Optical processes in semiconductors

4.1 Introduction
IVarious interesting properties of semiconductors such as energy band formation, mechanisms of electron
scattering and finally the electron transport were clearly discussed in the previous chapter. However, we have
not seen how an electron, having gained energy from external means, gets transported to higher energies.
When one electron leaving the energy level creates a hole, the process is called electron-hole pair generation.
Similarly, when an electron combines with the hole, the process is called recombination. In this chapter, we
examine various possibilities of electron-hole pair generation and also examine recombination mechanisms.
This electron-hole pair generation and recombination process is very important in device technology,
particularly in optoelectronic devices. This concept is the basis for the working principle of an LED (light
emitting diode) and semiconductor laser. Though we have generalised as optical processes, we will also see
how these processes influence other processes such as electrical properties of a device (such as p-n diodes). In
this chapter, we will review e-h processes involved in semiconductors and some of the intrinsic properties.
Creation and recombination of e-h pair essentially require external energies such as optical, electrical or
thermal energies. Such processes are mainly between the valence band and the conduction band. General
concept is the pair production (or recombination) within the volume, and hence, although the local carrier
concentration changes, overall space charge remain neutral. We can categorise the e-h pair channels into three
categories: radiative, nonradiative and thermal processes. Here we have to consider several time-scales,
energy bands and charge carrier concentrations of particles at the specified energy levels.
Before going deep into it, let us review few transitions that you learned in your previous classes related to
optics. If we give sufficient energy (energy equal to band gap), one electron raises from the valence band to
the conduction band, leaving a hole in the valence band. This is called absorption. Once the electron reaches
conduction band, it simply comes down and recombines with the hole (stay time depends on the energy level
life time). This recombination energy must be consumed and may get converted as a photon (luminescence) or
given away to the lattice as phonon or heat. The energy conversion of photon is called radiative transition and
conversion to phonon or heat energy is called nonradiative transition.
Radiative pair recombination (emission, also called luminescence) event takes place by emitting a photon
whose energy depends on the kinetic energy gained and the band gap of the material. This process could be
either stimulated (by population inversion) or just spontaneous. However, in reality, the nonradiative
processes greatly influence the radiative and also band-to-band transition processes.

For simplicity and for the time being, we designate band states as conduction and valence band (keep in view
the picture of direct and indirect band gaps) and the bound states are the impurity levels, phonon or
imperfections in the semiconductors. The bound states, unlike donor and acceptor states, they do not really
ionize, but act like traps or more like short time home for either electrons or holes.

Optical processes directly involve photon absorption and emission. This process is clearer in direct band gap
materials such as GaAs, where conduction minimum and valence band maximum lie at the zone center (k=0).
Hence it is easy for an electron to rise to the conduction band by absorbing a photon of energy equal to the
band gap Eg, and come down to the valence band and recombine with a hole by liberating the energy as
emitting photons. As such, the probability for radiative process in direct band gap materials is very high.
Whereas in indirect band gap material, such as Silicon, the process requires additional momentum or the
involvement of phonon, as the conduction and valence band centers do no match at k=0. In such cases,
phonon emission or absorption can assist the e-h recombination. As such, electron takes a long time, waiting
for such a phonon event to occur, at the conduction level. As we talked before there are defects traps those
acts as recombination centers or just a springboard. It is highly likely event that the e-h combination is
nonradiative and the excess of energy is dissipated as lattice heating. In other words, in indirect band gap
nonradiative processes dominate. Hence, these devices are considered ineffective as emitting devices. (Not for
so long: The recent discovery of converting Silicon as an efficient emitter, in reduced dimensions of silicon,
made such assumption obsolete. We shall discuss this in our spare time).
 Fig.3.1 (a) Showing absorption of photon when light of sufficient energy is incident (b) Photon Emission in
the absence of external photons (c) Photon emission in the presence of external photon
Another important channel of nonradiative process involves deep levels of either conduction or valence
bands. Here the process involves a third free carrier, which is eventually raised to higher energy levels via
intra band transitions. This comparatively high energy related process is very important in heavily doped
semiconductors and is called Auger recombination process.

Fig.3.2 Absorption process in (a) direct and (b) indirect band gap
As we discussed before, the e-h pair production or recombination involves either band to band or intra band
transitions. Let us see how we can export an electron from the valence band to conduction and later we will
explore various possibilities of the electron recombination with the leftover hole.
 Radiative and nonradiative recombination process
4.3 Radiative and nonradiative recombination process
Till now we considered various cases of electron hole pair generation, which is how an electron transports in
band-band or intraband transitions. Now let us see how the generated electron recaptures with a hole. As
mentioned in the introduction, the recombination of electron could be classified into three major categories:
(1) band to band recombination, emitting a photon (radiative),
(2) recombination by means of simply giving away energy to phonons and
(3) recombination by transferring kinetic energy to another electron and knocking out into higher energy
levels.

Radiative recombination
This Band-to-band recombination happens when an electron moves from its conduction band state to the
empty valence band state associated with the hole. The radiative recombination is a very important feature in
semiconductor optoelectronics. The generation and recombination rates are interrelated as both processes
follow the same path . The recombination rate is given by

Eq9 is born out of our previous discussion where the electron generation and recombination occurred between
two initial and final momentum vectors Ki and Kf. ( see Eq.1-3). Let us recap again, the absorption states

are , and emission states , However, the

situation is not simple in semiconductors. Here we have several exceptions (for example, the presence of
forbidden gap impurity levels and lattice related defect centers) those disobey the above general rule. In
general, the absorption is followed by both radiative and nonradiative recombinations. The radiative
recombination could be both spontaneous ( initial and final photon are incoherent) and stimulated (both
photons are in phase).
The spontaneous radiate recombination rate, without any further discussion, given as

integration over is needed to count the photons in 3D to get the rates for all the occupied and hole
states. here , Fermi functions of electrons holes and respective representations of f(E) and reduced
density of states Ncv are given in Eq.2.
Here the Eq10, takes different conductions depending of carrier injection (optical, electrical or thermal).
(i) Minority carrier injection:
If the electron density is greater than hole density, then fe(Ee) is almost unity and the radiative rate

is This means the radiative rates are proportional to the minority carrier densities.
(ii) Strong injection:
In this case very high densities of both electrons and holes are injected. In that case, both Fermi functions
could be treated as very sharp functions and hence the radiative rate is
Where Pn is the electron emission rate
Similarly the above two equations for holes also exist as

and

at equilibrium Eq15 and 16 are equal similarly Eq17=Eq18.

We know how to derive the electron density (n) and Fermi distribution (f(Et)) from lecture notes(2) Eq.16 and
20

one can derive using above expressions the reemitted rate Pn as

We are interested in the rate of change of carrier concentration (electrons and holes), which is given as

With little effort one can write Rt in terms of above quantities and defining terms

Above expression is called Shockley-read-hall* equation for recombination rate via deep levels in the band
gap. One can simplify the above expression by assuming
and Et = Efi

For low –level injection of n-type semiconductor ( n>>p) One would also write above Eq23. as, where p and
p0 are respectively the non-equilibrium and equilibrium hole electron concentrations (similarly for holes).
Hence the decay rates are not from the majority carriers (here electrons), but from minority carriers.
4.3.3 Auger♣ Non-radiative processes

Fig.3.13 Auger recombination representation: (a) 2e-1h and (b) 1e-2h recombination
As we discussed in the previous section, in the impact ionisation: one hot electron with energy greater than
bang gap scatters another electron into higher states in the valence band to produce two electron and one hole
(similarly for hole). The Auger processes are exactly opposite to this. The schematic representation of
possible electron hole recombination of this kind is given in the fig.3.13. There are two processes mainly in
this recombination
(1) one electron from conduction band recombines with hole in valence band (heavy-hole state) by giving
away energy to another electron in conduction band. The energy gained electron jumps to a higher state and
subsequently relaxes to valence band by giving energy as phonon . This is called conduction-conduction-
heavy hole conduction (CCHC) (just after the individual carriers in their respective states)
(2) one electron from conduction band recombines with hole in the valence band (heavy hole state) and
knocks one hole deep into the split-off level. This is conduction heavy hole-heavy hole-split
off (CHHS) process.
Keep in mind both the processes are non-radiative. The expression for the net Auger recombination rate is
similar to the band-to-band recombination but includes the density of the electrons or holes, which receive the
released energy from the electron-hole recombination.

Above expression involves both the processes. The non-radiative lifetimes can simply be written as
. At very high dopant levels, radiative and auger processes are more dominant. More generalised life time
representation is

Auger theory is highly dependent on many variants: approximations, band structure calculations and wave
functions.
The over all lifetime of recombination is

More or less the auger processes are not of much importance in wide band gap materials, as the auger
processes here is phonon assisted.