Physica E 14 (2002) 65 70

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Third generation photovoltaics: solar cells for 2020 and beyond

Martin A. Green
Special Research Centre for Third Generation Photovoltaics, University of New South Wales, Sydney, 2052, Australia

Abstract Many working in the eld of photovoltaics believe that rst generation silicon wafer-based solar cells sooner or later will be replaced by a second generation of lower cost thin-lm technology, probably also involving a di erent semiconductor. Historically, CdS, a-Si, CuInSe2 , CdTe and, more recently, thin-lm Si have been regarded as key thin-lm candidates. Since any mature solar cell technology is likely to evolve to the stage where costs are dominated by those of the constituent materials, be it silicon wafers or glass sheet, it is argued that photovoltaics will evolve, in its most mature form, to a third generation of high-e ciency thin-lm technology. By high e ciency, what is meant is energy conversion values double or triple the 15 20% range presently targeted. Tandem cells provide the best-known example of such high-e ciency approaches, where e ciency can be increased merely by adding more cells of di erent band gap to a stack. However, a range of other better-integrated approaches are possible that o er similar e ciency to an innite stack of such tandem cells. ? 2002 Elsevier Science B.V. All rights reserved.
Keywords: Photovoltaics; Solar cells; Conversion e ciency; E ciency limits

1. Introduction Most solar cells presently on the market are based on silicon wafers, the so-called rst generation technology. As this technology has matured, costs have become increasingly dominated by material costs, mostly those of the silicon wafer, the strengthened low-iron glass cover sheet, and those of other encapsulants. This trend is expected to continue as the photovoltaic industry continues to mature. A 1997 study [1] of costs of manufacturing in greatly increased 500 MW=y production volume suggests material costs in such volumes would account for over 70% of total manufacturing costs. This favours high-e ciency processing sequences that produce solar cells with high energy conversion e ciency, provided these

Tel.: +61-2-938-540-18; fax: +61-2-966-242-40. E-mail address: m.green@unsw.edu.au (M.A. Green).

can be fabricated without unduly complicated cell processing [1]. For the past 15 years, a switch to a second generation of thin-lm cell technology has seemed imminent. Regardless of semiconductor, thin-lms o er prospects for a major reduction in material costs by eliminating the silicon wafer. Thin lms also o er other advantages, particularly the increase in the unit of manufacturing from a silicon wafer (100 cm2 ) to a glass sheet (1 m2 ), about 100 times larger. In terms of energy conversion e ciency, this second generation technology, with time, might be expected to largely bridge the present gap between itself and rst generation product. As thin-lm second generation technology matures, costs again progressively will become dominated by those of the constituent materials, in this case, the top cover sheet and other encapsulants required to maintain a 30-year operating life. There

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will be a lower limit on such costs (say, US$30=m2 ) which, when combined with likely cell e ciency (15% or 150 Wp=m2 ), determines the lower limit on photovoltaic modules costs (US$0:20=Wp) and electricity generation costs (US$0:020:04 kWh1 ), assuming module costs are half of system costs and a range of insolation and cost-of-money scenarios. To progress further, conversion e ciency needs to be increased substantially. The Carnot limit on the conversion of sunlight to electricity is 95% as opposed to the theoretical upper limit of 33% for a standard solar cell. This suggests the performance of solar cells could be improved 23 times if di erent concepts were used to produce a third generation of high-performance, low-cost photovoltaic product. Fortunately, with the likely evolution of new materials technology over the coming decades, prospects for thin-lm cells based on new concepts appear to be quite good! In the following sections, possible third generation approaches are reviewed and implementation strategies are suggested [2]. 2. E ciency losses in standard cell Losses in a standard solar cell are shown in Fig. 1. A key loss process is process 1, whereby the photoexcited pair quickly loses energy in excess of the band gap. A low-energy red photon is just as e ective as a much higher energy blue photon. Balancing this loss with the loss of low-energy photons passing straight through the device alone limits conversion e ciency of a cell to about 44%. Another important loss process is process 4, recombination of the photoexcited electronhole pairs. This can be kept to a minimum by using material with high lifetimes for the photogenerated carriers, ensured by eliminating all unnecessary defects. The lifetime is then determined by radiative recombination in the cell, the inverse to photoexcitation. As shown in 1960 [3], this symmetry between light absorption and light emission can be used to derive quite fundamental limits on achievable solar cell performance. This approach revisits blackbody radiation, the topic that stimulated the birth of quantum mechanics. By relating the light emitted by an ideal cell to that emitted by a blackbody, Shockley and Queisser showed that the performance of a standard cell was

Energy

1
2 3 4' 4
usable (qV)

3' 1'
Fig. 1. Loss processes in a standard solar cell: (1) thermalisation loss; (2) and (3) junction and contact voltage loss; (4) recombination loss.

limited to 31.0% e ciency for an optimal cell with a band gap of 1:3 eV. This is lesser than the gure of 44% previously mentioned since the output voltage of the cell is less than the band gap potential, with the di erence made up by voltage drops at the contact and junction (Fig. 1). These drops can be reduced if sunlight is focussed to increase the photon density striking the cell. Under the maximum possible sunlight concentration (46,200 times!), the limiting e ciency increases to 40.8%. However, only direct sunlight can be focussed in this way. As the gure under maximal concentration gives the highest numerical value and also applies to the conversion of direct light even when unconcentrated, this e ciency is a useful gure in comparing the ultimate potential of any given approach. This e ciency is also more directly comparable with results from classical thermodynamics. For example, the conversion e ciency of energy from a source at 6000 K with a sink temperature of 300 K is limited by the Carnot e ciency (1 Tsink =Tsource ) to 95.0%. However, this value does not count the photons emitted by the cell as a waste, since it assumes they get back to the sun, helping it to maintain its temperature! Some of the schemes to be described, however, can approach this limit reasonably closely. 3. Tandem cells The key loss process 4 of Fig. 1 can be largely eliminated if the energy of the absorbed photon is just

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Solar cells

the Si:Ge:H alloy system. Modules with e ciencies up to 6 7% are available incorporating double- and triple-junction devices.

4. Multiple electron-hole pairs If, instead of giving up their excess energy as heat, the high-energy electronhole pair used it to create additional pairs as allowed by energy conservation, higher e ciency would be possible. Evidence for the creation of more than one pair by high-energy photons is documented [5], attributed to impact ionization by the photoexcited carriers. The limiting e ciency for an idealised cell capable of taking full advantage of this impact ionisation e ect is calculated as 85.9% for a cell of band gap approaching zero. This design allows, on energy grounds at least, many electronhole pairs to be generated by each incident photon. In reality, the measured e ect to date is so weak so as to produce negligible improvement in device performance. Competitive processes for the relaxation of the high-energy photoexcited carriers are too e cient. A more recent idea is based on Raman luminescence [2] (Fig. 3). Raman scattering is a generic term applied to the inelastic scattering of photons (scattering that results in a change in photon energy and also, usually, in direction). Formally, the scattering involves creation of a virtual electronhole pair by

Sunlight Decreasing band gap

Fig. 2. Tandem cell approach.

a little higher than the cell band gap. This leads to the tandem cell concept, where multiple cells are used each with di erent band gaps and each converting a narrow range of photon energies close to its band gap. Fortunately, just stacking the cells with the highest band gap cell uppermost as in Fig. 2 automatically achieves the desired ltering. Performance increases as the number of cells in the stack increases, with a direct sunlight conversion e ciency of 86.8% calculated for an innite stack of independently operated cells [4]. Having to independently operate each cell is a complication best avoided. Usually, cells are designed with their current outputs matched so that they can be connected in series. This constraint reduces performance. More importantly, it makes the design very sensitive to the spectral content of the sunlight. Once the output current of one cell in a series connection drops more than about 5% below that of the next worst, the best for overall performance is to short-circuit the low-output cell, otherwise it will consume, rather than generate power. Tandem cells are now in commercial production. Double and triple junction cells based on GaInP=GaAs=Ge have been developed for use on spacecraft with terrestrial e ciencies approaching 30%. Quadruple junction devices with e ciencies approaching 40% are presently under development. Tandem cells are also used to improve the performance and reliability of terrestrial amorphous silicon cells with stabilised e ciencies up to 12% conrmed for small-area triple-junction cells based on

Eu

hf in

hf out

E th

EL

Fig. 3. Device based on Raman luminescence.

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the photon in a process that conserves momentum but not necessarily energy. The virtual pair remains viable for a short time determined by the energy imbalance. During this period, for the Raman luminescence, the virtual pair relaxes emitting a photon of an energy that di ers from that of the original photon by the energy of the generated electronhole pair. An analysis of the e ciency of cells based on the Raman luminescence gives identical bounds to those based on impact ionisation. In principle, 85.9% e ciency is possible from such cells. The di erence may prove to be in the practicality of implementation. 5. Hot carrier cells When photoexcited carriers collide elastically with one another, no energy is lost. It is inelastic collisions with the atoms of the cell material that result in an energy loss (through phonon emission). In principle, if such atomic collisions can be avoided during the time it takes a photogenerated carrier to traverse the cell, the energy loss associated with process 1, of Fig. 1 can be avoided. The various time constants can be appreciated by imagining a direct band gap cell illuminated by a short pulse of monochromatic light such as from a laser. Such a pulse would create electrons in the conduction band and holes in the valence band of distinct energy and momentum as in Fig. 4. Collisions of these carriers occur in less than a picosecond, tending to smear this distribution. The peaked distributions will become broader and tend towards a Boltzmann type of distribution. If carriers collide elastically only with carriers of the same type, no energy is lost from this group. The temperature of the hot carrier distribution will be determined by the total number of carriers created by the laser pulse and the total energy given to each carrier type. Di erent temperatures are possible for electrons and holes unless e cient at sharing their energy. In the next phase, collisions with the lattice atoms become important. These result in energy loss (phonon emission). During this phase, the number of electrons and the number of holes remain constant, but the average energy and carrier temperature decrease due to this loss. The temperature of electrons and holes equalise and both reduce towards that of the host material. Finally, recombination in the semiconductor becomes

CB
1 2 3 4 5 6 7 8

VB

t < 0 t = 0+ <1ps -1ps Time

-1ns

~1s

Fig. 4. Energy relaxation of carriers after a short, high-intensity laser pulse at t = 0.

important. The distribution of electrons and holes retain the same general shape, determined by the ambient temperature, but the number of carriers at each energy reduces until nally reaching the levels prior to the laser pulse. A standard cell is designed to collect the carriers before they get too far into the latter recombination stage of this decay sequence. A hot carrier cell has to catch them before the carrier cooling stage. Carriers either have to traverse the cell very quickly or cooling rates have to be slowed in some way. Special contacts to prevent the contacts from cooling the carriers may also be required [6,7]. The limiting e ciency of this approach is 86.8% as for an innite tandem cell stack. However, to reach this limiting e ciency, carrier cooling rates would have to have been reduced su ciently or radiative recombination rates su ciently accelerated that the latter was faster than the former. A particular band structure also is required. 6. Multiband cells Standard cells rely on excitations between the valence and conduction band. A recent analysis [8] has shown advantages if a third band, nominally an impurity band, is included in the analysis (Fig. 5). This theory has been extended to an n-band cell and additional implementation approaches discussed. These include using excitations between minibands in superlattices, if phonon relaxation processes can be controlled, the use of semiconductors with multiple narrow bands, such as that reported for IVII and I3 VI compounds, or the use of high concentrations

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finite band width

1 2

hopping

3
Fig. 7. Multiple quantum well solar cell meeting the constraints of three-band theory. Fig. 5. Three-band solar cell.

4 4 3 2 2 1 1 3

impurity levels and shown that most of the benets also transfer to such impurity photovoltaic devices, if properly designed. 7. Thermophotovoltaic and thermophotonic devices Thermophotovoltaics is a well-established branch of photovoltaics where a light from a heated body other than the sun is used as the illumination. A recent development of this approach has been dubbed thermophotonics [2]. In this case, the exponentially enhanced light output of a device where the light is generated by band-to-band recombination is used to advantage. Fig. 8 shows the basic arrangement which is nearly symmetrical. Two diodes acting as solar cells=light emitters face each other, connected by a load. Heat is supplied to one to heat it hotter than the other and heat is extracted from the other to cool it. The devices are optically coupled but thermally isolated. The combination is able to convert heat supplied to the hotter device to electricity in the load with an e ciency approaching the Carnot e ciency, in principle. Basically, the heated device acts as an emitter of narrow bandwidth light within an energy, kT , of its band gap energy. This near-monochromatic light can be converted very e ciently by the cell. Moreover, light emitted by the cell is recycled back to help drive the light-emitting diode. Since the same current ows in the cell and source diode, the voltage across the diode will be smaller than that across the cell when the diode is at higher temperature. This results in power dissipation in the load.

Fig. 6. Four-band cell and equivalent circuit.

of impurities such as rare earths to form multiple impurity bands in wide band gap semiconductors. The limiting e ciency for an n-band cell is identical to the 86.8% gure for a large stack of tandem cells. However, the e ective cell connections in the n-band approach show much more redundancy than in a series connected tandem cell (Fig. 6). This suggests the approach may be more tolerant to spectral variations in sunlight. Recent work [9] has also already resolved a controversy as to whether an idealised cell incorporating multiple quantum wells can exceed the e ciency of an idealised standard cell. The structure of Fig. 7 shows a multiple quantum well cell that meets all the requirements, in principle, to attain limiting three-band cell performance. The previous question can now be answered in the a rmative! In fact, a source of energy other than photons can be used for excitation 3 of Fig. 7, provided it occurs through sources with nite chemical potential (e.g., hot phonons). The authors group has recently extended the multi-band approach to devices with discrete mid-gap

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R IL IC

8. Conclusion The authors prognosis is that material costs will, with the fullness of time, push photovoltaic evolution in the direction of the highest possible e ciency. Work to date suggests there is scope for improving solar cell performance by exploring approaches capable of giving e ciencies closer to thermodynamic limits. Low-dimensional structures seem to show some promise due to the small dimensions and new features o ered. A new Centre for Third Generation Photovoltaics commenced operation at the University of New South Wales in early 2000 supported by the Australian Research Council (ARC), with a 9-year programme to bring the most promising of these approaches to the proof-of-concept level. References
[1] T.M. Bruton, G. Luthardt, K-D. Rasch, K. Roy, I.A. Dorrity, B. Garrard, L. Teale, J. Alonso, U. Ugalde, K. Declerq, J. Nigs, J. Szlufcik, A. Rauber, W. Wettling, A. Vallera, A study of the manufacture at 500 MWp p.a. of crystalline silicon photovoltaic modules, Conference Record, 14th European Photovoltaic Solar Energy Conference, Barcelona, June, 1997, pp. 1116. [2] M.A. Green, Prog. Photovoltaics 9 (2001) 123. [3] W. Shockley, H.J. Queisser, J. Appl. Phys. 32 (1961) 510. [4] A. Marti, G.L. Araujo, Sol. Energy Mater. Sol. Cells 43 (1996) 203. [5] S. Kolodinski, J.H. Werner, T. Wittchen, H.J. Queisser, Sol. Energy Mater. Sol. Cells 33 (1994) 275. [6] R.T. Ross, A.J. Nozik, J. Appl. Phys. 53 (1982) 3813. [7] P. Wurfel, Sol. Energy Mater. Sol. Cells 46 (1997) 43. [8] A. Luque, A. Marti, Phys. Rev. Lett. 78 (1997) 5014. [9] M.A. Green, Mater. Sci. Eng. B 74 (2000) 118.

QL

P N

N P

QC

TL

TC

Fig. 8. Thermophotonic conversion (conceptual only, any nonradiative recombination would necessitate storage elements).

With on-going evolution in device design, both experimental solar cells and light emitting diodes are approaching the stage where internal recombination can be limited by radiative processes, a prerequisite for this scheme. If used to convert solar radiation in conjunction with a thermal absorber, energy conversion e ciency up to 85.4% is obtainable in principle. Alternatively, the approach could be used for maximally e cient conversion of fossil fuels or waste heat, particularly when the heat is available at low temperature.