### 5.1.2 Recombination and Luminescence

High Injection Approximations for Recombination Rates

| Luminescence is the word for light emission after some energy was deposited in the material.
|  | Photoluminescence describes light emission stimulated by exposing the material with light - necessarily with higher energy than the energy of the luminescence light. Sometimes this is also called fluorescence if the emission happens less than about 1 µs after the excitation and phosphorescence if it takes long - up to hours and days.
|  | Cathodoluminescence describes excitation by energy-rich electrons, chemoluminescence provides the necessary energy by chemical reactions.
|  | Here we are interested in electroluminescence, in particular in injection luminescence.
| Injection luminescence occurs if surplus carriers are injected into a semiconductor which then recombine via a radiating channel.
|  | This implies non-equilibrium, i.e. ne·nh > ni2 and net recombination rates U given by the basic equation from the Shockley-Read-Hall theory for direct semiconductors:
U = R - Gtherm = v s (ne nh -ni2) = r ni2[ exp( | EFe - EFh KT | )-1]
|  | Some, but not necessarily all of the recombination events described by U produce light, and these recombination channels are of particular interest for optoelectronics.
| Since optoelectronic devices usually are made to produce plenty of light, the deviation of the carrier concentrations from equilibrium must be large to obtain large values of U.
|  | If we write the concentrations, as before, as ne,h = ne,h(equ) + Dne,h, we now may use the simplest possible approximation called high injection approximation: Dne,h >> nmin(equ); i.e. the minority carrier concentration is far above equilibrium.
|  | The surplus carriers contained in Dne,h are always injected into the volume under consideration (called recombination zone), usually by forward currents across a junction. They always must come in equal numbers, i.e. in pairs to maintain charge neutrality; otherwise large electrical fields would be generated that would restore neutrality. We thus have
|  | Dne = Dnh
|  | The recombination volume usually is the space charge region of a junction or an other volume designed to have low carriere concentrations in equilibrium. Since the equilibrium concentration of both carrier types in the SCR are very low in the SCR, we may easily reach the high injection case. For a bulk piece of a (doped) semiconductor this is much more difficult - you would have to illuminate with extremely high intensity to increase the majority carrier density by some factor.
| The surplus concentration of carriers decays with a characteristic lifetime t which is given by the individual life times of all recombination channels open to the carriers. Since R >> Gtherm for the high injection case, we have in analogy to the approximation made for (small) deviations from equilibrium:
|  | U = R - Gtherm =ca. R = n/t.
|  | We call this approximation (where we negelct G) "high-injection" approximation or the high injection case because the high density of surplus carriers is usually provided by injecting them over a forwardly biased junction into the region of interest.
|  | Note that while the rate equations are formally the same for high or low injection (or everything in between), t is not a constant but may depend on the degree of injection as we will see.
|  | Now we have to look at all the possibilities for recombination - called recombination channels - that are open for carriers as possible ways back to equilibrium. Recombination channels generating light we will call radiative channels.
| The band-band recombination channel (with which we started above, using the full Shockley-Read-Hall equations) can now be extremely simplified:
|  | Rb-b = v·s(n2), or, considering that v·s may no longer be totally correct as the proportionality factor,
|  | Rb-b = Bb-b(n2) - and the index "b-b" denotes band-band recombination. The proportionality constant B is occasionally called a recombination coefficient.
| If we use the same approximations for the recombination channel via deep levels, we obtain a rather simple relation, too, for the recombination rate Rdl
|  | Rdl = Bdln with Bdl = recombination coefficient for this case.
| Recombination via band-band transitions and via deep levels was all we considered so far. What kind of other recombination channels are available, especially for direct semiconductors and the high injection case?
|  | There are several, some very special and specific and only relevant for certain materials and/or doping. In this subchapter we will look at the most important ones.
| Before we do that, however, we will give some thought to the equilibrium case.
|  | In thermal equilibrium, we still have generation and recombination described by the equilibrium rates Gtherm and Rtherm and Utherm = Gtherm - Rtherm = 0.
|  | Now a tough question comes up: If recombination occurs via band-band recombination and results in the emission of a photon, does this mean that our piece of semiconductor, just lying there, would emit photons and thus glow in the dark?
|  | Obviously that can not be. Energy would transported out of the semiconductor which means it would become cooler just lying there, a clear violation of the "second law". On the other hand, a single recombination event "does not know" if it belongs to equilibrium or non-equilibrium, so radiation must be produced, even in equilibrium. We seem to have a paradox.
| The apparent paradox becomes solved as soon as we consider that any piece of a material "glows" in the dark (or in the bright) because it emits and absorbs radiation leading to an equilibrium distribution of radiation intensity versus wave length - the famous "black body" radiation of Max Planck fame.
|  | Recombination events in equilibrium do produce light - but the photons mostly will become reabsorbed and, in general, will not leave the material. The small amount that does escape to the environment must be exactly balanced by electromagnetic radiation absorbed from the environment.
|  | This topic will be considered in more detail in an advanced module

Additional Recombination Channels

| So far we considered only band-band recombination and recombination via deep levels. There are, however, more recombination channels, some of which are particular to compound semiconductors.
| But first we look at universal mechanisms occurring in all semiconductors. They are:
|  | Auger recombination. In this case the energy of the recombination event is transferred to another electron in the conduction band (or hole on the valence band), which then looses its surplus energy by "thermalization", i.e. by transferring it to the phonons of the lattice. This means that no light is produced.
|  | Donor - Acceptor recombination or recombination via "shallow levels". This includes transitions from a donor level to an acceptor level or to the valence band, and transitions form the conduction band to an acceptor level.
|  | Mixed forms: From a donor level via a deep level to the conduction band, etc.
| Now for material specific recombination channels. The most important one with direct technical uses is recombination via "localized excitons".
|  | Excitons are something like hydrogen atoms - except that a hole and not a proton forms the nucleus. They are thus electron - hole pairs bound by electrostatic interaction. They can form in any semiconductor, are mobile and do not live very long at room temperature because their binding energy is very small. They decompose ("get ionized") into a free electron and a free hole. They will not normally disappear by recombination because they can not have the same wave vector and thus need a third partner.
|  | If you wonder why they do not simply recombine, think about it. They can not possibly have the same wave vector (how would they "circle" each other then?) and thus need a third partner.
|  | On occasion, however, they might become trapped at certain lattice defects and then recombine, emitting light. GaP, though an indirect semiconductor, can be made to emit light by enforcing this mechanism.
|  | We will cone back to excitons, more about them can be found in an advanced module.
| The picture below illustrates these points.

| The picture is far too simple and we will have to consider some of the processes in more detail later; especially recombination via excitons. Here we look at Auger recombination and donor - acceptor recombination.
|  | Even without going into details, it is rather clear that (radiating) donor - acceptor recombination in all 4 variants is not all that different from direct (and radiating) band-band recombination. Especially for relatively high doping concentrations, when the individual energy levels from the doping atoms overlap forming a small band in the band gap, we might simply add the dopant states to the states in the conduction or valence band, respectively.
|  | We then can treat donor-acceptor recombination as subsets of the band-band recombination, possibly adjusting the recombination coefficient Bdl somewhat.
| This leaves us with Auger recombination. This is an important recombination process that can not be avoided and that always reduces the quantum yield of radiation production.
|  | It has not been covered in the treatment of Shockley-Read-Hall recombination before, and we will not attempt a formal treatment here. It is, however, simple to understand in the context of the high-injection approximation used for optoelectronics.
|  | Since you need three carriers at the same time at the same place (the e- and h+ that recombine plus a third carrier to remove the energy), the Auger recombination rate, RA, must be proportional to the third power of the carrier density n, RA = BA(n3).
|  | This means that for large carrier concentrations n (always way above equilibrium) Auger recombination sooner or later will be the dominating process, limiting the yield of radiating transitions.

Total Recombination and Quantum Yield

| All recombination processes will occur independently and the total recombination rate will be determined by the combination of all channels.
|  | The situation is totally analogous to the flow of current through several resistors switched in parallel. The individual recombination rates Ri add up (like the currents) and for the total recombination rate we have
|  | Rtotal = SRi = Sn/ti = nS1/ti.
|  | The total recombination time ttotal is thus defined by
| 1 ttotal | = | 1 tb-b | + | 1 tdl | + | 1 tA | + | 1 texciton | +.....
|  | Since we are only interested in radiative and non-radiative channels, we may write this as
| 1 ttotal | = | 1 trad | + | 1 tnon-rad |
and
Rtotal = Rrad + Rnon-rad = | n trad | + | n tnon-rad |
| The quantum efficiency hqu introduced before now can be calculated. It is given by the fraction of Rrad relative to Rtotal, or
hqu = | Rrad Rtotal | = | 1/trad 1/trad +tnon-rad |
, or
hqu = | 1 1+ trad /tnon-rad |
| That is easy enough, but now need some numbers for the recombination coefficients in order to get some feeling for what is going on in different semiconductors.
|  | It should be clear that the Bi defined above are related to quantities like the thermal velocity, the capture cross sections, the density of deep (and shallow) levels, and so on - they depend to some extent on the particular circumstances of the semiconductor considered. e.g. doping, cleanliness, defect density, etc.
|  | It should also be clear the Bi are not absolute constants for a given materials but only useful as long as the approximations used are holding. in other words, there are no universal numbers for a certain semiconductor. We only can give typical numbers.
|  | With this disclaimers in mind, we use the following values (if two numbers are included, they come from different sources). Yellow denotes the indirect semiconductors and the GaP value is for the very unikely direct recombination without excitons.
(T = 300K) | Si | Ge | GaAs | InP | GaP
B | t [µs] | B | t [µs] | B | t [µs] | B | t [µs] | B | t [µs]
Bdl [s-1] | 1·105 |  |  |  | 1·108 |  |  |  |  |
Bb-b [cm3s-1] | 1·10-14 1,8·10-15 | 5500 | 5,3·10-14 | 200 | 3·10-10 7,2·10-10 | 0,015 | 1,26·10-9 | 0,008 | 5,4·105 | 2000
BA [cm6s-1] | 2·10-32 |  |  |  | 1·10-27 |  |  |  |  |
|  | Now we can construct a recombination rate - surplus carrier concentration diagram as follows:
| We can see a few interesting points:
|  | The recombination rate in Si is generally much smaller than in GaAs - a direct effect of the much larger lifetimes.
|  | Direct recombination in Si is not strictly forbidden - it is just very unlikely. At a typical carrier concentration of 1018 cm-3 we have about 1022 photons generated per s and cm-3 compared to about 5·1026 in GaAs.
|  | Rb-b in GaAs is comparable to the recombination rates of the Auger and deep level channels at concentrations of about (3 - 4) ·1017 cm-3; while in Si Rb-b is always much smaller than the other recombination rates.
|  | While for large carrier concentrations the Auger recombination process always dominates, it may still be useful to increase n: While the quantum efficiency goes down, the amount of light produced still increases linearly with n.
|  | For very large carrier concentrations (say 1019 cm-3 and beyond as occasionally encountered in power circuits), even Si may produce some visible light.
| The GaAs curves now provide a first answer to our second question about the quantum efficiency.
|  | For n = 1616 cm-3, we have about 3·1022 radiating recombination events per s and cm-3 out of a total of about 1024per s and cm-3 which gives a quantum efficiency of 3%.
|  | At the high concentration end, around n = 1616 cm-3, the situation is similar, the quantum efficiency is in the few percent range.
|  | The highest quantum efficiency is around 30 % for concentrations around n = 5·1017 cm-3.
| Of course, given the values of the recombination coefficients, we could calculate the quantum efficiency precisely, but that would not be very helpful because real devices are more sophisticated than the simple forwardly biased junction implicitly assumed in this consideration.
|  | This means that we now must look more closely at the important compound semiconductors, especially on how they are doped and what typical differences to Si occur.
|  | We will, however, first do a little exercise for injection across a straight p-n-junction in order to get acquainted with some real numbers for carrier densities produceable by injection.

Exercise 5.1.2-1
Calculate carrier densities from the forward current of junctions.