JP2014183244A - Process of manufacturing cuprate thin film solar cell - Google Patents

Process of manufacturing cuprate thin film solar cell Download PDF

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JP2014183244A
JP2014183244A JP2013057569A JP2013057569A JP2014183244A JP 2014183244 A JP2014183244 A JP 2014183244A JP 2013057569 A JP2013057569 A JP 2013057569A JP 2013057569 A JP2013057569 A JP 2013057569A JP 2014183244 A JP2014183244 A JP 2014183244A
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semiconductor layer
type semiconductor
solar cell
thin film
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JP6108346B2 (en
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Takeo Oku
健夫 奥
Kazuya Fujimoto
和也 藤本
Takeshi Akiyama
毅 秋山
Atsushi Suzuki
厚志 鈴木
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University of Shiga Prefecture
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Abstract

PROBLEM TO BE SOLVED: To provide a process of manufacturing a cuprate thin film solar cell having light conversion efficiency higher than those of the conventional cuprate thin film solar cells.SOLUTION: A cuprate thin film solar cell 10 has a structure in which a first electrode 14, an n-type semiconductor layer 16, a p-type semiconductor layer 18, and a second electrode 20 are laminated on a substrate 12 in this order. The p-type semiconductor layer 18 is formed on the n-type semiconductor layer 16 by electrocrystallization. An alkaline solution containing a soluble copper salt is used for the electrocrystallization. PH of the alkaline solution is adjusted by LiOH.

Description

本発明はヘテロ接合型の銅酸化物薄膜太陽電池の製造方法に関するものである。   The present invention relates to a method for producing a heterojunction copper oxide thin film solar cell.

近年、化石燃料に代わる新エネルギーとして、ほとんど無尽蔵でクリーンな太陽光を電気に変えることができる太陽電池が注目されている。シリコン系の太陽電池が主流であるが、材料面や製造プロセス面から高価格である。太陽電池の普及のためには、低価格化が必要不可欠となっている。   In recent years, solar cells that can convert almost inexhaustible and clean sunlight into electricity have attracted attention as a new energy alternative to fossil fuels. Silicon-based solar cells are the mainstream, but they are expensive in terms of materials and manufacturing processes. For the spread of solar cells, it is indispensable to reduce the price.

そこで、安価で簡単に太陽電池を製造するために、シリコン系以外の太陽電池の開発も盛んにおこなわれている。例えば、下記の特許文献１には、酸化物半導体を使用した太陽電池が開示されている。酸化物半導体は、シリコン系の太陽電池に比べて、製造が簡単であり、安価である。さらに、酸化物半導体は、直接遷移半導体であり、光吸収スペクトルが大きい利点がある。例えば、銅酸化物半導体は、バンドギャップが太陽光のスペクトルに近く理想的であり、ＣｕＯであれば１．５ｅＶ、Ｃｕ２Ｏであれば２．１ｅＶである（図５参照）。図５は、電極にＩＴＯとＡｕを使用している。このため、太陽電池に適しており、バンドギャップの大きいＣｕ２Ｏ系太陽電池が注目されている。特許文献１には、ＮａＯＨでｐＨを１２．５に調整し、電析によってＣｕ２Ｏを形成することが開示されている。 Therefore, in order to easily and inexpensively manufacture solar cells, solar cells other than silicon-based solar cells have been actively developed. For example, Patent Document 1 below discloses a solar cell using an oxide semiconductor. An oxide semiconductor is easier to manufacture and less expensive than a silicon-based solar cell. Further, an oxide semiconductor is a direct transition semiconductor and has an advantage of a large light absorption spectrum. For example, a copper oxide semiconductor has an ideal band gap close to the spectrum of sunlight, and is 1.5 eV for CuO and 2.1 eV for Cu 2 O (see FIG. 5). In FIG. 5, ITO and Au are used for the electrodes. Therefore, suitable for solar cell, larger Cu 2 O-based solar cell bandgap has attracted attention. Patent Document 1 discloses that the pH is adjusted to 12.5 with NaOH and Cu 2 O is formed by electrodeposition.

しかし、銅酸化物半導体を使用した太陽電池は、シリコン系の太陽電池に比べて変換効率が低く、変換効率を高めることが求められる。   However, a solar cell using a copper oxide semiconductor has a lower conversion efficiency than a silicon-based solar cell, and is required to increase the conversion efficiency.

特開２００７−１９４６０号公報JP 2007-19460 A

本発明の目的は、従来の銅酸化物薄膜太陽電池に比べて光変換効率の高い銅酸化物薄膜太陽電池の製造方法を提供することにある。   The objective of this invention is providing the manufacturing method of a copper oxide thin film solar cell with high photoconversion efficiency compared with the conventional copper oxide thin film solar cell.

本発明の銅酸化物薄膜太陽電池の製造方法は、基板を準備する工程と、前記基板の一面上に第１電極を形成する工程と、前記第１電極の上にｎ型半導体層を形成する工程と、前記ｎ型半導体層の上にｐ型半導体層を形成する工程と、前記ｐ型半導体層の上に第２電極を形成する工程とを含む。前記ｐ型半導体層を形成する工程が、水溶性銅塩を含むアルカリ性水溶液に対し、水酸化リチウムを用いてｐＨを調整する工程と、前記ｐＨを調整されたアルカリ性水溶液の中で、前記ｎ型半導体層の上に電析によってｐ型半導体層を形成する工程とを含む。   The method for manufacturing a copper oxide thin film solar cell of the present invention includes a step of preparing a substrate, a step of forming a first electrode on one surface of the substrate, and an n-type semiconductor layer on the first electrode. A step, a step of forming a p-type semiconductor layer on the n-type semiconductor layer, and a step of forming a second electrode on the p-type semiconductor layer. The step of forming the p-type semiconductor layer includes adjusting the pH using lithium hydroxide with respect to an alkaline aqueous solution containing a water-soluble copper salt, and the n-type in the alkaline aqueous solution adjusted to the pH. Forming a p-type semiconductor layer on the semiconductor layer by electrodeposition.

前記ｐＨを調整する工程によって、アルカリ性水溶液のｐＨを１０〜１４、好ましくは１２．５にする。前記ｐ型半導体層を形成する工程によって、Ｃｕ２Ｏ層を形成する。前記ｎ型半導体層を形成する工程は、電析によってＺｎＯ層を形成する。 By the step of adjusting the pH, the pH of the alkaline aqueous solution is adjusted to 10 to 14, preferably 12.5. A Cu 2 O layer is formed by the step of forming the p-type semiconductor layer. In the step of forming the n-type semiconductor layer, a ZnO layer is formed by electrodeposition.

本発明によると、電析をおこなうためのアルカリ水溶液のｐＨの調整剤として水酸化リチウムを使用することによって、ｐＨの調整剤として水酸化カリウムや水酸化ナトリウムを使用するよりも変換効率の良い太陽電池を製造することができる。   According to the present invention, by using lithium hydroxide as a pH adjuster of an alkaline aqueous solution for electrodeposition, the solar has better conversion efficiency than using potassium hydroxide or sodium hydroxide as a pH adjuster. A battery can be manufactured.

銅酸化物薄膜太陽電池の構成を模式的に示す図である。It is a figure which shows typically the structure of a copper oxide thin film solar cell. ＬｉＯＨでｐＨ調整をおこなって製造した銅酸化物薄膜太陽電池のＸ線回折パターンのグラフである。It is a graph of the X-ray-diffraction pattern of the copper oxide thin film solar cell manufactured by performing pH adjustment with LiOH. ３種類のｐＨ調整剤の違いによる電圧−電流密度特性の違いを示すグラフである。It is a graph which shows the difference in the voltage-current density characteristic by the difference in three types of pH adjusters. ３種類のｐＨ調整剤の違いによる分光感度特性の違いを示すグラフである。It is a graph which shows the difference in the spectral sensitivity characteristic by the difference in three types of pH adjusters. Ｃｕ２Ｏをｐ型半導体層に使用した銅酸化物薄膜太陽電池のエネルギーバンドの図である。The Cu 2 O is a diagram of the energy band of the copper oxide thin film solar cell using the p-type semiconductor layer.

本発明の銅酸化物薄膜太陽電池の製造方法について図面を使用して説明する。   The manufacturing method of the copper oxide thin film solar cell of this invention is demonstrated using drawing.

図１に示す銅酸化物薄膜太陽電池１０は、基板１２の上に第１電極１４、ｎ型半導体層１６、ｐ型半導体層１８および第２電極２０が順番に積層された構造である。   A copper oxide thin film solar cell 10 shown in FIG. 1 has a structure in which a first electrode 14, an n-type semiconductor layer 16, a p-type semiconductor layer 18, and a second electrode 20 are sequentially stacked on a substrate 12.

基板１２は、ガラスや樹脂でできた透明基板である。基板１２の一面上に第１電極１４が形成され、他面が光入射面となる。他面に反射防止膜を設けて、ｎ型半導体層１６とｐ型半導体層１８の接合部への光の入射効率を高めても良い。基板１２はフレキシブルなものであっても良い。   The substrate 12 is a transparent substrate made of glass or resin. The first electrode 14 is formed on one surface of the substrate 12, and the other surface is a light incident surface. An antireflection film may be provided on the other surface to increase the efficiency of light incident on the junction between the n-type semiconductor layer 16 and the p-type semiconductor layer 18. The substrate 12 may be flexible.

第１電極１４は、ＦＴＯ（fluorine doped tin oxide）やＩＴＯ（indium tin oxide）などの透明電極である。第１電極１４が陰極となる。１枚の基板１２に対して、第１電極１４は１つであっても良いし、複数に分割されていても良い。なお、ＦＴＯはＩＴＯに比べて耐温度性が良い。   The first electrode 14 is a transparent electrode such as FTO (fluorine doped tin oxide) or ITO (indium tin oxide). The first electrode 14 becomes a cathode. The number of the first electrodes 14 may be one for a single substrate 12, or a plurality of the first electrodes 14 may be divided. FTO has better temperature resistance than ITO.

ｎ型半導体層１６は、光をｐ型半導体層１８との接合面まで到達させることができ、ｎ型半導体の特性を有するものであれば良い。例えばｎ型半導体層１６はＺｎＯの層である。電析によって形成することができる。   The n-type semiconductor layer 16 may be any material as long as it can reach the junction surface with the p-type semiconductor layer 18 and has the characteristics of an n-type semiconductor. For example, the n-type semiconductor layer 16 is a ZnO layer. It can be formed by electrodeposition.

ｐ型半導体層１８は、銅酸化物半導体を使用する。銅酸化物半導体として、ＣｕＯやＣｕ２Ｏが挙げられるが、バンドギャップの大きいＣｕ２Ｏ（バンドギャップ２．１ｅＶ）を使用するのが好ましい。ｎ型半導体層１６とｐ型半導体層１８とはヘテロ接合になる。 The p-type semiconductor layer 18 uses a copper oxide semiconductor. Examples of the copper oxide semiconductor include CuO and Cu 2 O, but Cu 2 O (band gap 2.1 eV) having a large band gap is preferably used. The n-type semiconductor layer 16 and the p-type semiconductor layer 18 form a heterojunction.

ｐ型半導体層１８は電析によってｎ型半導体層１６の上に形成する。電析のために水溶性銅塩を含むアルカリ性溶液を使用する。水溶性銅塩としては、キレート錯体を形成できる２価の銅塩を使用することができる。例えば水溶性銅塩として、硫酸銅、塩化銅、硝酸銅、酢酸銅などが挙げられる。このアルカリ性溶液の水酸化物の沈殿を抑制するために錯化剤を配合する。錯化剤としては、銅（II）イオンとキレート錯体を形成できる化合物を使用することができ、乳酸、エチレンジアミン四酢酸（ＥＤＴＡ）、クエン酸、酒石酸、グリコール酸、リンゴ酸などのヒドロキシカルボン酸が挙げられる。   The p-type semiconductor layer 18 is formed on the n-type semiconductor layer 16 by electrodeposition. An alkaline solution containing a water-soluble copper salt is used for electrodeposition. As the water-soluble copper salt, a divalent copper salt capable of forming a chelate complex can be used. Examples of water-soluble copper salts include copper sulfate, copper chloride, copper nitrate, and copper acetate. A complexing agent is blended in order to suppress the precipitation of hydroxide in the alkaline solution. As the complexing agent, a compound capable of forming a chelate complex with a copper (II) ion can be used, and hydroxycarboxylic acids such as lactic acid, ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, glycolic acid, malic acid and the like can be used. Can be mentioned.

アルカリ性水溶液は、ＬｉＯＨによってｐＨを調整する。ＬｉＯＨでｐＨを調節することによって、従来のＫＯＨやＮａＯＨでｐＨを調節するよりも変換効率の良い太陽電池を製造することができる。ｐＨは、１０〜１４であり、好ましくは１２．５である。ｐＨを１２．５にすることによって、Ｃｕ２Ｏを（１１１）配向にすることができる。ｐＨが９．０になるとＣｕ２Ｏが（２００）配向になるため、変換効率が落ち、好ましくない。 The pH of the alkaline aqueous solution is adjusted with LiOH. By adjusting the pH with LiOH, it is possible to produce a solar cell with better conversion efficiency than when adjusting the pH with conventional KOH or NaOH. The pH is 10-14, preferably 12.5. By making the pH 12.5, Cu 2 O can be (111) oriented. When the pH is 9.0, Cu 2 O is in the (200) orientation, which is not preferable because the conversion efficiency decreases.

第２電極２０は、Ａｕなどの導電性の金属である。真空蒸着などで形成することができる。第２電極２０が陽極になる。第２電極２０は複数に分割されていても良い。   The second electrode 20 is a conductive metal such as Au. It can be formed by vacuum deposition or the like. The second electrode 20 becomes an anode. The second electrode 20 may be divided into a plurality of parts.

次に、上述した銅酸化物薄膜太陽電池１０の製造方法について説明する。（１）ガラスなどの基板１２を準備する。この準備には、基板１２を所望形状に切断したり、洗浄したりすることを含む。   Next, the manufacturing method of the copper oxide thin film solar cell 10 mentioned above is demonstrated. (1) A substrate 12 such as glass is prepared. This preparation includes cutting or cleaning the substrate 12 into a desired shape.

（２）基板１２の上に第１電極１４を形成する。第１電極１４としてＦＴＯを用いるのであれば、ＣＶＤ（chemical vapor deposition）やスプレー熱分解法などで形成することができる。なお、基板１２にＦＴＯを成膜したものを準備してもよい。   (2) The first electrode 14 is formed on the substrate 12. If FTO is used as the first electrode 14, it can be formed by CVD (chemical vapor deposition) or spray pyrolysis. Note that an FTO film formed on the substrate 12 may be prepared.

（３）第１電極１４の上にｎ型半導体層１６を形成する。例えば電析によってＺｎＯの層を形成する。電析のための溶液は、蒸留水の中に硝酸亜鉛六水和物を溶解させた溶液を使用できる。また、ＺｎＯをスパッタリングによって形成しても良い。   (3) The n-type semiconductor layer 16 is formed on the first electrode 14. For example, a ZnO layer is formed by electrodeposition. As a solution for electrodeposition, a solution in which zinc nitrate hexahydrate is dissolved in distilled water can be used. Further, ZnO may be formed by sputtering.

（４）ｎ型半導体層１６の上にｐ型半導体層１８を形成する。ｐ型半導体層１８は電析によってＣｕ２Ｏの層を形成する。電析のための溶液は、上述したアルカリ水溶液を使用する。アルカリ水溶液は、ＬｉＯＨでｐＨを調整する。 (4) A p-type semiconductor layer 18 is formed on the n-type semiconductor layer 16. The p-type semiconductor layer 18 forms a Cu 2 O layer by electrodeposition. The alkaline aqueous solution mentioned above is used for the solution for electrodeposition. The pH of the alkaline aqueous solution is adjusted with LiOH.

電析は、３電極法を用いる。作用電極を第１電極１４、参照電極をＡｇ／ＡｇＣｌの電極、対電極をＰｔの電極を使用する。   Electrodeposition uses a three-electrode method. The working electrode is the first electrode 14, the reference electrode is an Ag / AgCl electrode, and the counter electrode is a Pt electrode.

（５）ｐ型半導体層１８の上に第２電極２０を形成する。例えば、Ａｕを真空蒸着で形成し、第２電極２０とする。真空蒸着以外に、金属材料を塗布し、焼成して形成しても良い。   (5) The second electrode 20 is formed on the p-type semiconductor layer 18. For example, Au is formed by vacuum evaporation to form the second electrode 20. In addition to vacuum deposition, a metal material may be applied and baked.

実施例
ＦＴＯが成膜されたガラス基板を超音波洗浄した。蒸留水に０．０８ＭのＺｎＮＯ３を溶解させ、電析によりＺｎＯを成膜した。その際にｐＨの調整はおこなわず、ｐＨは５．４であった。電析は、電流密度５ｍＡ／ｃｍ２、電気量１．５Ｃ／ｃｍ２、温度６５℃であった。ＺｎＯの膜厚は１．０μｍであった。 Example A glass substrate on which an FTO film was formed was subjected to ultrasonic cleaning. 0.08M ZnNO 3 was dissolved in distilled water, and ZnO was deposited by electrodeposition. At that time, the pH was not adjusted, and the pH was 5.4. Electrodeposition had a current density of 5 mA / cm 2 , an amount of electricity of 1.5 C / cm 2 , and a temperature of 65 ° C. The film thickness of ZnO was 1.0 μm.

ＺｎＯの上に電析によりＣｕ２Ｏを成膜した。電析液は、０．４ＭのＣｕＳＯ４と０．３ＭのＬ乳酸を蒸留水に溶解させ、２．０ＭのＬｉＯＨでｐＨを１２．５にした。電析は、電流密度−１．５ｍＡ／ｃｍ２、電気量４．０Ｃ／ｃｍ２、温度６５℃であった。Ｃｕ２Ｏの膜厚は４．０μｍであった。 Cu 2 O was deposited on the ZnO by electrodeposition. As the electrodeposition solution, 0.4 M CuSO 4 and 0.3 M L lactic acid were dissolved in distilled water, and the pH was adjusted to 12.5 with 2.0 M LiOH. Electrodeposition a current density -1.5mA / cm 2, amount of electricity 4.0C / cm 2, at a temperature of 65 ° C.. The film thickness of Cu 2 O was 4.0 μm.

電析によって成膜されたＣｕ２Ｏの上に、蒸着によってＡｕを成膜し、１４０℃、２０分で熱処理した。 Au was formed into a film by vapor deposition on Cu 2 O formed by electrodeposition, and heat-treated at 140 ° C. for 20 minutes.

製作した銅酸化物薄膜太陽電池１０のＸ線解析パターンは図２のようになっており、（１１１）配向のｐ型半導体層１８が得られていた。結晶性が良く、成膜したときにＣｕ２Ｏにならない銅が少ない。 The X-ray analysis pattern of the manufactured copper oxide thin film solar cell 10 is as shown in FIG. 2, and a (111) -oriented p-type semiconductor layer 18 was obtained. The crystallinity is good, and there is little copper that does not become Cu 2 O when deposited.

比較例
上記の実施例はｐＨの調整をＬｉＯＨでおこなったが、比較例としてＬｉＯＨの代わりにＮａＯＨまたはＫＯＨを使用してｐＨを１２．５にした。ＮａＯＨまたはＫＯＨは２．０Ｍであった。このｐＨ調整以外は実施例と同じ条件で銅酸化物薄膜太陽電池を製造した。以下、実施例と比較例で挙げたｐＨ調整剤の異なる３種類の銅酸化物薄膜太陽電池の特性の違いについて説明する。 Comparative Example In the above examples, the pH was adjusted with LiOH. As a comparative example, the pH was adjusted to 12.5 using NaOH or KOH instead of LiOH. NaOH or KOH was 2.0M. Except for this pH adjustment, a copper oxide thin film solar cell was produced under the same conditions as in the Examples. Hereinafter, the difference in the characteristics of three types of copper oxide thin film solar cells having different pH adjusters mentioned in Examples and Comparative Examples will be described.

電圧―電流特性は図３のようになり、ＬｉＯＨでｐＨ調整した銅酸化物薄膜太陽電池が最も良い特性になり、ＫＯＨでｐＨ調整した銅酸化物薄膜太陽電池が最も悪い特性になった。表１に各太陽電池の特性評価を示す。表１は株式会社三永電機製作所製のソーラーシュミレーターで求めている。光電変換効率が１．４％になるなど、各特性においてＬｉＯＨでｐＨ調整した銅酸化物薄膜太陽電池が最も良い特性になっている。   The voltage-current characteristics are as shown in FIG. 3, and the copper oxide thin film solar cell adjusted in pH with LiOH has the best characteristics, and the copper oxide thin film solar cell adjusted in pH with KOH has the worst characteristics. Table 1 shows the characteristic evaluation of each solar cell. Table 1 is obtained with a solar simulator manufactured by Mitsunaga Electric Co., Ltd. A copper oxide thin film solar cell whose pH has been adjusted with LiOH is the best characteristic, such as a photoelectric conversion efficiency of 1.4%.

Figure 2014183244
Figure 2014183244

図４に分光感度特性を示すが、ＬｉＯＨでｐＨ調整した銅酸化物薄膜太陽電池のみが５０％を超え、ＬｉＯＨでｐＨ調整した銅酸化物薄膜太陽電池が最も良い特性になった。また、ＬｉＯＨでｐＨ調整した銅酸化物薄膜太陽電池のＣｕ２Ｏの成膜速度は、ＫＯＨやＮａＯＨでｐＨ調整した銅酸化物薄膜太陽電池のＣｕ２Ｏの成膜速度よりも約１．６倍速かった。 Although the spectral sensitivity characteristics are shown in FIG. 4, only the copper oxide thin film solar cell whose pH was adjusted with LiOH exceeded 50%, and the copper oxide thin film solar cell whose pH was adjusted with LiOH was the best. Moreover, the film formation rate of Cu 2 O of the copper oxide thin film solar cell whose pH is adjusted with LiOH is about 1.6 higher than the film formation rate of Cu 2 O of the copper oxide thin film solar cell whose pH is adjusted with KOH or NaOH. It was twice as fast.

以上のように、ｐ型半導体層１８を電析によって形成する際、溶液のｐＨをＬｉＯＨで調整することによって、従来よりも変換効率の良い銅酸化物薄膜太陽電池１０を製造することができる。   As described above, when the p-type semiconductor layer 18 is formed by electrodeposition, by adjusting the pH of the solution with LiOH, it is possible to manufacture the copper oxide thin film solar cell 10 having better conversion efficiency than conventional ones.

その他、本発明は、その主旨を逸脱しない範囲で当業者の知識に基づき種々の改良、修正、変更を加えた態様で実施できるものである。   In addition, the present invention can be carried out in a mode in which various improvements, modifications, and changes are added based on the knowledge of those skilled in the art without departing from the spirit of the present invention.

１０：銅酸化物薄膜太陽電池
１２：基板
１４：第１電極
１６：ｎ型半導体層
１８：ｐ型半導体層
２０：第２電極 10: Copper oxide thin film solar cell 12: Substrate 14: First electrode 16: n-type semiconductor layer 18: p-type semiconductor layer 20: second electrode

Claims (4)

基板を準備する工程と、
前記基板の一面上に第１電極を形成する工程と、
前記第１電極の上にｎ型半導体層を形成する工程と、
前記ｎ型半導体層の上にｐ型半導体層を形成する工程と、
前記ｐ型半導体層の上に第２電極を形成する工程と、
を含む銅酸化物薄膜太陽電池の製造方法であって、
前記ｐ型半導体層を形成する工程が、
水溶性銅塩を含むアルカリ性水溶液に対し、水酸化リチウムを用いてｐＨを調整する工程と、
前記ｐＨを調整されたアルカリ性水溶液の中で、前記ｎ型半導体層の上に電析によってｐ型半導体層を形成する工程と、
を含む銅酸化物薄膜太陽電池の製造方法。 Preparing a substrate;
Forming a first electrode on one surface of the substrate;
Forming an n-type semiconductor layer on the first electrode;
Forming a p-type semiconductor layer on the n-type semiconductor layer;
Forming a second electrode on the p-type semiconductor layer;
A method for producing a copper oxide thin film solar cell comprising:
Forming the p-type semiconductor layer comprises:
For an alkaline aqueous solution containing a water-soluble copper salt, adjusting the pH using lithium hydroxide,
Forming a p-type semiconductor layer by electrodeposition on the n-type semiconductor layer in an alkaline aqueous solution adjusted in pH;
The manufacturing method of the copper oxide thin film solar cell containing this. 前記ｐＨを調整する工程によって、アルカリ性水溶液のｐＨを１０〜１４にする請求項１の銅酸化物薄膜太陽電池の製造方法。 The manufacturing method of the copper oxide thin film solar cell of Claim 1 which makes pH of alkaline aqueous solution 10-14 by the process of adjusting the said pH. 前記ｐ型半導体層を形成する工程によって、Ｃｕ２Ｏ層を形成する請求項１または２の銅酸化物薄膜太陽電池の製造方法。 Wherein the step of forming a p-type semiconductor layer, the manufacturing method of the copper oxide thin film solar cell according to claim 1 or 2 to form a Cu 2 O layer. 前記ｎ型半導体層を形成する工程は、電析によってＺｎＯ層を形成する請求項１から３のいずれかの薄膜太陽電池の製造方法。 The method for producing a thin-film solar cell according to claim 1, wherein the step of forming the n-type semiconductor layer forms a ZnO layer by electrodeposition.
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