ZnO/CdS/Cu(In,Ga)Se, THIN FILM SOLAR CELLS WITH IMPROVED PERFORMANCE

Jonas Hedstrljm and H a a n Ohldn Swediih Institute of Microelectronics Marika Bodegbd, Angela Kylner, and Lars Stolt Dep. Solid State Electronics, Royal Institute of Technology, Stockholm

Dmti Hariskos, Martin Ruckh, and Hans-Werner Schock iir

Institut filr Physikalische Elektronik, Universitat Stuttgart

ABSTRACT

T i paper reports results from experiments conceming the hs growth of CuInSe, films on different substrate materials, uncoated, and coated with molybdenum. Specifically the effect on the structure, i.e. prefered orientation, of the polycrystalline films is investigated. It is found that soda-lime float glass results in the most oriented films and also that the highest solar cell conversion efficiency is obtained with devices made from such films. In another set of experiments the effect of various deposition conditions for the ZnO window layer is studied. It is found that optimum performance is not strongly dependent on the deposition process. The highly doped part of the window, ZnO:Al, has been replaced with IT0 on some devices and a comparison is made. Finally, ZnO/CdSICuInSe, and ZnO/CdS/Cu(In,Ga)Se, thin film devices exhibiting active area conversion efficiencies of 15.4% and 16.9%, respectively, are demonstrated.
INTRODUCTION Thin film solar cell technology offer the best hope for obtaining photovoltaic devices with low price and reasonable efficiency. One of the most promising thin fl materials in this im respect is CuInSq. Thin film cells based on this material have been previously reported to show an efficiency as high as 14.1% [l],and several groups have achieved above 12% efficiencies [2,3,4].We have recently reported further improvements of the n-ZnO/n-CdS/p-CuInSe, thin fl solar cell structure with a im A resulting conversion efficiency of 14.8% [5,6]. well-known approach to improve the performance of CuInSe,-based thin fl im solar cells is to alloy the CuInSe, with CuGaSe, thereby increasing the bandgap in order to obtain a better match to the solar spectrum [3]. In this paper we report from our current work with devices based on the quaternary Cu(In,Ga)Se, absorber material. Specifically, our results from trying to optimise the window layer is described. It is known that CuInSe, fls grows with a 412> im prefered orientation, especially when stoichiometric or slightly Cu-rich. It has been shown that the bi-layer approach (Boeing formula) results in the same degree of texture as stoichiometric

or Cu-rich single layers, but with a composition compatible with good devices [7], i.e. with a slight excess of the group III elements with respect to stoichiometry. Investigating large numbers of layers deposited at various conditions and on different substrates it can be concluded that many factors, not im. always under control, influence the texture of the f l s We have found that the high efficiency of our CuInSe, devices is correlated to the fact that the polycrystalline films are highly <112> textured. Another observation is that this textwe is most pronounced on soda-lime float-glass substrates and at relatively high deposition temperatures, 550C. We report here f a series of experiments addressing the issue of substrate influence on the structural properties of CuInSq thin films. EXPERIMENTAL Device Structure The solar cell structure used (see Fig. 1) is similar to the one reported in [ ] In the bulk of the experiments soda-lime I. float glass, nominally 0.8mm thick, has been used as substrates. To study substrate influence on the chalcopyrite film growth, soda-lime glass has been compared to borosilicate glass, sapphire, and sintered alumina. The molybdenum back contact is deposited with rf argon sputtering to a thickness of 0.8 pm. The typical sheet resistance is 0.2-0.3QAJ.

substrate

Fig. 1. Schematic drawing of the device structure.

0-7803-1220-1193 $3.00 0 1993 EEE

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In these experiments we have tried to keep the CdS buffer layer invariant. The CdS layers are deposited by solution growth using cadmium salt and thiourea [SI. The thickness of the CdS layer is estimated to about 20 nm except for the high performance cells reported at the end of the paper. In these devices the estimated thickness is 60 nm.

The selenium evaporation rate is kept constant during growth. The total evaporated mass corresponds to approximately 3 times what is necessary to form stoichiometric CuInSe,. That means a selenium flux of 1.5, at the highest copper and indium rates, to 6, at the lowest metal rates, times the amount momentarily incorporated in the growing film. During cool-down from the deposition temperature, which was 550C at the end of the process, the selenium flux is maintained at substrate temperatures higher than 4OO"C, in order to avoid selenium depletion of the selenide surface. Window Layer Deposition The window layer consists basically of two parts. First, about 50 nm of, usually high resistive, ZnO deposited by rf magnetron sputtering from a compound target. Various argodoxygen mixtures, ranging from zero to 20% 0, have been used. In the case of zero or very low oxygen concentrations (up to 0.1%) the resistivities of the ZnO films are not very high, typically around 0.5 a m . It is also studied how a p m ZnO target compares with a mixed Zn0:2wt%Al,O3 target. When a mixed target is used, with 0.1% 0, in the argon sputter gas, about the same resistivity is obtained as for a pure ZOO target. At the higher oxygen concentrations used, the deposited ZnO films have resistivities higher than Id Rcm using either ZnO or ZnO:Al,O, targets. The second part of the window layer is usually Zn0:Al. It is rf magnetron sputtered from a ZnO:2wt%A&03target in argon to a thickness of about 300 nm. The resulting sheet resistance is about 20 fMl. In some experiments the Zn0:Al have been replaced with IT0 (In,03:7%Sn0,) deposited by rf diode sputtering. About the same sheet resistance as for Zn0:Al was obtained with a similar thickness. Some cells were made with an all-CdS window. On top of the thin solution grown CdS layer, evaporated CdS was deposited. The first part undoped, and the second doped with gallium. Such cells show nearly the same performance, except for current. as cells with a ZnO window. Metal Grid and Antireflective Coating

Cu(In,Ga)Se, Deposition Cu, In, Ga, and Se are co-evaporated from elemental sources controlled by a quadrupole mass-spectrometer feedback system. The evaporation rates and substrate temperature are varied during the deposition of the CuInSe, layer according to specific profiles shown in Fig. 2. The rate profiles simulates in a stationary system an in-line coevaporation process [9]. The deposition time for the approximately 3 pm thick layer has been 60 minutes.
1000 L

Deposition time (min)

Figure 2: Cu and In evaporation rate and substrate temperature profiles during the coevaporation of the CuInSe, layer. When the quatemary chalcopyrite is deposited, the gallium rate is a constant fraction of the In-rate during the process. The In rate is reduced to obtain a composition with a Cu/(In+Ga) ratio slightly lower than unity, similar to optimized CuInSe, [5]. In all experiments reported here a gallium to indium ratio of 1:3 has been used. It results in a bandgap expansion of about 0.14 eV. For the quatemary, a higher starting temperature of 460C (cf. Fig. 2) as compared to CuInSe, was found to yield more oriented films. In the coevaporation system the Cu and In open boat type sources are separated (the Ga source is positioned between the Cu and In sources) to cause a compositional gradient corresponding to about 4% variation in the Cu/(In+Ga) ratio from one edge to the other of the 5 cm x 5 cm substrate. This makes it possible to study the influence of composition on cell performance and simplifies finding the optimum Cu/(In+Ga) ratio in the films.

To reduce resistive losses an Al grid -2 pm thick with a thin intermediate Ni layer is deposited. Some of the devices have been measured using a dual probe directly on the conductive oxide layer. With a probe distance of 1 mm this method roughly mimic the performance when using a metal grid. When this technique is utilized this is indicated in the text.
The most promising cells, for which record efficiencies are reported, have been coated with a MgF, antireflective layer Annealing To optimize cell performance the devices were postannealed in air at 200C. Annealing times were typically 2-10

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ln5 soda;lime

JL

Fig. 3. XRD-spectra of CuInSe, films on various molybdenum-coated (left hand side) and uncoated (right hand side) substrates. They are recorded with the same parameters and are not normalised. Parts are reduced (or magnified) as indicated in the figure. minutes. Longer times are required for CuInSe, compared to Cu(In,Ga)Sq, which in the case IT0 was used sometimes did deteriorate when annealed. Analysis Techniques The chalcopyrite f i l m s have been analysed by x-ray diffraction (XRD) using a standard 8/28 geometry. Most of the XRD work has been focused on evaluating the prefered orientation of the chalcopyrite films. This purpose has been served by recording the (112), (220)/(204), and (116)/(312) peaks. SEM has been used to inspect the grain structure both in a "flat-on" and a cross-section mode. SIMS and X P S have been used to investigate the presence of contaminants. The cell J-Vcharacteristics have been measured using ELH lamp based solar simulators. Reference cells are used to adjust the lamp intensity to simulate an AM 1 5 global solar spectrum. . The method works quite well for pure CuInSe, where the quantum efficiency curve is almost the same for all good devices. In the case of Cu(In,Ga)Se, based samples the quantum efficiency curve is not that well established and do depend on the gallium content, which directly influences the absorbtion edge. For the highest efficiencies reported here we have made corrections of the lamp intensity according to the specific quantum efficiency curve of a device. In addition, we made . outdoor measurements of the J, under Ah4 1 5 conditions. For these measurements, a calibrated pyranometer was used to measure the irradiance. All the reported efficiencies and short circuit currents are active area values.

FILM ORIENTATION
Substrate Influence CuInSe, films were deposited on different substrates, uncoated, and coated with molybdenum. In Fig. 3 we display the XRD spectra of CuInSe, on MO-coated and uncoated substrates, respectively. In the Mocoated case we clearly see that films on soda-lime glass have at least one order of magnitude higher (112)intensity than the others. The grains in the films on the other substrates are essentially randomly oriented. To check whether the structure of the molybdenum layer has any influence on the CuInSe, orientation we also measured some of the molybdenum peaks. The main MO peak, (1lo), had about the same intensity for both soda-lime and borosilicate glass, whereas the other substrate did show a substantially lower value. That was true especially for the sintered alumina, which is not surprising since it has a much lower flatness than the others, due to the way it is fabricated. Furthermore, a cross-check of a CuInSe, film on soda-lime with evaporated MO also indicated high <112> texture. The grain structure of evaporated MO may differ somewhat from sputterdeposited molybdenum. By comparing the results for CuInSe, films on soda-lime and borosilicate we can conclude that the orientation of the molybdenum grains does not determine the CuInSe, texture. Films on uncoated substrates show generally a higher <112> texture than corresponding films on coated substrates. CuInSe, on uncoated soda-lime shows virtually no other peak than the (112)(see Fig. 3. )

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20

40

60

20

40

60

28

28

Fig. 4. XRD-spectra of CuInSe, films made by interrupting the deposition process at times A and B, indicated in Fig. 2. These times correspond to temperatures 480C and 560C, respectively. The substrates are molybdenum-coated soda-lime (left hand side) and borosilicate glass (right hand side).

Fig. 5. SEM-micrographs of CuInSe, films made by interrupting the deposition process at times A and B, indicated in Fig. 2. These times correspond to temperatures 480C and 560"C,respectively. The substrates are molybdenum-coated soda-lime and borosilicate glass.

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Table I. Fill factors and open circuit voltages of cells on CuInSq deposited on various substrates. An all-CdS window structure was used for these cells. The cells have been annealed in oxygen for 15 minutes.
~~

Soda-lime
strong texture

Soda-lime random texture V,[mV] FF 0.65 386

Sapphire

VAmVI
~ ~~

FF 0.72

460

399

0.64

In another experiment samples were made by interrupting the CuInSe, deposition process at specific moments. In [6] this is reported in detail for soda-lime substrates. It was found that there is a dramatic difference between f i i s made by interrupting the process when the substrate temperature had reached 480Cand films made by interrupting the process at the point where the temperature ramp just reached 550C. These points are indicated by letters A and B in Fig. 2. Here, we show the XRD-spectra of CuInSe, on Molsoda-limeonly for those two temperatures, and we compare them with Corresponding spectra for samples on borosilicate glass (Fig. 4). It should be noted that the film is copper-rich during the complete process except for the very last minutes. SEM cross-sections of samples corresponding to the XRD-spectra in Fig. 4 are shown in Fig. 5. In these micrographs we see a dense and large-grained homogeneous CuInSq film on the soda-lime glass substrate already at 480C, which gets further improved going to 550C. On borosilicate the appearance, which decline at the higher temperature, is significantly less good as compared to soda-lime. Factors Influencing Orientation After having concluded that the structure of the MO-layer is not important in determining the orientation of the CuInSe, layer, essentially two factors remain. They are stress and contaminants. Stress will occur in the films when they are cooled from the growth temperature due to the difference in thermal expansion between the substrate and the f i i material. It has to be noted that the structure of the CuInSe, films may be established during cool-down and not during growth. That means, when we look at samples made by interrupting the process at different times, what we may interpret as a development of the structure during the growth process, instead is a result of cooling from different temperatures at different film compositions. In our experiments we have not been able to determine when the structure of the polycrystalline films is established. Clearly, if the structure of the fl is f i e d during coolim down, the stress in the film can play an important role. Especially when we compare soda-lime glass and borosilicate glass which have thermal expansion coefficients which are higher and lower than CuInSq, respectively (>lo and 4.5 p p d K as compared to 8 ppm/K). This will result in a compressive stress in the films on soda-lime and a tensile stress in the films on borosilicate. A compressive stress will of course favour the growth of a dense material. Indeed, a much higher frequency of cracks and voids was found by TEM in CuInSe, films on

borosilicate than on soda-lime glass [lo]. In another study aggregate structures, explained by shess, were observed in CuInSe, films on borosilicate glass [ 111.

The other possible factor influencing the growth is contaminants. We have looked at films with XPS and SIMS.In f i i s made on soda-lie glass substrates significant amounts of sodium are observed. With XPS only the top surface is analysed and there sodium concentrations of approximately 10% are measured. This sodium containing surface layer dissolves easily in water. SIMS profiles showing the distribution in depth are displayed in Fig. 6. No difference in sodium concentration is observed between the Mo-coated and uncoated substrate. Additional analysis of the increased sodium signal close to the surface of the CuInSe, f i b on the uncoated substrate, indicates that it is an artefact of the measurement. The increased sodium signal in the molybdenum layer is due to an increased ionization probability and cannot be interpreted as a higher sodium concentration. It is easy to conceive that the amounts of sodium found may strongly influence the formation of the polycrystalline film structure, whether that is determined during growth or during cooldown. Further experiments are needed to clarify the roles of the two factors discussed here.

Fig. 6. SIMS-profiles of CuInSe, f i i deposited on sodalime glass, with (solid line) and without (dotted line) sputterdepositedmolybdenum.

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Alumina Borosilicate 385 0.66 37 1 0.43

100

200

300

400

500

Sputtering time (s)

Table II. Fl factors and open circuit voltages of cells on CuInSe, and Cu(In,Ga)Se, made with ITOiZnO window structures with il the ZnO sputterdeposited in different Arlo, mixtures. Annealing times were 2 minutes for CuInSe, and 30 seconds for Cu(In,Ga)Se,. ZnO deposition gas mixture Target CuInSe, before anneal V,[mVl Ar ZnO ZnO ZnO ZnO ZnO:A&O, ZnO 424 429 452 409 0.66 0.69 0.68 0.67
441

CuInSe, after anneal V,[mV] 416 FF 0.67

Cu(In,Ga)Se, before anneal V,[mV] 582 586 FF 0.74 0.75 0.74 0.76 0.76 0.73

Cu(In,Ga)Se, after anneal V,[mV] 591 595 604 609 603 602 FF 0.73 0.74 0.74 0.73 0.74 0.72

FF 0.66

375

Ar : 0.01%0, Ar : 0.1% 0,
Ar : 2.5% 0,
A r : 2.5%0,

0.67 0.67 0.66 0.64

594 607 604 596

440 451 428

Ar : 10% 0,

Cell Performance In Table I cell performance parameters for a number of different CuInSe, devices are shown. In this experiment an allCdS window was used. It is evident that the textured sample on soda-lime glass substrate sticks out as the best performer. The others are about the same except for borosilicate which is very poor. Except for the untextured sample on soda-lime the CuInSe,-layers were deposited simultaneously. We would like to point to the two soda-lime samples, which have the same glass substrate and are equally processed except for the substrate holder-heater arrangement. For some, yet unexplained, reason films made with one of the set-ups are not oriented. Of course, something in the process has to be the cause to this, and that something may also alter other properties. It can be noted that sodium was observed by XPS in both films. Nevertheless, the im oriented fl on soda-lime is substantially better than the randomly oriented one. It is difficult to find chalcopyrite films, between which the only difference is texture. We must assume when the degree of texture is changed, other properties may change as well. What we do observe here, and in our daily work, is a correlation between strong <112> texture and good photovoltaic properties.

In the early stage of our work on Cu(In,Ga)Se, cells it was found that the intermediate ZnO optimised for pure CuInSe, (ZnO target and Ar/20%0, sputter gas) was not as good as when using pure argon without oxygen. That work resulted in a 15.4% active area device (AR-coated). Recently, we have tried other oxygedargon mixing ratios, and in Table I1 we list a number of devices made from the same CuInSe, and Cu(In,Ga)Se, layer. These were measured with the probes directly on the TCO. The table show no strong influence on cell performance by the deposition conditions. There is, however, a tendency that ZnO layers deposited in A o mixtures with 0.1% or 2.5% oxygen d , perform slightly better. It seems not important if a pure ZnO or a ZnO:%O, target was used. Similar ZnO resistivities are obtained independent on target for these oxygen concentrations. IT0 When designing thin film modules it is prefered if metal grids can be avoided. This requires that the sheet resistance of the TCO is sufficiently low. On the other hand, when the sheet resistance is lowered infra-red absorbtion will increase due to free carriers in the TCO, and current will be lost in the device. In searching for an optimum design one has to deal with the trade-off between these two mechanisms. It is not clear if Zn0:Al or IT0 will be the best choice. In this work we try to compare these materials. The question does then arise if I T 0 will make a good contact to the ZnO layer adjacent to the CdS, since it has a relatively low carrier concentration. We have found an improvement by using a contact layer consisting of highly doped Zn0:Al. The contact layer is about 15 nm thick and the same deposition conditions as for the conductive Zn0:Al top layer have been used. In order to compare Zn0:Al and I T 0 as TCO two Cu(In,Ga)Se, layers were divided and processed with the same CdS and high resistive ZnO layer (sputtered in 2.5%OJAr from a ZnO:Al,O, target). Two of the halves were coated with standard Zn0:Al and the others with a Zn0:Al contact layer and

OXIDE WINDOW
ZnO Optimisation In order to optimise the performance of Cu(In,Ga)Se, based solar cells we have carried out a series of experiments with different ZnO deposition conditions. The variations made concems the high resistive part of the window adjacent to the CdS layer. Generally, the deposition of the conductive layer directly on the CdS does not yield good performance. In the case of IT0 the junctions are essentially shunted and in the case of ZoO:Al, the devices often show a poorer performance as compared to when a layer of higher resistivity ZnO is used as an intermediate layer.

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Table III. Photovoltaic performance for Cu(In,Ga)Se, cells with ZnOAl and IT0 TCO layers. The cells are without ARcoating and the ones with ZnOAl are annealed but not the ones with ITO.

Cu(In,Ga)Se, layer

ZnO.A1
rl
J,[mAlcm21
32.4 33.1

IT0 FF
0.710 0.706

VJmVI

rl
14.2 13.8

J,[mA/cmZl
32.4 32.3

V,[mV]
600

FF
0.730 0.724

173 175

14.0
14.0

609
601

590

subsequently ITO. In Table III the cell results are displayed. The efficiencies of the cells are the same. There is an advantage for IT0 regarding fill factors and Zn0:Al regarding V,:s, but the differences are small. The results indicates that performance comparable to ZnOAl can be obtained with ITO. A general observation is that the effect of air annealing is weak on cells with IT0 (see Table 1 ) Cells on Cu(In,Ga)Se, 1. often deteriorated even after very short annealing times. HIGH PERFORMANCE CELLS With the window experiments described above in mind, we decided to use a window process for Cu(In,Ga)Se, consisting of about 50 nm ZnO sputtered in k . l % O , and a TCO layer of 300 nm Zn0:Al. The J-V characteristic of such a device under simulated AM 1.5 conditions, and a cell temperature of 25C. is shown in Fig 7. In the same figure the J-V curve of a device based on CuInSe, is displayed. It has a similar window except that the oxygen concentration during deposition of the intermediary ZnO was 20%. The devices have an antireflective coating of MgF,. The active area efficiencies, 15.4% and 16.9%, do both represent significant improvements compared to previously reported values.

The quantum efficiency curves for the devices in Fig. 7 are shown in Fig. 8. The very high values are basically the result of a successful AR-coating. The shift in long wavelength cut-off between the CuInSe, and the Cu(In,Ga)Se, cell corresponds to 0.14 eV, of which more than 0.12eV is reflected in the increased open-circuit voltage of the quaternary device. The quantum efficiency curves, multiplied with a standard global AM 1.5 spectrum, give short circuit currents which are the same (within 0.1 mA/cm2)as those measured outdoor at AM 1.5 sun elevation. The solar simulator (ELH) was adjusted to give these currents for the recording of the J-V curves. CONCLUSIONS The strongest <112> texture of the chalcopyrite films are found on soda-lime glass substrates. Possibly both stress and impurities, i.e. sodium, are of importance in establishing the texture and structure of the polycrystalline films. It is possible that strong texture in itself is not a prerequisite for good cell performance but it often occurs simultaneously with good photovoltaic properties of the CuInSe, and Cu(In,Ga)Se, films. Investigations Q the influence of window deposition f process on cell performance do not show any strong preference

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for any of the processes investigated. The best process found in this work is an intermediate layer (between the CdS and the TCO) of ZnO sputterdeposited in a mixture of argon and -1% oxygen, from a ZnO or a ZnO:Al,O, target. No significant efficiency difference was found between Cu(In,Ga)Se, cells with Zn0:Al and I T 0 as the highly conductive part of the window layer.
An optimised process has resulted in a Cu(In,Ga)Se, device with an active area efficiency of 16.9%. An efficiency of 15.4% is reported for a device with a CuInSe, absorber.

ACKNOWLEDGEMENTS This work is a collaboration within EUROCIS, a project in the European Communities JOULE II research program. The Swedish part has been sponsored by the Swedish Board for Industrial and Technical Development. The German part is cosponsored by the Bundesministerium fih Forschung und Technologie REFERENCES
[ 11 K.W. Mitchell, C. Eberspacher, J. Ermer, and D. Pier, Proc. 20th ZEEE Photovoltaic Specialists Con$, Las Vegas 1988 (Institute of Electrical and Electronics Engineers, New York 1988) p. 1384 [2] R.H. Mauch, M. Ruckh, J. Hedstrom, D. Lincot, J. Kessler, R. Klinger, L. Stolt, J. Vedel, and H.W. Schock, Proc. 10th E.C. Photovoltaic Solar Energy Conference, Lisbon 1991 (Kluwer Academic Publishers, Dordrecht 1991) p. 1415. [3] W.E. Devaney, W.S. Chen, J.M. Stewart, and R.A. Mickelsen, IEEE Trans. Electr. Dev. 37,428 (1990) [4] B. M. Basol, V.K. Kapur, and A. Halani, Proc. 22nd IEEE Photovoltaic Spec. Con$, Las Vegas 1991, (Institute of Electrical and Electronics Engineers, New York, 1991) p. 893. [5] L. Stolt, J. Hedstrom, J. Kessler, M. Ruckh, K.-0. Velthaus, H.-W. Schock, Appl. Phys. Lett. 62, 597 (1993) [6] L. Stolt, M. Bodegild, J. Hedstrom, J. Kessler, M. Ruckh, K.-0. Velthaus, H.-W. Schock, Proc. 11th E.C. Photovoltaic Solar Energy Con$, Montreux 1992 [7l H. Dittrich, T. Walter, H.-W. Schock, Proc. lOfh E. C. Photovoltaic Solar Energy Con$, Lisbon 1991 (Kluwer Academic Publishers, Dordrecht 1991) p. 917 [8] J. Kessler, K.O. Velthaus, M. Ruckh, R. Leichinger, H.W. Schock, D. Lincot, R. Ortega, J. Vedel, Proc. 6th Znt. Photovoltaic Science and Engineering Con$ New Delhi 1992, p. 1005. [9] R.H. Mauch, J. HedstrCim, D. Lincot, M. Ruckh, J. Kessler, R. Klinger, L. Stolt, J. Vedel, H.W. Schock, Proc. 22nd ZEEE Photovoltaic Specialists Con$, Las Vegas 1991, (Institute of Electrical and Electronics Engineers, New York 1991) p. 898 [lo] J. S. Chen, E. Kolawa, C.M. Garland, M.-A. Nicolet, Thin Solid Films 219, 183 (1992) [ l l ] L. Margulis, G, Hodes, A. Jakubowicz, D. Cahen, J. Appl. Phys. 66,3554 (1989)

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