Semiconductor Under Non-equilibrium

Non-equilibrium state, in a semiconductor, is said to occur when, under external factors such as
applied voltage, temperature variations, or light exposure, the charge carrier distributions-
electrons and holes-are not uniform. The presence of excess charge carriers and altered electrical
characteristics may result from this. Devices like photodiodes and transistors where carrier
behavior includes drift, diffusion, and recombination processes, require Non-equilibrium
conditions. [1]
If an external stimulation is given to the semiconductor, its thermal equilibrium concentration
may be accompanied by excess electrons in the conduction band and excess holes in the valence
band. Excess electrons and holes are produces ,which indicated that the semiconductor is no
longer in thermal equilibrium.

Carrier Injection
Carrier injection is a process of introducing additional charge carriers, electrons, or holes in a
semiconductor, normally through the application of an external force such as an electric field or
light. The process upsets the normal balance of the carriers in the material and drives it into a
nonequilibrium situation with excess carriers in addition to their equilibrium levels. The
semiconductor will try to go back to equilibrium through a recombination process where
electrons and holes will join giving out energy. Carrier injection plays an important role in
devices such as diodes and transistors, whereby it allows current to flow along with other
functions related to the device. [2] This can be influenced by many techniques as written below:
Electrical Biasing: With the application of forward bias to devices that contain a p-n junction,
carriers are injected from one region into another. In simpler words, electrons are injected from
the n-region into the p-region, as well as holes from the p-region into the n-region.
Optical Excitation: A semiconductor, exposed to light, may supply photons that have an energy
great enough to raise the electrons from the valence band to the conduction band, consequently
injecting extra carriers (electron-hole pairs) in the system.

Kinetics of Recombination and Generation Processes

In nonequilibrium semiconductors, recombination and generation control the process of
formation and neutralization of carriers, electrons, and holes, and how the system returns to its
state of equilibrium. Carrier generation is the term defining the creation of electron-hole pairs.
Recombination is when electrons in the conduction band combine with holes in the valence
band, freeing energy. Under non-equilibrium conditions, this recombination rate increases
because of the semiconductor attempting to reach its state of equilibrium by recombining the
excess carriers. Carrier generation is the term defining the creation of electron-hole pairs.
Generation and recombination are two types:
a. Direct band-to-band generation and recombination
b. The recombination through allowed energy states within the bandgap, referred to as
traps or recombination centers. [3]

a.Direct band-to-band generation and recombination

In thermal equilibrium, concentrations of electrons and holes in conduction and valence band do
not depend on time. However, because of the random character of the thermal process, electrons
are continuously thermally stimulated from the valence band into the conduction band.
Meanwhile, electrons in the conduction band can randomly wander through the crystal and "fall"
into the empty states of the valence band once they come near holes. This recombination process
annihilates an electron and a hole. The rate of electron and hole generation and recombination
has to be identical because the net carrier concentrations in thermal equilibrium cannot be time
dependent.

Let, Thermal-generation rates of electrons = Gn0

Thermal-generation rates of holes = Gp0, given in units of #/cm3 -s.
The recombination rates of electrons = Rn0
The recombination rates of holes = Rp0, again given in units of #/cm3 -s
For the direct band-to-band generation, the electrons and holes are created in pairs, so we must
have that, Gn0 = Gp0
In direct band-to-band recombination, electrons and holes recombine in pairs, so that,
Rn0 = Rp0
In thermal equilibrium, the concentrations of electrons and holes are independent of time;
therefore, the generation and recombination rates are equal, so we have
Gn0 = Gp0 =Rn0 = Rp0
For instance, when high-energy photons strike a semiconductor, electrons in the valence band
may be excited into the conduction band. This results in the creation of an electron–hole pair,
which consists of both an electron in the conduction band and a hole in the valence band. The
additional electrons and holes created are called excess electrons and excess holes.
Let, The generation rate of excess electrons = gn
The generation rate of excess holes = g p. These generation rates also have units of #/cm3 -s.
For the direct band-toband generation, the excess electrons and holes are also created in pairs, so
we must have gn = gp.

Fig: Relevant notation

When excess electrons and holes are generated, the electron concentration in the conduction
band and holes in the valence band have been increased above their thermal equilibrium value.
We may write: n = n0 + δn and p = p0 + δp
Under a steady-state condition, excess carrier generation does not result in continuous carrier
accumulation because recombination is taking place simultaneously. The recombination rate of
excess electrons, Rn and excess holes, Rp will be equal and is given by:
Rn=Rp=δn/τn0
Rn=Rp=δn/τp0
Where τ is the minority carrier lifetime, representing the average time an excess minority carrier exists
before recombining. [4]

Fig:Creation of excess electron and hole densities by photons

 Fig:Recombination of excess carriers reestablishing thermal equilibrium.

b.Indirect recombination or The recombination through allowed energy states within the
bandgap
In indirect recombination, electrons from the conduction band recombine with holes in the
valence band via intermediate states within the bandgap. These so-called trap levels or defect
states usually arise from impurities or other defects in the crystal lattice. The characteristics of
this recombination mechanism manifest particularly strongly in indirect bandgap materials such
as silicon.

The Shockley–Read–Hall Theory of Recombination

An allowed energy state, or trap, in the forbidden bandgap can act as a recombination center by
capturing electrons and holes with approximately equal probability. Approximately equal capture
probability implies that the capture cross sections for electrons and holes are approximately
equal. The Shockley–Read–Hall theory of recombination is based upon a single recombination
center, or trap, at an energy, Et within the bandgap.
There are four basic processes, shown in the figure below, that may occur at this single trap. We
will assume that the trap is an acceptor-type trap; that is, it is negatively charged when it contains
an electron and is neutral when it does not contain an electron. [5]
 Fig:The four basic trapping and emission processes for the case of an acceptor-type trap. [5]

The four basic processes are as follows:

Process 1(: Electron Capture): The capture of an electron from the conduction band by an
initially neutral empty trap.

Process 2(Electron Emission): The inverse of process 1-the emission of an electron that is
occupying a trap level out into the conduction band.

Process 3(Hole Capture): The capture of a hole from the valence band by a trap containing an
electron. Or we may consider the process to be the emission of an electron from the trap into the
valence band.

Process 4(Hall Emission): The reverse of process 3: the emission of a hole from a neutral trap to
the valence band. Alternatively, we might view this process as the capture of an electron by the
valence band.
 In Process 1: the electron capture rate (#/cm3-sec):
Rcn = CnNt(1-fF(Et))n
Cn=constant proportional to electron-capture cross section
Nt = total concentration in the conduction band
n = electron concentration in the conduction band
fF(Et)= Fermi function at the trap energy
 For Process 2: the electron emission rate (#/cm3-sec):
 Ren = EnNtfF(Et)
En=constant proportional to electron-capture cross section Cn
In thermal equilibrium, Rcn = Ren, using the Boltzmann approximation for the Fermi
function

 In nonequilibrium, excess electrons exist,

 In Process 3 and 4, the net rate at which holes are captured from the valence band is
given by

 In semiconductor, if the trap density is not too large, the excess electron and hole
concentrations are equal and the recombination rates of electrons and holes are equal.

 In thermal equilibrium, np = ni2  Rn = Rp = 0

Life Time in Low Level Injection

In low-level injection, the injected carrier concentration is small as compared to the majority
carrier concentration in the semiconductor. It is typical for low doped materials or when low
power devices are concerned.
Carrier lifetime refers to the average time before recombination takes place. In the case of low
injection, minority carriers are dominant in the recombination process; thus, lifetime is the most
critical parameter in determining device performance, such as solar cells or diodes. Longer
carrier lifetime means carriers have more time to contribute to current before they recombine.
For an n-type material in low-level injection,the concentration of electron,n 0 is considerably
larger than the excess hole concentration,Δp. Under these conditions the recombination processes
are dominated by the minority carriers-as in this case holes-and the expression for the
recombination rate of the excess carriers can be simplified:
R=Cp.Nt.Δp
where:
 Cp is the hole capture coefficient,
  Nt is the density of recombination centers,
 Δp represents the excess minority carrier hole concentration.
The rate is proportional to the minority carrier lifetime (τp) and to the concentration of
recombination centres. The minority carrier lifetime may hence be defined as:
τp= 1/ CpNt
Similarly, for a p-type material in the case of low injection, the excess minority carrier lifetime
for electrons is given by:
Τn= 1/ CnNt
where Cn is the electron capture coefficient. [5]
Therefore, the lifetime in low-level injection depends on the trap or recombination centre
density. The implication of this effect is that when the trap concentration increases, the minority
carrier lifetime decreases. This simplified model can enable the description of the recombination
dynamics; the minority carrier lifetime is a measure of the average time an excess carrier exists
before recombination, thus making it one of the fundamental factors for designing and analyzing
semiconductor devices.

Surface Recombination:
Surface recombination is the process within a device where the minority carrier combines in the
surface layer and seriously affects the overall performance. It depends on whether the contacts
could inject or extract charges, controlled by the faster carrier at its surface. It might thereby
have a huge effect on both the short-circuit current and the open-circuit voltage. High
recombination rates at the top surface have a particularly unfavorable influence on the short-
circuit current, since the top surface corresponds to the highest generation region of carriers in
the solar cell. This high top surface recombination is generally reduced by reducing the amount
of dangling silicon bonds at the top surface through the use of a "passivating" layer on the top
surface. Most of the electronics industry relies on the use of a thermally grown silicon dioxide
layer to passivate the surface due to low defect states at the interface. Most common in
commercial solar cells are dielectric layers including silicon nitride. [6]
 Fig: Techniques for reducing the impact of surface recombination [6]

The surface recombination is characterized by a Surface recombination velocity(S) and is

defined as
R
S= n 0

where R is the recombination rate and n0 is the carrier density.

Impact of Surface Recombination:

Device Efficiency: High surface recombination rates can seriously reduce the efficiency of solar
cells and other optoelectronic devices by reducing the effective carrier lifetime and,
consequently, the charge-carrier concentration.

Thin Films: In thin-film technologies, surface recombination becomes even more critical due to
the high surface-to-volume ratio; hence, a much larger fraction of carriers can recombine at the
surface.

Origin Of Recombination-Generation centers:

The R-G (or Ratnowsky-Godfrey) center recombination, which is a type of recombination
mechanism through semiconductors. Especially famous among those are wide bandgap materials
like gallium nitride (GaN) and other III-Nitride semiconductors. The second essential attribute of
this kind of recombination is the involvement of deep energy levels within the bandgap, which is
usually associated with defects or impurities.
 Fig: single set of recombination centers [7]
Here,

nr = the densities of electron-occupied

pr= empty recombination centers

Recombination Process:
In the R-G center, the recombination process involves the defect level capturing an electron from
the conduction band. After an electron has been trapped, it can recombine with the hole in the
valence band. In effect, the process enhances the recombination process.
Recombination rate depends upon the R-G centres' concentration and availability of free carriers.
Impact on Device Performance:
The performance of the optoelectronic devices, especially LEDs and laser diodes, can be
significantly performed due to recombination at the R-G center. High levels of R-G center
recombination might reduce the efficiency with lower light output and higher non-radiative
recombination losses.
The result, in terms of solar cells, might be lower open-circuit voltages and overall efficiency due
to the loss of charge carriers that could have contributed to the photocurrent.

Super Lattice Phenomena

A superlattice usually refers to a structure composed of periodic repetitions of units of layers of
different materials that have resulted in the appearance of some new physical phenomena and
allows the customization of electronic properties in semiconductor devices. It commonly consists
of two kinds of semiconductor materials in thin layers, typically ranging in thickness from a few
nanometers up to several micrometers, repeated periodically. Because of quantum confinement
effects, these superlattices support very special electronic and optical properties when charge
transporters (electrons and holes) have their movements restrained along particular directions. [8]
Quantum Confinement
When the dimensions of the semiconductor layers are reduced to nanoscale, quantum
confinement becomes responsible. Thus, the electrons and holes will act as if they were confined
in one or more dimensions.
 Energy Level: The energy levels in bulk semiconductors can take continuous values of
energy. The motion of charge carriers is then confined in the superlattice by the
confinement in such a way that discrete energy levels are obtained. Probably due to this
quantization, striking changes in the electronic properties like an increased effective mass
with changed band structure may appear.
 Density of States: The superlattice has a different density of states from that of the bulk.
Some optical transitions are enhanced from this point of view, which can lead to
improved efficiencies in emission and absorption of light.

Bandgap Engineering
Bandgap engineering could be interpreted as the ability to change electronic properties in
semiconductors with both composition and structure.
 Layer Thickness and Composition: Each layer in the superlattice may have a different
thickness in order to influence the electronic band structure. Materials, for instance, GaAs
and AlGaAs, are carefully chosen in order to engineer such a superlattice with a pre-
determined bandgap for specific applications.
 Applications: This ability in tuning the bandgap is essential in designing devices such as
lasers and photodetectors, which should operate at specified wavelengths. For instance,
the bandgap of a superlattice can be engineered either narrower or wider to allow the
development of devices capable of emitting or detecting light at targeted wavelengths. [9]

Unique Properties of Superlattices

Superlattices have a few unique properties that make them attractive for many applications.
Some of these include:
 Higher Mobility: Quantum effects in superlattices can make carrier mobility higher
than in bulk material for high-speed electronic devices.

 Thermal Properties: The periodic structure may affect thermal conductivity and thus
the possibility to tailor thermal management in a device.

 Optical Properties: Superlattices can also sustain novel optical properties, such as
photonic band gaps and increased light-matter interaction that may be applied in the
field of optoelectronics
Applications of Superlattices
1. Quantum Cascade Lasers: QCLs are surely the most famous device based on
superlattice structures among various applications. Here, superlattices of carefully
designed thickness and composition allow for laser light emission at specific infrared
wavelengths. Applications of QCLs are found in numerous areas of spectroscopy,
sensing, and telecommunications because QCLs are capable of coherent light-generation
in a wide range of wavelengths.
2. Infrared detectors: Superlattice structures can be used for infrared detectors, either
photoconductive detectors or photodiodes, to obtain sensitivity at any infrared
wavelength
3. High-electron-mobility transistors (HEMTs): The employment of superlattices
increases electron mobility, thus providing high-performance transistors for high-
frequency applications and power electronics.
4. Thermoelectric materials: Superlattices can be designed in such a way that their
thermoelectric efficiency is improved for better conversion of energy between heat and
electricity. [9]

References

[1] "fiveable," [Online]. Available: https://fiveable.me/key-terms/physics-models-semiconductor-

devices/non-equilibrium-conditions.

[2] "Photonics," [Online]. Available: https://www.photonics.com/EDU/carrier_injection/d2815.

[3] "wordpress.com," [Online]. Available:

https://drpradeepatuem.wordpress.com/wp-content/uploads/2019/10/carrier-generation-and-
recombination.pdf.

[4] [Online]. Available: https://hsic.sjtu.edu.cn/Assets/userfiles/sys_eb538c1c-65ff-4e82-8e6a-

a1ef01127fed/files/Lec8_Nonequilibrium_Excess_Carriers_in_Semiconductors.pdf.

[5] D. A. Neamen, Semiconductor Physics and Devices Basic Principles, McGraw-Hill.

[6] [Online]. Available: https://www.pveducation.org/pvcdrom/design-of-silicon-cells/surface-

recombination.

[7] [Online]. Available: https://www.sciencedirect.com/topics/engineering/recombination-centre.

[8] W. G. A. and J. W. Wilkins, "Quasiparticle Calculations in Solids," vol. Volume 548, pp. Pages 1-21,
2000.

[9] "Wikipedia," [Online]. Available: https://en.wikipedia.org/wiki/Superlattice.