Semiconductor under Non-equilibrium

Topics Included-

 Carrier Injection

 Kinetics Of Recombination And Generation Processes:

 Schokley-Read-Hall Theory of Recombination

 Life Time in Low Level Injection

 Surface Recombination

 Origin of Recombination-Generation Centers

 Super Lattice phenomena

Carrier Injection:

Adding more charge carriers (electrons or holes) to a semiconductor material is

known as carrier injection, and it is a basic procedure in semiconductor devices.
The functioning of several electronics, such as diodes, transistors, and light-
emitting diodes (LEDs), depends on this mechanism.

Types of Carrier Injection:

There are primarily two types of carrier injection:

1) Minority Carrier Injection:

Involves injecting minority carriers into a semiconductor region. For example,

injecting electrons into a p-type region or holes into an n-type region.

2) Majority Carrier Injection:

Involves injecting majority carriers into a semiconductor region. For example,

injecting electrons into an n-type region or holes into a p-type region.

Mechanisms of Carrier Injection:

There are some mechanisms of injecting carrier. Such as-

1) Forward Biasing a PN Junction:

Majority carriers can diffuse across a PN junction when it is forward-biased

because the junction's potential barrier is lowered. Minority carriers are injected
into the opposing region by this diffusion mechanism. A forward current results
from the injected minority carriers recombining with majority carriers.

2) Optical Injection:

Electrons from the valence band can be excited to move to the conduction band,
creating electron-hole pairs, by light with energy higher than the semiconductor's
bandgap. Photodiodes and solar cells both use this method.
3) Ionization by Impact:

When high-energy carriers strike lattice atoms, energy is transferred and new
electron-hole pairs are formed. This procedure is crucial for avalanche breakdown
in transistors and diodes.

4) Tunneling:

Electrons can tunnel across a thin potential barrier in some devices, such as tunnel
diodes, resulting in carrier injection.

Kinetics Of Recombination And Generation Processes:

The creation of electron-hole pairs and their recombination are delicately balanced
in semiconductor devices. The device's performance is greatly impacted by this
balance, especially when it comes to device speed and carrier lifetime.

In semiconductors away from their equilibrium state, recombination indicates the

speed in which holes and electrons disappear by meeting each other to restore the
equilibrium; on contrary hole-electrons pairs are created when carriers enter into
higher-energy states. Also, the creation of electron-hole pairs is known as carrier
generation.So recombination is going back to the conduction band with a hole, and
you know when that happens energy will be released because then electrons go
from high-energy states down low in energy. At non-equilibrium, that rate
increases even more as the semiconductor tries to revert back closer towards its
equilibrium state by recombining these extra carriers. Carrier generation refers to
the formation of eagerness by making 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

a) Direct band to band generation and recombination:

The concentration of electrons and holes in conduction (and valence) band reaches
a stead-state which macroscopically is time independent — i.e. the system satisfies
neutron spin-up boundary conditions with zero current flowing through it. Even so,
due to the stochastic nature of thermal operations electrons are thermally excited
from the valence band continuously into states of conduction. In the meantime,
electrons in the conduction band can unwittingly wander around a crystal and
"drop" down into these empty states of valence bands when they bump near holes.

Fig: Electron-hole generation and recombination [1]

 Let Gn0 and Gp0 be the thermal generation rates of electrons and holes
respectively
 For the direct band to band generation the electrons and holes are created in
pairs , so we must have that

Gn0=Gp0 (1)

 Let Rn0 and Rp0 the recombination rates of electrons and holes,
respectively, for a semiconductor in thermal equilibrium.
 In direct band-to-band recombination, electrons and holes recombine in
pairs, so that
Rn0 = Rp0 (2)
 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 (3)

 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 = gp. For the direct band-to band
generation, the excess electrons and holes are also created in pairs, so we
must have,
gn = g p
 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
p = p0 + δp
 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 [2]

Fig:Creation of excess electron and hole densities by photons [3]

Fig:Recombination of excess carriers reestablishing thermal equilibrium. [3]

b.Indirect recombination or The recombination through allowed energy states
within the bandgap:

In indirect recombination,electrons in conduction band will also combine with the

holes on valence band through intermidiate state within their energy gap. These are
called trap levels or defect states and typically result from impurities,
dislocations… in the crystal lattice. In indirect bandgap materials such as silicon,
the attributes of this recombination mechanism are particularly pronounced.

The Shockley–Read–Hall Theory of Recombination

A single recombination center, or trap, at an energy, Et, within the bandgap is the
foundation of the Shockley–Read–Hall theory of recombination. Because electrons
and holes are captured with roughly equal probability by an allowed energy state,
or trap, in the forbidden bandgap, it can serve as a recombination center. The
capture cross sections for electrons and holes are about identical when the capture
probability is roughly equal.

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.

Fig:The four basic trapping and emission processes for the case of an acceptor-type trap [3]
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
  Ec  Et 
E  n 'C  N exp
n n c  C  n
kT
 In nonequilibrium, excess electrons exist,

Rn  Rcn  Ren  Cn Nt n1  f F ( Et )  n' f F ( Et ) 
  In Process 3 and 4, the net rate at which holes are captured from the valence
band is given by

R p  C p N t pf F ( Et )  p ' (1  f F ( Et )) 
  Et  Ev 
p '  N v exp  
 kT
 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.
Cn n  C p p'
 f F ( Et ) 
Cn (n  n' )  C p ( p  p' )
CnC p N t (np  ni2 )
and Rn  R p  R
Cn (n  n' )  C p ( p  p' )

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

Life Time in Low Level Injection

Compared to the semiconductor's predominant carrier concentration, the injected

carrier concentration is low in low-level injection. It is common for materials with
low doping or for devices with minimal power. The average amount of time until
recombination occurs is known as carrier lifetime. Lifetime is the most important
factor in determining the performance of devices, like solar cells or diodes,
because minority carriers dominate the recombination process in the event of low
injection. Carriers with longer lifetimes have more time to add to the current before
recombining.
For an n-type material in low-level injection, the concentration of electron,n0 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.

As a result, the trap or recombination center density determines the longevity in
low-level injection. This result implies that the minority carrier lifespan reduces as
the trap concentration rises. One of the key considerations in the design and
analysis of semiconductor devices is the minority carrier lifetime, which is a
measure of the average amount of time an extra carrier exists prior to
recombination. This simplified model can allow the explanation of the
recombination dynamics.

Surface Recombination:

The process by which a minority carrier combines in the surface layer of a device
and significantly impairs overall performance is known as surface recombination.
The quicker carrier at its surface determines whether the contacts may inject or
remove charges. As a result, it could significantly impact both the open-circuit
voltage and the short-circuit current. The short-circuit current is especially
negatively impacted by high recombination rates at the top surface since this is
where the solar cell's strongest carrier production occurs. By using a "passivating"
layer on the top surface, the quantity of dangling silicon bonds at the top surface is
often decreased, lowering this high top surface recombination. Because of the low
defect states at the interface, the majority of the electronics industry depends on
passivating the surface via a thermally generated silicon dioxide layer. Silicon
nitride and other dielectric layers are most frequently seen in commercial solar
cells. [4]
 Fig: Techniques for reducing the impact of surface recombination [4]

The surface recombination is characterized by a Surface recombination

velocity(S) and is defined as
𝑅
S=
n0

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

Impact of Surface Recombination:

1) Reduction in Carrier Lifetime:

The average amount of time an electron or hole charge carrier is free before
recombining is known as its carrier lifetime. Since many charge carriers that reach
the surface can recombine before contributing to current or other activities, surface
recombination significantly reduces carrier lifespan. This is especially crucial for
materials like thin films or nanostructures that have a high surface-to-volume ratio.
2) Degradation of Light Emitting Diodes (LEDs) and Laser Diodes:
Surface recombination can lower the number of carriers available for radiative
recombination, which produces light, in optoelectronic devices like LEDs and laser
diodes. As a result, these devices' internal quantum efficiency (IQE) decreases,
resulting in less light being released for a given electrical input.
3) Thermal Impacts:
The device may heat up locally as a result of surface recombination reactions,
which normally release energy as heat. Over time, this may result in thermal
degradation that shortens the device's lifespan or calls for the adoption of extra
cooling solutions.

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 [5]

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

Generally speaking, a superlattice is a structure made up of recurring units of

layers of various materials that have produced new physical phenomena and
enabled the customization of electronic characteristics in semiconductor devices. It
usually consists of two types of semiconductor materials in thin layers that are
repeated at regular intervals and have thicknesses varying from a few nanometers
to several micrometers. When the movements of charge transporters (electrons and
holes) are restricted in specific directions, these superlattices offer extremely
unique electrical and optical features due to quantum confinement effects. [6]

Quantum Confinement:

Quantum confinement takes over when the semiconductor layers' sizes are lowered
to the nanoscale. As a result, it will appear as though the electrons and holes are
restricted 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. [7]

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.
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. [7]
References

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[3] N. D. A, Semiconductor Physics and Devices Basic Principles, McGraw-Hill. .

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

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

centre.

[6] W. G. A. a. J. W. Wilkins, " Quasiparticle Calculations in Solids," vol. 548, pp. 1-21, 2000.

[7] [Online]. Available: https://en.wikipedia.org/wiki/Superlattice.