given by Fermi–Dirac
statistics.

The product of the electron and hole densities ( and ) is a constant at equilibrium,
maintained by recombination and generation occurring at equal rates. When there is a surplus of carriers
(i.e., ), the rate of recombination becomes greater than the rate of generation, driving the system
back towards equilibrium. Likewise, when there is a deficit of carriers (i.e., ), the generation rate
becomes greater than the recombination rate, again driving the system back towards equilibrium.[1] As
the electron moves from one energy band to another, the energy and momentum that it has lost or
gained must go to or come from the other particles involved in the process (e.g. photons, electron, or the
system of vibrating lattice atoms).
Carrier generation
When light interacts with a material, it can either
be absorbed (generating a pair of free carriers or
an exciton) or it can stimulate a recombination
event. The generated photon has similar
properties to the one responsible for the event.
Absorption is the active process in photodiodes,
solar cells and other semiconductor
photodetectors, while stimulated emission is the
principle of operation in laser diodes.

Besides light excitation, carriers in

semiconductors can also be generated by an
external electric field, for example in light- The following image shows change in excess carriers
emitting diodes and transistors. being generated (green:electrons and purple:holes) with
increasing light intensity (generation rate /cm ) at the
When light with sufficient energy hits a center of an intrinsic semiconductor bar. Electrons have
semiconductor, it can excite electrons across the higher diffusion constant than holes leading to fewer
band gap. This generates additional charge excess electrons at the center as compared to holes.
carriers, temporarily lowering the electrical
resistance of materials. This higher conductivity in
the presence of light is known as photoconductivity. This conversion of light into electricity is widely
used in photodiodes.

Recombination mechanisms
Carrier recombination can happen through multiple relaxation channels. The main ones are band-to-
band recombination, Shockley–Read–Hall (SRH) trap-assisted recombination, Auger recombination
and surface recombination. These decay channels can be separated into radiative and non-radiative.
The latter occurs when the excess energy is converted into heat by phonon emission after the mean
lifetime , whereas in the former at least part of the energy is released by light emission or
luminescence after a radiative lifetime . The carrier lifetime is then obtained from the rate of both
type of events according to: [2]

From which we can also define the internal quantum efficiency or quantum yield, as:

Radiative recombination
Band-to-band radiative recombination

Band-to-band recombination is the name for the process of electrons jumping down from the
conduction band to the valence band in a radiative manner. During band-to-band recombination, a form
of spontaneous emission, the energy absorbed by a material is released in the form of photons. Generally
these photons contain the same or less energy than those initially absorbed. This effect is how LEDs
create light. Because the photon carries relatively little momentum, radiative recombination is
significant only in direct bandgap materials. This process is also known as bimolecular recombination[3].

This type of recombination depends on the density of electrons and holes in the excited state, denoted by
and respectively. Let us represent the carrier generation rate as and the radiative
recombination as . Then considering the case in which only band-to-band recombination occurs we
can express the change in carrier density as a function of time as:

In thermal equilibrium the radiative recombination is equal to thermal generation rate ,[4] with
the mass action law , it can be written as:

where is called the radiative recombination rate, is the intrinsic carrier density, and are the
equilibrium carrier densities. In the presence of electron hole pairs, the charge neutrality remains
and the non-equilibrium densities are given by [5]:

Then the net recombination rate becomes [4][5],

Solving this equation by considering charge neutrality, the radiative lifetime is then given by[4]

Stimulated emission
Stimulated emission is a process in which an incident photon interacts with an excited electron causing it
to recombine and emit a photon with the same properties of the incident one, in terms of phase,
frequency, polarization, and direction of travel. Stimulated emission together with the principle of
population inversion are at the heart of operation of lasers and masers. It has been shown by Einstein at
the beginning of the twentieth century that if the excited and the ground level are non degenerate then
the absorption rate and the stimulated emission rate are the same.[6] Else if level 1 and level 2
are -fold and -fold degenerate respectively, the new relation is:

Non-radiative recombination
Non-radiative recombination is a process in phosphors and semiconductors, whereby charge carriers
recombine with releasing phonon instead of photons. Non-radiative recombination in optoelectronics
and phosphors is an unwanted process, lowering the light generation efficiency and increasing heat
losses.

Non-radiative life time is the average time before an electron in the conduction band of a semiconductor
recombines with a hole. It is an important parameter in optoelectronics where radiative recombination is
required to produce a photon; if the non-radiative life time is shorter than the radiative, a carrier is more
likely to recombine non-radiatively. This results in low internal quantum efficiency.

Shockley–Read–Hall (SRH)

In Shockley-Read-Hall recombination (SRH), also called trap-assisted recombination, the electron in

transition between bands passes through a new energy state (localized state) created within the band gap
by a dopant or a defect in the crystal lattice; such energy states are called traps. Non-radiative
recombination occurs primarily at such sites. The energy is exchanged in the form of lattice vibration, a
phonon exchanging thermal energy with the material.

Since traps can absorb differences in momentum between the carriers, SRH is the dominant
recombination process in silicon and other indirect bandgap materials. However, trap-assisted
recombination can also dominate in direct bandgap materials under conditions of very low carrier
densities (very low level injection) or in materials with high density of traps such as perovskites. The
process is named after William Shockley, William Thornton Read[7] and Robert N. Hall,[8] who
published it in 1962.

Types of traps

Electron traps vs. hole traps

Even though all the recombination events can be described in terms of electron movements, it is
common to visualize the different processes in terms of excited electron and the electron holes they leave
behind. In this context, if trap levels are close to the conduction band, they can temporarily immobilize
excited electrons or in other words, they are electron traps. On the other hand, if their energy lies close
to the valence band they become hole traps.
Shallow traps vs. deep traps

The distinction between shallow and deep traps is commonly made depending on how close electron
traps are to the conduction band and how close hole traps are to the valence band. If the difference
between trap and band is smaller than the thermal energy kBT it is often said that it is a shallow trap.
Alternatively, if the difference is larger than the thermal energy, it is called a deep trap. This difference is
useful because shallow traps can be emptied more easily and thus are often not as detrimental to the
performance of optoelectronic devices.

SRH Model

In the SRH model, four things can happen involving trap levels:[9]

An electron in the conduction band can be trapped in an intragap

state.
An electron can be emitted into the conduction band from a trap level.
An electron hole in the valence band can be captured by a trap. This is
analogous to a filled trap releasing an electron into the valence band.
A captured hole can be released into the valence band. Analogous to
the capture of an electron from the valence band. Electron and hole trapping in
the Shockley-Read-Hall
When carrier recombination occurs through traps, we can replace the model
valence density of states by that of the intragap state. [10] The term is
replaced by the density of trapped electrons/holes .

Where is the density of trap states and is the probability of that occupied state. Considering a
material containing both types of traps, we can define two trapping coefficients and two de-
trapping coeficients . In equilibrium, both trapping and de-trapping should be balanced (
and ). Then, the four rates as a function of become:

Where and are the electron and hole densities when the quasi Fermi level matches the trap energy.

In steady-state condition, the net trapping rate of electrons should match the net recombination rate for
holes, in other words: . This eliminates the occupation probability and leads to
the Shockley-Read-Hall expression for the trap-assisted recombination:
Where the average lifetime for electrons and holes are defined as[10]:

Auger recombination

In Auger recombination the energy is given to a third carrier which is excited to a higher energy level
without moving to another energy band. After the interaction, the third carrier normally loses its excess
energy to thermal vibrations. Since this process is a three-particle interaction, it is normally only
significant in non-equilibrium conditions when the carrier density is very high. The Auger effect process
is not easily produced, because the third particle would have to begin the process in the unstable high-
energy state.

In thermal equilibrium the Auger recombination and thermal generation rate equal each other[11]

where are the Auger capture probabilities. The non-equilibrium Auger recombination rate
and resulting net recombination rate under steady-state conditions are[11]

The Auger lifetime is given by[12]

The mechanism causing LED efficiency droop was identified in 2007 as Auger recombination, which met
with a mixed reaction.[13] In 2013, an experimental study claimed to have identified Auger
recombination as the cause of efficiency droop.[14] However, it remains disputed whether the amount of
Auger loss found in this study is sufficient to explain the droop. Other frequently quoted evidence against
Auger as the main droop causing mechanism is the low-temperature dependence of this mechanism
which is opposite to that found for the drop.

Surface recombination

Trap-assisted recombination at the surface of a semiconductor is referred to as surface recombination.

This occurs when traps at or near the surface or interface of the semiconductor form due to dangling
bonds caused by the sudden discontinuation of the semiconductor crystal. Surface recombination is
characterized by surface recombination velocity which depends on the density of surface defects.[15] In
applications such as solar cells, surface recombination may be the dominant mechanism of
recombination due to the collection and extraction of free carriers at the surface. In some applications of
solar cells, a layer of transparent material with a large band gap, also known as a window layer, is used to
minimize surface recombination. Passivation techniques are also employed to minimize surface
recombination.[16]

Langevin recombination

For free carriers in low-mobility systems, the recombination rate is often described with the Langevin
recombination rate.[17] The model is often used for disordered systems such as organic materials (and
is hence relevant for organic solar cells[18]) and other such systems. The Langevin recombination
strength is defined as .

References
1. Elhami Khorasani, Arash; Schroder, Dieter K.; Alford, T. L. (2014). "Optically Excited MOS-Capacitor
for Recombination Lifetime Measurement". IEEE Electron Device Letters. 35 (10): 986–988.
Bibcode:2014IEDL...35..986K (https://ui.adsabs.harvard.edu/abs/2014IEDL...35..986K).
doi:10.1109/LED.2014.2345058 (https://doi.org/10.1109%2FLED.2014.2345058).
2. Pelant, Ivan; Valenta, Jan (2012-02-09), "Luminescence of disordered semiconductors",
Luminescence Spectroscopy of Semiconductors, Oxford University Press, pp. 242–262,
doi:10.1093/acprof:oso/9780199588336.003.0009 (https://doi.org/10.1093%2Facprof%3Aoso%2F97
80199588336.003.0009), ISBN 9780199588336
3. Stranks, Samuel D.; Burlakov, Victor M.; Leijtens, Tomas; Ball, James M.; Goriely, Alain; Snaith,
Henry J. (2014-09-11). "Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free
Charge, and Subgap States". Physical Review Applied. 2 (3): 034007.
doi:10.1103/PhysRevApplied.2.034007 (https://doi.org/10.1103%2FPhysRevApplied.2.034007).
4. Li, Sheng S., ed. (2006). Semiconductor Physical Electronics (http://cds.cern.ch/record/1066014).
p. 140. doi:10.1007/0-387-37766-2 (https://doi.org/10.1007%2F0-387-37766-2). ISBN 978-0-387-
28893-2.
5. NISOLI, MAURO. (2016). SEMICONDUCTOR PHOTONICS. SOCIETA EDITRICE ESCULAPI.
ISBN 978-8893850025. OCLC 964380194 (https://www.worldcat.org/oclc/964380194).
6. Svelto. (1989). Principles of Lasers ... p. 3. OCLC 249201544 (https://www.worldcat.org/oclc/249201
544).
7. Shockley, W.; Read, W. T. (1 September 1952). "Statistics of the Recombinations of Holes and
Electrons". Physical Review. 87 (5): 835–842. Bibcode:1952PhRv...87..835S (https://ui.adsabs.harva
rd.edu/abs/1952PhRv...87..835S). doi:10.1103/PhysRev.87.835 (https://doi.org/10.1103%2FPhysRe
v.87.835).
8. Hall, R.N. (1951). "Germanium rectifier characteristics". Physical Review. 83 (1): 228.
9. NISOLI, MAURO. (2016). SEMICONDUCTOR PHOTONICS. SOCIETA EDITRICE ESCULAPI.
ISBN 978-8893850025. OCLC 964380194 (https://www.worldcat.org/oclc/964380194).
10. Kandada, Ajay Ram Srimath; D'Innocenzo, Valerio; Lanzani, Guglielmo; Petrozza, Annamaria
(2016), Da Como, Enrico; De Angelis, Filippo; Snaith, Henry; Walker, Alison (eds.), "Chapter 4.
Photophysics of Hybrid Perovskites", Unconventional Thin Film Photovoltaics, Royal Society of
Chemistry, pp. 107–140, doi:10.1039/9781782624066-00107 (https://doi.org/10.1039%2F978178262
4066-00107), ISBN 9781782622932
11. Li, Sheng S., ed. (2006). Semiconductor Physical Electronics (http://cds.cern.ch/record/1066014).
p. 143. doi:10.1007/0-387-37766-2 (https://doi.org/10.1007%2F0-387-37766-2). ISBN 978-0-387-
28893-2.
12. Li, Sheng S., ed. (2006). Semiconductor Physical Electronics (http://cds.cern.ch/record/1066014).
p. 144. doi:10.1007/0-387-37766-2 (https://doi.org/10.1007%2F0-387-37766-2). ISBN 978-0-387-
28893-2.
13. Stevenson, Richard (August 2009) The LED’s Dark Secret: Solid-state lighting won't supplant the
lightbulb until it can overcome the mysterious malady known as droop (https://spectrum.ieee.org/sem
iconductors/optoelectronics/the-leds-dark-secret). IEEE Spectrum
14. Justin Iveland; Lucio Martinelli; Jacques Peretti; James S. Speck; Claude Weisbuch. "Cause of LED
Efficiency Droop Finally Revealed" (https://www.sciencedaily.com/releases/2013/04/130423102328.h
tm). Physical Review Letters, 2013. Science Daily. Retrieved 23 April 2013.
15. Nelson, Jenny (2003). The Physics of Solar Cells. London: Imperial College Press. p. 116. ISBN 978-
1-86094-340-9.
16. Eades, W.D.; Swanson, R.M. (1985). "Calculation of surface generation and recombination velocities
at the Si-SiO2 interface". Journal of Applied Physics. 58 (11): 4267–4276. doi:10.1063/1.335562 (http
s://doi.org/10.1063%2F1.335562). ISSN 0021-8979 (https://www.worldcat.org/issn/0021-8979).
17. https://blog.disorderedmatter.eu/2008/04/04/recombination-in-low-mobility-semiconductors-langevin-
theory/ (https://blog.disorderedmatter.eu/2008/04/04/recombination-in-low-mobility-semiconductors-la
ngevin-theory/)
18. Lakhwani, Girish; Rao, Akshay; Friend, Richard H. (2014). "Bimolecular Recombination in Organic
Photovoltaics". Annual Review of Physical Chemistry. 65 (1): 557–581. doi:10.1146/annurev-
physchem-040513-103615 (https://doi.org/10.1146%2Fannurev-physchem-040513-103615).
ISSN 0066-426X (https://www.worldcat.org/issn/0066-426X).

Further reading
N.W. Ashcroft and N.D. Mermin, Solid State Physics, Brooks Cole, 1976

External links
PV Lighthouse Recombination Calculator (http://www.pvlighthouse.com.au/calculators/Recombinatio
n%20calculator/Recombination%20calculator.aspx)
PV Lighthouse Band Gap Calculator (http://www.pvlighthouse.com.au/calculators/Band%20gap%20c
alculator/Band%20gap%20calculator.aspx)
PV Education (https://www.pveducation.org/pvcdrom/design-of-silicon-cells/surface-recombination)

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