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Vacuum 82 (2008) 11451150 www.elsevier.com/locate/vacuum

Thin-lm Si:H-based solar cells

C.R. Wronskia,1, B. Von Roedernb, A. Ko"odziejc,
a

Electrical Engineering Department, Pennsylvania State University, University Park, PA 16802, USA b National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, CO 80401-3393, USA c w, Poland AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Krako

Abstract Recent developments in the photovoltaic (PV) industry, driven by a shortage of solar grade Si feedstock to grow Si wafers or ribbons, have stimulated a strong renewed interest in thin-lm technologies and in particular in solar cells based on protocrystalline hydrogenated amorphous silicon (a-Si:H) or nanocrystalline/microcrystalline (nc/mc)-Si:H. There are a number of institutions around the world developing protocrystalline thin-lm Si:H technologies as well as those based on tandem and triple junction cells consisting of a-Si:H, a-Si:Ge:H and nc/mc-Si:H. There are also several large commercial companies actively marketing large production-scale plasmaenhanced chemical vapor deposition (PECVD) deposition equipment for the production of such modules. Reduction in the cost of the modules can be achieved by increasing their stabilized efciencies and the deposition rates of the Si:H materials. In this paper, recent results are presented which provide insights into the nature of protocrystalline Si:H materials, optimization of cell structures and their light-induced degradation that are helpful in addressing these issues. The activities in these areas that are being carried out in the United States are also briey reviewed. r 2008 Elsevier Ltd. All rights reserved.
Keywords: Thin silicon lm; Phase transition; Solar cells; Stability

1. Introduction 1.1. Amorphous and nanocrystalline Si lm-based photovoltaic (PV) modules Some 25 years ago, some researchers in the PV research arena predicted a rapid transition from wafer or ribbonbased Si modules to thin-lm amorphous silicon (a-Si)based modules [1]. This switch did not occur because the stabilized efciency of a-Si-based modules did not reach the expected 10% level. Also, the competing wafer (ribbon) Si-based technologies were able to implement, unforeseen then, advances in both performance and manufacturing cost reduction. However, a renewed interest in a-Si-based modules appears to be driven by the following factors: (a) Si feedstock shortages for wafer/ribbon Si; (b) the
Corresponding author. Fax: +48 12 633 23 98.

E-mail addresses: crwece@engr.psu.edu (C.R. Wronski), kolodzie@agh.edu.pl (A. Kolodziej). 1 Also for correspondence. 0042-207X/$ - see front matter r 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.vacuum.2008.01.043

advances in thin-lm processing; (c) the quest for a lowenergy budget (low-T process) solar module manufacturing process relying on practical limitless silane feedstock; (d) the advent of nanocrystalline/microcrystalline (nc/mc) Si solar cells that triggered hope for greater stabilized performance. Todays commercially available a-Si-based modules range in efciency (as rated by their manufacturers) 4.58.5% conversion efciency. This performance is high enough to compete with wafer/ribbon-based silicon modules in a number of applications. There is also the hope to further improvements in stabilized module performance. Research attempts to better the performance of a-Si:H and/or nc-Si:H-based solar cells currently focus on two primary factors that increase the cost of a-Si-based PV modules: (a) low stabilized solar cell/module efciency and (b) low deposition rates requiring signicant investment into capital-intensive vacuum deposition equipment. A key limitation on the stabilized efciencies of the a-Si:H cells are the light-induced defects associated with the StaeblerWronski effect (SWE) [2]. Recent progress in improving the understanding of this effect is discussed below in terms

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of the creation kinetics and nature of the light-induced defect states as well as their dependence on microstructure of the a-Si:H. Researchers pursued hydrogen dilution, also discussed below, as a mitigation scheme that can reduce the amount of StaeblerWronski degradation. Unfortunately, hydrogen dilution also lowers the deposition rate. Today, champion solar cells are made using deposition times as low as 0.1 nm/s, and commercial modules are produced at rates of 0.3 nm/s. This requires production times on the order of 30 min for the lm deposition; requiring large vacuum plasma-enhanced chemical vapor deposition (PECVD) coaters. Employing even higher hydrogen dilution results in the deposition of nc/mc lms, which have also been used to fabricate low-T deposited solar cells [3]. Some entities, especially in Europe and Japan, expect that the incorporation of an nc/mc-Si cell into a multijunction cell stack should improve its stabilized performance. 2. Hydrogen dilution and protocrystallinity Continuous progress in the performance of a-Si:H-based solar cells has been made by improving the quality of the materials and cell structures. This, however, has been achieved with approaches that were mainly empirical due, primarily, to the absence of a clear understanding of material growth and microstructure as well as the subtle and not so subtle differences in their properties. As a result even the improvements obtained by using a-Si:H materials deposited with hydrogen dilution of silane [4,5] were not understood. Thus it was difcult to control them and carry out improvements in a systematic way. However, recently the growth and microstructure of these hydrogen diluted protocrystalline Si:H materials has been characterized [6,7] and new insights have been obtained into both, their nature as well as their PV properties. Under protocrystalline Si:H growth conditions there is a unique evolutionary growth behavior, and the protocrystalline material itself exhibits unique optoelectronic properties. Using the real-time spectroscopic ellipsometry (RTSE), rst developed by Collins et al. [8,9], to characterize thin-lm growth and microstructure it has been shown that the thin-lm Si:H prepared under moderate-to-high H2-dilution conditions evolves from the amorphous phase to a mixed amorphous+nano/microcrystalline phase [(a+nc/mc)-Si:H] with the accumulated thickness of the layer. The thin-lm material in the amorphous regime of growth has been called protocrystalline a-Si:H and exhibits a higher degree of ordering than materials deposited under similar conditions without H2-dilution [10]. Despite the evolutionary nature of the Si:H materials prepared with moderate H2-dilution, they exhibit relatively uniform bulk properties over certain extended regions of thickness. Using phase diagrams as a guide, it is possible to identify and control this evolutionary nature in both lms as well as solar cell structures in which the effects of transitions between the

different phases in solar cell structures have been studied and characterized. A key capability of RTSE is the ability to generate deposition phase diagrams for different deposition conditions and substrate materials. These diagrams identify the ranges of thickness over which it is possible to obtain the pure protocrystalline phase and the ranges corresponding to the mixed-phase deposition as well as insights into the control of the phase transitions for applications in device fabrication. These uses of the phase diagram have allowed characterization of the bulk properties of protocrystalline Si:H lms as well as the fabrication of highly controlled cell structures. In Fig. 1, it is shown a schematic of the structure of Si:H lms derived from phase diagrams prepared as a function of hydrogen dilution R [H]/[SiH4] is shown for Si:H deposited onto an undiluted R 0 substrate layer at a substrate temperature of 200 1C. It can be seen that with decrease of R there is a continuous decrease of the thickness at which the transition of protocrystalline a-Si:H into the a+nc/mc phase occurs. This characteristic has very important consequences in the design of protocrystalline solar cells with different thickness, which until now have not been recognized. Another feature is the increase with R in the nucleation density of nc/mc-Si at the a-a+nc/mc transition which are key to the subsequent growth of the a+nc/mc mixed phase. A third point that can be made is the decrease with R of the range of boundaries between which the a+nc/mc-Si:H phase present before coalescing into the mc-Si:H phase. Deposition phase diagrams have also been developed to guide the increases in deposition rates in which the effects of higher power densities on the evolution of protocrystalline Si:H have been characterized [8]. Exemplary applications of phase diagrams have been demonstrated for tandem and triple solar cell structures with using a-Si:H, a-Si1xGex:H with low Ge content and mc-Si:H received by hydrogen dilution and higher than 300 1C substrates temperature [11]. RTSE studies have also indicated that the way to improve protocrystalline Si:H cells is to use what may be called phase engineering of Si:H solar cells that exploits microstructurally engineered structures for the improved

Fig. 1. Schematic of the structure of Si:H lms prepared as a function of R. The dashed and dotted lines identify the a-(a+nc/mc), and (a+nc/mc)-mc transitions, respectively. Also indicated are the corresponding densities Nd of nc-Si:H nuclei present at the a-(a+nc/mc) transition.

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performance [12]. Two examples are presented here to illustrate how the ability to control the microstructure of the materials allows phase engineering to be carried out in a systematic way. The rst shows how a protocrystalline a-Si:H silicon carbide pin cell structure has been optimized with a microstructurally engineered p/i interface region obtained by a two-step variation of the i-layer H2-dilution ratio [13,14]. This is illustrated with results on customized cells in which different thickness R=40 Si:H , R=10 layers were inserted into cells having 4000 A i-layers. The light IVs of cells having 100, 200, 300, and thick R=40 layers in the p/i interface region are 400 A shown in Fig. 2. The corresponding AFM images of the R 40 i-layers are shown in Fig. 3. The introduction of the thickness R 40 p/i interface regions of 100 and 200 A increases the Voc from the 0.88 V baseline value obtained without an interface region to 0.92 and 0.93 V, respectively, without altering the ll factors (FF). Subsequent increase , in the thickness of the R 40 layer to 300 and 400 A however, signicantly reduces both the Voc and the FF. These changes can be related to the transition into the mixed phase identied with SRTE and consistent with the AFM results in Fig. 3. The other example is for p-Si:H contacts on a-Si:H nip solar cells where the results of these layers deposited on a-Si:H clearly show a very strong thickness dependence of the electronic properties of the lm, as it evolves from protocrystalline Si:H to a (a+nc/mc)-Si:H mixed phase. The evolution of the microstructure with thickness in the p-Si:H layers deposited with constant doping ratio, but different R values, is illustrated in Fig. 4. In Fig. 4, the regions of protocrystalline Si:H, mixed (a+nc/mc)-Si:H, and purely microcrystalline Si:H phases can be clearly identied. Also shown in Fig. 4 are the 1 sun Voc values obtained from corresponding nip solar cell structures fabricated

Fig. 3. 2 2 mm2 AFM images of the R 40 Si:H lms at the same thickness used in the customized cell structures.

Fig. 2. Light IV characteristics of the customized pin solar cells fabricated with the two-step i-layer having different thickness p/i interface layers.

Fig. 4. Extended phase diagram for p-Si:H deposited on protocrystalline a-Si:H as function of R and thickness. Also shown is the 1 sun Voc for cell p-layers. structures with corresponding $200 A

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of these p-layers. The highest Voc is achieved with $200 A by the cell having a R 150 p-layer which is in the protocrystalline a-Si:H phase and where its growth is terminated at, or close to the transition into the mixed (a+nc/mc)-Si:H phase [15,16]. In the case of R=100, the p-layer is amorphous throughout its thickness and the thickness is nowhere close to the transition into a 200 A mixed phase. On the other hand, for the R=200 cell, the p-layer is in the form of a mixed (a+nc/mc)-Si:H phase right from the beginning and evolves into a purely microcrystalline phase . These results clearly point to at the thickness of $200 A the highest VOC being obtained with a protocrystalline a-Si:H p-layer which is deposited at a maximum R value that allows the desired thickness to be obtained without crossing the transition into the mixed-phase growth regime. It is interesting to point out here that until these deposition phase diagrams were obtained it was claimed that the optimum p contact layers were microcrystalline. This is the p-layers that were characterized were much thicker than in the solar cells so that transitions to the the 100200 A purely mc phase were present in those lms [17]. 3. Light-induced changes in thin lms and solar cells There is a serious challenge that has still to be overcome for further advances to be made in a-Si:H-based solar cell technology. It is the SWE, which was discovered in 1977 [2] but still imposes serious limitations on the performance of a-Si:H cells and panels. It is in the form of metastable defects that are created under illumination, which can be annealed out at temperatures above $150 1C. The reversible changes that occur between the annealed, initial, and the light soaked, degraded, states have become one of the most often investigated phenomena in a-Si:H-based material and solar cells. However, progress has been relatively slow in obtaining a denitive understanding and systematic control of the SWE. This is in large part due to the absence of a unique a-Si:H material so that the creation of the light-induced defects depends on the deposition conditions and resultant microstructure of the materials. It is also due to the studies focusing on the prevailing theories that attempted to explain all metastable phenomena solely in terms of a metastable light-induced neutral dangling bond defect [D0]. Nevertheless, an empirical approach has led to some progress being made over the years not only in improving the initial properties of a-Si:H-based material but also in reducing their SWE by optimizing the growth conditions to improve their microstructure. The development of protocrystalline a-Si:H materials has resulted in solar cells that not only have higher initial efciencies, but even more importantly better end of life performance [18]. The signicant improvements obtained with protocrystalline a-Si:H are illustrated in Fig. 5. Fig. 5 shows the changes of pin the FF under 1 sun illumination at 25 1C for a 4000 A

Fig. 5. Fill factor under 1 sun illumination at 25 1C for pin solar cells with 400 nm i-layers deposited with R 0 (K) and R 10 (W) at 200 1C as well as changes in the forward bias current in an a-Si:H cell (J) and the reciprocal of the current in the corresponding lm (.) for a carrier generation rate of 2 1016 cm2 s1.

solar cell with a protocrystalline (R 10) a-Si:H layer and an undiluted (R 0) intrinsic layer deposited under the same conditions. It can be pointed out here that in the corresponding lms after such degradation the densities of the neutral dangling bonds, D0, were the same. These light-induced defects affect both the hole and electron transport that results in the signicant reduction of the FF and performance in cells seen here and for example photoconductivity in corresponding thin-lm materials. For a long time there has been a striking absence of direct correlations between the results of such measurements on lms and cells, which has seriously limited the ability to systematically improve the stability of a-Si:H solar cells based on the optimization studies on thinlm materials. Recently however, results have been obtained which not only clearly establish direct and quantitative correlations between the light-induced defects created in a-Si:H lms and their corresponding cells but which have also shed new light on the nature of the lightinduced defects as well as the possible mechanisms for SWE. An example of such correlations is illustrated with results that are shown in Fig. 5. In Fig. 5, there are shown the excellent overlaps in the changes of the gap states under 1 sun illumination as reected in the solar cell by the recombination of injected carriers at 0.4 V forward bias [19] and in the corresponding lm by the reciprocal of the photocurrent for a carrier generation rate of 2 1016 cm2 s1 [20]. It is interesting to note that in the past, when the characterization of cells relied on efciencies or FF, such direct comparison of recombination through the midgap states as illustrated here could not be carried out. Similar direct correlations have also been now obtained between the results of the recombination currents in cells and the densities of midgap states in lms as measured with the Dual Beam Photoconductivity technique [20]. Results from such studies that are being carried out on both solar

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cells and their corresponding intrinsic thin lms have not only further substantiated the inadequacy of the extensive past characterization of light-induced changes in terms of just neutral dangling bond, D0, states [21], but also yielded important new information about the nature of the other states associated with SWE. These recent studies, which have also included the kinetics of the light-induced changes in the gap states of a-Si:H, have conrmed regimes with a t1/3 dependence such as it has been extensively reported for results on thin lms. However, they have also clearly established that the evolution of just the light-induced midgap defect states follow a t1/2 dependence, which is inconsistent with the rate equation for the creation of lightinduced defects that is generally used in modeling of SWE. The improved insights that are being developed into the nature of metastable defects point to new approaches for obtaining a better understanding of the role that microstructure plays in determining the stability of a-Si:H and the mechanisms responsible for SWE. This offers the real possibility of further improving the performance of a-Si:H-based solar panels. 4. Nanocrystalline/microcrystalline solar cells and micromorph multijunction cells In the mid-1990s, the University of Neuchatel (Switzerland) rst produced nc-Si solar cells and micromorph multijunction cells. The nc/mc-Si layers were obtained by high hydrogen dilution of the silane feed gas (490% of the gas being H2) as well as by changes in the frequency of the PECVD deposition (very high frequency, 50100 MHz, instead of the typical radio frequency 13.56 MHz). This invention spurred the hope of achieving greater stabilized efciency for a-Si lm-based solar cells and modules [3]. Hence, several research groups around the world prepared nc/mc-Si and micromorph multijunction [a-Si:H/nc/mc-Si:H] solar cells. The rst commercial offering has been recently introduced by the Sharp Corporation, followed by a recent announcement of very high volume manufacturing capacity [100 MWp annual capacity after 2010]. nc/mc-Si is a potential replacement for a-SiGe:H-based sub-cells in multijunction solar cells, because the nc-Si has absorption coefcients greater than a-Si [3]. Hence, an expectation exists of beating the performance of a-SiGe:Hbased cells and simultaneously eliminating the use of expensive GeH4 gas for manufacturing. Drawback to these schemes is that nc-Si solar cells have the absorber thicknesses about 10 times thicker than a-SiGe:H cells (1.52 mm) and that for these cells too, best results are obtained using slow deposition rates. Work by the Ju lich group suggested in 1999 that the best cells are obtained by growing the mixed-phase nc/mc layers [22] near the nanocrystalline/amorphous growth transition. These results were somewhat unexpected, but have been ubiquitously conrmed by other groups researching these materials. Since the microcrystalline deposition regime has

to be avoided when fabricating high-efciency solar cells, such cells can be referred to as nc-Si, although many groups also use the term microcrystalline for such cells. Based on the knowledge of a nanomicrocrystalline structure evolving with lm thickness (Fig. 1), Uni-Solar has implemented the graded hydrogen dilution (reducing dilution as the lms grow) to keep thicker lms near the nc/mc-Si to a-Si transition [23]. Only time will tell if nc-Si solar cells, when incorporated into multijunction structures, can enhance stabilized cell performance. The UniSolars current position is that nc/mc-Si cells are equivalent, but not yet better than a-SiGe:H-based solar cells. A concern with these rather thick cells is the long deposition time required. The performance of such cells is also extremely sensitive to processing detail, which may make scale up of the process (from R&D areas to commercial module areas) more challenging than PECVD deposition of a-Si:H-based cells. The United States PV program has supported a research effort on nc-Si solar cells at United Solar, and if better results can be obtained, they stand ready to implement manufacturing of nc-Si containing micromorph modules. 5. Conclusion and outlook In order to achieve further cost reduction for a-Si:Hbased PV modules, it is highly desirable to increase their stabilized performance and simultaneously increase their deposition rates. A study has been conducted on estimating the potential module cost for various PV technologies. This study compares commercial module performance of PV modules using different cell technology fabricated with comparable maturity in module manufacturing. It is argued that all successful PV technologies will eventually reach a similar degree of manufacturing maturity. It is then further assumed that a thin-lm module will eliminate the costs fraction attributable to the Si wafer in a crystalline Si PV module. Based on this analysis, a-Si-based thin-lm modules appear competitive, but in the near and midterm they may not provide the lowest-cost module option because of their lower performance [24]. However, the advantages of a low-temperature growth process, a virtually unlimited feedstock supply for manufacturing them, and the renewed interest from display manufacturing equipment manufactures is inherent to this PV technology. It is therefore imperative to continue work on overcoming the current stabilized performance shortfalls. References
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