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ELSEVIER Solar Energy Materials and Solar Cells 34 (1994) 193-199

High efficiency silicon solar cells by plasma-CVD method

K. F u j i m o t o *, Y. Sogawa, K. Shima, Y. O k a y a s u , K. K u m a g a i
Corporate Research and Development Laboratory, Tonen Corporation 1-3-1, Nishi-Tsurugaoka Ohi-machi, lruma-gun, Saitama 356, Japan

Abstract

We have succeeded in obtaining excellent Back Surface Field (BSF) structures by depositing a highly doped silicon layer on the back side of the substrate even though the textured wafer is used. The substantial increase of the spectral response in longer wavelength has been observed and an increase of Voc has also been found. The BSF formation technology, together with the low temperature grown thin a-Si emitter layer with appropriate bandgap, has enabled us to obtain a very high Js of 40.5 m A / c m 2, thus a high active area conversion efficiency of 18.9% (Vo= 0.592 V, FF = 0.789).

1. Introduction To reduce the manufacturing cost of a photovoltaic system, it is very effective to increase the conversion efficiency of solar ceils, given that the cell fabrication cost is kept inexpensive. The state-of-the-art semiconductor process technologies, such as point contact [1], buried contact [2], surface passivation [3], etc., have enabled the realization of more than 20% in conversion efficiency of silicon solar cells, although the fabrication process is very complicated and thus expensive. The aim of the present paper is to demonstrate that the low temperature deposition process, such as plasma-CVD method, is very effective for obtaining high efficiency silicon solar cells in a simple procedure. Low temperature deposition method has several advantages: (1) the method does not depend on the complicated, expensive, processes as described, (2) it is expected to eliminate the degradation of bulk silicon properties, e.g., the diffusion of impurities and the defect formation, that are inherent to high temperature process, and (3) the depth

* Corresponding author. 0927-0248/94/$07.00 1994 Elsevier Science B.V. All rights reserved SSDI 0 9 2 7 - 0 2 4 8 ( 9 4 ) 0 0 0 3 2 - N

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Table 1 BSF layer preparation condition Back pressure (Torr) Source gas Flow rate (sccm) Substrate temp. (C) RF power ( W / c m 2) Deposition pressure (Torr) Deposition rate ( n m / s ) 10-6 P H 3 / S i H 4 / H 2 = I).01/1/30 10 - 20 150 -200 001 - {).04 0.1 - 0.5 {}.01- 0.02

of the junction can be accurately controlled. In the deposition process it is possible to fabricate a very thin emitter layer (10 nm), which enhances the spectral response in shorter wavelengths. However, previous research has shown that the spectral response in longer wavelengths is inferior to the conventional solar cells [4]. At the 38th spring meeting of the Japan Society of Applied Physics in 1991, we proposed that the BSF structure by depositing a highly doped thin silicon layer was very effective for the increase of spectral response in longer wavelength and a high conversion efficiency of 16% was obtained using flat single-crystalline silicon wafers. Recently, we have studied the properties of the BSF layer and BSF effect in detail and the BSF structure was applied to well textured single silicon wafers. Consequently, the solar cells with very high Jsc of 40.5 m A / c m 2 have been obtained using all low temperature processes below 200C.

2. Experimental

2.1. BSF layers properties

BSF layers were mainly prepared with P H 3 / S i l l 4 mixed gases highly diluted by hydrogen as shown in Table 1. The epitaxially aligned films were obtained on the Si (100) surface and poly- or micro-crystalline films were obtained on the Si (111) surface, which were verified by reflection high-energy electron diffraction (RHEED) observation (Fig. 1). The mobility and carrier concentration of the very thin BSF layer were measured by the Hall effect with the structure of BSF layer(n +)/Cz-Si(p-) and the results are tabulated in Table 2. Both films have very high carrier concentration of around 1021//cm 3 which is more than that of the BSF layers prepared by other methods such as the thermal diffusion method, ion implantation, the Al paste method, and so on. The degree of the BSF effect was estimated from the effective diffusion length by the electrodeless surface photo-voltage (SPV) method using CMS-III (Semiconductor Diagnostics Incorporated) and solar cell performance. The diffusion length could be measured after only SC1 cleaning for N-type wafers. The surface of well-textured wafers consists of a pyramid with (111) planes and the BSF effect dependence of the wafer orientation was examined. Almost the

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K. Fujimoto et al. / Solar Energy Materials and Solar Cells 34 (1994) 193-199

Table 2 The electrical properties of BSF layer Crystal structure Carrier density (cm -3) Mobility (cm 2 / V s ) Resistivity (~2 cm) On Si (100) epitaxial ~ 102I 20 ~ 40 ~ 1 x 10 3 On Si (111) multi-crystalline ~ 102I 10 ~ 20 ~ 2 x 10 -3

same BSF effect was confirmed on Si (100) and Si (111). A-Si (n ) layers also showed the BSF effect but the degree of the photo response enhancement in the longer wavelength was smaller than that of crystalline BSF layer at our conditions. The BSF effect by film deposition is very sensitive to the back side surface condition such as contamination before deposition and careful pre-treatment is necessary. The BSF layer had better be prepared at first for good reproducibility.
2.2. Solar cells f a b r i c a t i o n

The solar cell structure and the fabrication sequence are shown in Fig. 2. N-type Cz-Si with resistivity of 1-5 [l cm was used for the substrate. The wafer was etched with potassium hydroxide (KOH) solutions in order to obtain textured surface. The thickness of the wafer after etching was about 350 Ixm. BSF layers and emitter layers were deposited by the PCVD-method. The deposited emitter layer properties affect the solar cell performance just like a-Si solar cells. The emitter layers with wide band gap and low resistivity are desired for high performance. A-SiC films and /zc-Si films were also examined but the solar cells with a-Si emitter layer showed higher performance. Takayama et al. [4] reported the usefulness of the buffer layer between a-Si(p ) and c-Si wafer. In this work, we have studied the way to get high performance without a buffer layer for the simplification of the process. After deposition of the emitter layers, indium-tin-oxide(ITO) films were fabricated by DC-magnetron sputtering as transparent conductive oxides and 1st

finger [A[g paste] I 2nd-AR coat[ MgF2] front electrode [ITO, 80nm] emitter layer [ a-Si(p+),- 10nm] Cz-Si wafer [n-,0.35mm] BSF layer [PCVD-Si(n+),20nm] back electrode [ AI]

BSF formation junction formation [ front electrode back electrode

I
fin[ger electrode I 2nd AR coat

a. b. Fig. 2. The solar cell structure (a) and the fabrication sequence (b).

K Fujimoto et aL/Solar Energy Materials and Solar Cells 34 (1994) 193-199

197

800 600 400

'

I on Si(lO0)[ C) on Si(111)

,_1

.o_ = 200
--3

20 40 60 80 100 n+ Film Thickness (nm)

Fig. 3. The effective diffusion length dependence on the thickness of BSF layer. The diffusion length was measured by SPV method.

anti-reflection flms. MgF 2 films were deposited by electron-beam evaporation as 2nd anti-reflection films. Silver paste with resin was used for the finger electrode by the screen printing technique. The resistivity of the silver paste after annealing at 200~C is as low as 1 10 -5 fl cm. The designed active cell area is 1.21 cm 2 but the real active cell area was 1.17 cm 2 which was measured by a laser microscope. The decrease of active area is due to the blot of the surface electrode. Al-films were evaporated for the back electrode and ohmic contact was obtained after annealing at about 200C. All these processes are performed below 200C.

3. Results and discussion Generally speaking, the degree of BSF effect depends on the wafer diffusion length and wafer thickness [5]. Wafers used in this work have diffusion length of about 300 ixm which was measured by the SPV method. This value of diffusion length is comparable with the wafer thickness and a considerable BSF effect is expected. In Fig. 3, the effective diffusion length by the SPV method dependence on the BSF layer thickness is shown and the increase of diffusion length has been observed for the wafers with BSF layer. The diffusion length more than wafer thickness is not accurate but the enhancement of BSF effect was obvious. High carrier concentration of BSF layers enables us to obtain good BSF effect with the thickness of as thin as 20 nm.. Recently, we have started computer simulation of the BSF effect dependence on the carrier concentration using the program of "VENUS" and it is indicated from the rough calculation that the BSF layers with higher carrier concentration shows higher solar cell performances. The details of the simulation such as BSF layer characteristics, the boundary conditions and emitter layer properties, etc,. must still be improved and the qualitative discussion will be carried out in the near future.

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K. Fujimoto et al. / Solar Energy Materials and Solar Cells 34 (1994) 193-199

do LU

0.8 0.6

g 0.4
0

--~ 0.2 -5 (.3 0 200

400 600 800 1000 1200 wave length (nm)

Fig. 4. The spectral response of the solar cells with BSF structure and without BSF structure. The increase of the spectral response in the longer wavelength has been observed.

The difference of the spectral response between the solar cells with and without BSF structure is shown in Fig. 4. It has been verified, as shown in Fig. 4, that the spectral response in the longer wavelength strongly depends on the back side structure. The effective diffusion length of the solar cells showing good BSF effect was estimated more than 1 mm from the spectral response for the longer wavelength (800 n m < A < 1000 nm), though the correct estimation is difficult in case of longer diffusion length more than the wafer thickness. The collection efficiency of about 50% at 1100 nm is comparable with surface passivated high efficiency solar cells [6]. The collection efficiency of more than 85% at 400 nm is also very high and this is due to the very thin emitter layer and very high J ..... of 40.5 m A / c m 2 was estimated from the collection efficiency and AM1.5 spectrum (100 m W / c m 2 ) .

50

I V0c: 0592 V I ~ Jsc= 40.50 mA;cm 2 / / FF= 0789 ~/ / elf.= 18.9 % I

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0

30
"E 2 0 Voc = 0.575 V Jsc =37.96 mA/cm 2 I FF= 0.782 I

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0.4 0.6 Voltage (V)

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Fig, 5. The characteristics of the solar cells with good BSF layer. Solid line: with BSF layer. Broken line: without BSF layer.

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199

The photo current-voltage characteristics of the solar cells with good BSF effect is shown in Fig. 5. Voc and FF were measured at about 25C after Jsc was set at calculated value and the very high efficiency of 18.9% was obtained. The Voc of the solar cell with BSF structure is higher than that without BSF structure. However, the Vo:value of the well-textured solar cells was 20-30 mV smaller than that of the flat surface solar ceils at the same condition and the solar cells with an emitter layer thicker than 40 nm had Vo-values near the values of flat solar cells, but the thicker emitter solar cells showed an decrease of J,c and conversion efficiency. It is considered that this problem is due to the structure of the interface between the emitter layer and the well textured wafers. This problem will be overcome due to the optimization of the emitter layer preparation condition including buffer layer insertion.

4. Conclusion
Crystalline silicon solar cells fabricated by the low temperature PCVD-method have been studied and an excellent BSF structure has been obtained by depositing a highly doped silicon thin layer on the back of the substrate. The substantial enhancement of the spectral response in longer wavelength was observed and a very high Jsc of 40.5 m A / c m 2 has been achieved. The BSF formation technology and thin a-Si emitter layer with appropriate bandgap has enabled us to obtain very high active area efficiency of 18.9%.

Acknowledgement
This work is supported by NEDO (New Energy and Industrial Technology development Organization), as part of the New-Sunshine Program under Ministry of International Trade and Industry.

References
[1] R.R. King, R.A. Sinton and R.M. Swanson, Appl. Phys. Lett. 54 (1989) 1460-1462. [2] M.A. Green, Proc. 10th EC Photovoltaic Solar Energy Conf., 1991, pp. 250-253. [3] M.A. Green, A.W. Blakers, J. Shi, E.M, Keller and S.R. Wenham, IEEE Trans. Electr. Dev. 31 (1984) 679-683. [4] T. Takayama, M. Taguchi, S. Kuroda, T. Matsuyama, M. Tanaka, S. Tsuda, S. Nakano and Y. Kuwano, Proc. l l t h EC Photovoltaic Solar Energy Conf., 1992, pp. 1057-1060. [5] J. Knobloch, A. Aberle, W. Warta and B. Voss, Technical Digest 5th Int. Phtovoltaic Specialists Conf., 1990, pp. 955-958. [6] C.M. Chong, S.R. W e n h a m and M.A. Green, Appl. Phys. Lett. 52 (1988) 407-409.