Thin Solid Films 430 (2003) 16

Status report: solar cell related research and development using amorphous and microcrystalline silicon deposited by HW(Cat)CVD
Bernd Schroeder
Department of Physics and Center of Materials Science, University of Kaiserslautern, P.O. Box 3049, D-67653 Kaiserslautern, Germany

Abstract This article reviews the research and development of a-Si:H and mc-Si:H based solar cells by using hot wire chemical vapor deposition (HWCVD). The groups involved and the present status of conversion efficiencies attained are listed and will be discussed for different cell structures realized entirely or partly using this method. There are three main advantages of HWCVD: a quite simple set up, higher useable deposition rates and higher stability of HW-a-Si:H. It will be discussed how these advantages can be exploited to make HWCVD an alternative to plasma enhanced chemical vapor deposition. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Hot-wire CVD; Amorphous silicon; Microcrystalline silicon; Solar cells

1. Introduction The so-called hot wire or thermocatalytic chemical vapor deposition (HWCVD or CatCVD, respectively) of amorphous or microynanocrystalline silicon has recently emerged as a promising alternative to the conventional plasma enhanced chemical vapor deposition (PECVD), which is predominantly used for deposition of these materials for R&D as well as for commercial applications. Although HWCVD was first reported by Wiesmann et al. w1x, it took quite a long time to achieve device quality a-Si:H films w2,3x by this method. The first solar cell device containing HWCVDdeposited collection layer was reported in 1993 w4x. Driven by only a few groups, the conversion efficiencies of single pin and nip solar cells with intrinsic a-Si:H layers prepared by HWCVD could be increased to initial values of h)10% in the nineties w5,6x. In 2000, the first pin w7x, nip w8x and pinpin w9x solar cell structures were prepared entirely by HWCVD. More recently integration of microcrystalline silicon (mc-Si:H) into HWCVD solar cells appears to be the main subject of R&D. There have also been first attempts to prepare solar cells on medium size area w10x. At present, approximately 40 laboratories worldwide are involved in HWCVD R&D work, some in basic research, most
E-mail address: bs@rhrk.uni-kl.de (B. Schroeder).

of them dealing with different application possibilities (for a listing: see Bouree w11x). About a dozen of these laboratories are fabricating solar cells (Table 1). This article will review the present state of development for different solar cell structures incorporating variable HWCVD deposited materials and discuss the advantages as well as disadvantages of using this method. 2. Solar cell structures entirely deposited by HWCVD There are only four groups involved in preparation of the whole cell structure by HWCVD: viz. NREL, Kaiserslautern, JAIST and Barcelona. The reason for the combined PECVDyHWCVD deposition technique being mainly used is that most laboratories involved are equipped with state of the art PECVD deposition systems and dispose of knowledge to prepare p- and ndoped layers by PECVD. The deposition of amorphous and microcrystalline n-layers by HWCVD is quite easy w12x, it can occur under the same parameter conditions used for deposition of corresponding high quality intrinsic layers. However, the preparation of p-window layers by HWCVD seems to be problematic. Attempts to incorporate carbon by using different source gases in the HWCVD process to form an amorphous p-SiC:H window layer have led to formation of inhomogeneous

0040-6090/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0040-6090(03)00070-1

B. Schroeder / Thin Solid Films 430 (2003) 16

Table 1 Listing of institutions which have published results on a-Si:Hymc-Si:H based solar cells where at least the photovoltaic active layer was deposited by HWCVD Institution Realized structures nip nip nip nip nipnip pin pinynip pinynip pinpin nipynip nipnip nipnip nip pin pin pin, nip pinpin pin pin pin Schottky junction cell Layer deposited by HWCVD all all n, i n, i n, i (a-SiGe) i allyall allyall all iyi iyi iyi i p, i i iyi i all all i i Active layer a-Si:H mc-Si:H a-Si:H a-SiGe:H a-SiGey(a-Si:H) a-Si:H a-Si:H mc-Si:H a-Si:Hya-Si:H a-Si:Hymc-Si:H a-Si:Hymc-Si:H a-Si:Hya-Si:H mc-Si:H a-Si:H a-Si:H mc-Si:H a-Si:Hymc-Si:H a-Si:H mc-Si:H a-Si:H mc-Si:H Maximum hinitial (%) 8.7 6.0 9.9 7.0 11.7 10.2 8.9y6.3 3.6y2.6 7.0 7.2y4.4 8.1 8.5 5.1y6.1 7.5 7.6 9.4y7.4 10.9 5.3 2.0y3.0 8.6 1.46 Maximum hstable (%) 5.5 7.8 Ref.

NRELa NRELyUSSCb

w8x w19x w8,29x w29x w29x w5x w7xyw16x w48xyw17x w9x w22x w41x w42x w25xyw11x w43x w21x w23x w28x w15x w44xyw45x w46x w47x

University Kaiserslautern

7.0 5.3y

University Utrecht

Ecole Polytech. TITc FZ Juelich

6.3

JAISTd University Barcelona MV Systems Korea Institute of Energy Research

a b

National Renew. Energy Laboratory. United Solar System Corporation. c Tokyo Institute of Technology. d Japanese Institute of Technology.

p-type films and consequently to unstable pyi interfaces and cell structures w12,13x. 2.1. Cells with a-Si:H absorber(s) The highest initial conversion efficiencies reported for cells containing the above mentioned p-SiC:Hwindow layers are hinitials8.9% for pin structures w7x, and hinitial)7% for pinpin structures w8x. Due to the structural instabilities mentioned above the highest stabilized conversion efficiency of such cells (pin cell with ethane as carbon source gas) amounts only to hstabils 5.3% w13x. In pinpin cells containing p-a-SiC:H layers especially the pyn-tunnel junction is affected by the instability of the p-layer w9x. As a result there is increasing interest in p-mc-Si:H to replace the p-a-SiC:H layer. Incorporating a p-mc-Si:H layer in an all HW pin structure cells, very high fill factors up to FFs73% and open circuit voltages Vocs900 mV have been obtained. However, due to the low transparency of the p-mc-Si:H layer used in this case, the short circuit current jsc and the resulting conversion efficiency hinitials7.8% was quite low w14x. First attempts to prepare all HWCVD aSi:H pin solar cells at JAIST resulted in hinitials5.3% w15x.

All HWCVD nip solar cells with high efficiencies have only been prepared with microcrystalline p-layer so far. The highest initial conversion efficiency for a nip solar cell with amorphous collection layer is reported by NREL (in collaboration with the United Solar System Corporation (USSC)) yielding minitials8.7% w8x. This solar cell contains the highly reflecting textured Agy ZnO-coated SS back reflector substrate developed by USSC. Without this sophisticated back reflector, the conversion efficiency reduces to hinitials7.12% w8x. The reported nip solar cells were prepared with a edge material grown under conditions near the transition from amorphous to microcrystalline growth between the amorphous i-layer and the microcrystalline p-layer. After 1000 h of one sun light soaking a stable efficiency without using the USSC developed back reflector of hstables5.4% was obtained w8x. First attempts in our group to deposit all HWCVD nip solar cell structures resulted in an initial conversion efficiency of hinitials 6.2% w16,17x. The only all HWCVD tandem solar cell fabricated until now is the pinpin structure of our group showing a conversion efficiency of hs7.0% after some degradation w9x. The development of a tunnel or recombination junction with at least one doped microcrystalline

B. Schroeder / Thin Solid Films 430 (2003) 16

Fig. 1. Thickness dependence of AM 1.5 IV measurement results of pin (closed symbols) and nip (open symbols) solar cells containing HWmc-Si:H collection layers (after Klein et al. w23x).

layer between the two pin devices with intrinsic icollection layers of different thicknesses was the key to realize the tandem structure with a low series resistance and a high fill factor. While the fill factor FFs71% and the open circuit voltage Vocs1.63 V of this tandem structure showed already high values, the short circuit current and the stability, however, were still insufficient, due to the high absorption and instability of the p-layers used (see above). 2.2. Cells with mc-Si:H absorber All HWCVD solar cells with microcrystalline collection layer showed very low conversion efficiencies of around hs23% for a very long time w14,17,18,44,48x. Very recently Schropp et al. reported on an all HWCVD nip solar cell with hs5.97%, containing a microcrystalline collection layer deposited just above the edge of the amorphousymicro-crystalline phase transition w19x. When the microcrystalline i-layer was deposited with rdeps1 nmys the conversion efficiency still amounted to hs4.9% w19x. 3. Single junction and tandem solar cells partly deposited by HWCVD As already mentioned above, many groups are investigating solar cells where only the intrinsic collection layer is fabricated by HWCVD. On one hand they take advantage of the available equipment to deposit doped layers by PECVD and avoid the development of such films by HWCVD, while on the other hand, at the present state of development it is more important to gain knowledge about the applicability of the collection

layers obtained by HWCVD. This becomes clear by taking into account the advantages expected for solar cells prepared by HWCVD method, viz. higher deposition rates and higher stability, which are important only for the i-layer deposition. To evaluate the results obtained by the combined deposition, it has to be taken into account that air brakes are possibly involved which can reduce the interface quality and as a consequence, the cell parameters. 3.1. Single cells with a-Si:H absorbers For simple pin and nip solar cells the maximum conversion efficiencies have already been obtained more than 3 years ago, hinitials10.2% for pin cells w5x and hinitials9.8% for nip cells w6x. This is also valid for the highest stabilized efficiency reported, for pin structures hstables7.0% w5x and for nip structures hstables7.8% w20x. The Juelich and Utrecht groups obtained hinitial)7% for pin or nip structures, respectively w21,22x. 3.2. Single cells with mc-Si:H and a-SiGe:H absorber Tremendous progress has recently been made by Klein et al. w23x in integrating mc-Si:H absorption layers deposited by HWCVD into pin and nip solar cell structures achieving initial conversion efficiencies of minitials9.4 and 7.4%, respectively. Some details of their outstanding results are shown in Fig. 1. The key factor in their mc-Si:H material related investigations was the reduction of the defect density by deposition near the amorphous to microcrystalline phase transition (see also Finger et al. w24x). This way, a highly conductive mc-

B. Schroeder / Thin Solid Films 430 (2003) 16

Si:H with a compact morphology and effective grain boundary passivation could be achieved. The conversion efficiency of a pin solar cell containing this optimized HW-material yielded even higher values in comparison to optimized all PECVD cells of this group w23,24x. Two other laboratories have also prepared nip cells with mc-Si:H absorber achieving efficiencies around 5% w22,25x. Until now only two papers are published about solar cells containing a graded HWCVD a-SiGe:H absorber layer with a minimum energy gap of 1.5 eV. For pin cell structure Lill and Schroeder yielded hinitials6.4% w26x and very recently Wang et al. reported hinitials 7.3% for a nip cell w27x. 3.3. Tandem solar cell structures Very recently, low energy band gap materials deposited by HWCVD have been combined with a-Si:H cells to make tandem structures with high efficiency. Klein et al. w28x integrated a-Si:H (0.4 mm) and mc-Si:H (1.4 mm) absorbers deposited by HWCVD into a pinpin tandem solar cell with doped PECVD layers achieved hinitials10.9% for the resulting pinpin tandem structure w28x. Wang et al. combined the a-SiGe:H cell reported in Section 3.2 with a USSC high conversion efficiency a-Si:H structure to make a nipnip solar cell with hinitials 11.7% w29x, the highest value ever obtained for a solar cell containing HWCVD collection layer. From the Utrecht group, nipnip tandem structures with HWCVD collection layers were prepared, the mc-Si:Hya-Si:H tandem yielded hinitials8.1% and the a-Si:Hya-Si:H tandem hinitials8.5%, respectively w22x. 3.4. Silicon wafer based solar cells with emitters deposited by HWCVD Hetero and homojunction silicon solar cells have been produced by Seitz et al. depositing n- and p-type amorphous, microcrystalline and epitaxial HWCVD grown emitters on p- and n-type crystalline silicon wafers w30x. The highest conversion efficiency of any solar cell ever reported containing a HWCVD functional layer is hstables15.2% and has been obtained depositing a HWCVD n-a-Si:H emitter on a textured p-c-Si wafer w30x. 4. Large area solar cell deposition by HWCVD Scale up of a-Si:H based solar cells, entirely or partly prepared by HWCVD, requires research on the deposition process in large area HWCVD systems. A first study on large area HWCVD deposition for solar cell application was carried out by Ledermann et al. w31x. In a detailed study the influence of gas supply and filament arrangement was investigated as well as the optimization
Fig. 2. Initial efficiencies for small solar cells with i-layers deposited in nine sections of a 20=20 cm2 substrate w32x.

of process parameters towards achieving thickness uniformity as well as the material quality was reported by Pfluger et al. w32x. On a medium size area of 20=20 cm2, these authors obtained a very small distribution in conversion efficiencies of small area solar cells with hinitials(6.1q0.2)% (Fig. 2). Investigations on large area HWCVD of intrinsic layers for solar cells were also carried out by Morrison et al. w33x. Masuda et al. w34x have discussed guiding principles for large area HWCVD and Ishibashi presented a special development of a HWCVD apparatus for large area deposition of aSi:H w35x. Very recently Monte Carlo simulations of the HWCVD process with respect to large area deposition w36x as well as a project study for the HWCVD of aSi:H based solar cells moving into industrial production has been reported w37x. 5. Discussion Since it has been shown that the HWCVD method yields material properties for a-Si:H and mc-Si:H films comparable to PECVD, these materials were consequently incorporated into different solar cell structures in the past few years. The groups involved are listed in Table 1. The table also contains the solar cell structure realized by these groups and the maximum conversion efficiencies obtained for these structures. Taking into account the short research and development time and the small number of research groups involved, both in comparison to the use of the PECVD method, the maximum conversion efficiencies achieved for different solar cell structures using the HWCVD method (Table 2) are very impressive. Of course the maximum conversion efficiencies gained by PECVD have not yet been matched completely by HWCVD, however, this can be expected due to the lack of perfection of the technology.

B. Schroeder / Thin Solid Films 430 (2003) 16 Table 2 Maximum initial conversion efficiency of different solar cell structures containing a-Si:H, mc-Si:H, a-SiGe:H films deposited by HWCVD Structure (1) Solar cells entirely prepared by HWCVD pin nip pin nip pinpin (2) Solar cells containing functional layer(s) deposited by HWCVD pin nip pin nip pin nip nipnip pinpin nipnip nipnip pn heterojunction HW active layer(s) a-Si:H a-Si:H mc-Si:H mc-Si:H a-Si:Hya-Si:H a-Si:H a-Si:H a-SiGe:H a-SiGe:H mc-Si:H mc-Si:H a-Si:Hya-Si:H mc-Si:Hya-Si:H mc-Si:Hya-Si:H a-SiGe:Hy(PECVD a-Si:H) c-Si (HW n-layer) Initial h (%) 8.9 8.7 3.6 6.0 7.0 10.2 9.9 6.4 7.4 9.4 7.4 8.5 10.9 8.1 11.7 15.2

Ref. w7x w8x w48x w19x w9x w5x w6x w26x w29x w23x w23x w22x w28x w22x w29x w30x

The following advantages are attributed to the HWCVD: the requirement of a much simpler set-up for deposition, higher useable deposition rates, and higher stability of the HWCVD-a-Si:H material. As reported in Section 4 there exist a couple of investigations w3136x which show that the HWCVD method can already be applied for deposition over medium size areas of 20=20 cm2. Of course only i-layer deposition has been realized and the next step to the required one square meter industrial production need has only been investigated in a theoretical project study w37x. However, the thickness uniformity as well as the film quality of the medium size deposition appear quite optimistic. The deposition rate of a-Si:H films incorporated in solar cells in industrial production is still of the order of 0.10.3 nmy s, the same rate is required to obtain maximum conversion efficiencies by PECVD. The deposition rates used in the HWCVD, also to gain maximum efficiency values, are generally of the order of 0.5=1.5 nmys w5,6x. However, as shown by Mahan et al. w38x the deposition rate for a-Si:H films in nip structures can be raised to ultra high values of 12 nmys, compromising the initial conversion efficiency of the corresponding solar cells by only approximately 10%. Although the very high hinitials9.4% for mc-Si:H w23x has been obtained at low rates, Schropp et al. w19x have already shown that the rate can be enhanced to 1 nmys without a large reduction in h. Since there do not exist any problems to deposit HWCVD-n-type layers, at least iand n-layers could be fabricated by this method at higher rates. Although the higher stability of HWCVDa-Si:H films deposited at high temperatures ()300 8C) has been shown some years ago w39,40x, these films could not be incorporated into solar cells showing a comparable improved stability. As in the case of PECVD

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