JP2014107510A - Compound thin film solar cell - Google Patents

Compound thin film solar cell Download PDF

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JP2014107510A
JP2014107510A JP2012261515A JP2012261515A JP2014107510A JP 2014107510 A JP2014107510 A JP 2014107510A JP 2012261515 A JP2012261515 A JP 2012261515A JP 2012261515 A JP2012261515 A JP 2012261515A JP 2014107510 A JP2014107510 A JP 2014107510A
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compound
thin film
film solar
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JP6104576B2 (en
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Akihiko Asano
明彦 浅野
Toshiaki Yamaura
敏明 山浦
Tsuyoshi Yagioka
剛 八木岡
Masanori Nagahashi
正典 長橋
Hideki Sunayama
英樹 砂山
Masahiro Saito
雅弘 斎藤
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Showa Shell Sekiyu KK
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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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Abstract

PROBLEM TO BE SOLVED: To provide a compound thin film solar cell which uses a commonly-available stainless substrate and has good device characteristics.SOLUTION: A compound thin film solar cell comprises: a stainless substrate; an insulation layer deposited on a predetermined surface of the stainless substrate; a first electrode layer deposited on the insulation layer; a compound light absorption layer deposited on the first electrode layer; and a second electrode layer deposited on the compound light absorption layer, in which average roughness Ra of the predetermined surface is 85 nm and under.

Description

本発明は、化合物系薄膜太陽電池に関する。   The present invention relates to a compound-based thin film solar cell.

近年、燃料が不要であり温室効果ガスを排出しない太陽光発電が注目されており、例えば、ステンレス基板上にＣＩＳ系薄膜等の化合物系薄膜を形成した化合物系薄膜太陽電池が知られている。このような化合物系薄膜太陽電池において、良好な素子特性を得るためには、ステンレス基板の表面が平坦であることが必要であり、例えば、ステンレス基板上に絶縁層を形成することなく直接電極や化合物層を形成した化合物系薄膜太陽電池において、ステンレス基板の表面の平均粗さＲａが３０ｎｍ以下でなければならないことが開示されている（例えば、特許文献１参照）。   In recent years, photovoltaic power generation that does not require fuel and does not emit greenhouse gases has attracted attention. For example, a compound thin film solar cell in which a compound thin film such as a CIS thin film is formed on a stainless steel substrate is known. In such a compound-based thin film solar cell, in order to obtain good element characteristics, the surface of the stainless steel substrate needs to be flat. For example, the direct electrode or the electrode without forming an insulating layer on the stainless steel substrate. In a compound thin film solar cell in which a compound layer is formed, it is disclosed that the average roughness Ra of the surface of the stainless steel substrate must be 30 nm or less (see, for example, Patent Document 1).

特開２０１２−９７３４１号公報JP 2012-97341 A

しかしながら、表面の平均粗さＲａが３０ｎｍ以下のステンレス基板は、既に太陽電池用ステンレス基板として一部で市販されてはいるものの、それは一般的なステンレス基板の表面粗さを低減することを目的にした特殊な圧延工程を経て製造される特殊品である。   However, although a stainless steel substrate having an average surface roughness Ra of 30 nm or less is already commercially available as a stainless steel substrate for solar cells, it is intended to reduce the surface roughness of a general stainless steel substrate. It is a special product manufactured through a special rolling process.

本発明は、上記の点に鑑みてなされたものであり、一般に入手可能なステレンス基板を用いた素子特性が良好な化合物系薄膜太陽電池を提供することを課題とする。   This invention is made | formed in view of said point, and makes it a subject to provide the compound type thin film solar cell with a favorable element characteristic using the generally available stainless steel substrate.

本化合物系薄膜太陽電池は、ステンレス基板と、前記ステンレス基板の所定の面に製膜された絶縁層と、前記絶縁層上に製膜された第１の電極層と、前記第１の電極層上に製膜された化合物系光吸収層と、前記化合物系光吸収層上に製膜された第２の電極層と、を有し、前記所定の面の平均粗さＲａが８５ｎｍ以下であることを要件とする。   The compound-based thin film solar cell includes a stainless steel substrate, an insulating layer formed on a predetermined surface of the stainless steel substrate, a first electrode layer formed on the insulating layer, and the first electrode layer. A compound-based light absorption layer formed on the film, and a second electrode layer formed on the compound-based light absorption layer, wherein the average roughness Ra of the predetermined surface is 85 nm or less. Is a requirement.

開示の技術によれば、一般に入手可能なステレンス基板を用いた素子特性が良好な化合物系薄膜太陽電池を提供できる。   According to the disclosed technology, it is possible to provide a compound-based thin film solar cell having good device characteristics using a generally available stainless steel substrate.

本実施の形態に係るＣＩＳ系の化合物系薄膜太陽電池を例示する断面図である。It is sectional drawing which illustrates the CIS type compound thin film solar cell which concerns on this Embodiment.

以下、図面を参照して発明を実施するための形態について説明する。各図面において、同一構成部分には同一符号を付し、重複した説明を省略する場合がある。   Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and redundant description may be omitted.

なお、以下の実施の形態等は、ＣＩＳ系の化合物系薄膜太陽電池を例にとって説明するが、本発明は、ＣＩＳ系以外の化合物系薄膜太陽電池にも適用可能である。本発明を適用可能なＣＩＳ系以外の化合物系薄膜太陽電池の一例として、光吸収層が銅（Ｃｕ）、亜鉛（Ｚｎ）、錫（Ｓｎ）、及びカルコゲン元素（セレン（Ｓｅ）又は硫黄（Ｓ））を含有する化合物からなるＣＺＴＳ系の化合物系薄膜太陽電池を挙げることができる。又、本発明を適用可能なＣＩＳ系以外の化合物系薄膜太陽電池の他の例として、光吸収層がカドミウム（Ｃｄ）及びテルル（Ｔｅ）を含有する化合物からなるＣｄＴｅ系の化合物系薄膜太陽電池等を挙げることができる。   In addition, although the following embodiment etc. demonstrate taking a CIS type compound thin film solar cell as an example, this invention is applicable also to compound type thin film solar cells other than a CIS type. As an example of a compound-based thin film solar cell other than the CIS system to which the present invention can be applied, the light absorption layer has copper (Cu), zinc (Zn), tin (Sn), and a chalcogen element (selenium (Se) or sulfur (S And CZTS-based compound thin film solar cells made of a compound containing)). As another example of a compound-based thin film solar cell other than the CIS system to which the present invention can be applied, a CdTe-based compound thin-film solar cell in which the light absorption layer is made of a compound containing cadmium (Cd) and tellurium (Te). Etc.

図１は、本実施の形態に係るＣＩＳ系の化合物系薄膜太陽電池を例示する断面図である。図１を参照するに、化合物系薄膜太陽電池１０は、基板１１と、絶縁層１２と、第１の電極層１３と、光吸収層１４と、第２の電極層１５とを有し、基板１１上に、絶縁層１２、第１の電極層１３、光吸収層１４、及び第２の電極層１５が順次積層されている。以下、化合物系薄膜太陽電池１０を構成する各要素について説明する。   FIG. 1 is a cross-sectional view illustrating a CIS-based compound thin-film solar battery according to this embodiment. Referring to FIG. 1, a compound-based thin film solar cell 10 includes a substrate 11, an insulating layer 12, a first electrode layer 13, a light absorption layer 14, and a second electrode layer 15. 11, an insulating layer 12, a first electrode layer 13, a light absorption layer 14, and a second electrode layer 15 are sequentially stacked. Hereinafter, each element which comprises the compound type thin film solar cell 10 is demonstrated.

基板１１は、絶縁層１２、第１の電極層１３、光吸収層１４、及び第２の電極層１５を形成する基体となる部分であり、材質はステンレスである。なお、基板１１として、熱膨張率がＣＩＳ系の光吸収層に近いフェライト系ステンレス基板（例えば、ＳＵＳ４３０）を用いると、熱処理時又は熱処理後に光吸収層が剥離することを防止でき好適である。基板１１の厚さは、例えば、０．２〜０．６ｍｍ程度とすることができる。   The substrate 11 is a portion that serves as a base on which the insulating layer 12, the first electrode layer 13, the light absorption layer 14, and the second electrode layer 15 are formed, and the material thereof is stainless steel. Note that it is preferable to use a ferritic stainless steel substrate (for example, SUS430) having a thermal expansion coefficient close to that of a CIS-based light absorption layer as the substrate 11 because the light absorption layer can be prevented from peeling off during or after the heat treatment. The thickness of the board | substrate 11 can be about 0.2-0.6 mm, for example.

本実施の形態では、基板１１の絶縁層１２が製膜される面の平均粗さＲａは８５ｎｍ以下とされている。但し、基板１１の絶縁層１２が製膜される面の平均粗さＲａを３２ｎｍ以上かつ６２ｎｍ以下とすることが好ましい。平均粗さＲａをこのような数値範囲とすることの技術的な意義については、後述の実施例において説明する。   In the present embodiment, the average roughness Ra of the surface of the substrate 11 on which the insulating layer 12 is formed is 85 nm or less. However, the average roughness Ra of the surface of the substrate 11 on which the insulating layer 12 is formed is preferably 32 nm or more and 62 nm or less. The technical significance of setting the average roughness Ra in such a numerical range will be described in the examples described later.

絶縁層１２は、基板１１の所定の面（図１では上面）に形成されている。絶縁層１２の材料としては、ガラスを用いることが好ましい。ガラスの一例としては、シリカ（ＳｉＯ２）、ＣａＯ、Ｂ２Ｏ３、ＳｒＯ、ＢａＯ、Ａｌ２Ｏ３、ＺｎＯ、ＺｒＯ２、ＭｇＯのうちの少なくとも一つを成分とするガラスや低融点ガラスを挙げることができる。絶縁層１２の材料としてガラスが好ましい理由は、例えば絶縁層１２の材料として有機樹脂を用いると、光吸収層１４を製膜する際の熱処理によりダメージを受けるおそれがあるが、耐熱性の高いガラスを用いることにより、このような問題を回避できるからである。 The insulating layer 12 is formed on a predetermined surface (the upper surface in FIG. 1) of the substrate 11. As a material of the insulating layer 12, it is preferable to use glass. As an example of glass, glass or low melting point glass containing at least one of silica (SiO 2 ), CaO, B 2 O 3 , SrO, BaO, Al 2 O 3 , ZnO, ZrO 2 , and MgO as a component. Can be mentioned. The reason why glass is preferable as the material of the insulating layer 12 is that, for example, when an organic resin is used as the material of the insulating layer 12, there is a risk of being damaged by heat treatment when the light absorption layer 14 is formed. This is because such a problem can be avoided by using.

絶縁層１２は、例えば、スリットコーター、乾燥炉、及びベーク炉を順次用いて基板１１の所定の面に製膜できる。或いは、絶縁層１２を、スパッタ法やプラズマＣＶＤ法、スピンコーター、ディップコーター、スクリーン印刷法等を用いて基板１１の所定の面に製膜してもよい。   The insulating layer 12 can be formed on a predetermined surface of the substrate 11 by sequentially using, for example, a slit coater, a drying furnace, and a baking furnace. Alternatively, the insulating layer 12 may be formed on a predetermined surface of the substrate 11 using a sputtering method, a plasma CVD method, a spin coater, a dip coater, a screen printing method, or the like.

なお、絶縁層１２を同一材質や異なる材質を組み合わせた複数の層から構成してもよく、その場合には、アルカリバリア機能を有する層を有してもよい。アルカリバリア機能とは、ナトリウム（Ｎａ）やカリウム（Ｋ）等のアルカリ金属成分が光吸収層１４に過剰に拡散することを防止する機能である。   Note that the insulating layer 12 may be composed of a plurality of layers in which the same material or different materials are combined. In that case, the insulating layer 12 may have a layer having an alkali barrier function. The alkali barrier function is a function of preventing an alkali metal component such as sodium (Na) or potassium (K) from being excessively diffused into the light absorption layer 14.

絶縁層１２の厚さは、１０μｍ以上かつ５０μｍ以下とすることが好ましい。なお、発明者らの検討により、絶縁層１２の厚さが１０μｍ未満となると、化合物系薄膜太陽電池１０の変換効率が低下することがわかっている。これは、基板１１の上面の表面粗さが、絶縁層１２上に形成する各層の平坦性に影響を及ぼすためであると考えられる。又、絶縁層１２の厚さが５０μｍよりも大きくなると、絶縁層１２の機械的強度が低下したり、基板１１から剥離しやすくなるため好ましくない。   The thickness of the insulating layer 12 is preferably 10 μm or more and 50 μm or less. In addition, when the thickness of the insulating layer 12 becomes less than 10 micrometers by the inventors' examination, it turns out that the conversion efficiency of the compound type thin film solar cell 10 falls. This is presumably because the surface roughness of the upper surface of the substrate 11 affects the flatness of each layer formed on the insulating layer 12. Further, it is not preferable that the thickness of the insulating layer 12 is larger than 50 μm because the mechanical strength of the insulating layer 12 is reduced or the insulating layer 12 is easily peeled off from the substrate 11.

第１の電極層１３は、絶縁層１２上に形成されている。第１の電極層１３の材料としては、例えば、モリブデン（Ｍｏ）を用いることができる。第１の電極層１３の材料として、セレン（Ｓｅ）や硫黄（Ｓ）に対する耐食性を有するチタン（Ｔｉ）やタングステン（Ｗ）等を用いてもよい。第１の電極層１３の厚さは、例えば、数１０ｎｍ〜数μｍ程度とすることができる。第１の電極層１３は、例えば、ＤＣマグネトロンスパッタ法を用いて絶縁層１２上に製膜できる。或いは、第１の電極層１３を、イオンビーム蒸着法等を用いて絶縁層１２上に製膜してもよい。   The first electrode layer 13 is formed on the insulating layer 12. As a material of the first electrode layer 13, for example, molybdenum (Mo) can be used. As a material of the first electrode layer 13, titanium (Ti), tungsten (W), or the like having corrosion resistance against selenium (Se) or sulfur (S) may be used. The thickness of the first electrode layer 13 can be, for example, about several tens of nm to several μm. The first electrode layer 13 can be formed on the insulating layer 12 by using, for example, a DC magnetron sputtering method. Alternatively, the first electrode layer 13 may be formed on the insulating layer 12 using an ion beam evaporation method or the like.

光吸収層１４は、ｐ型半導体からなる層であり、第１の電極層１３上に形成されている。光吸収層１４は、照射された太陽光等を光電変換する部分である。光吸収層１４が光電変換することにより生じた起電力は、第１の電極層１３及び第２の電極層１５に各々はんだ等で取り付けられた図示しない電極リボン（銅箔リボン）から外部に電流として取り出すことができる。光吸収層１４の厚さは、例えば、数μｍ〜数１０μｍ程度とすることができる。   The light absorption layer 14 is a layer made of a p-type semiconductor and is formed on the first electrode layer 13. The light absorption layer 14 is a part that photoelectrically converts irradiated sunlight and the like. The electromotive force generated by the photoelectric conversion of the light absorption layer 14 is caused by a current from an electrode ribbon (copper foil ribbon) (not shown) attached to the first electrode layer 13 and the second electrode layer 15 with solder or the like to the outside. Can be taken out as. The thickness of the light absorption layer 14 can be set to, for example, about several μm to several tens of μm.

光吸収層１４としては、例えば、I-III-VI2族元素からなるＣＩＳ系の化合物、例えば、銅（Ｃｕ），インジウム（Ｉｎ），セレン（Ｓｅ）からなる化合物や、銅（Ｃｕ），インジウム（Ｉｎ），ガリウム（Ｇａ），セレン（Ｓｅ），硫黄（Ｓ）からなる化合物等を用いることができる。   As the light absorption layer 14, for example, a CIS compound composed of an I-III-VI2 group element, for example, a compound composed of copper (Cu), indium (In), selenium (Se), copper (Cu), indium A compound composed of (In), gallium (Ga), selenium (Se), sulfur (S), or the like can be used.

具体的な化合物の一例を挙げれば、２セレン化銅インジウム（ＣｕＩｎＳｅ２）、２イオウ化銅インジウム（ＣｕＩｎＳ２）、２セレン・イオウ化銅インジウム（ＣｕＩｎ（ＳＳｅ）２）、２セレン化銅ガリウム（ＣｕＧａＳｅ２）、２イオウ化銅ガリウム（ＣｕＧａＳ２）、２セレン化銅インジウム・ガリウム（Ｃｕ（ＩｎＧａ）Ｓｅ２）、２イオウ化銅インジウム・ガリウム（Ｃｕ（ＩｎＧａ）Ｓ２）、２セレン・イオウ化銅インジウム・ガリウム（Ｃｕ（ＩｎＧａ）（ＳＳｅ）２）等である。 An example of a specific compound is copper indium diselenide (CuInSe 2 ), copper indium disulfide (CuInS 2 ), copper indium selenium sulfide (CuIn (SSe) 2 ), copper gallium selenide (CuGaSe 2 ), copper gallium disulfide (CuGaS 2 ), copper indium gallium selenide (Cu (InGa) Se 2 ), copper indium gallium sulphide (Cu (InGa) S 2 ), 2 selenium For example, copper indium gallium sulfide (Cu (InGa) (SSe) 2 ).

光吸収層１４は、例えば、スパッタ法や蒸着法等により銅（Ｃｕ），ガリウム（Ｇａ），インジウム（Ｉｎ）等を含むプリカーサ膜を形成し、セレン化水素（Ｈ２Ｓｅ）雰囲気中、硫化水素（Ｈ２Ｓ）雰囲気中、又は、セレン化水素（Ｈ２Ｓｅ）及び硫化水素（Ｈ２Ｓ）雰囲気中で熱処理することにより製膜できる（セレン化／硫化過程）。 The light absorption layer 14 is formed, for example, by forming a precursor film containing copper (Cu), gallium (Ga), indium (In), etc. by sputtering or vapor deposition, and in a hydrogen selenide (H 2 Se) atmosphere. A film can be formed by heat treatment in a hydrogen (H 2 S) atmosphere or in a hydrogen selenide (H 2 Se) and hydrogen sulfide (H 2 S) atmosphere (selenization / sulfurization process).

光吸収層１４は、銅（Ｃｕ），ガリウム（Ｇａ），インジウム（Ｉｎ），及びセレン（Ｓｅ）を蒸着することにより製膜してもよい。又、光吸収層１４は、銅（Ｃｕ），ガリウム（Ｇａ），インジウム（Ｉｎ），及び硫黄（Ｓ）を蒸着することにより製膜してもよい。又、光吸収層１４は、銅（Ｃｕ），ガリウム（Ｇａ），インジウム（Ｉｎ），及びセレン（Ｓｅ）と硫黄（Ｓ）を蒸着することにより製膜してもよい。   The light absorption layer 14 may be formed by evaporating copper (Cu), gallium (Ga), indium (In), and selenium (Se). The light absorption layer 14 may be formed by vapor-depositing copper (Cu), gallium (Ga), indium (In), and sulfur (S). The light absorption layer 14 may be formed by evaporating copper (Cu), gallium (Ga), indium (In), selenium (Se), and sulfur (S).

なお、光吸収層１４として、例えば、銅（Ｃｕ），亜鉛（Ｚｎ），錫（Ｓｎ），カルコゲン元素からなるＣＺＴＳ系の化合物を用いてもよい。具体的な化合物の一例を挙げれば、４イオウ化２銅スズ・亜鉛（Ｃｕ２ＺｎＳｎＳ４）、４セレン・イオウ化２銅スズ・亜鉛（Ｃｕ２ＺｎＳｎ（ＳＳｅ）４）等である。 As the light absorption layer 14, for example, a CZTS compound composed of copper (Cu), zinc (Zn), tin (Sn), or a chalcogen element may be used. An example of a specific compound is tetrasulfuric dicopper tin / zinc (Cu 2 ZnSnS 4 ), selenium tetrasulfuric dicopper tin / zinc (Cu 2 ZnSn (SSe) 4 ), or the like.

光吸収層１４上にバッファ層（図示せず）を形成してもよい。バッファ層は、光吸収層１４からの電流の漏出を防止する機能を有する高抵抗の層である。バッファ層の材料としては、例えば、亜鉛化合物、硫化亜鉛（ＺｎＳ）、硫化カドミウム（ＣｄＳ）、硫化インジウム（ＩｎＳ）等を用いることができる。バッファ層の厚さは、例えば、数ｎｍ〜数１０ｎｍ程度とすることができる。バッファ層は、例えば、溶液成長法（ＣＢＤ法）や有機金属気相成長法（ＭＯＣＶＤ法）、アトミックレイヤーデポジション法（ＡＬＤ法）等により、光吸収層１４上に製膜できる。   A buffer layer (not shown) may be formed on the light absorption layer 14. The buffer layer is a high-resistance layer having a function of preventing current leakage from the light absorption layer 14. As a material of the buffer layer, for example, a zinc compound, zinc sulfide (ZnS), cadmium sulfide (CdS), indium sulfide (InS), or the like can be used. The thickness of the buffer layer can be, for example, about several nm to several tens of nm. The buffer layer can be formed on the light absorption layer 14 by, for example, a solution growth method (CBD method), a metal organic chemical vapor deposition method (MOCVD method), an atomic layer deposition method (ALD method), or the like.

なお、第１の電極層１３と光吸収層１４との間にアルカリバリア層を形成してもよい。アルカリバリア層は、ナトリウム（Ｎａ）やカリウム（Ｋ）等のアルカリ金属成分が光吸収層１４に過剰に拡散することを防止するために設ける層である。アルカリバリア層の材料としては、例えば、シリカ（ＳｉＯ２）等を用いることができる。アルカリバリア層の厚さは、例えば、５〜１００ｎｍ程度とすることができる。 Note that an alkali barrier layer may be formed between the first electrode layer 13 and the light absorption layer 14. The alkali barrier layer is a layer provided to prevent alkali metal components such as sodium (Na) and potassium (K) from being excessively diffused into the light absorption layer 14. As a material of the alkali barrier layer, for example, silica (SiO 2 ) or the like can be used. The thickness of the alkali barrier layer can be about 5 to 100 nm, for example.

第２の電極層１５は、ｎ型半導体からなる透明な層であり、光吸収層１４上に形成されている。第２の電極層１５としては、例えば、酸化亜鉛系薄膜（ＺｎＯ）やＩＴＯ薄膜等の透明導電膜を用いることができる。酸化亜鉛系薄膜（ＺｎＯ）を用いる場合には、硼素（Ｂ）やアルミニウム（Ａｌ）やガリウム（Ｇａ）等をドーパントとして添加することにより、低抵抗化でき好適である。第２の電極層１５の厚さは、例えば、０．１μｍ〜数μｍ程度とすることができる。光吸収層１４と第２の電極層１５とは、ｐｎ接合を形成している。第２の電極層１５は、例えば、ＭＯＣＶＤ法やスパッタ法、蒸着法等により、光吸収層１４上に製膜できる。   The second electrode layer 15 is a transparent layer made of an n-type semiconductor, and is formed on the light absorption layer 14. As the second electrode layer 15, for example, a transparent conductive film such as a zinc oxide-based thin film (ZnO) or an ITO thin film can be used. In the case of using a zinc oxide-based thin film (ZnO), the resistance can be reduced by adding boron (B), aluminum (Al), gallium (Ga), or the like as a dopant. The thickness of the second electrode layer 15 can be, for example, about 0.1 μm to several μm. The light absorption layer 14 and the second electrode layer 15 form a pn junction. The second electrode layer 15 can be formed on the light absorption layer 14 by, for example, MOCVD, sputtering, vapor deposition, or the like.

以上のように、基板１１上に、絶縁層１２、第１の電極層１３、光吸収層１４、及び第２の電極層１５を順次積層後、充填材、カバーガラス、アルミフレーム、バックシートを取り付けるが、本発明とは無関係のため説明は省略する。   As described above, the insulating layer 12, the first electrode layer 13, the light absorption layer 14, and the second electrode layer 15 are sequentially laminated on the substrate 11, and then the filler, the cover glass, the aluminum frame, and the back sheet are laminated. Although attached, it is irrelevant to the present invention and will not be described.

［実施例］
まず、基板１１として、上面（絶縁層１２が形成される面）の平均粗さＲａが２４ｎｍである、厚さ０．３ｍｍのフェライト系ステンレス基板（ＳＵＳ４３０）を準備した。次に、基板１１の上面に、スリットコーターを用いて、シリカ（ＳｉＯ２）を主成分とするガラスからなる厚さ２０μｍの絶縁層１２を製膜した。次に、絶縁層１２上に、ＤＣマグネトロンスパッタ法を用いて、モリブデン（Ｍｏ）からなる厚さ０．５μｍの第１の電極層１３を製膜した。 [Example]
First, as the substrate 11, a 0.3 mm-thick ferritic stainless steel substrate (SUS430) having an average roughness Ra of the upper surface (surface on which the insulating layer 12 is formed) of 24 nm was prepared. Next, an insulating layer 12 having a thickness of 20 μm made of glass containing silica (SiO 2 ) as a main component was formed on the upper surface of the substrate 11 using a slit coater. Next, a first electrode layer 13 made of molybdenum (Mo) and having a thickness of 0.5 μm was formed on the insulating layer 12 by using a DC magnetron sputtering method.

次に、第１の電極層１３上に、光吸収層１４として、厚さ１〜３μｍ程度のI-III-VI2族元素からなるＣＩＳ系の化合物系薄膜を製膜した。具体的には、第１の電極層１３上に、銅（Ｃｕ），ガリウム（Ｇａ），インジウム（Ｉｎ）を含む積層構造の金属プリカーサ膜をスパッタ法で製膜した後、セレン化及び硫化を行って、２セレン・イオウ化銅インジウム・ガリウム（Ｃｕ（ＩｎＧａ）（ＳＳｅ）２）を形成した。 Next, a CIS-based compound thin film made of an I-III-VI2 group element having a thickness of about 1 to 3 μm was formed on the first electrode layer 13 as the light absorption layer 14. Specifically, a metal precursor film having a laminated structure containing copper (Cu), gallium (Ga), and indium (In) is formed on the first electrode layer 13 by sputtering, and then selenization and sulfidation are performed. And formed selenium disulfide copper indium gallium (Cu (InGa) (SSe) 2 ).

次に、光吸収層１４上に、ＭＯＣＶＤ法を用いて、硼素（Ｂ）を添加した酸化亜鉛（ＺｎＯ：Ｂ）からなる厚さ０．５〜２．５μｍ程度の第２の電極層１５を製膜した。以上により試料番号１の化合物系薄膜太陽電池が完成した。   Next, a second electrode layer 15 made of zinc oxide (ZnO: B) added with boron (B) and having a thickness of about 0.5 to 2.5 μm is formed on the light absorption layer 14 by MOCVD. A film was formed. The compound type thin film solar cell of sample number 1 was completed by the above.

同様の方法により、基板１１の上面の平均粗さＲａのみを異ならせた化合物系薄膜太陽電池（試料番号２〜７）を作製した。そして、試料番号１〜７の化合物系薄膜太陽電池について、それぞれ変換効率（％）の測定を行い、太陽電池としての特性を評価した。各試料の平均粗さＲａ及び評価結果を表１に示す。   By the same method, compound type thin film solar cells (sample numbers 2 to 7) in which only the average roughness Ra of the upper surface of the substrate 11 was varied were produced. And about the compound type thin film solar cell of the sample numbers 1-7, the conversion efficiency (%) was measured, respectively, and the characteristic as a solar cell was evaluated. Table 1 shows the average roughness Ra and the evaluation results of each sample.

なお、試料番号１で基板１１として使用したフェライト系ステンレス基板は、表面仕上げ記号がＢＡのステンレス素材を電解複合研磨して製造されたものである。試料番号２〜４で基板１１として使用したフェライト系ステンレス基板は、表面仕上げ記号がＢＡの通常に市販されているステンレス素材をそのまま使用したものである。試料番号５で基板１１として使用したフェライト系ステンレス基板は、表面仕上げ記号が２Ｂの通常に市販されているステンレス素材をそのまま使用したものである。   The ferritic stainless steel substrate used as the substrate 11 in the sample number 1 is manufactured by electrolytic composite polishing of a stainless steel material whose surface finish symbol is BA. The ferritic stainless steel substrate used as the substrate 11 in the sample numbers 2 to 4 is a stainless steel material that is usually commercially available and has a surface finish symbol of BA. The ferritic stainless steel substrate used as the substrate 11 in the sample number 5 is a stainless steel material that is usually commercially available with a surface finish symbol of 2B.

Figure 2014107510
Figure 2014107510

表１に示すように、基板１１の上面の平均粗さＲａが３０ｎｍ以下である試料番号１及び２の化合物系薄膜太陽電池では、素子特性良否の目安としての変換効率は１３．３６％であった。一方、通常に市販されている素材をそのまま使用した試料番号３〜５の化合物系薄膜太陽電池では、試料番号１及び２の化合物系薄膜太陽電池を上回る変換効率が得られた。   As shown in Table 1, in the compound thin film solar cells of Sample Nos. 1 and 2 in which the average roughness Ra of the upper surface of the substrate 11 is 30 nm or less, the conversion efficiency as a measure of the device characteristics is 13.36%. It was. On the other hand, the conversion efficiency exceeding the compound type thin film solar cell of the sample numbers 1 and 2 was acquired in the compound type thin film solar cell of the sample numbers 3-5 which used the raw material normally marketed as it is.

又、基板１１の上面の平均粗さＲａが８５ｎｍと大きいと試料番号６の化合物系薄膜太陽電池でも比較的良好な変換効率が得られた。しかし、基板１１の上面の平均粗さＲａが９８ｎｍと更に大きい試料番号７の化合物系薄膜太陽電池では、試料番号１〜６の化合物系薄膜太陽電池のような良好な特性は得られなかった。   When the average roughness Ra of the upper surface of the substrate 11 was as large as 85 nm, a relatively good conversion efficiency was obtained even in the compound thin film solar cell of Sample No. 6. However, the compound-type thin film solar cell of Sample No. 7 having a larger average roughness Ra of the upper surface of the substrate 11 of 98 nm could not obtain good characteristics as the compound-type thin film solar cells of Sample Nos. 1-6.

つまり、従来、化合物系薄膜太陽電池に用いる基板の上面の平均粗さＲａの上限とされていた３０ｎｍを超えても、８５ｎｍ以下の範囲であれば良好な素子特性を得ることができた。又、平均粗さＲａが３２ｎｍ以上かつ６２ｎｍ以下の範囲においては、更に良好な素子特性を得ることができた。これは、本実施例で作製した化合物系薄膜太陽電池の上記構成よって初めて成し得たものである。   In other words, even when the upper limit of the average roughness Ra of the upper surface of the substrate used in the compound-based thin film solar cell has been conventionally exceeded, excellent element characteristics can be obtained within the range of 85 nm or less. Further, in the range where the average roughness Ra is 32 nm or more and 62 nm or less, further excellent device characteristics can be obtained. This can be achieved for the first time by the above-described configuration of the compound thin film solar cell produced in this example.

換言すれば、従来は、ステンレス基板上に絶縁層を形成することなく直接電極や化合物層を形成した化合物系薄膜太陽電池において、ステンレス基板の上面の平均粗さＲａが３０ｎｍ以下でなければならないとされていた。しかしながら、発明者らは、ステンレス基板上に絶縁層を介して電極層や光吸収層等を製膜する場合には、上面の平均粗さＲａが８５ｎｍ以下のステンレス基板を使用すれば良好な素子特性を得られることを実験的に見出した。   In other words, conventionally, in a compound thin film solar cell in which an electrode and a compound layer are directly formed without forming an insulating layer on a stainless steel substrate, the average roughness Ra of the upper surface of the stainless steel substrate must be 30 nm or less. It had been. However, when forming an electrode layer, a light absorption layer, or the like on an insulating layer on a stainless steel substrate, the inventors use a stainless steel substrate having an upper surface with an average roughness Ra of 85 nm or less. It was experimentally found that characteristics can be obtained.

このように、本実施例によれば、特殊品である太陽電池用ステンレス基板を用いずとも、例えば表面仕上げ記号がＢＡや２Ｂの通常に市販されており一般に入手可能なステンレス基板をそのままを用いて、前者（特殊品）を用いた場合と同様な素子特性の化合物系薄膜太陽電池を製造することができる。   Thus, according to the present embodiment, without using a special stainless steel substrate for solar cells, for example, a generally available stainless steel substrate with a surface finish symbol of BA or 2B is used as it is. Thus, a compound-based thin-film solar cell having the same device characteristics as when the former (special product) is used can be manufactured.

以上、好ましい実施の形態及び実施例について詳説したが、上述した実施の形態及び実施例に制限されることはなく、特許請求の範囲に記載された範囲を逸脱することなく、上述した実施の形態及び実施例に種々の変形及び置換を加えることができる。   The preferred embodiments and examples have been described in detail above, but the present invention is not limited to the above-described embodiments and examples, and the above-described embodiments are not deviated from the scope described in the claims. Various modifications and substitutions can be made to the embodiments.

１０ 化合物系薄膜太陽電池
１１ 基板
１２ 絶縁層
１３ 第１の電極層
１４ 光吸収層
１５ 第２の電極層 DESCRIPTION OF SYMBOLS 10 Compound type thin film solar cell 11 Board | substrate 12 Insulating layer 13 1st electrode layer 14 Light absorption layer 15 2nd electrode layer

Claims (5)

ステンレス基板と、
前記ステンレス基板の所定の面に製膜された絶縁層と、
前記絶縁層上に製膜された第１の電極層と、
前記第１の電極層上に製膜された化合物系光吸収層と、
前記化合物系光吸収層上に製膜された第２の電極層と、を有し、
前記所定の面の平均粗さＲａが８５ｎｍ以下である化合物系薄膜太陽電池。 A stainless steel substrate,
An insulating layer formed on a predetermined surface of the stainless steel substrate;
A first electrode layer formed on the insulating layer;
A compound light-absorbing layer formed on the first electrode layer;
A second electrode layer formed on the compound light absorption layer,
A compound-based thin film solar cell having an average roughness Ra of the predetermined surface of 85 nm or less. 前記ステンレス基板はフェライト系ステンレス基板である請求項１記載の化合物系薄膜太陽電池。   The compound thin film solar cell according to claim 1, wherein the stainless steel substrate is a ferritic stainless steel substrate. 前記所定の面の平均粗さＲａが３２ｎｍ以上かつ６２ｎｍ以下である請求項１又は２記載の化合物系薄膜太陽電池。   The compound-based thin film solar cell according to claim 1 or 2, wherein the predetermined surface has an average roughness Ra of 32 nm or more and 62 nm or less. 前記絶縁層がガラスである請求項１乃至３の何れか一項記載の化合物系薄膜太陽電池。   The compound-based thin film solar cell according to any one of claims 1 to 3, wherein the insulating layer is glass. 前記絶縁層の厚さが１０μｍ以上かつ５０μｍ以下である請求項１乃至４の何れか一項記載の化合物系薄膜太陽電池。   5. The compound-based thin film solar cell according to claim 1, wherein the insulating layer has a thickness of 10 μm to 50 μm.
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