JPH10313125A - Formation of thin film - Google Patents

Formation of thin film

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Publication number
JPH10313125A
JPH10313125A JP9120410A JP12041097A JPH10313125A JP H10313125 A JPH10313125 A JP H10313125A JP 9120410 A JP9120410 A JP 9120410A JP 12041097 A JP12041097 A JP 12041097A JP H10313125 A JPH10313125 A JP H10313125A
Authority
JP
Japan
Prior art keywords
layer
thin film
crystalline
film
solar cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP9120410A
Other languages
Japanese (ja)
Inventor
Sae Takagi
小枝 高木
Hitoshi Sannomiya
仁 三宮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to JP9120410A priority Critical patent/JPH10313125A/en
Publication of JPH10313125A publication Critical patent/JPH10313125A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/545—Microcrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/546—Polycrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

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  • Chemical Vapour Deposition (AREA)
  • Photovoltaic Devices (AREA)

Abstract

PROBLEM TO BE SOLVED: To form a thin film, which is high in quality and is good in crystallizability, aiming at the enhancement of the conversion efficiency of a thin-film solar cell. SOLUTION: Pulse discharge is performed, while VHF band high-frequency power is applied to a substrate, using a plasma CVD method to form a crystalline Si thin film on the substrate. By setting a power frequency in a frequency of 27.12 to 81.36 MHz, the dark conductivity of a thin-film solar cell is increased more than that in the case where an RF(radio frequency) band power frequency is used, and the dark conductivity is increased more than that in the case where continuous discharge (duty (= on time/on time + off time) 100%) is performed by performing the pulse discharge (duty less than 100%.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、太陽電池等におけ
る結晶性薄膜の形成方法に関する。The present invention relates to a method for forming a crystalline thin film in a solar cell or the like.

【０００２】[0002]

【従来の技術】一般に薄膜太陽電池は、ガラス等の透光
性絶縁基板上にＳｎＯ2やＩＴＯ等の透明導電膜が形成
され、その上に非晶質半導体のｐ層、ｉ層、ｎ層がこの
順に積層されて光電変換活性層が形成され、その上に金
属薄膜の裏面電極が積層されてなる構造と、金属基板電
極の上に非晶質半導体のｎ層、ｉ層、ｐ層がこの順に積
層されて光電変換活性層が形成され、その上に透明導電
膜が積層されてなる構造とがある。これらのうち、前者
のｐ−ｉ−ｎ層の順に積層する方法は、透光性絶縁基板
が太陽電池の表面カバーガラスを兼ねることができる
点、またＳｎＯ2等の耐プラズマ性透明導電膜が開発さ
れて、この上に非晶質半導体の光電変換活性層をプラズ
マＣＶＤ法で積層することが可能になった点、等から多
用されるようになり、現在の主流となっている。2. Description of the Related Art In general, a thin-film solar cell has a transparent conductive film such as SnO 2 or ITO formed on a light-transmitting insulating substrate such as glass, and a p-layer, an i-layer and an n-layer of an amorphous semiconductor are formed thereon. Are laminated in this order to form a photoelectric conversion active layer, on which a back electrode of a metal thin film is laminated, and an n-, i-, and p-layer of an amorphous semiconductor on a metal substrate electrode. There is a structure in which a photoelectric conversion active layer is formed by stacking in this order, and a transparent conductive film is stacked thereon. Among these, the former method of laminating in the order of the pin layers is characterized in that the light-transmitting insulating substrate can also serve as the surface cover glass of the solar cell, and that a plasma-resistant transparent conductive film such as SnO 2 is used. It has been widely used because it has been developed and an amorphous semiconductor photoelectric conversion active layer can be stacked thereon by a plasma CVD method.

【０００３】上記透光性絶縁基板（ガラス）／透明導電
膜／ｐ−ｉ−ｎ半導体／裏面電極構造を持つアモルファ
ス太陽電池では、これまでの精力的な研究・開発にも拘
わらず、変換効率が１０ｃｍ角の素子で１０〜１２％と
いうレベルに留まっている。これまで太陽電池には主に
非晶質材料が用いられてきたが、これ以上の変換効率向
上を図るための方法の１つとして、結晶性Ｓｉ薄膜を適
用することがあげられる。例えば特開昭５７−１８７９
７１号公報には、非晶質太陽電池のｐ層あるいはｎ層を
結晶Ｓｉから構成することが記載されている。[0003] In the above-mentioned amorphous solar cell having the translucent insulating substrate (glass) / transparent conductive film / pin semiconductor / backside electrode structure, the conversion efficiency is high despite the vigorous research and development. Is 10 to 12% for a 10 cm square element. Until now, amorphous materials have been mainly used for solar cells, but one of the methods for further improving the conversion efficiency is to apply a crystalline Si thin film. For example, JP-A-57-1879
No. 71 describes that a p-layer or an n-layer of an amorphous solar cell is made of crystalline Si.

【０００４】なお、これらに用いられる非晶質半導体の
薄膜形成は、原料ガスのグロー放電分解によるプラズマ
ＣＶＤ法や、光ＣＶＤ法による気相成長により形成さ
れ、これらの方法は大面積の薄膜形成が可能という利点
を有する。A thin film of an amorphous semiconductor used in these methods is formed by a plasma CVD method by glow discharge decomposition of a source gas or a vapor phase growth by a photo CVD method. Is possible.

【０００５】さらに、非晶質材料を形成するプラズマＣ
ＶＤプロセスにおいて、パウダー（Ｓｉの重合した粉状
のもの）の生成を減少させるために、パルス放電が近年
用いられるようになってきた。このような技術に関して
は特公平７−４７８２３号（特開平５−１５６４５１
号）公報に記載されている。Further, a plasma C for forming an amorphous material
In the VD process, pulse discharge has recently been used to reduce the production of powder (polymerized powder of Si). Such a technique is disclosed in Japanese Patent Publication No. Hei 7-47823 (JP-A-5-156451).
No.) publication.

【０００６】ここで、薄膜形成に利用されるグロー放電
プラズマの周波数は１３．５６ＭＨｚのＲＦ（無線周波
数）が主流であり、ついで２．４５ＧＨｚのマイクロ波
プラズマが研究されている。工業用に割当てられている
高周波がＲＦとマイクロ波だけであることから、ＲＦと
マイクロ波以外の高周波帯における周波数効果について
はほとんど研究が行われなかった。しかし近年、ＲＦと
マイクロ波との間に位置する高高周波を用いたアモルフ
ァス膜および結晶性薄膜の適用が検討されている。例え
ば太陽電池素子のｉ層での結晶性薄膜（７０ＭＨｚで成
膜）の適用については「ＩＮＴＲＩＮＳＩＣ ＭＩＣＲ
ＯＣＲＹＳＴＡＬＬＩＮＥ ＳＩＬＩＣＯＮ（μｃ−Ｓ
ｉ：Ｈ）−ＡＰＲＯＭＩＳＩＮＧ ＮＥＷ ＴＨＩＮ
ＦＩＬＭＳＯＬＡＲ ＣＥＬＬ ＭＡＴＥＲＩＡＬ」
（Ａ．Ｓｈａｈ他 ＦｉｒｓｔＷＣＰＥＣ；Ｄｅｓ．５
−９，１９９４；Ｈａｗａｉｉ）に記載されている。Here, the frequency of glow discharge plasma used for forming a thin film is mainly 13.56 MHz RF (radio frequency), and microwave plasma of 2.45 GHz has been studied. Few studies have been conducted on the frequency effects in high-frequency bands other than RF and microwave, since only RF and microwaves are allocated for industrial use. However, in recent years, application of an amorphous film and a crystalline thin film using high frequency located between RF and microwave has been studied. For example, regarding the application of a crystalline thin film (formed at 70 MHz) in the i-layer of a solar cell element, see “INTRINSIC MICR”.
OCRYSTALLINE SILICON (μc-S
i: H) -APROMISING NEW THIN
FILMSOLAR CELL MATERIAL "
(A. Shah et al. First WCPEC; Des. 5
-9, 1994; Hawaii).

【０００７】[0007]

【発明が解決しようとする課題】ところで、ｐ層あるい
はｎ層に結晶性薄膜を形成すれば開放電圧は向上するこ
とが考えられるが、ｐ層およびｎ層では光の吸収損失を
抑制するための薄膜化を行うと、充分な結晶性が得られ
ないという問題がある。これは、薄膜太陽電池に適用す
るためｐ型あるいはｎ型の結晶性薄膜を１０〜２０ｎｍ
の薄膜にすると、厚膜状態（２００ｎｍ以上）では１Ｓ
／ｃｍ程度の導電率のものが１０-6Ｓ／ｃｍまで低下す
る。すなわち薄膜化により結晶性が低下することになる
からである。The open-circuit voltage can be improved by forming a crystalline thin film on the p-layer or the n-layer. However, the p-layer and the n-layer are required to suppress light absorption loss. When the thickness is reduced, there is a problem that sufficient crystallinity cannot be obtained. This means that a p-type or n-type crystalline thin film is applied to a thin-film solar cell by 10 to 20 nm.
Thin film, 1S in thick film state (200 nm or more)
/ Cm of conductivity is reduced to 10 -6 S / cm. That is, crystallinity is reduced by thinning.

【０００８】また、結晶性薄膜を形成する場合に、結晶
性の改善を図るために単に高高周波のプラズマＣＶＤを
適用してだけでは、結晶粒径の拡大および薄膜中の欠陥
準位の低減を図ることができず、結晶性の向上には不十
分である。Further, when a crystalline thin film is formed, simply applying high-frequency plasma CVD to improve the crystallinity can increase the crystal grain size and reduce the defect level in the thin film. It cannot be achieved, and is insufficient for improving the crystallinity.

【０００９】このように、結晶性薄膜の形成において、
高高周波を用いただけでは結晶性の向上には結びつか
ず、ｐ層およびｎ層での薄膜結晶性の向上、ｉ層での結
晶粒径拡大といった結晶性の良好な薄膜形成が困難であ
った。Thus, in forming a crystalline thin film,
The use of high frequency alone did not lead to an improvement in crystallinity, and it was difficult to form a thin film with good crystallinity such as an improvement in crystallinity of the thin film in the p-layer and the n-layer and an increase in the crystal grain size in the i-layer.

【００１０】また、パルス放電による薄膜形成は非晶質
薄膜には適用されているが、結晶性薄膜には適用されて
いないのが現状である。Further, thin film formation by pulse discharge has been applied to amorphous thin films, but has not been applied to crystalline thin films at present.

【００１１】そこで、本発明は、上記に鑑み、ＲＦとマ
イクロ波との間に位置するＶＨＦ帯の高高周波およびパ
ルス放電を併用することにより、太陽電池等における変
換効率の向上を目指して高品質かつ結晶性の良好な薄膜
を形成することを目的とする。[0011] In view of the above, the present invention aims at improving the conversion efficiency in a solar cell or the like by using both high frequency and pulse discharge in the VHF band located between RF and microwave. Another object is to form a thin film having good crystallinity.

【００１２】[0012]

【課題を解決するための手段】本発明による課題解決手
段は、プラズマＣＶＤ法を用い、ＶＨＦ帯の高高周波電
力を印加しながらパルス放電を行って基板上に結晶性薄
膜を形成するものであり、薄膜の結晶性を改善する。特
に、プラズマＣＶＤ装置で使用する高高周波のパルス変
調電源の電源周波数を２７．１２ＭＨｚ〜８１．３６Ｍ
Ｈｚとすることにより、ＲＦ帯の電源周波数を使用する
よりも暗導電率が増加し、また連続放電よりもパルス放
電することによっても、暗導電率が増加する。The object of the present invention is to form a crystalline thin film on a substrate by performing a pulse discharge while applying a high frequency power in a VHF band by using a plasma CVD method. Improve the crystallinity of the thin film. In particular, the power supply frequency of the high-frequency pulse modulation power supply used in the plasma CVD apparatus is 27.12 MHz to 81.36 M
When the frequency is set to Hz, the dark conductivity is increased as compared with the case of using the power supply frequency in the RF band, and the dark conductivity is increased by performing pulse discharge rather than continuous discharge.

【００１３】これにより、従来の薄膜形成方法では困難
であった結晶性Ｓｉ薄膜のｐ層およびｎ層での光の吸収
損失の低減を図れて薄膜結晶性の向上となり、またｉ層
での結晶粒径拡大といった結晶性の良好な薄膜形成が可
能となる。As a result, the absorption loss of light in the p-layer and the n-layer of the crystalline Si thin film, which has been difficult with the conventional thin film forming method, can be reduced, and the crystallinity of the thin film can be improved. It is possible to form a thin film having good crystallinity such as an increase in particle size.

【００１４】そこで、これを薄膜太陽電池の製造に適用
すると、高品質かつ結晶性の良好な薄膜が得られ、太陽
電池の短絡電流値が増大し、長波長光の吸収が増加し
て、高効率な太陽電池の実現が可能となる。Therefore, when this is applied to the production of a thin-film solar cell, a thin film of high quality and good crystallinity is obtained, the short-circuit current value of the solar cell is increased, and the absorption of long wavelength light is increased. An efficient solar cell can be realized.

【００１５】[0015]

【発明の実施の形態】本発明の実施形態に係る結晶性Ｓ
ｉ薄膜のｐ層またはｎ層の形成方法を説明する。本発明
では、プラズマＣＶＤ法を用い、ＶＨＦ帯の高高周波電
力を印加しながらパルス放電を行って基板上に結晶性薄
膜を形成する。まず、周知のプラズマＣＶＤ装置には高
高周波（ＶＨＦ帯）のパルス変調電源を接続する。高高
周波として、ＲＦ帯より高い１３．５６ＭＨｚから３０
０ＭＨｚの電源周波数を使用する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Crystalline S according to an embodiment of the present invention
A method for forming the p layer or the n layer of the i thin film will be described. In the present invention, a crystalline thin film is formed on a substrate by performing pulse discharge while applying high-frequency power in a VHF band by using a plasma CVD method. First, a high-frequency (VHF band) pulse modulation power supply is connected to a known plasma CVD apparatus. As high frequency, from 13.56 MHz higher than RF band to 30
Use a power supply frequency of 0 MHz.

【００１６】まず、結晶性ｐ層を形成する場合、基板温
度２００度、シラン／水素＝１／１００（あるいはＳｉ
Ｈ4とＣＨ4との混合ガス）、Ｂ2Ｈ6ガス＝０．５％、圧
力０．３Ｔｏｒｒ，電源周波数８１．３６ＭＨｚ、パワ
ー３０Ｗ、パルス放電のパルス幅（ｄｕｔｙ＝ＯＮ時間
／（ＯＮ時間＋ＯＦＦ時間））３８％とする。これによ
って形成した結晶性ｐ層の暗導電率としては５Ｓ／ｃｍ
が得られた。First, when a crystalline p-layer is formed, the substrate temperature is 200 ° C., and silane / hydrogen = 1/100 (or Si
Mixed gas of H 4 and CH 4), B 2 H 6 gas is 0.5% pressure 0.3 Torr, power supply frequency 81.36MHz, power 30 W, pulse discharge pulse width (duty = ON time / (ON time + OFF time)) 38%. The dark conductivity of the crystalline p-layer thus formed is 5 S / cm.
was gotten.

【００１７】ここで、パルス放電のパルス幅に対する薄
膜特性の一連の検討として、基板温度、ガス流量、圧
力、電源周波数、パワーを一定にしたままパルス幅（ｄ
ｕｔｙ）を変化させた。表１にパルス幅を変化させた
Ａ，Ｂ，Ｃ，Ｄの薄膜形成条件を示し、そして薄膜特性
としてｐ層の暗導電率を測定した結果を図１に示す。図
１より、連続放電（ｄｕｔｙ＝１００％）を行ったＤよ
りパルス放電を行ったＡ，Ｂ，Ｃでは、暗導電率が向上
することがわかる。特に、ｄｕｔｙ＝４０〜８０％にお
いて、その効果は顕著である。Here, as a series of studies on the characteristics of the thin film with respect to the pulse width of the pulse discharge, the pulse width (d) is kept constant while the substrate temperature, gas flow rate, pressure, power supply frequency and power are kept constant.
uty) was changed. Table 1 shows the conditions for forming the thin films of A, B, C, and D with the pulse width changed, and FIG. 1 shows the results of measuring the dark conductivity of the p-layer as a thin film characteristic. From FIG. 1, it is understood that dark conductivity is improved in A, B, and C in which pulse discharge is performed than D in which continuous discharge (duty = 100%) is performed. In particular, when the duty is 40 to 80%, the effect is remarkable.

【００１８】[0018]

【表１】 [Table 1]

【００１９】次に、表２に示すパルス幅（ｄｕｔｙ＝１
００％）を一定にして電源周波数を変化させたＥ，Ｆ，
Ｇに対して、ｐ層の暗導電率を測定した結果を図２に示
す。図２より、電源周波数はＲＦ帯（１３．５６ＭＨ
ｚ）のＧよりはＶＨＦ帯のＤ，Ｅ，Ｆにおいて特性が向
上することがわかる。なお、Ｄは表１のものと同じであ
る。特に、２７．１２〜８１．３６ＭＨｚの範囲、その
中でも電源周波数が高いほど暗導電率が高くなる。した
がって、高高周波電力を印加しながらパルス放電を行う
ことにより、薄膜結晶性が向上し、特に電源周波数を高
く、パルス幅が短いほど結晶性の向上が顕著となる。Next, the pulse width (duty = 1) shown in Table 2 is used.
00%) and changing the power supply frequency, E, F,
FIG. 2 shows the results of measuring the dark conductivity of the p layer with respect to G. From FIG. 2, the power supply frequency is in the RF band (13.56 MHz).
It can be seen that the characteristics are improved in D, E, and F in the VHF band rather than G in z). D is the same as that in Table 1. In particular, the dark conductivity increases as the power supply frequency increases in the range of 27.12 to 81.36 MHz. Therefore, by performing pulse discharge while applying high-frequency power, the crystallinity of the thin film is improved. In particular, the higher the power supply frequency and the shorter the pulse width, the more remarkable the crystallinity.

【００２０】[0020]

【表２】 [Table 2]

【００２１】また、結晶性ｎ層を形成する場合は、上記
結晶性ｐ層の形成条件においてＢ2Ｈ6ガスの代わりにＰ
Ｈ3ガスを原料ガスの０．５％程度導入する。他の条件
は同じである。薄膜特性はｐ層の場合と同様、電源周波
数が高くパルス幅が短い程薄膜下での結晶性が向上す
る。[0021] In the case of forming a crystalline n-layer, P instead of B 2 H 6 gas in the formation conditions of the crystallinity p layer
H 3 gas is introduced at about 0.5% of the source gas. Other conditions are the same. As in the case of the p-layer, the higher the power supply frequency and the shorter the pulse width, the better the crystallinity under the thin film.

【００２２】ところで一般的に、高高周波技術は非晶質
薄膜の成膜速度の向上に効果があり、またパルス放電は
非晶質薄膜の形成時に発生するパウダーを抑制する効果
がある。しかしながら、結晶性Ｓｉ薄膜の形成技術はこ
れらの非晶質薄膜の形成技術とは異なる技術が必要であ
る。すなわち、結晶性Ｓｉ薄膜の形成にはプラズマ密度
と電子温度の両方を高くすることが重要であることを本
発明者は見いだした。プラズマ密度を向上するためには
高高周波の適用が効果的であり、他研究機関から結晶性
の改善の報告もあるが、高高周波だけではプラズマ密度
は上がるが電子温度は低下する。そこで、結晶性をさら
に改善するために、本発明者は電子温度に着目して、パ
ルス放電を併用することにより大幅な結晶性の改善を図
ることに成功した。パルス放電においては図３に示すよ
うに、放電開始数十マイクロ秒（μｓ）は過渡的に電子
温度が高い状態にあり、この特性を利用することにより
電子温度を上昇させることができ、結晶性の改善を図る
ことが可能となった。In general, high-frequency technology has an effect on improving the film forming rate of an amorphous thin film, and pulse discharge has an effect on suppressing powder generated at the time of forming an amorphous thin film. However, a technique for forming a crystalline Si thin film requires a technique different from those for forming these amorphous thin films. That is, the present inventor has found that it is important to increase both the plasma density and the electron temperature in forming a crystalline Si thin film. In order to improve the plasma density, it is effective to use a high frequency, and there are reports from other research institutes on the improvement of the crystallinity. However, the high frequency alone increases the plasma density but decreases the electron temperature. Then, in order to further improve the crystallinity, the present inventor succeeded in remarkably improving the crystallinity by using pulse discharge together with focusing on the electron temperature. In the pulse discharge, as shown in FIG. 3, the electron temperature is transiently high for several tens of microseconds (μs), and the electron temperature can be increased by using this characteristic, and the crystallinity can be increased. It became possible to improve.

【００２３】また、パルス放電の効果として、上記のよ
うに電子温度を上昇させる効果とともに堆積速度を自由
に制御でき、これによっても結晶性の改善に効果を与え
ている。電子温度の上昇のためプラズマに投入するパワ
ーを増大させることが大きなポイントとなるが、これは
成膜速度を大きくする影響を与える。しかし、成膜速度
が大きくなると、一般に結晶性は低下する。そのため、
成膜速度が大きくなりすぎないように、パルスのＯＮ時
間を長くしすぎたり、パルス幅を大きくしすぎないとい
ったパルスの間隔の制御を行うことが重要である。成膜
速度の目安としては約１Å／秒となる。以上のような２
点の効果に基づいて、パルス放電を行うことによって従
来の連続放電よりも結晶性の良好な薄膜を得ることが可
能となる。しかも、パルス放電を行うことにより、パウ
ダーの発生も当然抑制できるので、高品質な薄膜を形成
できる。As an effect of the pulse discharge, the deposition rate can be freely controlled together with the effect of increasing the electron temperature as described above, and this also has an effect on improving the crystallinity. An important point is to increase the power supplied to the plasma to increase the electron temperature, but this has the effect of increasing the deposition rate. However, as the deposition rate increases, the crystallinity generally decreases. for that reason,
It is important to control the pulse interval such that the ON time of the pulse is not too long or the pulse width is not too large so that the film formation rate does not become too high. The standard of the film forming speed is about 1 / sec. 2 as above
By performing the pulse discharge based on the effect of the point, it becomes possible to obtain a thin film having better crystallinity than the conventional continuous discharge. In addition, by performing pulse discharge, generation of powder can be naturally suppressed, so that a high-quality thin film can be formed.

【００２４】次に、結晶性Ｓｉ薄膜のｉ層の形成方法を
説明する。まず、プラズマＣＶＤ装置には高高周波（Ｖ
ＨＦ帯）のパルス変調電源を接続する。結晶性ｉ層を形
成する場合、表３のＨに示すように、基板温度２３０
度、シラン／水素＝１／１００、圧力０．２Ｔｏｒｒ、
パワー１００Ｗ、電源周波数８１．３６ＭＨｚ、パルス
幅（ｄｕｔｙ）９％で成膜を行う。なお、表３中、Ｉは
ＲＦ電源を用い、連続放電によって結晶性ｉ層を形成す
る場合の薄膜形成条件である。Next, a method for forming the i-layer of the crystalline Si thin film will be described. First, a high frequency (V
(HF band) pulse modulation power supply is connected. When the crystalline i-layer is formed, as shown in Table 3H, the substrate temperature 230
Degree, silane / hydrogen = 1/100, pressure 0.2 Torr,
Film formation is performed at a power of 100 W, a power supply frequency of 81.36 MHz, and a pulse width (duty) of 9%. In Table 3, I is a thin film forming condition when a crystalline i-layer is formed by continuous discharge using an RF power source.

【００２５】そして、Ｉの場合、ｉ層は非常に微小な微
結晶粒（直径約３００Å）の集合体であったが、本発明
のＨの場合、粒径５００Å（Ｘ線測定）、厚さ４μｍの
柱状構造の結晶性Ｓｉ薄膜を得た。このように、ｉ層の
結晶粒径の拡大が図れることにより、長波長光の吸収が
増加することになり、長波長感度の向上を達成できる。In the case of I, the i-layer was an aggregate of very fine crystal grains (about 300 ° in diameter). In the case of H of the present invention, the particle size was 500 ° (measured by X-ray) and the thickness was A crystalline Si thin film having a columnar structure of 4 μm was obtained. As described above, by increasing the crystal grain size of the i-layer, the absorption of long-wavelength light increases, and the long-wavelength sensitivity can be improved.

【００２６】[0026]

【表３】 [Table 3]

【００２７】次に、本発明の薄膜形成方法を適用した薄
膜太陽電池を図４に示す。この薄膜太陽電池は、透光性
絶縁基板１の上に順に積層された透明導電膜２、結晶性
ｐ層３、非晶質ｉ層４、非晶質ｎ層５および裏面電極６
からなる。Next, a thin-film solar cell to which the thin-film forming method of the present invention is applied is shown in FIG. This thin-film solar cell includes a transparent conductive film 2, a crystalline p-layer 3, an amorphous i-layer 4, an amorphous n-layer 5, and a back electrode 6, which are sequentially laminated on a translucent insulating substrate 1.
Consists of

【００２８】ここで、本実施形態の薄膜太陽電池の特徴
は、図５に示す従来構造の太陽電池の非晶質ｐ層７のａ
−ＳｉＣの代わりに結晶性の良好な結晶性ｐ層３を用い
るところにある。以下、この太陽電池の製造方法を説明
する。まず、透光性絶縁基板１として厚さ１ｍｍ程度の
ガラス基板を用いる。ここではガラスを用いているが、
透光性絶縁基板１であれば、高分子フィルムであっても
かまわない。この上にＣＶＤ法等により透明導電膜２を
約１μｍの膜厚で形成する。この透明導電膜２は凹凸状
の形状であることが望ましく、またその材料としてはＺ
ｎＯ、またはＺｎＯを表面に少なくとも数１０ｎｍコー
トしたＳｎＯ2およびＩＴＯが望ましい。これは結晶性
ｐ層３を形成するときにＴＣＯ（透明導電性酸化物膜）
に与えるプラズマダメージを避けるためである。Here, the feature of the thin-film solar cell of the present embodiment is that the amorphous p-layer 7 of the conventional solar cell shown in FIG.
-The point is that a crystalline p-layer 3 having good crystallinity is used instead of -SiC. Hereinafter, a method for manufacturing this solar cell will be described. First, a glass substrate having a thickness of about 1 mm is used as the translucent insulating substrate 1. Here, glass is used,
As long as it is a translucent insulating substrate 1, it may be a polymer film. A transparent conductive film 2 is formed thereon with a thickness of about 1 μm by a CVD method or the like. The transparent conductive film 2 is desirably in an uneven shape.
It is desirable to use SnO 2 or ITO whose surface is coated with nO or ZnO at least several tens nm. This is because when forming the crystalline p-layer 3, TCO (transparent conductive oxide film)
This is to avoid plasma damage to the device.

【００２９】透明導電膜２の上にプラズマＣＶＤ法等の
方法で高高周波パルス放電を用いて結晶性ｐ層３が形成
される。形成条件は表１中のＡと同じ、基板温度２００
度、シラン／水素＝１／１００、Ｂ2Ｈ6ガス＝０．５
％、圧力０．３Ｔｏｒｒ、パワー３０Ｗ、電源周波数８
１．３６ＭＨｚ、パルス幅３８％で成膜を行う。結晶性
ｐ層３の膜厚は１０ｎｍから３０ｎｍ程度が望ましい。
これは厚すぎると光の吸収損失が大きくなるためであ
る。なお、結晶性ｐ層３はカーボンを含んでいてもよ
く、ｐ層側から光照射が行われる場合にｐ層３内での光
吸収をより少なくすることができ、ｉ層４への到達光が
増加するので、変換効率が増大する。A crystalline p layer 3 is formed on the transparent conductive film 2 by using a high frequency pulse discharge by a method such as a plasma CVD method. The formation conditions were the same as A in Table 1;
Degree, silane / hydrogen = 1/100, B 2 H 6 gas = 0.5
%, Pressure 0.3 Torr, power 30 W, power frequency 8
Film formation is performed at 1.36 MHz and a pulse width of 38%. The thickness of the crystalline p-layer 3 is preferably about 10 nm to 30 nm.
This is because light absorption loss increases when the thickness is too large. The crystalline p-layer 3 may contain carbon, and when light is irradiated from the p-layer side, light absorption in the p-layer 3 can be further reduced, and light reaching the i-layer 4 can be reduced. , The conversion efficiency increases.

【００３０】結晶性ｐ層３の上には、ＣＶＤ法等により
ａ−Ｓｉ：Ｈのｉ層４、ａ−Ｓｉ：Ｈのｎ層５が順次積
層される。なお、ｉ層４にはａ−ＳｉＧｅ：Ｈのｉ層や
ａ−ＳｉＣ：Ｈのｉ層のような合金層でもよい。ｉ層４
の膜厚は１００ｎｍから６００ｎｍ程度が望ましい。ま
た、ａ−Ｓｉ：Ｈのｎ層５は結晶性ｎ層でもよい。ｎ層
５の膜厚は数１０ｎｍである。On the crystalline p layer 3, an i-layer 4 of a-Si: H and an n-layer 5 of a-Si: H are sequentially laminated by a CVD method or the like. The i-layer 4 may be an alloy layer such as an i-layer of a-SiGe: H or an i-layer of a-SiC: H. i layer 4
Is desirably about 100 nm to 600 nm. Further, the a-Si: H n layer 5 may be a crystalline n layer. The thickness of the n-layer 5 is several tens nm.

【００３１】次に裏面電極６は、反射率の比較的高い金
属であるＡｌやＡｇを用いて、真空蒸着法等により形成
する。膜厚としては数１００ｎｍから１μｍ程度であ
る。簡素化して裏面電極６を金属電極のみとしている
が、裏面での反射光を有効に利用するために、透明導電
膜をａ−Ｓｉ：Ｈのｎ層５と裏面電極６の間に形成して
もよい。Next, the back electrode 6 is formed by using a metal having a relatively high reflectivity, such as Al or Ag, by a vacuum deposition method or the like. The thickness is about several hundred nm to about 1 μm. For simplicity, only the metal electrode is used as the back electrode 6, but a transparent conductive film is formed between the n-layer 5 of a-Si: H and the back electrode 6 in order to effectively use the light reflected on the back surface. Is also good.

【００３２】本発明の薄膜形成方法により作製した単層
の薄膜太陽電池の特性は、ＡＭ１．５（１００ｍＷ／ｃ
ｍ2）においてＩｓｃ：１９．１ｍＡ／ｃｍ2、Ｖｏｃ：
０．９２Ｖ、Ｆ．Ｆ．：０．７３、Ｐｍａｘ：１２．８
ｍＷ／ｃｍ2である。The characteristics of the single-layer thin-film solar cell manufactured by the thin-film forming method of the present invention are as follows: AM1.5 (100 mW / c
m 2 ), Isc: 19.1 mA / cm 2 , Voc:
0.92V, F.I. F. : 0.73, Pmax: 12.8
mW / cm 2 .

【００３３】なお、本実施形態の太陽電池は光電変換層
が単層であるが、ａ−ＳｉＧｅ：Ｈのｉ層やａ−Ｓｉ
Ｃ：Ｈのｉ層のような合金層を用いて、タンデム構造あ
るいはトリプル構造のように積層されたものでもよい。Although the solar cell of this embodiment has a single photoelectric conversion layer, the i-layer of a-SiGe: H or the a-Si
It may be stacked like a tandem structure or a triple structure using an alloy layer such as an i layer of C: H.

【００３４】他の実施形態の薄膜太陽電池を図６に示
す。この薄膜太陽電池は、透光性絶縁基板１の上に順に
積層された透明導電膜２、結晶性ｐ層３、結晶性ｉ層
８、結晶性ｎ層９および裏面電極６からなる。FIG. 6 shows a thin-film solar cell according to another embodiment. This thin-film solar cell includes a transparent conductive film 2, a crystalline p-layer 3, a crystalline i-layer 8, a crystalline n-layer 9, and a back electrode 6, which are sequentially laminated on a translucent insulating substrate 1.

【００３５】以下、この太陽電池の製造方法を説明する
が、上記実施形態の太陽電池のものとｉ層およびｎ層を
除いて同じである。まず、透光性絶縁基板１として厚さ
１ｍｍ程度のガラス基板を用いる。この上に透明導電膜
２を約１μｍの膜厚で形成する。透明導電膜２の上にプ
ラズマＣＶＤ法等の方法で高高周波パルス放電により、
表１中のＡと同じ形成条件で結晶性ｐ層３を形成する。
結晶性ｐ層３の膜厚は１０ｎｍから３０ｎｍ程度が望ま
しい。結晶性ｐ層３の上には結晶性ｉ層８、結晶性ｎ層
９が順次積層される。ｉ層８の膜厚は４μｍ程度が望ま
しい。ｉ層８の形成条件としては表３中のＨと同じ、基
板温度２３０度、シラン／水素＝１／１００、圧力０．
２Ｔｏｒｒ、パワー１００Ｗ、電源周波数８１．３６Ｍ
Ｈｚ、パルス幅９％で成膜を行う。ｎ層９の形成条件と
しては、基板温度２００度、シラン／水素＝１／１０
０、ＰＨ3ガス＝０．５％、圧力０．２Ｔｏｒｒ、パワ
ー２５Ｗ、電源周波数８１．３６ＭＨｚ、パルス幅３８
％（ＯＮ時間３０μｓ、ＯＦＦ時間５０μｓ）で成膜を
行う。ｎ層９の膜厚は数１０ｎｍである。次に裏面電極
６を形成する。裏面電極６は反射率の比較的高い金属で
あるＡｌやＡｇを用いている。膜厚としては数１００ｎ
ｍから１μｍ程度である。なお、各層３，８，９の高高
周波パルス放電に関する形成条件を表４にまとめて示し
ている。Hereinafter, a method for manufacturing this solar cell will be described, which is the same as that of the solar cell of the above embodiment except for the i-layer and the n-layer. First, a glass substrate having a thickness of about 1 mm is used as the translucent insulating substrate 1. A transparent conductive film 2 is formed thereon with a thickness of about 1 μm. On the transparent conductive film 2, a high-frequency pulse discharge is performed by a method such as a plasma CVD method.
The crystalline p-layer 3 is formed under the same forming conditions as A in Table 1.
The thickness of the crystalline p-layer 3 is preferably about 10 nm to 30 nm. A crystalline i-layer 8 and a crystalline n-layer 9 are sequentially stacked on the crystalline p-layer 3. The thickness of the i-layer 8 is preferably about 4 μm. The conditions for forming the i-layer 8 were the same as those of H in Table 3, that is, the substrate temperature was 230 ° C., silane / hydrogen = 1/100, and the pressure was 0.
2 Torr, power 100W, power frequency 81.36M
The film is formed at a frequency of 9 Hz and a pulse width of 9%. The conditions for forming the n-layer 9 include a substrate temperature of 200 ° C. and silane / hydrogen = 1/10.
0, PH 3 gas = 0.5%, pressure 0.2 Torr, power 25 W, power supply frequency 81.36 MHz, pulse width 38
% (ON time 30 μs, OFF time 50 μs). The thickness of the n-layer 9 is several tens nm. Next, the back electrode 6 is formed. The back electrode 6 is made of a metal having a relatively high reflectance, such as Al or Ag. Several hundred n in film thickness
m to about 1 μm. Table 4 summarizes the conditions for forming the high-frequency pulse discharge of each of the layers 3, 8, and 9.

【００３６】[0036]

【表４】 [Table 4]

【００３７】上記の薄膜形成方法により作製した単層の
薄膜太陽電池の特性は、ＡＭ１．５（１００ｍＷ／ｃｍ
2）において、Ｉｓｃ：２８．１ｍＡ／ｃｍ2、Ｖｏｃ：
０．５７Ｖ、Ｆ．Ｆ．：０．６４、Ｐｍａｘ：１０．３
ｍＷ／ｃｍ2である。The characteristics of the single-layer thin-film solar cell manufactured by the above-mentioned thin-film forming method are AM1.5 (100 mW / cm).
2 ) In Isc: 28.1 mA / cm 2 , Voc:
0.57 V, F.I. F. : 0.64, Pmax: 10.3
mW / cm 2 .

【００３８】なお、この太陽電池では光電変換層が単層
であるが、ａ−Ｓｉあるいはａ−ＳｉＧｅセルを上部セ
ルとして用い、この結晶性薄膜Ｓｉセルを下部セルとし
て用いることにより、さらに高い効率が期待される。ま
た、ａ−Ｓｉ／ａ−ＳｉＧｅ／結晶性薄膜Ｓｉの３層構
造としても効果的である。Although the photoelectric conversion layer is a single layer in this solar cell, higher efficiency can be obtained by using an a-Si or a-SiGe cell as an upper cell and using this crystalline thin film Si cell as a lower cell. There is expected. It is also effective as a three-layer structure of a-Si / a-SiGe / crystalline thin film Si.

【００３９】なお、本発明は、上記実施形態に限定され
るものではなく、本発明の範囲内で上記実施形態に多く
の修正および変更を加え得ることは勿論である。例え
ば、上記実施形態の太陽電池とは逆に、透光性絶縁基板
の上にｎ層、ｉ層、ｐ層の順に積層して光電変換活性層
を形成した構造の薄膜太陽電池としてもよい。この場
合、結晶性ｎ層はカーボンを含んでいてもよい。It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that many modifications and changes can be made to the above-described embodiment within the scope of the present invention. For example, contrary to the solar cell of the above embodiment, a thin-film solar cell having a structure in which a photoelectric conversion active layer is formed by stacking an n-layer, an i-layer, and a p-layer in this order on a light-transmitting insulating substrate may be used. In this case, the crystalline n-layer may contain carbon.

【００４０】[0040]

【発明の効果】以上の説明から明らかな通り、本発明に
よると、ＶＨＦ帯の高高周波にパルス放電を加えること
により、パウダーの発生が抑制されて欠陥の少ない高品
質で、かつ導電率の低下しない結晶性の良好な薄膜を形
成することができる。As is apparent from the above description, according to the present invention, by applying a pulse discharge to a high frequency in the VHF band, powder generation is suppressed, high quality with few defects, and a decrease in conductivity. A thin film with good crystallinity can be formed.

【００４１】このように、Ｓｉ薄膜の結晶性の向上を達
成できることにより、ｐ層およびｎ層での光の吸収損失
が少なくなるので、ｉ層への到達光の増加により短絡電
流値が向上し、しかも高い開放電圧が得られる。また、
ｉ層での結晶粒径の大型化を図れ、長波長光の吸収を増
加させることができる。したがって、長波長感度の向上
および変換効率の向上となり、高効率な薄膜太陽電池の
実現が可能となる。As described above, since the crystallinity of the Si thin film can be improved, the absorption loss of light in the p-layer and the n-layer is reduced, and the short-circuit current value is improved by increasing the light reaching the i-layer. In addition, a high open-circuit voltage can be obtained. Also,
The crystal grain size in the i-layer can be increased, and absorption of long-wavelength light can be increased. Therefore, the long-wavelength sensitivity and the conversion efficiency are improved, and a highly efficient thin-film solar cell can be realized.

【図面の簡単な説明】[Brief description of the drawings]

【図１】暗導電率に対する高高周波下でのパルス放電の
効果を示す図FIG. 1 shows the effect of pulse discharge under high frequency on dark conductivity.

【図２】暗導電率に対する電源周波数の影響を示す図FIG. 2 is a diagram showing an influence of a power supply frequency on dark conductivity.

【図３】パルス放電における高周波入力後の電子温度の
時間的変化を示す図FIG. 3 is a diagram showing a temporal change of an electron temperature after a high frequency input in a pulse discharge.

【図４】本発明の実施形態の太陽電池の構成を示す断面
図FIG. 4 is a cross-sectional view illustrating a configuration of a solar cell according to an embodiment of the present invention.

【図５】従来の太陽電池の構成を示す断面図FIG. 5 is a cross-sectional view showing a configuration of a conventional solar cell.

【図６】他の実施形態の太陽電池の構成を示す断面図FIG. 6 is a cross-sectional view illustrating a configuration of a solar cell according to another embodiment.

【符号の説明】[Explanation of symbols]

１ 透光性絶縁基板 ２ 透明導電膜 ３ 結晶性ｐ層 ４ 非晶質ｉ層 ５ 非晶質ｎ層 ６ 裏面電極 ７ 非晶質ｐ層 ８ 結晶性ｉ層 ９ 結晶性ｎ層 REFERENCE SIGNS LIST 1 translucent insulating substrate 2 transparent conductive film 3 crystalline p-layer 4 amorphous i-layer 5 amorphous n-layer 6 back electrode 7 amorphous p-layer 8 crystalline i-layer 9 crystalline n-layer

Claims (8)

【特許請求の範囲】[Claims] 【請求項１】 プラズマＣＶＤ法を用いた薄膜の形成方
法であって、ＶＨＦ帯の高高周波電力を印加しながらパ
ルス放電を行って基板上に結晶性薄膜を形成することを
特徴とする薄膜形成方法。1. A method for forming a thin film using a plasma CVD method, comprising forming a crystalline thin film on a substrate by performing pulse discharge while applying high-frequency power in a VHF band. Method. 【請求項２】 薄膜が結晶性Ｓｉからなるｐ層であるこ
とを特徴とする請求項１記載の薄膜形成方法。2. The method according to claim 1, wherein the thin film is a p-layer made of crystalline Si. 【請求項３】 薄膜が結晶性Ｓｉからなるｎ層であるこ
とを特徴とする請求項１記載の薄膜形成方法。3. The method according to claim 1, wherein the thin film is an n-layer made of crystalline Si. 【請求項４】 結晶性Ｓｉの薄膜はカーボンを含んでい
ることを特徴とする請求項２または３記載の薄膜形成方
法。4. The method according to claim 2, wherein the crystalline Si thin film contains carbon. 【請求項５】 薄膜が結晶性Ｓｉからなるｉ層であるこ
とを特徴とする請求項１記載の薄膜形成方法。5. The method according to claim 1, wherein the thin film is an i-layer made of crystalline Si. 【請求項６】 電源周波数が２７．１２ＭＨｚ〜８１．
３６ＭＨｚとされたことを特徴とする請求項１ないし５
のいずれかに記載の薄膜形成方法。6. A power supply frequency between 27.12 MHz and 81.12 MHz.
The frequency is set to 36 MHz.
The thin film forming method according to any one of the above. 【請求項７】 ｐ層、ｉ層、ｎ層が積層されてなる非晶
質Ｓｉ太陽電池において、各層のうち少なくとも１層に
請求項１記載の薄膜形成方法によって結晶性薄膜を形成
することを特徴とする太陽電池の製造方法。7. An amorphous Si solar cell comprising a p-layer, an i-layer and an n-layer laminated, wherein a crystalline thin film is formed on at least one of the layers by the thin-film forming method according to claim 1. A method for manufacturing a solar cell. 【請求項８】 ｐ層、ｉ層、ｎ層が積層されてなる薄膜
結晶Ｓｉ太陽電池において、各層のうち少なくとも１層
に請求項１記載の薄膜形成方法によって結晶性薄膜を形
成することを特徴とする太陽電池の製造方法。8. A thin-film crystalline Si solar cell in which a p-layer, an i-layer, and an n-layer are stacked, wherein a crystalline thin film is formed on at least one of the layers by the thin-film forming method according to claim 1. Solar cell manufacturing method.
JP9120410A 1997-05-12 1997-05-12 Formation of thin film Pending JPH10313125A (en)

Priority Applications (1)

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JP9120410A JPH10313125A (en) 1997-05-12 1997-05-12 Formation of thin film

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Application Number Priority Date Filing Date Title
JP9120410A JPH10313125A (en) 1997-05-12 1997-05-12 Formation of thin film

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JPH10313125A true JPH10313125A (en) 1998-11-24

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Family Applications (1)

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Cited By (7)

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JP2002151719A (en) * 2000-11-13 2002-05-24 Sharp Corp Thin-film solar cell and manufacturing method thereof
EP1505174A1 (en) * 2003-07-30 2005-02-09 Sharp Kabushiki Kaisha Manufacturing method of silicon thin film solar cell
JP2005183620A (en) * 2003-12-18 2005-07-07 Sharp Corp Method for manufacturing silicon thin film solar battery
US7041342B2 (en) * 1999-07-26 2006-05-09 Schott Glas Thin-film solar cells and method of making
JP2008004813A (en) * 2006-06-23 2008-01-10 Sharp Corp Silicon-based thin film photoelectric conversion element and manufacturing method and manufacturing apparatus therefor
WO2009037815A1 (en) * 2007-09-21 2009-03-26 Nissin Electric Co., Ltd. Photovoltaic device and method for manufacturing the same
WO2011116510A1 (en) * 2010-03-23 2011-09-29 福建钧石能源有限公司 Method for depositing thin film

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7041342B2 (en) * 1999-07-26 2006-05-09 Schott Glas Thin-film solar cells and method of making
JP2002151719A (en) * 2000-11-13 2002-05-24 Sharp Corp Thin-film solar cell and manufacturing method thereof
JP4674956B2 (en) * 2000-11-13 2011-04-20 シャープ株式会社 Thin film solar cell and manufacturing method thereof
EP1505174A1 (en) * 2003-07-30 2005-02-09 Sharp Kabushiki Kaisha Manufacturing method of silicon thin film solar cell
JP2005050905A (en) * 2003-07-30 2005-02-24 Sharp Corp Method for manufacturing silicon thin film solar cell
JP2005183620A (en) * 2003-12-18 2005-07-07 Sharp Corp Method for manufacturing silicon thin film solar battery
JP4497914B2 (en) * 2003-12-18 2010-07-07 シャープ株式会社 Method for producing silicon thin film solar cell
JP2008004813A (en) * 2006-06-23 2008-01-10 Sharp Corp Silicon-based thin film photoelectric conversion element and manufacturing method and manufacturing apparatus therefor
WO2009037815A1 (en) * 2007-09-21 2009-03-26 Nissin Electric Co., Ltd. Photovoltaic device and method for manufacturing the same
WO2011116510A1 (en) * 2010-03-23 2011-09-29 福建钧石能源有限公司 Method for depositing thin film

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