JP4197863B2 - Photovoltaic device manufacturing method - Google Patents

Photovoltaic device manufacturing method Download PDF

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JP4197863B2
JP4197863B2 JP2001298513A JP2001298513A JP4197863B2 JP 4197863 B2 JP4197863 B2 JP 4197863B2 JP 2001298513 A JP2001298513 A JP 2001298513A JP 2001298513 A JP2001298513 A JP 2001298513A JP 4197863 B2 JP4197863 B2 JP 4197863B2
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transparent conductive
conductive film
photovoltaic device
substrate
semiconductor layer
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JP2003101048A (en
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武志 山本
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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    • 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
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

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Description

【０００１】
【発明の属する技術分野】
本発明は、光起電力装置の製造方法に関し、特に、透明導電膜を形成する方法に関する。
【０００２】
【従来の技術】
ＨＩＴ（Heterojunction with Intrinsic Thin-layer）型の光起電力装置は、シリコンウエハ上に非晶質半導体層，透明導電膜，集電極を順次形成して構成され、シリコンウエハとは反対側から入射する光を主に利用した光起電力装置である。このＨＩＴ型光起電力装置は、結晶系の光起電力装置に比べて低温状態で製造プロセスが可能であり、低コスト化及び高変換効率化を図れる光起電力装置として期待されている。
【０００３】
１枚のシリコンウエハにて高い変換出力を得るためには、光電変換面積を増やすことが重要であり、そのために透明導電膜の形成面積をできる限り大きくすることが行われている。
【０００４】
【発明が解決しようとする課題】
このように透明導電膜の形成面積を大きくしようとした場合、シリコンウエハに形成された非晶質半導体層上に透明導電膜を形成する際に、非晶質半導体層が形成されていない部分にまで透明導電膜が形成されることがある。このような場合に、この余分に形成された透明導電膜とシリコンウエハとでリークが起こり、光電変換特性の劣化の原因となるという問題がある。
【０００５】
本発明は斯かる事情に鑑みてなされたものであり、形成した透明導電膜の端部に高抵抗化処理を施すことにより、上述したようなリークを防止でき、高い歩留りと高い変換特性とを実現できる光起電力装置の製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
第１発明に係る光起電力装置の製造方法は、基板上に半導体層、透明導電膜及び集電極がこの順に形成されており、主に前記集電極側から光を入射する光起電力装置を製造する方法において、前記基板上の中央部分に前記半導体層を形成し、前記半導体層上に前記透明導電膜を形成すると共に、前記基板の前記半導体層よりも外側の部分上に形成された前記透明導電膜に選択的に高抵抗化処理を施すことを特徴とする。
【０００７】
第１発明にあっては、基板上の中央部分に半導体層及び透明導電膜を形成した後、透明導電膜の中央の有効部分をマスキングして、基板の半導体層よりも外側の部分上に形成された透明導電膜を選択的に高抵抗化する。よって、半導体層の形成領域を越えて余分に透明導電膜が形成されても、その部分は高抵抗化されるため、基板とのリークは生じない。
【０００８】
第２発明に係る光起電力装置の製造方法は、第１発明において、前記高抵抗化処理は、酸素プラズマ処理であることを特徴とする。
【０００９】
第２発明にあっては、酸素プラズマ処理によって透明導電膜の端部のみを選択的に高抵抗化する。よって、容易に高抵抗化処理を行える。
【００１０】
第３発明に係る光起電力装置の製造方法は、第１発明において、前記高抵抗化処理は、酸素雰囲気中でのエネルギービーム照射処理であることを特徴とする。
【００１１】
第３発明にあっては、酸素雰囲気中でのエネルギービーム照射によって透明導電膜の端部のみを選択的に高抵抗化する。よって、容易に高抵抗化処理を行える。
【００１２】
【発明の実施の形態】
以下、本発明をその実施の形態を示す図面を参照して具体的に説明する。
（第１実施の形態）
図１は、第１実施の形態による光起電力装置の製造方法の工程図である。まず、約１Ω・ｃｍ，厚さ３００μｍのｎ型（１００）シリコンウエハを通常洗浄して、不純物を除去して基板１を準備する（図１（ａ））。
【００１３】
次に、基板１上の一方の表面に、プラズマＣＶＤ方法にて、ｉ型非晶質シリコン層２及びｐ型非晶質シリコン層３をこの順に形成する（図１（ｂ））。具体的には、公知のＲＦプラズマＣＶＤ装置（１３．５６ＭＨｚ）を用いて、基板温度：１００〜２５０℃，反応圧力：０．２〜０．６Ｔｏｒｒ，ＲＦパワー：１０〜１００Ｗ／ｃｍ2 の条件にて、ｉ型非晶質シリコン層２及びｐ型非晶質シリコン層３の夫々の膜厚を５０Å以下とした。
【００１４】
次に、ｐ型非晶質シリコン層３上に、スパッタ法にて、透明導電膜４を形成する（図１（ｃ））。具体的には、公知のマグネトロンスパッタ装置を用いて、基板温度：２５０℃以下，ガス流量：Ａｒが２００ｓｃｃｍ以下でＯ2 が５０ｓｃｃｍ以下，パワー：０．５〜３ｋＷの条件にて、膜厚１０００Å程度のＩＴＯ膜を形成した。ここで、形成した透明導電膜４の端部では、下地層（ｐ型非晶質シリコン層３／ｉ型非晶質シリコン層２）よりも外側の部分に起因する微小リークが発生し、光電変換特性低下の原因となる。
【００１５】
そこで、第１実施の形態では、酸素プラズマ処理により、透明導電膜４の端部（ハッチングを付した部分）のみに選択的に高抵抗化処理を施す（図１（ｄ））。具体的には、上記のＲＦプラズマＣＶＤ装置（１３．５６ＭＨｚ）を用いて、基板温度：２００℃，Ｏ2 ：２００ｓｃｃｍ，圧力：５０Ｐａ，パワー：３００ｍＷ／ｃｍ2 の条件にて酸素プラズマを発生させ、中央の有効部分をＳＵＳ，Ａｌ等の金属製のマスク材７にてマスキングして、透明導電膜４の端部にのみ酸素を選択的に導入して高抵抗化した。
【００１６】
図２は、ガラス基板上に形成したＩＴＯ膜（膜厚：１０００Å）に対して公知のＲＦプラズマＣＶＤ法による酸素プラズマ処理を行った場合のプラズマ処理時間とシート抵抗との関係を示すグラフである。図２のシート抵抗は、酸素プラズマ処理を行わなかった場合のシート抵抗に対する規格化値で表している。図２の結果から、プラズマ処理時間の増加に従ってシート抵抗が増加することを確認でき、この第１実施の形態における酸素プラズマ処理によって、透明導電膜４（ＩＴＯ膜）の端部を十分に高抵抗化できることが分かる。
【００１７】
最後に、透明導電膜４上に櫛形の集電極５及びバスバー電極をプラス側の電極として形成すると共に、基板１の裏面に裏面電極６をマイナス側の電極として形成して（図１（ｅ））、光起電力装置を製造する。具体的には、エポキシ樹脂にＡｇの微粉末を練り込んだＡｇペーストをスクリーン印刷法にて厚さ約１０〜３０μｍ，幅１００〜５００μｍにて透明導電膜４上に塗布した後、１５０〜２５０℃で焼成硬化させることにより、複数の互いに平行な枝部を有する櫛形の集電極５と集電極５に流れる電流を集合させるバスバー電極とを形成すると共に、基板１の裏面にＡｌを蒸着させて裏面電極６を形成した。
【００１８】
第１実施の形態にあって、透明導電膜４を形成した後に下地の非晶質半導体層（ｐ型非晶質シリコン層３／ｉ型非晶質シリコン層２）の形成領域の周囲１ｍｍ内側にマスキングを行い、上記の条件（基板温度：２００℃，Ｏ2 ：２００ｓｃｃｍ，圧力：５０Ｐａ，パワー：３００ｍＷ／ｃｍ2 ）にて、プラズマ処理の時間を変化させた複数種の光起電力装置を製造した。製造したこれらの光起電力装置について開放電圧Ｖocと曲線因子ＦＦとの積を測定した。図３は、酸素プラズマ処理時間とＶoc×ＦＦとの関係を示すグラフである。図３のＶoc×ＦＦの値は、酸素プラズマ処理を行わなかった場合のＶoc×ＦＦの値で規格化している。
【００１９】
図３の結果から、酸素プラズマ処理時間の増加に伴ってＶoc×ＦＦの値が改善されていることが分かる。これは、ＩＴＯ膜の端部が選択的に高抵抗化されたために、端部のリークに伴うＶoc×ＦＦが抑制されたことに起因する。上記プラズマ条件では、処理時間が１２０秒以上になった場合に、Ｖoc×ＦＦの値が変化しないことが分かるが、この特性（Ｖoc×ＦＦ）はプラズマ処理の条件及びＩＴＯの膜質に大きく影響されることは勿論である。
【００２０】
なお、プラズマ処理時にマスク材を用いなくてもよいように、端部領域に対応した開口型放電電極を用いて基板近傍のみにプラズマを生成させた場合でも、マスク材を使用した場合と同様の効果が得られることを確認した。
【００２１】
（第２実施の形態）
図４は、第２実施の形態による光起電力装置の製造方法の工程図である。第１実施の形態と同様に、ｎ型（１００）シリコンウエハからなる基板１を準備し（図４（ａ））、基板１上の一方の表面に、ｉ型非晶質シリコン層２及びｐ型非晶質シリコン層３をこの順に形成し（図４（ｂ））、ｐ型非晶質シリコン層３上に、透明導電膜４を形成する（図４（ｃ））。
【００２２】
次に、酸素雰囲気でのエネルギビーム照射により、透明導電膜４の端部（ハッチングを付した部分）のみに選択的に高抵抗化処理を施す（図４（ｄ））。具体的には、中央の有効部分をＳＵＳ，Ａｌ等の金属製のマスク材７にてマスキングし、形成した透明導電膜４の端部の非晶質半導体層の形成領域の周囲１ｍｍを含む外側部分にのみ酸素雰囲気中でエキシマレーザによってレーザビームを照射して、照射領域の高抵抗化を行った。
【００２３】
図５は、ガラス基板上に形成したＩＴＯ膜（膜厚：１０００Å）に対して酸素雰囲気中でのエキシマレーザビームによりレーザ処理を行った場合のレーザパワーとシート抵抗との関係を示すグラフである。図５のシート抵抗は、レーザ処理を行わなかった場合のシート抵抗に対する規格化値で表している。図５の結果から、レーザパワーの増加に従ってシート抵抗が増加することを確認でき、この第２実施の形態におけるレーザビーム照射によって、透明導電膜４（ＩＴＯ膜）の端部を十分に高抵抗化できることが分かる。
【００２４】
最後に、第１実施の形態と同様に、櫛形の集電極５及びバスバー電極と裏面電極６とを形成して（図４（ｅ））、光起電力装置を製造する。
【００２５】
第２実施の形態にあって、透明導電膜４を形成した後に下地の非晶質半導体層（ｐ型非晶質シリコン層３／ｉ型非晶質シリコン層２）の形成領域の周囲１ｍｍ内側にマスキングを行い、酸素雰囲気中でエキシマレーザビームを照射してその照射部に選択的に酸素を導入し、そのレーザパワーを変化させた複数種の光起電力装置を製造した。製造したこれらの光起電力装置について開放電圧Ｖocと曲線因子ＦＦとの積を測定した。図６は、レーザパワーとＶoc×ＦＦとの関係を示すグラフである。図６のＶoc×ＦＦの値は、レーザパワーを０．１Ｊ／ｃｍ2 とした場合のＶoc×ＦＦの値で規格化している。
【００２６】
図６の結果から、レーザパワーが０．２５Ｊ／ｃｍ2 である場合にＶoc×ＦＦの値が最も大きくなり、最適なレーザパワーが存在することが分かる。レーザパワーが強くなり過ぎると、下地の非晶質半導体層が微結晶化して新たなリーク成分となる。
【００２７】
なお、エキシマレーザビームの代わりに、他のエネルギビームを照射しても、また、スポット状プラズマによる処理を施しても、同様の効果が得られることを確認した。
【００２８】
（第３実施の形態）
夫々にｉ型非晶質シリコン層２／ｐ型非晶質シリコン層３及び透明導電膜４を形成した複数の基板１を積み重ねて、その積重体の最表面及び最裏面をダミーウエハを用いて固定治具にて覆った状態で、第１実施の形態による酸素プラズマ処理または第２実施の形態によるエキシマレーザビームの照射処理を行うことにより、各ウエハでの透明導電膜４の端部を高抵抗化できる。この第３実施の形態では、一度に複数枚のウエハに対する処理を行えるので、生産性が極めて高い。
【００２９】
なお、酸素プラズマ処理，エネルギビームの照射処理以外に、ＨＣｌ溶液への浸漬、または、ＨＣｌプラズマ処理によっても、透明導電膜４の端部の高抵抗化は可能である。また、半導体層として非晶質シリコンを用いる場合について説明したが、結晶系シリコンにて構成しても同様の効果を奏する。更に、透明導電膜４としてＩＴＯ膜を用いることとしたが、ＺｎＯ膜でも良いことは勿論である。。また、基板の裏面にｉ型非晶質シリコン，ｎ型非晶質シリコン，透明導電膜，集電極を形成した場合には、裏面側にも本発明を適用することができる。
【００３０】
【発明の効果】
以上のように本発明では、基板上に半導体層及び透明導電膜を形成した後、透明導電膜の中央の有効部分をマスキングして、端部のみを選択的に高抵抗化するようにしたので、基板と余分な透明導電膜とのリークを防止でき、高い歩留りと高い光電変換特性とを実現することができる。
【００３１】
また、酸素プラズマ処理または酸素雰囲気中でのエネルギービーム照射処理によって、透明導電膜の端部の高抵抗化を図るようにしたので、容易に高抵抗化処理を行うことができる。
【図面の簡単な説明】
【図１】第１実施の形態による光起電力装置の製造方法の工程図である。
【図２】第１実施の形態における酸素プラズマ処理時間とシート抵抗との関係を示すグラフである。
【図３】第１実施の形態における酸素プラズマ処理時間とＶoc×ＦＦとの関係を示すグラフである。
【図４】第２実施の形態による光起電力装置の製造方法の工程図である。
【図５】第２実施の形態におけるレーザパワーとシート抵抗との関係を示すグラフである。
【図６】第２実施の形態におけるレーザパワーとＶoc×ＦＦとの関係を示すグラフである。
【符号の説明】
１ 基板
２ ｉ型ａ−Ｓｉ層
３ ｐ型ａ−Ｓｉ層
４ 透明導電膜
５ 集電極
６ 裏面電極
７ マスク材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a photovoltaic device, and more particularly to a method for forming a transparent conductive film.
[0002]
[Prior art]
A HIT (Heterojunction with Intrinsic Thin-layer) type photovoltaic device is formed by sequentially forming an amorphous semiconductor layer, a transparent conductive film, and a collector electrode on a silicon wafer, and enters from the opposite side of the silicon wafer. It is a photovoltaic device mainly using light. This HIT type photovoltaic device can be manufactured at a lower temperature than a crystalline photovoltaic device, and is expected as a photovoltaic device capable of reducing cost and increasing conversion efficiency.
[0003]
In order to obtain a high conversion output with one silicon wafer, it is important to increase the photoelectric conversion area. For this reason, the formation area of the transparent conductive film is increased as much as possible.
[0004]
[Problems to be solved by the invention]
When an attempt is made to increase the formation area of the transparent conductive film in this way, when the transparent conductive film is formed on the amorphous semiconductor layer formed on the silicon wafer, the portion where the amorphous semiconductor layer is not formed is formed. A transparent conductive film may be formed. In such a case, there is a problem that leakage occurs between the excessively formed transparent conductive film and the silicon wafer, resulting in deterioration of photoelectric conversion characteristics.
[0005]
The present invention has been made in view of such circumstances, and by applying a high resistance treatment to the end portion of the formed transparent conductive film, leakage as described above can be prevented, and high yield and high conversion characteristics can be achieved. An object of the present invention is to provide a method for manufacturing a photovoltaic device that can be realized.
[0006]
[Means for Solving the Problems]
According to a first aspect of the present invention, there is provided a method for manufacturing a photovoltaic device comprising: a semiconductor layer, a transparent conductive film, and a collector electrode formed on a substrate in this order; In the manufacturing method, the semiconductor layer is formed in a central portion on the substrate, the transparent conductive film is formed on the semiconductor layer, and the substrate is formed on a portion outside the semiconductor layer of the substrate. A high resistance treatment is selectively performed on the transparent conductive film .
[0007]
In the first invention, after the semiconductor layer and the transparent conductive film are formed in the central portion on the substrate, the effective portion in the center of the transparent conductive film is masked and formed on the portion outside the semiconductor layer of the substrate. The resistance of the transparent conductive film is selectively increased. Therefore, even if an additional transparent conductive film is formed beyond the formation region of the semiconductor layer, the portion is increased in resistance, so that no leakage with the substrate occurs.
[0008]
According to a second aspect of the present invention, there is provided a method for producing a photovoltaic device according to the first aspect, wherein the high resistance treatment is an oxygen plasma treatment.
[0009]
In the second invention, only the end portion of the transparent conductive film is selectively increased in resistance by oxygen plasma treatment. Therefore, the resistance increasing process can be easily performed.
[0010]
According to a third aspect of the present invention, there is provided a method for manufacturing a photovoltaic device according to the first aspect, wherein the high resistance treatment is an energy beam irradiation treatment in an oxygen atmosphere.
[0011]
In the third invention, the resistance of only the end portion of the transparent conductive film is selectively increased by the energy beam irradiation in an oxygen atmosphere. Therefore, the resistance increasing process can be easily performed.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings showing embodiments thereof.
(First embodiment)
FIG. 1 is a process diagram of a method of manufacturing a photovoltaic device according to the first embodiment. First, an n-type (100) silicon wafer having a thickness of about 1 Ω · cm and a thickness of 300 μm is usually cleaned to remove impurities to prepare a substrate 1 (FIG. 1A).
[0013]
Next, an i-type amorphous silicon layer 2 and a p-type amorphous silicon layer 3 are formed in this order on one surface of the substrate 1 by a plasma CVD method (FIG. 1B). Specifically, using a known RF plasma CVD apparatus (13.56 MHz), conditions of substrate temperature: 100 to 250 ° C., reaction pressure: 0.2 to 0.6 Torr, RF power: 10 to 100 W / cm 2 Thus, the film thickness of each of the i-type amorphous silicon layer 2 and the p-type amorphous silicon layer 3 was set to 50 mm or less.
[0014]
Next, a transparent conductive film 4 is formed on the p-type amorphous silicon layer 3 by sputtering (FIG. 1C). Specifically, using a known magnetron sputtering apparatus, the substrate temperature is 250 ° C. or less, the gas flow rate is 200 sccm or less, the O 2 is 50 sccm or less, and the power is 0.5 to 3 kW. An ITO film of a degree was formed. Here, at the end of the formed transparent conductive film 4, a minute leak is generated due to a portion outside the base layer (p-type amorphous silicon layer 3 / i-type amorphous silicon layer 2), and the photoelectric layer This may cause deterioration of conversion characteristics.
[0015]
Therefore, in the first embodiment, only the end portion (hatched portion) of the transparent conductive film 4 is selectively subjected to high resistance treatment by oxygen plasma treatment (FIG. 1D). Specifically, using the above RF plasma CVD apparatus (13.56 MHz), oxygen plasma is generated under the conditions of the substrate temperature: 200 ° C., O 2 : 200 sccm, pressure: 50 Pa, power: 300 mW / cm 2. The central effective portion was masked with a metal mask material 7 such as SUS or Al, and oxygen was selectively introduced only into the end of the transparent conductive film 4 to increase the resistance.
[0016]
FIG. 2 is a graph showing the relationship between the plasma processing time and the sheet resistance when an oxygen plasma treatment by a known RF plasma CVD method is performed on an ITO film (film thickness: 1000 mm) formed on a glass substrate. . The sheet resistance in FIG. 2 is expressed as a normalized value with respect to the sheet resistance when oxygen plasma treatment is not performed. From the result of FIG. 2, it can be confirmed that the sheet resistance increases as the plasma processing time increases. By the oxygen plasma processing in the first embodiment, the end portion of the transparent conductive film 4 (ITO film) has a sufficiently high resistance. It can be seen that
[0017]
Finally, a comb-shaped collector electrode 5 and a bus bar electrode are formed as positive electrodes on the transparent conductive film 4, and a back electrode 6 is formed as a negative electrode on the back surface of the substrate 1 (FIG. 1 (e)). ) To manufacture photovoltaic devices. Specifically, an Ag paste obtained by kneading Ag fine powder in an epoxy resin is applied on the transparent conductive film 4 with a thickness of about 10 to 30 μm and a width of 100 to 500 μm by a screen printing method, and then 150 to 250. By baking and curing at 0 ° C., a plurality of comb-shaped collector electrodes 5 having mutually parallel branches and a bus bar electrode for collecting current flowing through the collector electrodes 5 are formed, and Al is evaporated on the back surface of the substrate 1. A back electrode 6 was formed.
[0018]
In the first embodiment, after the transparent conductive film 4 is formed, 1 mm inside the periphery of the formation region of the underlying amorphous semiconductor layer (p-type amorphous silicon layer 3 / i-type amorphous silicon layer 2) A plurality of types of photovoltaic devices in which the plasma treatment time was changed under the above conditions (substrate temperature: 200 ° C., O 2 : 200 sccm, pressure: 50 Pa, power: 300 mW / cm 2 ) Manufactured. The product of the open circuit voltage Voc and the fill factor FF was measured for these produced photovoltaic devices. FIG. 3 is a graph showing the relationship between the oxygen plasma processing time and Voc × FF. The value of Voc × FF in FIG. 3 is normalized by the value of Voc × FF when oxygen plasma treatment is not performed.
[0019]
From the result of FIG. 3, it can be seen that the value of Voc × FF is improved as the oxygen plasma treatment time increases. This is because the end portion of the ITO film is selectively increased in resistance, so that Voc × FF accompanying the end portion leakage is suppressed. Under the above plasma conditions, it can be seen that the value of Voc × FF does not change when the processing time exceeds 120 seconds, but this characteristic (Voc × FF) is greatly influenced by the conditions of plasma processing and the film quality of ITO. Of course.
[0020]
In addition, even when the plasma is generated only in the vicinity of the substrate using the opening-type discharge electrode corresponding to the end region so that the mask material does not have to be used at the time of the plasma processing, the same as when the mask material is used It was confirmed that an effect was obtained.
[0021]
(Second Embodiment)
FIG. 4 is a process diagram of a method for manufacturing a photovoltaic device according to the second embodiment. Similar to the first embodiment, a substrate 1 made of an n-type (100) silicon wafer is prepared (FIG. 4A), and an i-type amorphous silicon layer 2 and p are formed on one surface of the substrate 1. A type amorphous silicon layer 3 is formed in this order (FIG. 4B), and a transparent conductive film 4 is formed on the p type amorphous silicon layer 3 (FIG. 4C).
[0022]
Next, the high resistance treatment is selectively performed only on the end portion (hatched portion) of the transparent conductive film 4 by energy beam irradiation in an oxygen atmosphere (FIG. 4D). Specifically, the outside including 1 mm around the formation region of the amorphous semiconductor layer at the end of the transparent conductive film 4 formed by masking the central effective portion with a metal mask material 7 such as SUS or Al. Only the part was irradiated with a laser beam with an excimer laser in an oxygen atmosphere to increase the resistance of the irradiated region.
[0023]
FIG. 5 is a graph showing the relationship between laser power and sheet resistance when laser processing is performed on an ITO film (thickness: 1000 mm) formed on a glass substrate with an excimer laser beam in an oxygen atmosphere. . The sheet resistance in FIG. 5 is expressed as a normalized value with respect to the sheet resistance when laser processing is not performed. From the result of FIG. 5, it can be confirmed that the sheet resistance increases as the laser power increases, and the end of the transparent conductive film 4 (ITO film) is sufficiently increased in resistance by the laser beam irradiation in the second embodiment. I understand that I can do it.
[0024]
Finally, as in the first embodiment, the comb-shaped collector electrode 5, the bus bar electrode, and the back electrode 6 are formed (FIG. 4E) to manufacture the photovoltaic device.
[0025]
In the second embodiment, after the transparent conductive film 4 is formed, 1 mm inside the periphery of the formation region of the underlying amorphous semiconductor layer (p-type amorphous silicon layer 3 / i-type amorphous silicon layer 2) Were masked, irradiated with an excimer laser beam in an oxygen atmosphere, and oxygen was selectively introduced into the irradiated portion to produce a plurality of types of photovoltaic devices in which the laser power was changed. The product of the open circuit voltage Voc and the fill factor FF was measured for these produced photovoltaic devices. FIG. 6 is a graph showing the relationship between laser power and Voc × FF. The value of Voc × FF in FIG. 6 is normalized by the value of Voc × FF when the laser power is 0.1 J / cm 2 .
[0026]
From the results of FIG. 6, it can be seen that when the laser power is 0.25 J / cm 2 , the value of Voc × FF is the largest, and there is an optimum laser power. When the laser power becomes too strong, the underlying amorphous semiconductor layer is microcrystallized and becomes a new leak component.
[0027]
It has been confirmed that the same effect can be obtained by irradiating with another energy beam instead of the excimer laser beam or by processing with spot plasma.
[0028]
(Third embodiment)
A plurality of substrates 1 each formed with an i-type amorphous silicon layer 2 / p-type amorphous silicon layer 3 and a transparent conductive film 4 are stacked, and the top and bottom surfaces of the stacked body are fixed using a dummy wafer. The oxygen plasma treatment according to the first embodiment or the excimer laser beam irradiation treatment according to the second embodiment is performed in a state of being covered with a jig, whereby the end of the transparent conductive film 4 on each wafer is subjected to high resistance. Can be In the third embodiment, since a plurality of wafers can be processed at a time, productivity is extremely high.
[0029]
In addition to oxygen plasma treatment and energy beam irradiation treatment, the resistance of the end portion of the transparent conductive film 4 can be increased by immersion in HCl solution or HCl plasma treatment. Further, although the case where amorphous silicon is used as the semiconductor layer has been described, the same effect can be obtained even if it is composed of crystalline silicon. Further, although an ITO film is used as the transparent conductive film 4, it goes without saying that a ZnO film may be used. . In addition, when i-type amorphous silicon, n-type amorphous silicon, a transparent conductive film, and a collector electrode are formed on the back surface of the substrate, the present invention can also be applied to the back surface side.
[0030]
【The invention's effect】
As described above, in the present invention, after the semiconductor layer and the transparent conductive film are formed on the substrate, the effective portion at the center of the transparent conductive film is masked to selectively increase the resistance only at the end. In addition, leakage between the substrate and the extra transparent conductive film can be prevented, and high yield and high photoelectric conversion characteristics can be realized.
[0031]
Further, since the resistance of the end portion of the transparent conductive film is increased by the oxygen plasma process or the energy beam irradiation process in an oxygen atmosphere, the resistance increase process can be easily performed.
[Brief description of the drawings]
FIG. 1 is a process diagram of a method for manufacturing a photovoltaic device according to a first embodiment.
FIG. 2 is a graph showing a relationship between oxygen plasma processing time and sheet resistance in the first embodiment.
FIG. 3 is a graph showing the relationship between oxygen plasma processing time and Voc × FF in the first embodiment.
FIG. 4 is a process diagram of a method for manufacturing a photovoltaic device according to a second embodiment.
FIG. 5 is a graph showing the relationship between laser power and sheet resistance in the second embodiment.
FIG. 6 is a graph showing the relationship between laser power and Voc × FF in the second embodiment.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Substrate 2 i-type a-Si layer 3 p-type a-Si layer 4 Transparent conductive film 5 Collector electrode 6 Back electrode 7 Mask material

Claims (3)

基板上に半導体層、透明導電膜及び集電極がこの順に形成されており、主に前記集電極側から光を入射する光起電力装置を製造する方法において、前記基板上の中央部分に前記半導体層を形成し、前記半導体層上に前記透明導電膜を形成すると共に、前記基板の前記半導体層よりも外側の部分上に形成された前記透明導電膜に選択的に高抵抗化処理を施すことを特徴とする光起電力装置の製造方法。In a method of manufacturing a photovoltaic device in which a semiconductor layer, a transparent conductive film, and a collector electrode are formed in this order on a substrate, and light is incident mainly from the collector electrode side, the semiconductor is formed at a central portion on the substrate. Forming a layer , forming the transparent conductive film on the semiconductor layer, and selectively subjecting the transparent conductive film formed on a portion outside the semiconductor layer of the substrate to a high resistance treatment. A method of manufacturing a photovoltaic device characterized by the above. 前記高抵抗化処理は、酸素プラズマ処理である請求項１記載の光起電力装置の製造方法。  The method for manufacturing a photovoltaic device according to claim 1, wherein the high resistance treatment is an oxygen plasma treatment. 前記高抵抗化処理は、酸素雰囲気中でのエネルギービーム照射である請求項１記載の光起電力装置の製造方法。  The method for manufacturing a photovoltaic device according to claim 1, wherein the high resistance treatment is energy beam irradiation in an oxygen atmosphere.
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