Chapter 3

Up and Down-Conversion Mechanisms

3.1 Introduction
The main lossmechanisms in conventional singleenergy threshold solar
cells are the transmission andthermalisation losses. Up and down-
conversion are suitable candidates to minimize these losses.
Oneapplication in which this idea has been realised is the useof
luminescent layers on the front surface of solarcells. In this case the
luminescent layer shifts incidenthigh-energy photons towards lower
energies for which thesolar cell works more efficiently.While suitable to
reduce losses due to specificdeficiencies of certain solar cells, this
approach is notsuitable to increase the efficiency above the Shockley-
Queisser limit for conventional solar cells[]. Contrary,significant
improvements over the Shockley-Queisserlimit are predicted if the
luminescent layers are used as upordown-converters, as discussed below.

3.2 Up-conversion Mechanism

Up-conversion describes the physical process of aconversion of incident
light by a material towards higherenergies. For photovoltaicapplications
up-conversion can be used to transform subband-gap light, which is
transmitted by a normal solar cell,to energies above the hand-gap. We
restrict ourconsiderations here to up-conversion by sequentialground-state
excitation I excited state excitation.
Figure (3-1). Device schematic of (a) a solar cell incombination with an
up-converter. (b) a solar cell incombination with a down-converter. In
both cases areflector is located at the rear surface and the converterand
the solar cell are electronically isolated from eachother (possibly, but not
necessarily by a separate insulatinglayer, as shown)[].

A schematic diagram of a photovoltaic system, inwhich this effect would

be used, is shown in Figure (3-1) (a). Anup-converter is located at the
rear surface of a bifacialsolar cell and absorbs the sub-hand-gap radiation
that thesolar cell transmits. Inside the up-converter the sub-
bandgapradiation is partially converted to photons withenergies above the
band-gap and these photons can then beabsorbed in the solar cell. As an
additional electron hole(eh)-pair is generated in the linear process, up-
conversionrepresents a possible way to utilize sub-band-gap photonsand
thus reduce the transmission losses of a conventionalsolar cell.

3.3 Down-conversion Mechanism

A red shift of the emitted photon fluxagainst theincident spectrum is often

observed e.g. inphotoluminescence experiments, which is referred to
asthe Stokes-shift. Rather than just shifting the energy ofincident photons
it is also possible that incident high-energyphotons are transformed by a
material into two ormore lower- energy photons, which we will refer to
hereas down-conversionand which is also known as quantum-cutting. Fig
(3-1) (b) shows a device schematic of a solar cellin combination with a
down-converter. The downconverterideally transforms incident photons
withenergies exceeding ntimes the hand-gap energy of thesolar cell
material into n lower energy photons, which canthen be used for the
generation of n eh-pairs inside thesolar cell. Down-conversion thus
represents a method formultiple eh-pair generation per incident high-
energyphoton and can be used to reduce the thermalisationlosses.
Because the absorption of high-energy photons inthe solar cell must be
avoided, the converter must be located on the front surface for
semiconductor solar cells. Fig (b).

3.4 Principle of Up/Down-Conversion

Any material with radiative transitions between more thantwo energy

levels could be used, in principle, as an upandas a down-converter. The
energy diagram of an almostideal material for up- and down-conversion
is shown inFig(3-2). It consists of a semiconductor with valence-
andConduction band and with an intermediate level (IL) lyinginside the
forbidden gap. The arrows in Fig. (3-2)indicate the three types of
transitions in such a material,between electronic states in the valence-
band and the conduction-band, between the conduction-band and the
ILand between the valenceband and the 1L.Up-conversion by
GSAiESAinvolves a two-stepexcitation of electrons from the valence
band via theintermediate level into the conduction band by absorptionof
two low energy photons followed by a radiativetransition of the electron
from the conduction band into thevalence band.
Figure (3-2). Energy diagram of a material that could be usedas an up- or
down-converter. Dotted arrows indicateintermediate transitions via the 1L
and solid arrowsindicate band-band transitions. Processes involved
indown- and up-conversion, respectively areplotted in light-greyand in
dark grey on the left and on the right,respectively.Finite transition
probabilities are required for the threetypes of transitions in Fig.3-1
which, according to theprinciple of detailed balance, are allowed in
bothdirections[].
As a result neither up -conversion or down-conversioncan ever be a 100%
efficient process becauseeh-pairs will always partially recombine via both
directband-band transitions and the two-step process involvingthe IL
depending on the relative probabilities for thesetwo recombination
mechanisms, the material representedin Fig. (3-1) could be used as an
efficient up- or as a downconverter.

3.5 DISCUSSION

General aspects ofthe new concepts the main advantage of combining

solar cells withup- or down-converters against other concepts is that they
can be applied to existing solar cells.This alsohas the fundamental
advantage that by stacking aluminescent layer behind a solarcell, without
making anymodifications to the solar cell itself, we can only improvethe
efficiency, whereas a significant deterioration of thesolar cell material is
connected e.g. with the implantationof impurities into a semiconductor
for an IPV-device.
The limiting efficiency of a solar cell with aluminescent up-converter on
the rearsurface has been analyzed inalimiting value of 63.17% is found
formaximum concentration of the sunlight, which is identicalto the
limiting efficiency that was calculated earlier for anIPV-device and a
substantial improvement over theShockley-Queisser limit. For non-
concentrated sunlight nosignificant improvement is found for a
luminescenceconverter with energy levels[].
Theproduction of an efficient up -converter by implantingimpurities into
a semiconductor thus seems unlikely due tothe above-mentioned
enhanced probability for nonradiativerecombination. The three-band
nature of thematerial should rather be an intrinsic property as forexample
in many rare earth elements.Promising initial experimental results with
externalquantum efficiencies onthe order of 5*10-4at wavelengthsaround
1550nm obtained with bifacial silicon solar cells incombination with non-
optimized commercial upconversionphosphors are presented at this
conference.
Significant efficiency improvements have also beenpredicted for non-
concentrated sunlight for a solar cell incombination with a down-
converter SI. Amaximumefficiency of 38.6% was found for non-
concentratedsunlight and for a converter with one IL, which is
asignificant improvement over the Shockley-Queisser limit. Importantly
the highest limiting efficiencies are found forband-gap energies close to
1.leV, which certainly makesthis approach particularly interesting for
silicon solar cells.
Adown converter utilizing transmitted high-energyphotons could thus be
located behind such a solarcell. Aneven higher efficiency limit of 39.6%
is calculatedfor that geometry SI[].
The easiest and most promising implementation ofthe up - and down-
conversion concept, respectively, seemsto be the use of separate
luminescent layers comprisingluminescent centers like rare-earth and
transition-metalcompounds or quantum dots incorporated in a
transparenthost matrix. As mentioned above the limiting
efficiencycalculations in SIrevealed that the efficiencyimprovement is
highest if the refractive index of thesolar cell and of the converter are
matched. For siliconsolar cells transparent host materials ideally with
n=3.5would thus be required. Finding such materials, however,appears to
be problematic.
 Chapter 4
Summary and Conclusion

Photovoltaic devices in combination with up- and down-conversion are

two promising new “third generation” approaches. Significant
improvements of the limiting efficiency over the Shockley-Queisser limit
are predicted for these two concepts under idealizing assumptions. Such
major efficiency improvements have also been predicted theoretically for
other concepts like hot-cannier solar cells or the use of impact ionisation.
However, the fact that the concepts discussed here may he applied, in
principle, to any existing solar cell by, combination of the solar cell with
a separate luminescence converter isa major advantage of these concepts
over these other third-generation approaches. While commercially
available up- and down-conversion phosphors, which convert incident
light into the visible spectral range, are readily available and suitable for
proof of concept studies, a thorough investigation of potential materials
for conversion into the NIR isnecessary for further progress.