JP2005196982A - Dye-sensitized solar cell - Google Patents

Dye-sensitized solar cell Download PDF

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JP2005196982A
JP2005196982A JP2003435173A JP2003435173A JP2005196982A JP 2005196982 A JP2005196982 A JP 2005196982A JP 2003435173 A JP2003435173 A JP 2003435173A JP 2003435173 A JP2003435173 A JP 2003435173A JP 2005196982 A JP2005196982 A JP 2005196982A
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electrode
metal
dye
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Ichiro Gonda
一郎 権田
Yasuo Okuyama
康生 奥山
Keizo Furusaki
圭三 古崎
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Niterra Co Ltd
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NGK Spark Plug 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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    • Y02E10/542—Dye sensitized solar cells

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell with excellent photoelectric conversion efficiency through restrained thermal loss at current collection by reduced inner resistance of a conductive member. <P>SOLUTION: The dye-sensitized solar cell 106 is provided with a translucent substrate 1 (a glass substrate etc.), a substrate 2 (a ceramic substrate etc.) a semiconductor electrode 3 (made of titania etc.) having sensitizing dyes (metal complex dyes etc.), a catalyst electrode 4 arranged in opposition to the semiconductor electrode 3 (made of platinum etc.), and electrolyte 5 at least contained in a part of the semiconductor electrode 3 and filled at least between the semiconductor electrode 3 and the catalyst electrode 4 (electrolyte combining I<SB>2</SB>, LiI, etc.). The semiconductor electrode 3 consists of a semiconductor layer 31 or the like having sensitizing dyes provided at least at a part of the surface of a metal mesh body 71, and the catalyst electrode 4 consists of a catalyst layer 41 or the like provided at least at a part of the surface of a metal mesh body 72. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、光エネルギーを電気エネルギーに直接変換する色素増感型太陽電池に関する。更に詳しくは、この太陽電池を構成する導電性部材の内部抵抗を低減させることで、熱損失等による光電変換効率の低下が抑えられた色素増感型太陽電池に関する。更に、電解質に対する耐腐食性の高いタングステンを含有する金属線状体及び／又は金属網状体を用いた半導体電極及び／又は触媒電極とすることで、耐久性がより向上した色素増感型太陽電池に関する。   The present invention relates to a dye-sensitized solar cell that directly converts light energy into electrical energy. More specifically, the present invention relates to a dye-sensitized solar cell in which a decrease in photoelectric conversion efficiency due to heat loss or the like is suppressed by reducing an internal resistance of a conductive member constituting the solar cell. Furthermore, a dye-sensitized solar cell with improved durability by using a semiconductor electrode and / or a catalyst electrode using a metal wire and / or metal network containing tungsten having high corrosion resistance to the electrolyte. About.

現在、太陽光発電では、単結晶シリコン、多結晶シリコン、アモルファスシリコン及びこれらを組み合わせたＨＩＴ（Ｈｅｔｅｒｏｊｕｎｃｔｉｏｎ ｗｉｔｈ Ｉｎｔｒｉｎｓｉｃ Ｔｈｉｎ−ｌａｙｅｒ）等を用いた太陽電池が実用化され、主力技術となっている。これらの太陽電池では光電変換の効率も２０％に近く優れている。しかし、シリコン系太陽電池は素材製造にかかるエネルギーコストが高く、環境負荷などの面でも課題が多く、価格及び材料供給等における制限もある。一方、Ｇｒａｔｚｅｌ等により提案された色素増感型太陽電池が安価な太陽電池として注目されている（例えば、非特許文献１及び特許文献１参照。）。この太陽電池は、増感色素を担持させたチタニア多孔質電極と対極との間に電解質を介在させた構造を有し、現行のシリコン系太陽電池に比べて光電変換効率は低いものの、材料、製法等の面で大幅なコストダウンが可能である。   At present, in solar power generation, solar cells using single crystal silicon, polycrystalline silicon, amorphous silicon, and HIT (Heterojunction with Intrinsic Thin-layer) combined with these have been put into practical use and have become the main technology. These solar cells have an excellent photoelectric conversion efficiency of nearly 20%. However, silicon-based solar cells are expensive in terms of energy production, have many problems in terms of environmental impact, and have limitations in price and material supply. On the other hand, a dye-sensitized solar cell proposed by Gratzel et al. Has attracted attention as an inexpensive solar cell (see, for example, Non-Patent Document 1 and Patent Document 1). This solar cell has a structure in which an electrolyte is interposed between a titania porous electrode supporting a sensitizing dye and a counter electrode, and although the photoelectric conversion efficiency is lower than that of the current silicon-based solar cell, the material, Significant cost reduction is possible in terms of manufacturing method.

この色素増感型太陽電池の光電変換効率を高めるためには、光照射により発生した電子を効率よく集めることが重要であり、そのためには導電性部材の内部抵抗を低減する必要がある。特に、十分な透光性が必要であるため極薄に形成される透光性導電層等では、内部抵抗の増大による熱損失がより問題であり、更に透光性導電層等の面積、即ち、太陽電池の面積が大きくなるほど、抵抗増大による光電変換効率の低下が顕著となる。そこで、電子を効率よく集めるための種々の形態の集電電極が提案されている（例えば、特許文献２及び特許文献３参照。）。   In order to increase the photoelectric conversion efficiency of the dye-sensitized solar cell, it is important to efficiently collect electrons generated by light irradiation. For this purpose, it is necessary to reduce the internal resistance of the conductive member. In particular, in a translucent conductive layer that is formed extremely thin because sufficient translucency is necessary, heat loss due to an increase in internal resistance is more problematic, and furthermore, the area of the translucent conductive layer, that is, As the area of the solar cell increases, the decrease in photoelectric conversion efficiency due to increased resistance becomes more significant. Accordingly, various forms of collecting electrodes for efficiently collecting electrons have been proposed (see, for example, Patent Document 2 and Patent Document 3).

特開平１−２２０３８０号公報Japanese Patent Laid-Open No. 1-220380 Ｎａｔｕｒｅ誌（第３５３巻、ｐｐ．７３７−７４０、１９９１年）Nature (Vol. 353, pp. 737-740, 1991) 特開２０００−２３１９４２号公報JP 2000-231942 A 特開２０００−２８５９７７号公報JP 2000-285777 A

本発明は、上記の状況に鑑みてなされたものであり、金属線状体等からなる集電電極の表面に半導体層又は触媒層が設けられ、集電電極と半導体電極及び／又は触媒電極とが一体となった特定の構造を備えることで、透光性導電層を必ずしも必要とせず、光電変換効率が向上した色素増感型太陽電池を提供することを目的とする。また、特に、電解質等に対する耐腐食性の高いタングステンを含有する金属線状体等を用いることにより、優れた耐久性をも併せて有する色素増感型太陽電池を提供することを目的とする。   The present invention has been made in view of the above situation, and a semiconductor layer or a catalyst layer is provided on the surface of a collector electrode made of a metal linear body or the like, and the collector electrode, the semiconductor electrode and / or the catalyst electrode, It is an object of the present invention to provide a dye-sensitized solar cell having an improved photoelectric conversion efficiency without necessarily requiring a light-transmitting conductive layer. It is another object of the present invention to provide a dye-sensitized solar cell having excellent durability by using a metal linear body containing tungsten having high corrosion resistance against an electrolyte or the like.

本発明は以下のとおりである。
１．透光性基板１と、該透光性基板１に対向して配設された基板２と、該透光性基板１と該基板２との間の該透光性基板１の側に配設された、増感色素３３を有する半導体電極３と、該基板２の表面に設けられた触媒電極４と、該半導体電極３の少なくとも一部に含有され、且つ少なくとも該半導体電極３と該触媒電極４との間に充填された電解質５と、を備え、該半導体電極３は、金属線状体６１の表面の少なくとも一部に設けられた、該増感色素３３を有する半導体層３１、及び金属網状体７１の表面の少なくとも一部に設けられた、該増感色素３３を有する半導体層３２のうちの少なくとも一方からなることを特徴とする色素増感型太陽電池。
２．上記金属線状体６１及び上記金属網状体７１のうちの少なくとも一方がタングステンを含有する上記１．に記載の色素増感型太陽電池。
３．上記金属線状体６１と上記半導体層３１との間、及び上記金属網状体７１と上記半導体層３２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８１が設けられている上記１．又は２．に記載の色素増感型太陽電池。
４．透光性基板１と、該透光性基板１に対向して配設された基板２と、該透光性基板１の表面に設けられた、増感色素３３を有する半導体電極３と、該透光性基板１と該基板２との間に該半導体電極３に対向して配設された触媒電極４と、該半導体電極３の少なくとも一部に含有され、且つ少なくとも該半導体電極３と該触媒電極４との間に充填された電解質５と、を備え、該触媒電極４は、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１、及び金属網状体７２の表面の少なくとも一部に設けられた触媒層４２のうちの少なくとも一方からなることを特徴とする色素増感型太陽電池。
５．上記金属線状体６２及び上記金属網状体７２のうちの少なくとも一方がタングステンを含有する上記４．に記載の色素増感型太陽電池。
６．上記金属線状体６２と上記触媒層４１との間、及び上記金属網状体７２と上記触媒層４２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８２が設けられている上記４．又は５．に記載の色素増感型太陽電池。
７．透光性基板１と、該透光性基板１に対向して配設された基板２と、該透光性基板１と該基板２との間の該透光性基板１の側に配設された、増感色素３２を有する半導体電極３と、該透光性基板１と該基板２との間に該半導体電極３に対向して配設された触媒電極４と、該半導体電極３の少なくとも一部に含有され、且つ該半導体電極３と該触媒電極４との間に充填された電解質５と、を備え、該半導体電極３は、金属線状体６１の表面の少なくとも一部に設けられた、該増感色素３３を有する半導体層３１、及び金属網状体７１の表面の少なくとも一部に設けられた、該増感色素３３を有する半導体層３２のうちの少なくとも一方からなり、該触媒電極４は、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１、及び金属網状体７２の表面の少なくとも一部に設けられた触媒層４２のうちの少なくとも一方からなることを特徴とする色素増感型太陽電池。
８．上記金属線状体６１、上記金属網状体７１、上記金属線状体６２及び上記金属網状体７２のうちの少なくとも一つがタングステンを含有する上記７．に記載の色素増感型太陽電池。
９．上記金属線状体６１と上記半導体層３１との間、及び上記金属網状体７１と上記半導体層３２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８１が設けられている上記７．又は８．に記載の色素増感型太陽電池。
１０．上記金属線状体６２と上記触媒層４１との間、及び上記金属網状体７２と上記触媒層４２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８２が設けられている上記７．又は８．に記載の色素増感型太陽電池。
１１．上記半導体電極３がチタニアを含有する上記１．乃至１０．のうちのいずれか１項に記載の色素増感型太陽電池。
１２．上記触媒電極４が貴金属及びカーボンのうちの少なくとも一方を含有する上記１．乃至１１．のうちのいずれか１項に記載の色素増感型太陽電池。 The present invention is as follows.
1. Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, and disposed on the side of translucent substrate 1 between translucent substrate 1 and substrate 2 The semiconductor electrode 3 having the sensitizing dye 33, the catalyst electrode 4 provided on the surface of the substrate 2, and contained in at least a part of the semiconductor electrode 3 and at least the semiconductor electrode 3 and the catalyst electrode 4, the semiconductor electrode 3 is provided on at least a part of the surface of the metal linear body 61, the semiconductor layer 31 having the sensitizing dye 33, and a metal A dye-sensitized solar cell comprising at least one of the semiconductor layers 32 having the sensitizing dye 33 provided on at least a part of the surface of the net-like body 71.
2. At least one of the metal linear body 61 and the metal net body 71 contains tungsten. 2. A dye-sensitized solar cell according to 1.
3. A conductive layer 81 made of a conductive oxide is provided between at least one of the metal wire 61 and the semiconductor layer 31 and between the metal network 71 and the semiconductor layer 32. Above 1. Or 2. 2. A dye-sensitized solar cell according to 1.
4). A translucent substrate 1, a substrate 2 disposed opposite to the translucent substrate 1, a semiconductor electrode 3 having a sensitizing dye 33 provided on the surface of the translucent substrate 1, A catalyst electrode 4 disposed between the translucent substrate 1 and the substrate 2 so as to face the semiconductor electrode 3; and at least a part of the semiconductor electrode 3; and at least the semiconductor electrode 3 and the semiconductor electrode 3 An electrolyte 5 filled between the catalyst electrode 4 and the catalyst electrode 4, the catalyst layer 41 provided on at least a part of the surface of the metal linear body 62, and the surface of the metal network 72. A dye-sensitized solar cell comprising at least one of the catalyst layers 42 provided at least in part.
5). At least one of the metal linear body 62 and the metal net body 72 contains tungsten. 2. A dye-sensitized solar cell according to 1.
6). A conductive layer 82 made of a conductive oxide is provided between at least one of the metal wire 62 and the catalyst layer 41 and between the metal network 72 and the catalyst layer 42. 4. above. Or 5. 2. A dye-sensitized solar cell according to 1.
7). Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, and disposed on the side of translucent substrate 1 between translucent substrate 1 and substrate 2 A semiconductor electrode 3 having a sensitizing dye 32, a catalyst electrode 4 disposed between the translucent substrate 1 and the substrate 2 so as to face the semiconductor electrode 3, and the semiconductor electrode 3 An electrolyte 5 contained at least in part and filled between the semiconductor electrode 3 and the catalyst electrode 4. The semiconductor electrode 3 is provided on at least a part of the surface of the metal linear body 61. The catalyst layer comprising at least one of the semiconductor layer 31 having the sensitizing dye 33 and the semiconductor layer 32 having the sensitizing dye 33 provided on at least a part of the surface of the metal network 71. The electrode 4 includes a catalyst layer 41 provided on at least a part of the surface of the metal linear body 62, and a metal network Dye-sensitized solar cell characterized by comprising at least one of the catalyst layer 42 provided on at least a portion of the second surface.
8). 6. The metal wire 61, the metal network 71, the metal wire 62, and at least one of the metal network 72 contains tungsten. 2. A dye-sensitized solar cell according to 1.
9. A conductive layer 81 made of a conductive oxide is provided between at least one of the metal wire 61 and the semiconductor layer 31 and between the metal network 71 and the semiconductor layer 32. Above 7. Or 8. 2. A dye-sensitized solar cell according to 1.
10. A conductive layer 82 made of a conductive oxide is provided between at least one of the metal wire 62 and the catalyst layer 41 and between the metal network 72 and the catalyst layer 42. Above 7. Or 8. 2. A dye-sensitized solar cell according to 1.
11. 1. The semiconductor electrode 3 containing titania. To 10. The dye-sensitized solar cell of any one of these.
12 The catalyst electrode 4 contains at least one of a noble metal and carbon. To 11. The dye-sensitized solar cell of any one of these.

半導体電極３が、金属線状体６１の表面の少なくとも一部に設けられた半導体層３１及び／又は金属網状体７１の表面の少なくとも一部に設けられた半導体層３２からなる本発明の色素増感型太陽電池、触媒電極４が、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１及び／又は金属網状体７２の表面の少なくとも一部に設けられた触媒層４２からなる本発明の他の色素増感型太陽電池、並びに半導体電極３が、金属線状体６１の表面の少なくとも一部に設けられた半導体層３１及び／又は金属網状体７１の表面の少なくとも一部に設けられた半導体層３２からなり、触媒電極４が、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１及び／又は金属網状体７２の表面の少なくとも一部に設けられた触媒層４２からなる本発明の更に他の色素増感型太陽電池では、透光性導電層を必ずしも必要としないため内部抵抗が低減され、光電変換効率が向上する。また、透光性導電層がない場合、透光性基板側の透光率も高くなり、結果として光電変換効率がより向上する。
また、金属線状体６１及び／又は金属網状体７１がタングステンを含有する場合、金属線状体６２及び／又は金属網状体７２がタングステンを含有する場合、並びに金属線状体６１、金属網状体７１、金属線状体６２及び金属網状体７２のうちの少なくとも一つがタングステンを含有する場合は、集電電極である金属線状体等が電解質に腐食され難く、耐久性に優れた色素増感型太陽電池とすることができる。
更に、金属線状体６１と半導体層３１との間及び／又は金属網状体７１と半導体層３２との間に、導電性酸化物からなる導電層８１が設けられている場合、並びに金属線状体６２と触媒層４１との間及び／又は金属網状体７２と触媒層４２との間に、導電性酸化物からなる導電層８２が設けられている場合は、金属線状体及び金属網状体と、半導体層及び触媒層との間の密着性が高く、耐久性に優れた色素増感型太陽電池とすることができる。
また、半導体電極３がチタニアを含有する場合は、光電変換効率の高い色素増感型太陽電池とすることができる。
更に、触媒電極４が貴金属及びカーボンのうちの少なくとも一方を含有する場合は、優れた触媒作用を有する電極とすることができ、光電変換効率の高い色素増感型太陽電池とすることができる。 The dye enhancement of the present invention, wherein the semiconductor electrode 3 comprises a semiconductor layer 31 provided on at least a part of the surface of the metal linear body 61 and / or a semiconductor layer 32 provided on at least a part of the surface of the metal network 71. The sensitive solar cell, the catalyst electrode 4 is composed of a catalyst layer 41 provided on at least a part of the surface of the metal linear body 62 and / or a catalyst layer 42 provided on at least a part of the surface of the metal network 72. Another dye-sensitized solar cell of the present invention and the semiconductor electrode 3 are provided on at least a part of the surface of the semiconductor layer 31 and / or the metal network 71 provided on at least a part of the surface of the metal linear body 61. A catalyst comprising the semiconductor layer 32 provided and the catalyst electrode 4 provided on at least part of the surface of the catalyst layer 41 and / or metal network 72 provided on at least part of the surface of the metal linear body 62. Layer 42 or Comprising the further sensitized solar cell other dyes of the present invention, it is internally because it does not necessarily require a light-transmitting conductive layer resistance decreased, the photoelectric conversion efficiency is improved. Moreover, when there is no translucent conductive layer, the transmissivity on the translucent substrate side is also increased, and as a result, the photoelectric conversion efficiency is further improved.
Moreover, when the metal linear body 61 and / or the metal net-like body 71 contain tungsten, when the metal linear body 62 and / or the metal net-like body 72 contains tungsten, the metal linear body 61 and the metal net-like body 71, when at least one of the metal linear body 62 and the metal network body 72 contains tungsten, the metal linear body, which is a collecting electrode, is hardly corroded by the electrolyte, and has excellent durability. Type solar cell.
Furthermore, when the conductive layer 81 made of a conductive oxide is provided between the metal linear body 61 and the semiconductor layer 31 and / or between the metal network 71 and the semiconductor layer 32, When the conductive layer 82 made of a conductive oxide is provided between the body 62 and the catalyst layer 41 and / or between the metal network 72 and the catalyst layer 42, the metal linear body and the metal network In addition, a dye-sensitized solar cell having high adhesion between the semiconductor layer and the catalyst layer and excellent durability can be obtained.
Moreover, when the semiconductor electrode 3 contains titania, it can be set as a dye-sensitized solar cell with high photoelectric conversion efficiency.
Furthermore, when the catalyst electrode 4 contains at least one of a noble metal and carbon, it can be set as the electrode which has the outstanding catalytic action, and can be set as the dye-sensitized solar cell with high photoelectric conversion efficiency.

以下、本発明を詳細に説明する。
上記「透光性基板１」としては、ガラス、樹脂シート等からなる基板が挙げられる。樹脂シートは特に限定されず、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリフェニレンスルフィド、ポリカーボネート、ポリスルフォン、ポリエチリデンノルボルネン等からなる樹脂シートが挙げられる。
尚、透光性とは、波長４００〜９００ｎｍの可視光の透過率が１０％以上であることを意味する。また、この透過率は６０％以上、特に８５％以上であることが好ましい。以下、透光性の意味及び好ましい透過率はすべて同様である。
透過率（％）＝（透過した光量／入射した光量）×１００
透光性基板１の厚さは材質によっても異なり、特に限定されないが、上記の透過率が６０〜９９％、特に８５〜９９％となる厚さであることが好ましい。 Hereinafter, the present invention will be described in detail.
Examples of the “translucent substrate 1” include substrates made of glass, resin sheets, and the like. The resin sheet is not particularly limited, and examples thereof include resin sheets made of polyester such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polycarbonate, polysulfone, and polyethyleneidene norbornene.
In addition, translucency means that the transmittance | permeability of visible light with a wavelength of 400-900 nm is 10% or more. The transmittance is preferably 60% or more, particularly 85% or more. Hereinafter, the meaning of translucency and preferable transmittance are all the same.
Transmittance (%) = (transmitted light amount / incident light amount) × 100
The thickness of the translucent substrate 1 varies depending on the material and is not particularly limited. However, it is preferable that the transmissivity is 60 to 99%, particularly 85 to 99%.

透光性基板１に対向して配設される上記「基板２」は、透光性を有していてもよく、透光性を有していなくてもよい。透光性を有する基板２は、透光性基板１の場合と同様にガラス、樹脂シート等を用いて形成することができる。樹脂シートである場合、このシートの形成に用いる樹脂としては、ポリエステル、ポリフェニレンスルフィド、ポリカーボネート、ポリスルフォン、ポリエチリデンノルボルネン等の熱可塑性樹脂などが挙げられる。この基板２が透光性を有する基板である場合、その厚さは材質によっても異なり、特に限定されないが、上記の透過率が６０〜９９％、特に８５〜９９％となる厚さであることが好ましい。   The “substrate 2” disposed opposite to the light-transmitting substrate 1 may have a light-transmitting property or may not have a light-transmitting property. The substrate 2 having a light-transmitting property can be formed using glass, a resin sheet, or the like as in the case of the light-transmitting substrate 1. In the case of a resin sheet, examples of the resin used for forming the sheet include thermoplastic resins such as polyester, polyphenylene sulfide, polycarbonate, polysulfone, and polyethylidene norbornene. When the substrate 2 is a light-transmitting substrate, the thickness varies depending on the material and is not particularly limited, but the above-described transmittance is 60 to 99%, particularly 85 to 99%. Is preferred.

透光性を有していない基板２はセラミックにより形成することができる。セラミック基板は強度が大きく、この基板が支持基板となって優れた耐久性を有する色素増感型太陽電池とすることができる。セラミック基板の形成に用いるセラミックは特に限定されず、酸化物系セラミック、窒化物系セラミック、炭化物系セラミック等の各種のセラミックを用いることができる。酸化物系セラミックとしては、アルミナ、ムライト、ジルコニア等が挙げられる。また、窒化物系セラミックとしては、窒化ケイ素、サイアロン、窒化チタン、窒化アルミニウム等が挙げられる。更に、炭化物系セラミックとしては、炭化ケイ素、炭化チタン、炭化アルミニウム等が挙げられる。セラミックとしては、アルミナ、窒化ケイ素、ジルコニア等が好ましく、アルミナが特に好ましい。   The substrate 2 that does not have translucency can be formed of ceramic. The ceramic substrate has high strength, and this substrate can be used as a support substrate to provide a dye-sensitized solar cell having excellent durability. The ceramic used for forming the ceramic substrate is not particularly limited, and various ceramics such as an oxide ceramic, a nitride ceramic, and a carbide ceramic can be used. Examples of the oxide ceramic include alumina, mullite, zirconia and the like. Examples of the nitride ceramic include silicon nitride, sialon, titanium nitride, and aluminum nitride. Further, examples of the carbide-based ceramic include silicon carbide, titanium carbide, and aluminum carbide. As the ceramic, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable.

基板２がセラミックからなる場合、その厚さは特に限定されないが、１００μｍ〜５ｍｍとすることができ、３００μｍ〜４ｍｍ、特に５００μｍ〜２ｍｍ、更に７００μｍ〜１．５ｍｍとすることができる。セラミック基板の厚さが１００μｍ〜５ｍｍ、特に５００μｍ以上であれば、この強度の大きい基板が支持基板となり、優れた耐久性を有する色素増感型太陽電池とすることができる。   When the board | substrate 2 consists of ceramics, the thickness is not specifically limited, However, It can be referred to as 100 micrometers-5 mm, 300 micrometers-4 mm, Especially 500 micrometers-2 mm, Furthermore, it can be set as 700 micrometers-1.5 mm. When the thickness of the ceramic substrate is 100 μm to 5 mm, particularly 500 μm or more, the substrate having this high strength becomes a support substrate, and a dye-sensitized solar cell having excellent durability can be obtained.

本発明の色素増感型太陽電池及び本発明の更に他の色素増感型太陽電池における上記「半導体電極３」は、透光性基板１と基板２との間の透光性基板１の側に配設される。この透光性基板１の側とは、透光性基板１に接して配設されるか、透光性基板１の表面と半導体電極３の表面との間の距離が５０μｍ以下、特に２０μｍ以下、更に５μｍ以下であることを意味する。この距離が５０μｍ以下、特に２０μｍ以下であれば、半導体電極３に十分な光が照射され、優れた光電変換効率を有する色素増感型太陽電池とすることができる。
この半導体電極３は、図１のように、金属線状体６１の表面の少なくとも一部に設けられた、増感色素を有する半導体層３１、及び図４及び図５のように、金属網状体７１の表面の少なくとも一部に設けられた、増感色素を有する半導体層３２のうちの少なくとも一方からなる。半導体層３１、３２の各々は、金属線状体６１、金属網状体７１のそれぞれの全表面の９０％以上、特に９５％以上に設けられることが好ましく、全表面に設けられていることがより好ましい。 The “semiconductor electrode 3” in the dye-sensitized solar cell of the present invention and still another dye-sensitized solar cell of the present invention is the translucent substrate 1 side between the translucent substrate 1 and the substrate 2. It is arranged. The translucent substrate 1 side is disposed in contact with the translucent substrate 1 or the distance between the surface of the translucent substrate 1 and the surface of the semiconductor electrode 3 is 50 μm or less, particularly 20 μm or less. Furthermore, it means that it is 5 μm or less. When this distance is 50 μm or less, particularly 20 μm or less, the semiconductor electrode 3 is irradiated with sufficient light, and a dye-sensitized solar cell having excellent photoelectric conversion efficiency can be obtained.
The semiconductor electrode 3 includes a semiconductor layer 31 having a sensitizing dye provided on at least a part of the surface of the metal linear body 61 as shown in FIG. 1, and a metal network as shown in FIGS. It consists of at least one of the semiconductor layers 32 having a sensitizing dye provided on at least a part of the surface of 71. Each of the semiconductor layers 31 and 32 is preferably provided on 90% or more, particularly 95% or more of the entire surface of each of the metal linear body 61 and the metal network 71, and more preferably provided on the entire surface. preferable.

また、本発明の他の色素増感型太陽電池における半導体電極３は、透光性基板１の表面に設けられる。   Further, the semiconductor electrode 3 in another dye-sensitized solar cell of the present invention is provided on the surface of the translucent substrate 1.

上記「半導体層３１」及び上記「半導体層３２」並びに本発明の他の色素増感型太陽電池における半導体電極３の電極基体は、金属酸化物、金属硫化物等により形成することができる。金属酸化物としては、チタニア、酸化スズ、酸化亜鉛、五酸化二ニオブ等の酸化ニオブ、酸化タンタル、ジルコニア等が挙げられる。また、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸バリウム等の複酸化物を用いることもできる。更に、金属硫化物としては、硫化亜鉛、硫化鉛、硫化ビスマス等が挙げられる。   The electrode substrate of the semiconductor electrode 3 in the “semiconductor layer 31” and the “semiconductor layer 32” and the other dye-sensitized solar cell of the present invention can be formed of a metal oxide, a metal sulfide, or the like. Examples of the metal oxide include titania, tin oxide, zinc oxide, niobium oxide such as niobium pentoxide, tantalum oxide, and zirconia. In addition, double oxides such as strontium titanate, calcium titanate, and barium titanate can also be used. Furthermore, examples of the metal sulfide include zinc sulfide, lead sulfide, and bismuth sulfide.

半導体層３１、３２及び本発明の他の色素増感型太陽電池における半導体電極３の電極基体の作製方法は特に限定されず、例えば、金属酸化物、金属硫化物等の微粒子を含有するペーストを、半導体層３１の場合は金属線状体６１の表面の少なくとも一部に塗布し、半導体層３２の場合は金属網状体７１の表面の少なくとも一部に塗布し、本発明の他の色素増感型太陽電池における半導体電極３の電極基体の場合は透光性基板１の表面に塗布し、その後、焼成することにより作製することができる。ペーストの塗布方法は特に限定されず、スプレーコート法、浸漬法等が挙げられる。このようにして作製された半導体層３１、３２及び電極基体は微粒子が集合してなる集合体の形態で形成される。   There are no particular limitations on the method of manufacturing the electrode base of the semiconductor electrode 3 in the semiconductor layers 31 and 32 and other dye-sensitized solar cells of the present invention. For example, a paste containing fine particles such as metal oxides and metal sulfides is used. In the case of the semiconductor layer 31, it is applied to at least a part of the surface of the metal linear body 61, and in the case of the semiconductor layer 32, it is applied to at least a part of the surface of the metal network 71, and other dye sensitization of the present invention. In the case of the electrode base of the semiconductor electrode 3 in the solar cell, it can be produced by applying it to the surface of the translucent substrate 1 and then firing it. The method for applying the paste is not particularly limited, and examples thereof include a spray coating method and a dipping method. The semiconductor layers 31 and 32 and the electrode substrate thus fabricated are formed in the form of an aggregate formed by collecting fine particles.

更に、半導体層３１、３２及び本発明の他の色素増感型太陽電池における半導体電極３の電極基体は、半導体層３１の場合は金属線状体６１の表面の少なくとも一部に、半導体層３２の場合は金属網状体７１の表面の少なくとも一部に、及び本発明の他の色素増感型太陽電池における半導体電極３の電極基体の場合は透光性基板１の表面に、金属酸化物、金属硫化物等の微粒子及び少量の有機高分子等が分散されたコロイド溶液を塗布し、その後、乾燥し、次いで、加熱して有機高分子を分解させて除去することにより作製することもできる。このコロイド溶液も、スプレーコート法、浸漬法等の各種の方法により塗布することができる。この方法により作製した半導体層３１、３２及び電極基体も微粒子が集合してなる集合体の形態で形成される。   Furthermore, in the case of the semiconductor layer 31, the electrode base of the semiconductor electrode 3 in the semiconductor layers 31 and 32 and another dye-sensitized solar cell of the present invention is formed on at least a part of the surface of the metal linear body 61. In the case of the above, at least a part of the surface of the metal network 71, and in the case of the electrode substrate of the semiconductor electrode 3 in the other dye-sensitized solar cell of the present invention, the surface of the translucent substrate 1, the metal oxide, It can also be produced by applying a colloidal solution in which fine particles such as metal sulfide and a small amount of organic polymer are dispersed, then drying, and then heating to decompose and remove the organic polymer. This colloidal solution can also be applied by various methods such as spray coating and dipping. The semiconductor layers 31 and 32 and the electrode base produced by this method are also formed in the form of an aggregate formed by collecting fine particles.

半導体層３１及び半導体層３２の各々の厚さは特に限定されないが、０．１〜１００μｍとすることができ、１〜９０μｍ、特に１５〜８０μｍ、更に３０〜７０μｍであることが好ましい。各々の半導体層の厚さが０．１〜１００μｍ、特に１５〜８０μｍであれば、光電変換が十分になされ、発電効率が向上する。また、電極基体の厚さも特に限定されないが、０．１〜１００μｍとすることができ、１〜５０μｍ、特に２〜４０μｍ、更に５〜３０μｍであることが好ましい。電極基体の厚さが０．１〜１００μｍであれば、光電変換が十分になされ、発電効率が向上する。   The thickness of each of the semiconductor layer 31 and the semiconductor layer 32 is not particularly limited, but may be 0.1 to 100 μm, preferably 1 to 90 μm, particularly 15 to 80 μm, and more preferably 30 to 70 μm. When the thickness of each semiconductor layer is 0.1 to 100 μm, particularly 15 to 80 μm, photoelectric conversion is sufficiently performed and power generation efficiency is improved. The thickness of the electrode substrate is not particularly limited, but may be 0.1 to 100 μm, preferably 1 to 50 μm, particularly 2 to 40 μm, and more preferably 5 to 30 μm. When the thickness of the electrode substrate is 0.1 to 100 μm, photoelectric conversion is sufficiently performed and power generation efficiency is improved.

更に、半導体層３１は、その強度及び金属線状体６１との密着性を向上させるため、半導体層３２は、その強度及び金属網状体７１との密着性を向上させるため、電極基体は、その強度及び透光性導電層２１との密着性を向上させるため、熱処理することが好ましい。熱処理の温度及び時間は特に限定されないが、熱処理温度は４０〜７００℃、特に１００〜５００℃、熱処理時間は１０分〜１０時間、特に２０分〜５時間とすることが好ましい。尚、電極基体の場合、透光性基板１として樹脂シートを用いるときは、樹脂が熱劣化しないように低温で熱処理することが好ましい。   Further, the semiconductor layer 31 improves its strength and adhesion to the metal linear body 61, and the semiconductor layer 32 improves its strength and adhesion to the metal network 71. In order to improve strength and adhesion to the light-transmitting conductive layer 21, heat treatment is preferably performed. The temperature and time of the heat treatment are not particularly limited, but the heat treatment temperature is preferably 40 to 700 ° C., particularly 100 to 500 ° C., and the heat treatment time is preferably 10 minutes to 10 hours, particularly preferably 20 minutes to 5 hours. In the case of an electrode substrate, when a resin sheet is used as the translucent substrate 1, it is preferable to perform heat treatment at a low temperature so that the resin is not thermally deteriorated.

半導体電極３が有する上記「増感色素」としては、光電変換の作用を向上させる錯体色素及び有機色素を用いることができる。錯体色素としては金属錯体色素が挙げられ、有機色素としてはポリメチン色素、メロシアニン色素等が挙げられる。金属錯体色素としてはルテニウム錯体色素及びオスミウム錯体色素等が挙げられ、ルテニウム錯体色素が特に好ましい。更に、光電変換がなされる波長域を拡大し、光電変換効率を向上させるため、増感作用が発現される波長域の異なる２種以上の増感色素を併用することもできる。この場合、照射される光の波長域と強度分布とによって併用する増感色素の種類及びそれらの量比を設定することが好ましい。また、増感色素は半導体電極に結合するための官能基を有することが好ましい。この官能基としては、カルボキシル基、スルホン酸基、シアノ基等が挙げられる。   As said "sensitizing dye" which the semiconductor electrode 3 has, the complex dye and organic dye which improve the effect | action of a photoelectric conversion can be used. Examples of complex dyes include metal complex dyes, and examples of organic dyes include polymethine dyes and merocyanine dyes. Examples of the metal complex dye include a ruthenium complex dye and an osmium complex dye, and a ruthenium complex dye is particularly preferable. Furthermore, in order to expand the wavelength range in which photoelectric conversion is performed and improve the photoelectric conversion efficiency, two or more sensitizing dyes having different wavelength ranges in which a sensitizing action is exhibited can be used in combination. In this case, it is preferable to set the type of sensitizing dye to be used in combination and the amount ratio thereof depending on the wavelength range and intensity distribution of the irradiated light. The sensitizing dye preferably has a functional group for bonding to the semiconductor electrode. Examples of this functional group include a carboxyl group, a sulfonic acid group, and a cyano group.

半導体層３１、３２及び電極基体に増感色素を付着させる方法は特に限定されず、例えば、増感色素を有機溶媒に溶解させた溶液に、金属線状体６１及びその表面に設けられた半導体層３１、金属網状体７１及びその表面に設けられた半導体層３２、透光性基板１の表面に設けられた電極基体、を浸漬し、各々の半導体層及び電極基体に溶液を含侵させ、その後、有機溶媒を除去することにより付着させることができる。また、この溶液を、半導体層３１、３２及び電極基体に塗布し、その後、有機溶媒を除去することにより付着させることもできる。この塗布方法としては、スプレーコート法、浸漬法等が挙げられる。増感色素は、半導体層３１、３２及び電極基体の各々の少なくとも表面に付着しておればよいが、半導体層３１、３２及び電極基体の各々の内部においても付着していることが好ましい。通常、増感色素は、半導体層３１、３２及び電極基体の各々の全体に付着している。   The method for attaching the sensitizing dye to the semiconductor layers 31 and 32 and the electrode substrate is not particularly limited. For example, the metal linear body 61 and the semiconductor provided on the surface thereof in a solution obtained by dissolving the sensitizing dye in an organic solvent. The layer 31, the metal network 71 and the semiconductor layer 32 provided on the surface of the layer 31, the electrode base provided on the surface of the translucent substrate 1 are immersed, and each semiconductor layer and the electrode base are impregnated with the solution. Then, it can be made to adhere by removing an organic solvent. Alternatively, the solution can be applied to the semiconductor layers 31 and 32 and the electrode substrate, and then adhered by removing the organic solvent. Examples of the coating method include a spray coating method and a dipping method. The sensitizing dye may be attached to at least the surface of each of the semiconductor layers 31 and 32 and the electrode substrate, but it is preferable that the sensitizing dye is also attached to the inside of each of the semiconductor layers 31 and 32 and the electrode substrate. Usually, the sensitizing dye is attached to the entirety of each of the semiconductor layers 31 and 32 and the electrode substrate.

増感色素の付着量は、半導体層３１、３２及び電極基体１ｇに対して０．０１〜１ミリモル、特に０．５〜１ミリモルであることが好ましい。付着量が０．０１〜１ミリモルであれば、半導体電極３における光電変換が効率よくなされる。また、半導体層３１、３２及び電極基体に付着しなかった増感色素が電極周辺に遊離していると、光電変換効率が低下することがある。そのため、増感色素を付着させる処理の後、半導体電極３を洗浄して余剰の増感色素を除去することが好ましい。この除去は、洗浄槽を用いてアセトニトリル等の極性溶媒及びアルコール系溶媒などの有機溶媒で洗浄することにより行うことができる。また、半導体層及び電極基体に多くの増感色素を付着させるためには、半導体層及び電極基体を加熱して、浸漬、塗布等の処理を行うことが好ましい。この場合、半導体層及び電極基体の表面に水が吸着するのを避けるため、加熱後、常温に降温させることなく４０〜８０℃で速やかに処理することが好ましい。   The adhesion amount of the sensitizing dye is preferably 0.01 to 1 mmol, particularly 0.5 to 1 mmol with respect to the semiconductor layers 31 and 32 and the electrode substrate 1 g. When the adhesion amount is 0.01 to 1 mmol, photoelectric conversion in the semiconductor electrode 3 is efficiently performed. Moreover, if the sensitizing dye that has not adhered to the semiconductor layers 31 and 32 and the electrode substrate is liberated around the electrode, the photoelectric conversion efficiency may be lowered. Therefore, it is preferable to remove the excess sensitizing dye by washing the semiconductor electrode 3 after the process of attaching the sensitizing dye. This removal can be performed by washing with a polar solvent such as acetonitrile and an organic solvent such as an alcohol solvent using a washing tank. Moreover, in order to attach many sensitizing dyes to the semiconductor layer and the electrode substrate, it is preferable to heat the semiconductor layer and the electrode substrate and perform a treatment such as dipping or coating. In this case, in order to avoid water adsorbing on the surfaces of the semiconductor layer and the electrode substrate, it is preferable to perform the treatment promptly at 40 to 80 ° C. without heating to room temperature after heating.

本発明の他の色素増感型太陽電池及び本発明の更に他の色素増感型太陽電池における上記「触媒電極４」は、透光性基板１と基板２との間に該半導体電極３に対向して配設される。触媒電極４は基板２に接して配設されていてもよく、基板２とは離間して配設されていてもよい。このように、基板２と触媒電極４との距離は特定されないが、半導体電極３の表面と触媒電極４の表面との間の距離を２００μｍ以下とすることができ、この距離は、１００μｍ以下、特に５０μｍ以下、更に２０μｍ以下であることが好ましい。この距離が２００μｍ以下、特に５０μｍ以下であれば、光電変換効率を十分に高くすることができる。
この触媒電極４は、図１のように、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１、及び図４及び図５のように、金属網状体７２の表面の少なくとも一部に設けられた触媒層４２のうちの少なくとも一方からなる。触媒層４１、４２の各々は、金属線状体６１、金属網状体７１のそれぞれの全表面の９０％以上、特に９５％以上に設けられることが好ましく、全表面に設けられていることがより好ましい。 The above-mentioned “catalyst electrode 4” in another dye-sensitized solar cell of the present invention and still another dye-sensitized solar cell of the present invention is formed on the semiconductor electrode 3 between the translucent substrate 1 and the substrate 2. Opposed to each other. The catalyst electrode 4 may be disposed in contact with the substrate 2 or may be disposed away from the substrate 2. Thus, although the distance between the substrate 2 and the catalyst electrode 4 is not specified, the distance between the surface of the semiconductor electrode 3 and the surface of the catalyst electrode 4 can be 200 μm or less, and this distance is 100 μm or less, In particular, it is preferably 50 μm or less, more preferably 20 μm or less. If this distance is 200 μm or less, particularly 50 μm or less, the photoelectric conversion efficiency can be sufficiently increased.
The catalyst electrode 4 includes a catalyst layer 41 provided on at least a part of the surface of the metal linear body 62 as shown in FIG. 1 and at least one of the surfaces of the metal network 72 as shown in FIGS. It consists of at least one of the catalyst layers 42 provided in the part. Each of the catalyst layers 41 and 42 is preferably provided on 90% or more, particularly 95% or more of the entire surface of each of the metal linear body 61 and the metal network 71, and more preferably provided on the entire surface. preferable.

また、本発明の色素増感型太陽電池における触媒電極４は、基板２の表面に設けられる。   Further, the catalyst electrode 4 in the dye-sensitized solar cell of the present invention is provided on the surface of the substrate 2.

触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４は、触媒活性を有する物質、又は触媒活性を有する物質を含有する、金属、導電性酸化物及び導電性高分子のうちの少なくとも１種、により形成することができる。触媒活性を有する物質としては、白金、金、ロジウム等の貴金属（但し、銀は電解質等に対する耐腐食性が低いため好ましくない。以下、電解質等が接触し得る部分には同様に銀は好ましくない。）、カーボンブラック等が挙げられ、これらは併せて導電性を有する。貴金属は１種のみ用いてもよいし、２種以上を用いてもよい。触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４は、触媒活性を有し、且つ電気化学的に安定な貴金属により形成することが好ましく、触媒活性が高く、電解質溶液に溶解され難い白金を用いることが特に好ましい。尚、貴金属とカーボンブラックとを併用することもできる。   The catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention include a substance having catalytic activity or a substance having catalytic activity among metals, conductive oxides, and conductive polymers. Can be formed by at least one of the following. As a substance having catalytic activity, noble metals such as platinum, gold and rhodium (however, silver is not preferred because of its low corrosion resistance to electrolytes, etc. Hereinafter, silver is also not preferred for the parts where the electrolyte etc. can contact) .), Carbon black and the like, and these have conductivity together. Only one type of noble metal may be used, or two or more types may be used. The catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention are preferably formed of a noble metal that has catalytic activity and is electrochemically stable. It is particularly preferable to use platinum that is hardly dissolved. In addition, a noble metal and carbon black can be used in combination.

触媒活性を有さない、金属、導電性酸化物及び導電性高分子等を用いる場合、触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４に混合されて用いられる金属としては、アルミニウム、銅、クロム、ニッケル、タングステン等が挙げられる。更に、触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４に混合されて用いられる導電性酸化物としては、酸化スズ、フッ素ドープ酸化スズ、酸化インジウム、スズドープ酸化インジウム、酸化亜鉛等が挙げられる。また、触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４に混合されて用いられる導電性高分子としては、ポリアニリン、ポリピロール、ポリアセチレン等が挙げられる。更に、この導電性高分子としては、導電性を有さない樹脂に各種の導電性物質を配合して調製したものを用いることもできる。この樹脂は特に限定されず、熱可塑性樹脂でも熱硬化性樹脂でもよい。熱可塑性樹脂としては、熱可塑性ポリエステル樹脂、ポリアミド、ポリオレフィン、ポリ塩化ビニル等が挙げられる。また、熱硬化性樹脂としては、エポキシ樹脂、熱硬化性ポリエステル樹脂、フェノール樹脂等が挙げられる。導電性物質も特に限定されず、金、白金等の貴金属及び銅、アルミニウム、ニッケル、クロム、タングステン等の金属、カーボンブラック、ポリアニリン、ポリピロール、ポリアセチレン等の導電性ポリマーなどが挙げられる。導電性物質としては、導電性と触媒活性とを併せて有する貴金属及びカーボンブラックが特に好ましい。導電性物質は１種のみ用いてもよく、２種以上を用いてもよい。
触媒活性を有さない、金属、導電性酸化物及び導電性高分子等を用いる場合、上記の触媒活性を有する物質の含有量は、金属、導電性酸化物、導電性高分子等を１００質量部とした場合に、１〜９９質量部、特に５０〜９９質量部であることが好ましい。 In the case of using a metal, a conductive oxide, a conductive polymer, or the like that does not have catalytic activity, as a metal used by being mixed with the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention. Includes aluminum, copper, chromium, nickel, tungsten, and the like. Furthermore, as the conductive oxide used by being mixed with the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention, tin oxide, fluorine-doped tin oxide, indium oxide, tin-doped indium oxide, oxidation Zinc etc. are mentioned. Examples of the conductive polymer used by being mixed with the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention include polyaniline, polypyrrole, and polyacetylene. Further, as the conductive polymer, those prepared by blending various conductive substances with a resin having no conductivity can also be used. This resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include thermoplastic polyester resin, polyamide, polyolefin, polyvinyl chloride, and the like. Moreover, as a thermosetting resin, an epoxy resin, a thermosetting polyester resin, a phenol resin, etc. are mentioned. The conductive material is not particularly limited, and examples thereof include noble metals such as gold and platinum, metals such as copper, aluminum, nickel, chromium, and tungsten, and conductive polymers such as carbon black, polyaniline, polypyrrole, and polyacetylene. As the conductive substance, a noble metal and carbon black having both conductivity and catalytic activity are particularly preferable. Only one type of conductive material may be used, or two or more types may be used.
When metals, conductive oxides, conductive polymers, etc. that do not have catalytic activity are used, the content of the above-mentioned substances having catalytic activity is 100 masses of metals, conductive oxides, conductive polymers, etc. Parts, preferably 1 to 99 parts by mass, particularly 50 to 99 parts by mass.

このように、触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４は、導電性及び触媒活性を有する物質により形成することができる。また、触媒活性を有する物質を含有する、金属、導電性酸化物及び導電性高分子のうちの少なくとも１種により形成することもできる。更に、触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４は、１種の材料のみからなる層により形成されていてもよく、２種以上の材料からなる混合層により形成されていてもよい。また、単層体でもよく、金属層、導電性酸化物層、導電性高分子層、並びに金属、導電性酸化物及び導電性高分子のうちの２種以上からなる混合層のうちの２層以上からなる多層体でもよい。   Thus, the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention can be formed of a material having conductivity and catalytic activity. Further, it can be formed of at least one of a metal, a conductive oxide and a conductive polymer containing a substance having catalytic activity. Furthermore, the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention may be formed by a layer made of only one kind of material or may be formed by a mixed layer made of two or more kinds of materials. May be. Moreover, a single layer body may be sufficient and two layers of the mixed layer which consists of 2 or more types of a metal layer, a conductive oxide layer, a conductive polymer layer, and a metal, a conductive oxide, and a conductive polymer The multilayer body which consists of the above may be sufficient.

触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４の作製方法は特に限定されず、触媒活性を有する物質からなる場合は、触媒活性を有する物質の微粒子を含有するペーストを、触媒層４１のときは金属線状体６２の表面の少なくとも一部に塗布し、触媒層４２のときは金属網状体７２の表面の少なくとも一部に塗布し、本発明の色素増感型太陽電池における触媒電極４のときは基板２の表面に塗布し、その後、焼成して形成することができる。また、触媒活性を有する物質を含有する金属、導電性酸化物からなる場合も、触媒活性を有する物質の場合と同様の方法により形成することができる。この塗布方法としては、スクリーン印刷法、ドクターブレード法、スキージ法、スピンコート法等の各種の方法が挙げられる。   The method for producing the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention is not particularly limited. When the catalyst electrode 4 is made of a substance having catalytic activity, a paste containing fine particles of the substance having catalytic activity is used. In the case of the catalyst layer 41, it is applied to at least part of the surface of the metal linear body 62, and in the case of the catalyst layer 42, it is applied to at least part of the surface of the metal network 72, and the dye-sensitized solar of the present invention. In the case of the catalyst electrode 4 in the battery, it can be formed by coating on the surface of the substrate 2 and then firing. In addition, when a metal containing a substance having catalytic activity or a conductive oxide is used, it can be formed by the same method as in the case of a substance having catalytic activity. Examples of the coating method include various methods such as a screen printing method, a doctor blade method, a squeegee method, and a spin coating method.

更に、触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４は、スパッタリング法、蒸着法、イオンプレーティング法等により、触媒層４１のときは金属線状体６２の表面の少なくとも一部に、触媒層４２のときは金属網状体７２の表面の少なくとも一部に、本発明の色素増感型太陽電池における触媒電極４のときは基板２の表面に、金属等を堆積させて形成することもできる。また、触媒活性を有する物質を含有する導電性高分子からなる触媒層４１、４２及び本発明の色素増感型太陽電池における触媒電極４は、導電性高分子と、粉末状又は繊維状等の触媒活性を有する物質とを、バンバリーミキサ、インターナルミキサー、オープンロール等の装置により混練して調製した樹脂組成物をフィルムに成形し、このフィルムを金属線状体６２、金属網状体７２、及び基板２の表面に接合して形成することができる。更に、樹脂組成物を溶媒に溶解又は分散させて調製した溶液又は分散液を、金属線状体６２、金属網状体７２、及び基板２の表面に塗布し、乾燥して、溶媒を除去し、必要に応じて加熱して形成することもできる。尚、触媒層４１、触媒層４２、及び本発明の色素増感型太陽電池における触媒電極４が混合層であるときは、含有される材料の種類に応じて、上記の各種の方法等のうちの適宜の方法により形成することができる。   Furthermore, the catalyst layers 41 and 42 and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention are formed on the surface of the metal linear body 62 when the catalyst layer 41 is formed by sputtering, vapor deposition, ion plating, or the like. A metal or the like is deposited on at least a part, at least part of the surface of the metal network 72 in the case of the catalyst layer 42, or on the surface of the substrate 2 in the case of the catalyst electrode 4 in the dye-sensitized solar cell of the present invention. It can also be formed. Further, the catalyst layers 41 and 42 made of a conductive polymer containing a substance having catalytic activity and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention include a conductive polymer and a powdery or fibrous form. A resin composition prepared by kneading a substance having catalytic activity with an apparatus such as a Banbury mixer, an internal mixer, or an open roll is formed into a film, and the film is formed into a metal linear body 62, a metal network 72, and It can be formed by bonding to the surface of the substrate 2. Further, a solution or dispersion prepared by dissolving or dispersing the resin composition in a solvent is applied to the surfaces of the metal linear body 62, the metal network 72, and the substrate 2, and dried to remove the solvent, It can also be formed by heating as required. In addition, when the catalyst layer 41, the catalyst layer 42, and the catalyst electrode 4 in the dye-sensitized solar cell of the present invention are mixed layers, depending on the type of material contained, It can be formed by any appropriate method.

触媒層４１及び触媒層４２の各々の厚さは電池性能に特に影響は与えず、金属線状体６２及び金属網状体７２の表面に僅かでも触媒物質が付着しておれば触媒電極４として機能する。この触媒電極４では、集電電極として機能する金属線状体６２及び金属網状体７２の各々の電気抵抗を十分に低くすることができ、触媒層４１、４２の厚さが２０ｎｍ以下、特に１５ｎｍ以下（通常、１０ｎｍ以上）であっても十分な触媒機能を有する電極とすることができる。また、本発明の色素増感型太陽電池における触媒電極４の厚さも特に限定されないが、単層体及び多層体のいずれの場合も、５０ｎｍ〜１０μｍ、特に１００ｎｍ〜５μｍであることが好ましい。この触媒電極の厚さが５０ｎｍ〜１０μｍであれば、十分に抵抗の低い触媒電極とすることができる。この触媒電極４の場合も、十分に電気抵抗の低い集電電極を付設したときは更に薄くすることができ、２０ｎｍ以下、特に１５ｎｍ以下（通常、１０ｎｍ以上）とすることもできる。   The thickness of each of the catalyst layer 41 and the catalyst layer 42 does not particularly affect the battery performance, and functions as the catalyst electrode 4 as long as even a small amount of the catalyst substance adheres to the surfaces of the metal linear body 62 and the metal net body 72. To do. In this catalyst electrode 4, the electric resistance of each of the metal linear body 62 and the metal network 72 functioning as a collecting electrode can be sufficiently reduced, and the thickness of the catalyst layers 41, 42 is 20 nm or less, particularly 15 nm. Even if it is below (usually 10 nm or more), it can be set as the electrode which has sufficient catalyst function. Further, the thickness of the catalyst electrode 4 in the dye-sensitized solar cell of the present invention is not particularly limited, but it is preferably 50 nm to 10 μm, particularly preferably 100 nm to 5 μm in both cases of a single layer body and a multilayer body. When the thickness of the catalyst electrode is 50 nm to 10 μm, a sufficiently low resistance catalyst electrode can be obtained. In the case of the catalyst electrode 4 as well, when a collector electrode having a sufficiently low electric resistance is attached, the thickness can be further reduced to 20 nm or less, particularly 15 nm or less (usually 10 nm or more).

集電電極として機能する上記「金属線状体６１、６２」及び上記「金属網状体７１、７２」は、電解質に対する耐腐食性に優れた金属により形成されるか、少なくとも耐腐食性に優れた金属を含有することが好ましい。この金属としては、タングステン、ニッケル、チタン及び白金、金等の貴金属などが挙げられる。金属としては、より耐腐食性に優れるタングステン及び白金が好ましく、耐腐食性に優れ、且つ安価であるタングステンが特に好ましい。タングステンを用いる場合、金属線状体６１、６２及び金属網状体７１、７２は、純タングステン（この純タングステンとは、９９．９８％以上の純度であるタングステンをそのまま使用し、他の金属を混合しないことを意味する。）からなるものでもよく、タングステンと他の金属との混合物からなるものでもよい。これらのうちでは、純タングステンからなる線状体及び網状体が、電解質に対する耐腐食性に特に優れるため好ましい。   The “metal linear bodies 61 and 62” and the “metal net bodies 71 and 72” functioning as current collecting electrodes are formed of a metal having excellent corrosion resistance against an electrolyte, or at least excellent in corrosion resistance. It is preferable to contain a metal. Examples of the metal include noble metals such as tungsten, nickel, titanium, platinum, and gold. As the metal, tungsten and platinum that are more excellent in corrosion resistance are preferable, and tungsten that is excellent in corrosion resistance and inexpensive is particularly preferable. In the case of using tungsten, the metal linear bodies 61 and 62 and the metal net bodies 71 and 72 are pure tungsten (this pure tungsten is used as it is with a purity of 99.98% or more and mixed with other metals). Or a mixture of tungsten and another metal. Among these, a linear body and a net body made of pure tungsten are preferable because they are particularly excellent in corrosion resistance to an electrolyte.

タングステンと他の金属とを併用する場合は、タングステンと他の金属との合計を１００質量％とした場合に、タングステンの含有量は９５質量％以上、特に９８質量％以上、更に９９．９質量％以上（１００質量％であってもよい。但し、この１００質量％とは、９９．９８％以上の純度であるタングステンをそのまま使用し、他の金属を混合しないことである。）とすることが好ましい。タングステンの含有量が９５質量％以上であれば、集電効率が高く、且つ電解質に対する耐腐食性に優れ、十分な耐久性を有する半導体電極及び触媒電極とすることができる。   When tungsten and other metals are used in combination, the content of tungsten is 95% by mass or more, particularly 98% by mass or more, and further 99.9% by mass, when the total of tungsten and other metals is 100% by mass. % Or more (100 mass% may be used. However, the 100 mass% means that tungsten having a purity of 99.98% or more is used as it is and other metals are not mixed). Is preferred. When the content of tungsten is 95% by mass or more, a semiconductor electrode and a catalyst electrode having high current collection efficiency, excellent corrosion resistance to the electrolyte, and sufficient durability can be obtained.

金属線状体６１、６２の径方向の断面形状は特に限定されず、円形、楕円形及び三角形、四角形等の多角形のいずれであってもよい。更に、金属線状体の径方向の寸法（断面形状が円形であるときは直径、その他の形状であるときは最大寸法とする。）も特に限定されず、１〜２００μｍ、特に５〜１００μｍ、更に２０〜７５μｍのものを用いることができる。金属線状体が大径であるほど電気抵抗が低くなるため好ましく、一方、半導体層及び触媒層の厚さにもよるが、小径であるほど受光面の反対側にも光が到達し易くなるため好ましい。金属線状体の径方向の寸法が１〜２００μｍ、更に２０〜７５μｍであれば、集電電極として十分に機能し、且つ受光面の反対側にも光が到達し易い半導体電極とすることもでき、好ましい。尚、金属線状体の表面に半導体層又は触媒層を設ける際の作業性等にも何ら問題はない。   The cross-sectional shape in the radial direction of the metal linear bodies 61 and 62 is not particularly limited, and may be any of a polygon such as a circle, an ellipse, a triangle, and a quadrangle. Furthermore, the dimension in the radial direction of the metal linear body (diameter when the cross-sectional shape is circular, and maximum dimension when the cross-sectional shape is other) is not particularly limited, and is 1 to 200 μm, particularly 5 to 100 μm, Furthermore, a 20-75 micrometer thing can be used. The larger the diameter of the metal linear body, the lower the electric resistance, which is preferable. On the other hand, depending on the thickness of the semiconductor layer and the catalyst layer, the smaller the diameter, the easier the light reaches the opposite side of the light receiving surface. Therefore, it is preferable. If the dimension of the metal linear body in the radial direction is 1 to 200 μm, and further 20 to 75 μm, a semiconductor electrode that functions sufficiently as a current collecting electrode and can easily reach the other side of the light receiving surface can also be obtained. It is possible and preferable. There is no problem in workability and the like when the semiconductor layer or the catalyst layer is provided on the surface of the metal linear body.

また、金属線状体６１の表面に半導体層３１が設けられた半導体電極３、及び金属線状体６２の表面に触媒層４１が設けられた触媒電極４の、平面方向における配置も特に限定されないが、略同じ長さの半導体電極３及び触媒電極４を等間隔に平行に配設することが好ましい。更に、金属線状体６１の表面に半導体層３１が設けられた半導体電極３を、透光性基板１の全面に対して均等に配置させること、及び金属線状体６２の表面に触媒層４１が設けられた触媒電極４を、基板２の全面に対して均等に配置させること、がより好ましい。また、金属線状体６１の表面に半導体層３１が設けられた半導体電極３、及び金属線状体６２の表面に触媒層４１が設けられた触媒電極４を、隣り合う各々の半導体電極３及び触媒電極４のそれぞれが互いに密接するようにして配設することもできる。   Further, the arrangement in the planar direction of the semiconductor electrode 3 in which the semiconductor layer 31 is provided on the surface of the metal linear body 61 and the catalyst electrode 4 in which the catalyst layer 41 is provided on the surface of the metal linear body 62 is not particularly limited. However, it is preferable to arrange the semiconductor electrode 3 and the catalyst electrode 4 having substantially the same length in parallel at equal intervals. Furthermore, the semiconductor electrode 3 provided with the semiconductor layer 31 on the surface of the metal linear body 61 is arranged uniformly over the entire surface of the translucent substrate 1, and the catalyst layer 41 on the surface of the metal linear body 62. It is more preferable that the catalyst electrode 4 provided with is disposed evenly with respect to the entire surface of the substrate 2. Further, the semiconductor electrode 3 provided with the semiconductor layer 31 on the surface of the metal linear body 61 and the catalyst electrode 4 provided with the catalyst layer 41 on the surface of the metal linear body 62 are connected to each adjacent semiconductor electrode 3 and Each of the catalyst electrodes 4 may be disposed so as to be in close contact with each other.

金属網状体７１、７２としては、金属線状体を編織することにより形成された網状体を用いることができる。この場合、用いる金属線状体の径方向の断面形状は特に限定されず、円形、楕円形及び三角形、四角形等の多角形のいずれであってもよい。また、金属線状体の径方向の寸法（断面形状が円形であるときは直径、その他の形状であるときは最大寸法とする。）も特に限定されず、１〜１００μｍとすることができ、１５〜８５μｍ、特に３０〜７０μｍのものを用いることができる。更に、網目の大きさも特に限定されず、各々の網目の面積を１〜４００００μｍ２とすることができ、この網目の面積は、１００〜３００００μｍ２、特に１０００〜２００００μｍ２であることが好ましい。金属線状体の径方向の寸法が１〜１００μｍ、特に１５〜８５μｍであり、且つ網目の面積が１〜４００００μｍ２、特に１０００〜２００００μｍ２であれば、集電電極として十分に機能し、その表面に半導体層又は触媒層を設ける際の作業性等にも何ら問題はない。 As the metal nets 71 and 72, a net formed by knitting a metal linear body can be used. In this case, the radial cross-sectional shape of the metal linear body to be used is not particularly limited, and may be any of a circle, an ellipse, a triangle, a polygon such as a quadrangle, and the like. Further, the radial dimension of the metal linear body (the diameter when the cross-sectional shape is circular, and the maximum dimension when the cross-sectional shape is other) is not particularly limited, and can be 1 to 100 μm, The thing of 15-85 micrometers, especially 30-70 micrometers can be used. Furthermore, the size of the mesh is not particularly limited, the area of each mesh can be 1～40000Myuemu 2, the area of the mesh is preferably 100～30000Myuemu 2, in particular 1000~20000μm 2. 1~100μm the radial dimension of the metal wire-like body, in particular 15～85Myuemu, and the area of the mesh is 1～40000Myuemu 2, especially if a 1000～20000Myuemu 2, sufficiently functions as a collector electrode, its There is no problem in workability when the semiconductor layer or the catalyst layer is provided on the surface.

金属網状体７１、７２としては、金属シートに多数の貫通孔を設けた網状体を用いることもできる。この金属シートの厚さは特に限定されないが、１〜２００μｍとすることができ、５〜１００μｍ、更に２０〜７５μｍのものを用いることができる。また、貫通孔の平面形状も特に限定されず、円形、楕円形及び三角形、四角形等の多角形のいずれであってもよい。この貫通孔の平面方向の面積（上記の網目に相当する。）も特に限定されず、各々の貫通孔の面積を１〜４００００μｍ２とすることができ、この貫通孔の面積は、１００〜３００００μｍ２、特に１０００〜２００００μｍ２であることが好ましい。金属シートの厚さが１〜２００μｍ、更に２０〜７５μｍであり、且つ貫通孔の面積が１〜４００００μｍ２、特に１０００〜２００００μｍ２であれば、集電電極として十分に機能し、その表面に半導体層又は触媒層を設ける際の作業性等にも何ら問題はない。更に、貫通孔の配置も特に限定されないが、金属シートの全面に均等に配置されていることが好ましい。
尚、半導体層３２は、図４のように、金属網状体７１の表面に、金属網状体７１の平面形状と同一形状のシート状に形成されていてもよく、図５のように、網目の少なくとも一部に半導体層３２が形成されておらず、貫通部３３となっていてもよい。また、触媒層４２は、図４のように、金属網状体７２の表面に、金属網状体７２の平面形状と同一形状のシート状に形成されていてもよく、図５のように、網目の少なくとも一部に触媒層４２が形成されておらず、貫通部４３となっていてもよい。 As the metal nets 71 and 72, a net having a large number of through holes in a metal sheet can be used. The thickness of the metal sheet is not particularly limited, but may be 1 to 200 μm, 5 to 100 μm, and further 20 to 75 μm. Further, the planar shape of the through hole is not particularly limited, and may be any of a circle, an ellipse, a polygon such as a triangle, a quadrangle, and the like. The area of the through hole in the plane direction (corresponding to the mesh) is not particularly limited, and the area of each through hole can be 1 to 40000 μm 2, and the area of the through hole is 100 to 30000 μm. 2 and particularly preferably 1000 to 20000 μm 2 . The thickness of the metal sheet is 1 to 200 [mu] m, a further 20～75Myuemu, and the through hole of the area 1～40000Myuemu 2, especially if a 1000～20000Myuemu 2, sufficiently functions as a collector electrode, a semiconductor on the surface thereof There is no problem in workability or the like when the layer or the catalyst layer is provided. Furthermore, the arrangement of the through holes is not particularly limited, but it is preferable that the through holes are arranged uniformly over the entire surface of the metal sheet.
4, the semiconductor layer 32 may be formed on the surface of the metal mesh 71 in the form of a sheet having the same shape as the planar shape of the metal mesh 71. As shown in FIG. The semiconductor layer 32 may not be formed at least in part, and may be the through portion 33. Further, the catalyst layer 42 may be formed on the surface of the metal mesh 72 as shown in FIG. 4 in the form of a sheet having the same shape as the planar shape of the metal mesh 72. As shown in FIG. The catalyst layer 42 may not be formed at least in part, and may be the through portion 43.

金属線状体６１と半導体層３１との間及び／又は金属網状体７１と半導体層３２との間には、導電性酸化物からなる導電層８１を設けることができる。更に、金属線状体６２と触媒層４１との間及び／又は金属網状体７２と触媒層４２との間には、導電性酸化物からなる導電層８２を設けることができる（金属線状体６１、６２の場合について図示した図２参照）。この導電層８１、８２を設けることで、金属線状体及び金属網状体と、半導体層及び触媒層とを十分に密着させることができる。導電層８１、８２の形成に用いる導電性酸化物は特に限定されず、酸化スズ、フッ素ドープ酸化スズ、酸化インジウム、スズドープ酸化インジウム、酸化亜鉛等が挙げられる。また、導電層８１、８２の厚さは材質によっても異なり、特に限定されないが、１００ｎｍ〜１μｍ、特に２００〜５００ｎｍであることが好ましい。更に、導電層８１、８２の形成方法も特に限定されないが、導電性酸化物の微粒子を含有するペーストを、金属線状体６１、６２、金属網状体７１、７２の表面に塗布し、加熱する等の方法により形成することができる。この塗布方法としては、ドクターブレード法、スキージ法、スピンコート法等の各種の方法が挙げられる。導電層８１、８２は、導電性酸化物を用いたスパッタリング法、真空蒸着法、イオンプレーティング法等により形成することもできる。   A conductive layer 81 made of a conductive oxide can be provided between the metal linear body 61 and the semiconductor layer 31 and / or between the metal network 71 and the semiconductor layer 32. Furthermore, a conductive layer 82 made of a conductive oxide can be provided between the metal linear body 62 and the catalyst layer 41 and / or between the metal network 72 and the catalyst layer 42 (metal linear body). FIG. 2 illustrating the cases of 61 and 62). By providing the conductive layers 81 and 82, the metal linear body and the metal net body can be sufficiently adhered to the semiconductor layer and the catalyst layer. The conductive oxide used for forming the conductive layers 81 and 82 is not particularly limited, and examples thereof include tin oxide, fluorine-doped tin oxide, indium oxide, tin-doped indium oxide, and zinc oxide. The thickness of the conductive layers 81 and 82 varies depending on the material and is not particularly limited, but is preferably 100 nm to 1 μm, particularly preferably 200 to 500 nm. Further, the method for forming the conductive layers 81 and 82 is not particularly limited, but a paste containing conductive oxide fine particles is applied to the surfaces of the metal linear bodies 61 and 62 and the metal net bodies 71 and 72 and heated. It can be formed by such a method. Examples of the coating method include various methods such as a doctor blade method, a squeegee method, and a spin coating method. The conductive layers 81 and 82 can also be formed by a sputtering method, a vacuum evaporation method, an ion plating method, or the like using a conductive oxide.

上記「電解質５」は、半導体電極３の少なくとも一部に含有され、且つ透光性基板１と基板２との間に形成された空間のうちの、少なくとも半導体電極３と触媒電極４との間に充填される。電解質５は、通常、半導体電極３の全体に含有され、また、透光性基板１と基板２との間に形成された空間の全体に充填される。透光性基板１と、半導体層３１、３２との間に間隙がある場合は、この間隙に電解質５が充填されていてもよい。更に、基板２と、触媒層４１、４２との間に間隙がある場合は、この間隙に電解質５が充填されていてもよい。   The “electrolyte 5” is contained in at least a part of the semiconductor electrode 3, and is at least between the semiconductor electrode 3 and the catalyst electrode 4 in a space formed between the translucent substrate 1 and the substrate 2. Filled. The electrolyte 5 is usually contained in the entire semiconductor electrode 3 and filled in the entire space formed between the translucent substrate 1 and the substrate 2. When there is a gap between the translucent substrate 1 and the semiconductor layers 31 and 32, the gap 5 may be filled with the electrolyte 5. Further, when there is a gap between the substrate 2 and the catalyst layers 41 and 42, the gap 5 may be filled with the electrolyte 5.

電解質としては、（１）Ｉ２とヨウ化物、（２）Ｂｒ２と臭化物、（３）フェロシアン酸塩−フェリシアン酸塩、フェロセン−フェリシニウムイオン等の金属錯体、（４）ポリ硫化ナトリウム、アルキルチオール−アルキルジスルフィド等のイオウ化合物、（５）ビオロゲン色素、（６）ヒドロキノン−キノン、などを含有する電解質が挙げられる。（１）におけるヨウ化物としては、ＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＣａＩ２等の金属ヨウ化物、及びテトラアルキルアンモニウムヨーダイド、ピリジニウムヨーダイド、イミダゾリウムヨーダイド等の４級アンモニウム化合物のヨウ素塩などが挙げられる。また、（２）における臭化物としては、ＬｉＢｒ、ＮａＢｒ、ＫＢｒ、ＣｓＢｒ、ＣａＢｒ２等の金属臭化物、及びテトラアルキルアンモニウムブロマイド、ピリジニウムブロマイド等の４級アンモニウム化合物の臭素塩などが挙げられる。これらの電解質のうちでは、Ｉ２と、ＬｉＩ及びピリジニウムヨーダイド、イミダゾリウムヨーダイド等の４級アンモニウム化合物のヨウ素塩とを組み合わせてなる電解質が特に好ましい。これらの電解質は１種のみを用いてもよいし、２種以上を用いてもよい。 Examples of the electrolyte include (1) I 2 and iodide, (2) Br 2 and bromide, (3) metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ion, and (4) sodium polysulfide. And electrolytes containing sulfur compounds such as alkylthiol-alkyldisulfides, (5) viologen dyes, (6) hydroquinone-quinones, and the like. As iodide in (1) is, LiI, NaI, KI, CsI, metal iodide such as CaI 2, and tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide iodine salt of quaternary ammonium compounds such as id, etc. Is mentioned. As the bromide in (2), LiBr, NaBr, KBr, CsBr, CaBr 2 , etc. of the metal bromide, and tetra-alkyl ammonium bromide, bromine salts of quaternary ammonium compounds such as pyridinium bromide and the like. Among these electrolytes, an electrolyte obtained by combining I 2 and an iodine salt of a quaternary ammonium compound such as LiI, pyridinium iodide, and imidazolium iodide is particularly preferable. These electrolytes may use only 1 type and may use 2 or more types.

電解質５は、各種の添加剤等とともに溶媒に配合し、電解質溶液として用いることができる。この溶媒は、粘度が低く、イオン易動度が高く、十分なイオン伝導性を有するものであることが好ましい。このような溶媒としては、（１）エチレンカーボネート、プロピレンカーボネート等のカーボネート類、（２）３−メチル−２−オキサゾリジノン等の複素環化合物、（３）ジオキサン、ジエチルエーテル等のエーテル類、（４）エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテル等の鎖状エーテル類、（５）メタノール、エタノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、ポリプロピレングリコールモノアルキルエーテル等のモノアルコール類、（６）エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン等の多価アルコール類、（７）アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル類、（８）ジメチルスルフォキシド、スルフォラン等の非プロトン極性物質などが挙げられる。   The electrolyte 5 can be blended in a solvent together with various additives and used as an electrolyte solution. This solvent preferably has a low viscosity, a high ion mobility, and sufficient ion conductivity. Examples of such solvents include (1) carbonates such as ethylene carbonate and propylene carbonate, (2) heterocyclic compounds such as 3-methyl-2-oxazolidinone, (3) ethers such as dioxane and diethyl ether, (4 ) Chain ethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, (5) methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl Monoalcohols such as ether and polypropylene glycol monoalkyl ether, (6) ethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as polyglycol, polypropylene glycol and glycerin, (7) nitriles such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, and (8) aprotic such as dimethyl sulfoxide and sulfolane. Examples include polar substances.

電解質溶液を用いる場合、この溶液は、透光性基板１と基板２との間を、半導体電極３等の周囲において樹脂又はガラスにより封着し、形成される密閉空間に電解質溶液を注入し、含有、充填させることができる。この密閉空間への電解質溶液の注入は、透光性基板１の側からでも、基板２の側からでもよく、穿孔し易い側に注入口を設け、この注入口から注入することが好ましい。尚、注入口は１個でよいが、空気抜きのため更に他の孔を設けることもできる。このように空気抜きのための孔を設けることで、電解質溶液をより容易に注入することができる。   In the case of using an electrolyte solution, this solution is sealed between the translucent substrate 1 and the substrate 2 with resin or glass around the semiconductor electrode 3 and the like, and the electrolyte solution is injected into the formed sealed space, It can be contained and filled. The electrolyte solution may be injected into the sealed space from the translucent substrate 1 side or from the substrate 2 side, and it is preferable to provide an injection port on the side that is easily perforated and to inject from this injection port. In addition, although one injection port is sufficient, another hole can also be provided for air venting. Thus, by providing the hole for air venting, the electrolyte solution can be injected more easily.

半導体電極３等の周囲の封着に用いられる樹脂としては、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂、熱硬化性ポリエステル樹脂等の熱硬化性樹脂が挙げられる。更に、この封着はガラスにより行うこともでき、特に長期の耐久性を必要とする太陽電池では、ガラスにより封着することが好ましい。   Examples of the resin used for sealing around the semiconductor electrode 3 and the like include thermosetting resins such as epoxy resin, urethane resin, polyimide resin, and thermosetting polyester resin. Furthermore, this sealing can also be performed with glass, and it is preferable to seal with glass particularly in a solar cell that requires long-term durability.

本発明の色素増感型太陽電池では、基板２と触媒電極４との間に第２集電電極９２が設けられた図７の色素増感型太陽電池１０１−２、及び図１１の色素増感型太陽電池１０３−２とすることができる。この第２集電電極９２は、触媒電極４を白金、金等の導電性に優れる貴金属により形成し、特に２０ｎｍ以上、更に１μｍ以上（通常、１０μｍ以下）と厚くした場合は、導電性の観点からは設ける必要はないが、コストの面では設けることが好ましい。即ち、白金等は高価であるため、触媒電極４をできるだけ薄層とすることが好ましいが、薄層であると抵抗が高くなるため、タングステン、チタン、ニッケル等の金属からなる第２集電電極９２を設けることで、集電効率を向上させるとともに、コストを低減することができる。更に、触媒電極４を前記の導電性酸化物に触媒活性を有する物質を配合した組成物等により形成したときは、触媒電極４の抵抗はより高くなるため、第２集電電極９２を設け、集電効率を高めることがより好ましい。   In the dye-sensitized solar cell of the present invention, the dye-sensitized solar cell 101-2 of FIG. 7 in which the second collector electrode 92 is provided between the substrate 2 and the catalyst electrode 4, and the dye-sensitized solar cell of FIG. It can be set as the sensitive solar cell 103-2. The second current collecting electrode 92 is formed from a noble metal having excellent conductivity such as platinum or gold, and when the thickness is particularly 20 nm or more, and further 1 μm or more (usually 10 μm or less), the viewpoint of conductivity. However, it is preferable to provide it from the viewpoint of cost. That is, since platinum or the like is expensive, it is preferable to make the catalyst electrode 4 as thin as possible. However, since the resistance becomes high when the layer is thin, the second collector electrode made of a metal such as tungsten, titanium, or nickel. By providing 92, the current collection efficiency can be improved and the cost can be reduced. Further, when the catalyst electrode 4 is formed of a composition in which the conductive oxide is mixed with a substance having catalytic activity, the resistance of the catalyst electrode 4 becomes higher. Therefore, the second collector electrode 92 is provided, It is more preferable to increase the current collection efficiency.

第２集電電極９２の形状は特に限定されないが、基板２の側では透光性は必須でないため平面状とすることができる。この第２集電電極９２が平面状である場合、抵抗の低い第２集電電極９２とするためには、触媒電極４と類似の平面形状であり、且つ触媒電極４に対して５０％以上、特に６５％以上、更に８０％以上（同面積でもよい。）の面積の平面状の電極であることが好ましい。更に、触媒電極４と相似形に配設されることがより好ましい。また、第２集電電極９２は、線状の電極からなり且つ特定の電極パターンにより形成されている電極とすることもできる。この特定のパターンは特に限定されず、例えば、格子状、櫛歯状、放射状等とすることができる。この線状の電極からなり且つ特定の電極パターンにより形成されている第２集電電極９２の場合、線状の電極の幅及び厚さは特に限定されず、その電気抵抗及びコスト等を勘案し設定することが好ましい。第２集電電極９２が線状の電極からなり且つ特定の電極パターンにより形成されている電極である場合、第２集電電極９２の全面積は特に限定されないが、触媒電極４の全面積に対して０．１％以上、特に５％以上、更に１０％以上とすることができる。また、この全面積は９０％以上とすることもでき、このように面積の広い第２集電電極９２であれば、集電効率をより高めることができる。   Although the shape of the 2nd current collection electrode 92 is not specifically limited, Since translucency is not essential on the board | substrate 2 side, it can be made into planar shape. When the second current collecting electrode 92 has a planar shape, the second current collecting electrode 92 has a planar shape similar to that of the catalyst electrode 4 and 50% or more of the catalyst electrode 4 in order to obtain the second current collecting electrode 92 having a low resistance. In particular, a planar electrode having an area of 65% or more, more preferably 80% or more (or the same area) is preferable. Furthermore, it is more preferable that the catalyst electrode 4 is arranged in a similar shape. Moreover, the 2nd current collection electrode 92 can also be used as the electrode which consists of a linear electrode and is formed with the specific electrode pattern. This specific pattern is not particularly limited, and may be, for example, a lattice shape, a comb shape, a radial shape, or the like. In the case of the second collector electrode 92 made of this linear electrode and formed by a specific electrode pattern, the width and thickness of the linear electrode are not particularly limited, taking into account its electrical resistance, cost, etc. It is preferable to set. When the second current collecting electrode 92 is an electrode made of a linear electrode and formed by a specific electrode pattern, the total area of the second current collecting electrode 92 is not particularly limited, but the total area of the catalyst electrode 4 On the other hand, it can be 0.1% or more, particularly 5% or more, and further 10% or more. In addition, the total area can be 90% or more, and the current collection efficiency can be further improved with the second current collecting electrode 92 having a large area.

本発明の他の色素増感型太陽電池では、透光性基板１の表面に第１集電電極９１が設けられた図９の色素増感型太陽電池１０２−２、及び図１３の色素増感型太陽電池１０４−２とすることができる。特に、電池面積が２ｃｍ２以上、更に４ｃｍ２以上と大きい場合は、第１集電電極９１を設けることが好ましい。この第１集電電極９１の形状は透光性が保持される限り特に限定されず、線状の電極からなり且つ特定の電極パターンにより形成されている電極とすることができる。例えば、格子状、櫛歯状、放射状等の形状の電極とすることができる。更に、この線状の電極からなり且つ特定の電極パターンにより形成されている第１集電電極９１の場合、線状の電極の幅及び厚さは特に限定されず、その電気抵抗及びコスト等を勘案し設定することが好ましい。第１集電電極９１の全面積は、半導体電極３の全面積に対して０．１〜２０％、特に０．１〜５％、更に０．１〜１％であることが好ましい。第１集電電極９１の全面積が半導体電極３の全面積に対して０．１〜２０％であれば、半導体電極３に照射される光量を十分に保持することができ、且つ集電効率を高めることができる。 In another dye-sensitized solar cell of the present invention, the dye-sensitized solar cell 102-2 in FIG. 9 in which the first current collecting electrode 91 is provided on the surface of the translucent substrate 1, and the dye sensitizing in FIG. It can be set as the sensitive solar cell 104-2. In particular, the battery area 2 cm 2 or more, if greater and 4 cm 2 or more, it is preferable to provide the first collector electrode 91. The shape of the first current collecting electrode 91 is not particularly limited as long as the translucency is maintained, and may be an electrode made of a linear electrode and formed by a specific electrode pattern. For example, an electrode having a lattice shape, a comb shape, a radial shape, or the like can be used. Furthermore, in the case of the first collector electrode 91 made of this linear electrode and formed by a specific electrode pattern, the width and thickness of the linear electrode are not particularly limited, and the electrical resistance, cost, etc. It is preferable to set in consideration. The total area of the first current collecting electrode 91 is preferably 0.1 to 20%, particularly 0.1 to 5%, and more preferably 0.1 to 1% with respect to the total area of the semiconductor electrode 3. If the total area of the first current collecting electrode 91 is 0.1 to 20% with respect to the total area of the semiconductor electrode 3, the amount of light applied to the semiconductor electrode 3 can be sufficiently maintained, and the current collecting efficiency can be maintained. Can be increased.

第１集電電極９１及び第２集電電極９２を設ける方法は特に限定されないが、例えば、所定のパターンが形成されたマスクを用いて、マグネトロンスパッタ法及び電子ビ−ム蒸着法等の物理的蒸着法などでタングステン、チタン、ニッケル等の金属を堆積させ、その後、フォトリソグラフィー等によりパターニングする方法が挙げられる。また、各々の金属成分を含有するメタライズインクを用いてスクリーン印刷法等によりパターニングし、その後、焼成する方法などにより形成することができる。物理的蒸着法などに用いる金属としては、タングステン、チタン、ニッケルの他、白金、金等の貴金属、銅等を用いることもできる。この金属としては、耐腐食性に優れるタングステン、チタン、ニッケル、貴金属等を用いることが好ましい。更に、メタライズインクに含有される金属としても、タングステン、チタン、ニッケル、白金、金等の貴金属、銅等を用いることができる。この金属としては、耐腐食性に優れるタングステン、チタン、ニッケル、貴金属等を用いることが好ましい。   The method of providing the first collector electrode 91 and the second collector electrode 92 is not particularly limited. For example, a physical pattern such as a magnetron sputtering method or an electron beam deposition method using a mask on which a predetermined pattern is formed is used. Examples thereof include a method of depositing a metal such as tungsten, titanium, or nickel by an evaporation method or the like and then patterning by photolithography or the like. Moreover, it can form by the method of patterning by the screen-printing method etc. using the metallized ink containing each metal component, and baking it after that. As a metal used for physical vapor deposition or the like, in addition to tungsten, titanium and nickel, noble metals such as platinum and gold, copper and the like can be used. As this metal, it is preferable to use tungsten, titanium, nickel, noble metal, etc. which are excellent in corrosion resistance. Further, as the metal contained in the metallized ink, noble metals such as tungsten, titanium, nickel, platinum and gold, copper and the like can be used. As this metal, it is preferable to use tungsten, titanium, nickel, noble metal, etc. which are excellent in corrosion resistance.

以下、実施例により本発明を具体的に説明する。
以下のようにして図１１に示す色素増感型太陽電池１０３−２を作製した。
実施例１
（１）金属網状体の表面に半導体層が設けられた半導体電極の作製
直径５０μｍのタングステンワイヤを編織して得られ、縦１００ｍｍ、横１００ｍｍ、網目の面積が１００００μｍ２のタングステン網状体７１を印刷台に載置し、粒径が１０〜２０ｎｍのチタニア粒子を含有するペースト（Ｓｏｌａｒｏｎｉｘ社製、商品名「Ｔｉ−Ｎｏｎｏｘｉｄｅ Ｄ／ＳＰ」）を用いて室温（２５℃）でスクリーン印刷した。その後、１２０℃で１時間乾燥し、次いで、４８０℃で３０分焼成して、タングステン網状体７１の表面に厚さ５０μｍの半導体層３２を形成した。その後、この半導体層３２が形成されたタングステン網状体７１を、ルテニウム錯体（Ｓｏｌａｒｏｎｉｘ社製、商品名「５３５ｂｉｓ−ＴＢＡ」）のエタノール溶液に１０時間浸漬し、チタニア焼結粒子に、４００〜６００ｎｍの波長域の光を吸収する増感色素であるルテニウム錯体を付着させて半導体電極３を形成した。 Hereinafter, the present invention will be described specifically by way of examples.
The dye-sensitized solar cell 103-2 shown in FIG. 11 was produced as follows.
Example 1
(1) Fabrication of a semiconductor electrode provided with a semiconductor layer on the surface of a metal mesh body A tungsten mesh body 71 obtained by weaving a tungsten wire having a diameter of 50 μm and having a length of 100 mm, a width of 100 mm, and a mesh area of 10,000 μm 2 is printed. It mounted on the stand and screen-printed at room temperature (25 degreeC) using the paste (The product name "Ti-Nonoxide D / SP" by Solaronix, Inc.) containing the titania particle | grain with a particle size of 10-20 nm. Then, it was dried at 120 ° C. for 1 hour, and then baked at 480 ° C. for 30 minutes to form a semiconductor layer 32 having a thickness of 50 μm on the surface of the tungsten network 71. Thereafter, the tungsten network 71 on which the semiconductor layer 32 is formed is dipped in an ethanol solution of a ruthenium complex (manufactured by Solaronix, trade name “535bis-TBA”) for 10 hours. The semiconductor electrode 3 was formed by attaching a ruthenium complex, which is a sensitizing dye that absorbs light in the wavelength range.

（２）触媒電極及び第２集電電極の作製
純度９９．９質量％のアルミナ粉末１００質量部に、焼結助剤として５質量部のマグネシア、カルシア及びシリカの混合粉末及び２質量部のバインダ並びに溶媒を配合してスラリーを調製し、このスラリーを用いてドクターブレード法により厚さ２．５ｍｍのアルミナグリーンシートを作製した。その後、タングステン成分を含有するメタライズインクを用いて、アルミナグリーンシートの表面に、スクリーン印刷法により厚さ１０μｍの第２集電電極９２となる導電塗膜を形成した。次いで、この導電塗膜の表面に、白金成分を含有するメタライズインクを用いて、厚さ２．４μｍの触媒電極４となる導電塗膜を形成した。その後、還元雰囲気にて１５００℃で２時間保持して一体焼成し、縦１００ｍｍ、横１００ｍｍ、厚さ１ｍｍのアルミナ基板２の表面に、縦９０ｍｍ、横９０ｍｍ、厚さ８μｍの第２集電電極９２を形成し、更にこの触媒電極４の表面に縦９０ｍｍ、横９０ｍｍ、厚さ２μｍの触媒電極４を形成した。 (2) Production of catalyst electrode and second collector electrode 100 parts by mass of alumina powder having a purity of 99.9% by mass, 5 parts by mass of magnesia, calcia and silica mixed powder and 2 parts by mass of binder as a sintering aid In addition, a slurry was prepared by blending a solvent, and an alumina green sheet having a thickness of 2.5 mm was prepared using this slurry by a doctor blade method. Thereafter, using a metallized ink containing a tungsten component, a conductive coating film to be the second current collecting electrode 92 having a thickness of 10 μm was formed on the surface of the alumina green sheet by a screen printing method. Subsequently, the conductive coating film used as the catalyst electrode 4 with a thickness of 2.4 micrometers was formed on the surface of this conductive coating film using the metallized ink containing a platinum component. Thereafter, it is integrally fired by holding at 1500 ° C. for 2 hours in a reducing atmosphere, and a second collector electrode having a length of 90 mm, a width of 90 mm, and a thickness of 8 μm is formed on the surface of the alumina substrate 2 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm 92 was formed, and a catalyst electrode 4 having a length of 90 mm, a width of 90 mm, and a thickness of 2 μm was formed on the surface of the catalyst electrode 4.

（３）色素増感型太陽電池の作製
アルミナ基板２の第２集電電極９２及び触媒電極４が形成されていない部分に、熱可塑性樹脂からなる厚さ６０μｍの接着剤シート（Ｓｏｌａｒｏｎｉｘ社製、商品名「ＳＸ１１７０−６０」）を配設した。その後、上記（１）で作製した半導体電極３の端部から５ｍｍの範囲のチタニア焼結粒子を除去してタングステン網状体を露出させ、この露出部を接着剤シートの表面に載置した。次いで、タングステン網状体の露出部が載置された接着剤シートの表面に、更に厚さ６０μｍの接着剤シートを配置した。その後、この接着剤シートの表面に、縦１００ｍｍ、横１００ｍｍ、厚さが１ｍｍのガラス基板１を配置し、次いで、アルミナ基板２の側を下にして１００℃に調温されたホットプレートに載せ、５分加熱してガラス基板１とアルミナ基板２とを接合し、シール部Ｓを形成した。その後、アルミナ基板２の所定位置に設けられた電解質溶液の注入口からヨウ素電解液（Ｓｏｌａｒｏｎｉｘ社製、商品名「Ｉｏｄｏｌｙｔｅ ＰＮ−５０」）を注入し、ガラス基板１とセラミック基板２との間にヨウ素電解液を充填した。ヨウ素電解液充填後、注入口は上記の接着剤を用いて封止した。尚、電力はタングステン網状体７１及び第２集電電極９２の各々から取り出した。 (3) Production of dye-sensitized solar cell An adhesive sheet (manufactured by Solaronix, made of thermoplastic resin) on the portion of the alumina substrate 2 where the second collector electrode 92 and the catalyst electrode 4 are not formed. Product name “SX1170-60”) was provided. Thereafter, the titania sintered particles in a range of 5 mm from the end portion of the semiconductor electrode 3 produced in the above (1) were removed to expose the tungsten network, and this exposed portion was placed on the surface of the adhesive sheet. Next, an adhesive sheet having a thickness of 60 μm was further disposed on the surface of the adhesive sheet on which the exposed portion of the tungsten network was placed. Thereafter, a glass substrate 1 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm is disposed on the surface of the adhesive sheet, and then placed on a hot plate adjusted to 100 ° C. with the alumina substrate 2 side down. The glass substrate 1 and the alumina substrate 2 were joined by heating for 5 minutes, and the seal part S was formed. Thereafter, an iodine electrolytic solution (manufactured by Solaronix, trade name “Iodolyte PN-50”) is injected from an electrolyte solution injection port provided at a predetermined position of the alumina substrate 2, and between the glass substrate 1 and the ceramic substrate 2. Filled with iodine electrolyte. After filling with the iodine electrolyte, the inlet was sealed with the above adhesive. The electric power was taken out from each of the tungsten mesh 71 and the second current collecting electrode 92.

（４）色素増感型太陽電池の性能評価
上記（１）〜（３）により作製した色素増感型太陽電池１０３−２に、ＡＭ１．５にスペクトル調整したソーラーシミュレータによって、照射強度１００ｍＷ／ｃｍ２の擬似太陽光を照射したところ、変換効率７．０％の特性を有していた。 (4) Performance Evaluation of Dye-Sensitized Solar Cell Irradiation intensity of 100 mW / cm is applied to the dye-sensitized solar cell 103-2 produced by the above (1) to (3) using a solar simulator whose spectrum is adjusted to AM1.5. When irradiated with the artificial sunlight of No. 2 , the conversion efficiency was 7.0%.

実施例２
以下のようにして図１３に示す色素増感型太陽電池１０４−２を作製した。
（１）半導体電極及び第１集電電極の作製
縦１００ｍｍ、横１００ｍｍ、厚さが１ｍｍのガラス基板１の表面に、ＤＣスパッタリングによりタングステンを堆積させ、フォトリソグラフィーにより幅３０μｍ、間隔５００μｍ、厚さ１μｍの格子状の第１集電電極９１を形成した。その後、この第１集電電極９１が形成されたガラス基板１の表面に、粒径が１０〜２０ｎｍのチタニア粒子を含有するスラリー（Ｓｏｌａｒｏｎｉｘ社製、商品名「Ｔｉ−Ｎｏｎｏｘｉｄｅ Ｄ／ＳＰ」）をスクリーン印刷法により塗布し、１２０℃で１時間乾燥し、次いで、４８０℃で３０分焼成して、縦９０ｍｍ、横９０ｍｍ、厚さ２０μｍのチタニア電極層（電極基体）を形成した。次いで、この積層体を、ルテニウム錯体（Ｓｏｌａｒｏｎｉｘ社製、商品名「５３５ｂｉｓ−ＴＢＡ」）のエタノール溶液に１０時間浸漬して、チタニア焼結粒子に、４００〜６００ｎｍの波長域の光を吸収する増感色素であるルテニウム錯体を付着させて半導体電極３を形成した。 Example 2
The dye-sensitized solar cell 104-2 shown in FIG. 13 was produced as follows.
(1) Fabrication of semiconductor electrode and first collector electrode Tungsten is deposited by DC sputtering on the surface of a glass substrate 1 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm, and a width of 30 μm and a gap of 500 μm by thickness. A 1 μm grid-shaped first collector electrode 91 was formed. Thereafter, a slurry containing titania particles having a particle diameter of 10 to 20 nm (made by Solaronix, trade name “Ti-Nonoxide D / SP”) is formed on the surface of the glass substrate 1 on which the first current collecting electrode 91 is formed. It was applied by screen printing, dried at 120 ° C. for 1 hour, and then baked at 480 ° C. for 30 minutes to form a titania electrode layer (electrode substrate) having a length of 90 mm, a width of 90 mm, and a thickness of 20 μm. Next, this laminate is immersed in an ethanol solution of a ruthenium complex (trade name “535bis-TBA” manufactured by Solaronix) for 10 hours, and the titania sintered particles absorb light in a wavelength region of 400 to 600 nm. A semiconductor electrode 3 was formed by attaching a ruthenium complex as a dye-sensitive material.

（２）金属網状体の表面に触媒層が設けられた触媒電極の作製
直径５０μｍのタングステンワイヤを編織して得られ、縦１００ｍｍ、横１００ｍｍ、網目の面積が１００００μｍ２のタングステン網状体７２の表面に、白金成分を含有するメタライズインクを用いて、スクリーン印刷により触媒電極４となる導電塗膜を形成した。その後、還元雰囲気にて１５００℃で焼成し、厚さ１μｍの触媒層４２を形成し、触媒電極４とした。 (2) Production of a catalyst electrode having a catalyst layer provided on the surface of a metal network The surface of a tungsten network 72 obtained by weaving a tungsten wire having a diameter of 50 μm and having a length of 100 mm, a width of 100 mm, and a mesh area of 10,000 μm 2 In addition, a conductive coating film to be the catalyst electrode 4 was formed by screen printing using a metallized ink containing a platinum component. Thereafter, firing was performed at 1500 ° C. in a reducing atmosphere to form a catalyst layer 42 having a thickness of 1 μm.

（３）アルミナ基板の作製
純度９９．９質量％のアルミナ粉末１００質量部に、焼結助剤として５質量部のマグネシア、カルシア及びシリカの混合粉末及び２質量部のバインダ並びに溶媒を配合してスラリーを調製し、このスラリーを用いてドクターブレード法により厚さ２．５ｍｍのアルミナグリーンシートを作製した。その後、還元雰囲気にて１５００℃で２時間保持して焼成し、厚さ２ｍｍのアルミナ基板２を作製した。 (3) Preparation of Alumina Substrate To 100 parts by mass of alumina powder with a purity of 99.9% by mass, 5 parts by mass of mixed powder of magnesia, calcia and silica, 2 parts by mass of binder and solvent are blended as a sintering aid. A slurry was prepared, and using this slurry, an alumina green sheet having a thickness of 2.5 mm was prepared by a doctor blade method. Thereafter, the alumina substrate 2 having a thickness of 2 mm was produced by maintaining and firing at 1500 ° C. for 2 hours in a reducing atmosphere.

（４）色素増感型太陽電池の作製
上記（３）で作製したアルミナ基板２の一面の周縁部の全周に渡って熱可塑性樹脂からなる幅５ｍｍ、厚さ６０μｍの接着剤シート（Ｓｏｌａｒｏｎｉｘ社製、商品名「ＳＸ１１７０−６０」）を配設した。その後、上記（２）で作製した触媒電極４の端部から５ｍｍの範囲の白金焼結粒子を除去してタングステン網状体を露出させ、この露出部を接着剤シートの表面に載置した。次いで、タングステン網状体の露出部が載置された接着剤シートの表面に、更に厚さ６０μｍの接着剤シートを配置した。その後、この接着剤シートの表面に、上記（１）で半導体電極３と第１集電電極９１とが形成されたガラス基板１を、半導体電極３が触媒電極４に対向するようにして配置し、次いで、アルミナ基板２の側を下にして１００℃に調温されたホットプレートに載せ、５分加熱してガラス基板１とアルミナ基板２とを接合し、シール部Ｓを形成した。その後、アルミナ基板２の所定位置に設けられた電解質溶液の注入口からヨウ素電解液（Ｓｏｌａｒｏｎｉｘ社製、商品名「Ｉｏｄｏｌｙｔｅ ＰＮ−５０」）を注入し、ガラス基板１とセラミック基板２との間にヨウ素電解液を充填した。ヨウ素電解液充填後、注入口は上記の接着剤を用いて封止した。尚、電力は第１集電電極９１及びタングステン網状体７２の各々から取り出した。
このようにして作製した色素増感型太陽電池１０４−２の性能を実施例１の場合と同様にして評価したところ、変換効率６．４％の特性を有していた。 (4) Production of dye-sensitized solar cell Adhesive sheet (Solaronix) having a width of 5 mm and a thickness of 60 μm made of a thermoplastic resin over the entire circumference of the peripheral portion of one surface of the alumina substrate 2 produced in (3) above. Product name “SX1170-60”). Thereafter, the platinum sintered particles in a range of 5 mm from the end portion of the catalyst electrode 4 produced in the above (2) were removed to expose the tungsten network, and this exposed portion was placed on the surface of the adhesive sheet. Next, an adhesive sheet having a thickness of 60 μm was further disposed on the surface of the adhesive sheet on which the exposed portion of the tungsten network was placed. Thereafter, the glass substrate 1 on which the semiconductor electrode 3 and the first current collecting electrode 91 are formed in (1) above is disposed on the surface of the adhesive sheet so that the semiconductor electrode 3 faces the catalyst electrode 4. Next, the glass substrate 1 and the alumina substrate 2 were bonded to each other by placing them on a hot plate adjusted to 100 ° C. with the alumina substrate 2 side down, and the seal portion S was formed. Thereafter, an iodine electrolytic solution (manufactured by Solaronix, trade name “Iodolyte PN-50”) is injected from an electrolyte solution injection port provided at a predetermined position of the alumina substrate 2, and between the glass substrate 1 and the ceramic substrate 2. Filled with iodine electrolyte. After filling with the iodine electrolyte, the inlet was sealed with the above adhesive. The electric power was taken out from each of the first collector electrode 91 and the tungsten mesh body 72.
When the performance of the dye-sensitized solar cell 104-2 thus produced was evaluated in the same manner as in Example 1, it had a conversion efficiency of 6.4%.

実施例３
以下のようにして図１５に示す色素増感型太陽電池１０６を作製した。
実施例２の（３）で作製したアルミナ基板２の一面の周縁部の全周に渡って熱可塑性樹脂からなる幅５ｍｍ、厚さ６０μｍの接着剤シート（Ｓｏｌａｒｏｎｉｘ社製、商品名「ＳＸ１１７０−６０」）を配設した。その後、実施例２の（２）で作製した触媒電極４の端部から５ｍｍの範囲の白金焼結粒子を除去してタングステン網状体を露出させ、この露出部を接着剤シートの表面に載置した。次いで、タングステン網状体の露出部が載置された接着剤シートの表面に、更に厚さ６０μｍの接着剤シートを配置した。その後、この接着剤シートの表面に、実施例１の（１）で作製した半導体電極３の端部から５ｍｍの範囲のチタニア焼結粒子を除去してタングステン網状体を露出させ、この露出部を接着剤シートの表面に載置した。次いで、タングステン網状体の露出部が載置された接着剤シートの表面に、更に厚さ６０μｍの接着剤シートを配置した。その後、この接着剤シートの表面に、縦１００ｍｍ、横１００ｍｍ、厚さが１ｍｍのガラス基板１を配置し、次いで、アルミナ基板２の側を下にして１００℃に調温されたホットプレートに載せ、５分加熱してガラス基板１とアルミナ基板２とを接合し、シール部Ｓを形成した。その後、アルミナ基板２の所定位置に設けられた電解質溶液の注入口からヨウ素電解液（Ｓｏｌａｒｏｎｉｘ社製、商品名「Ｉｏｄｏｌｙｔｅ ＰＮ−５０」）を注入し、ガラス基板１とセラミック基板２との間にヨウ素電解液を充填した。ヨウ素電解液充填後、注入口は上記の接着剤を用いて封止した。尚、電力はタングステン網状体７１、７２の各々から取り出した。
このようにして作製した色素増感型太陽電池１０６の性能を実施例１の場合と同様にして評価したところ、変換効率７．２％の特性を有していた。 Example 3
The dye-sensitized solar cell 106 shown in FIG. 15 was produced as follows.
An adhesive sheet made of a thermoplastic resin having a width of 5 mm and a thickness of 60 μm over the entire periphery of one peripheral surface of the alumina substrate 2 produced in Example 3 (3) (trade name “SX1170-60” manufactured by Solaronix). )). Thereafter, the platinum sintered particles in a range of 5 mm from the end of the catalyst electrode 4 produced in (2) of Example 2 were removed to expose the tungsten network, and this exposed portion was placed on the surface of the adhesive sheet. did. Next, an adhesive sheet having a thickness of 60 μm was further disposed on the surface of the adhesive sheet on which the exposed portion of the tungsten network was placed. Thereafter, the titania sintered particles in a range of 5 mm from the end of the semiconductor electrode 3 produced in (1) of Example 1 were removed on the surface of the adhesive sheet to expose the tungsten network, and this exposed portion was It was mounted on the surface of the adhesive sheet. Next, an adhesive sheet having a thickness of 60 μm was further disposed on the surface of the adhesive sheet on which the exposed portion of the tungsten network was placed. Thereafter, a glass substrate 1 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm is disposed on the surface of the adhesive sheet, and then placed on a hot plate adjusted to 100 ° C. with the alumina substrate 2 side down. The glass substrate 1 and the alumina substrate 2 were joined by heating for 5 minutes, and the seal part S was formed. Thereafter, an iodine electrolytic solution (manufactured by Solaronix, trade name “Iodolyte PN-50”) is injected from an electrolyte solution injection port provided at a predetermined position of the alumina substrate 2, and between the glass substrate 1 and the ceramic substrate 2. Filled with iodine electrolyte. After filling with the iodine electrolyte, the inlet was sealed with the above adhesive. The electric power was taken out from each of the tungsten nets 71 and 72.
When the performance of the dye-sensitized solar cell 106 thus produced was evaluated in the same manner as in Example 1, it had a conversion efficiency of 7.2%.

尚、本発明では、上記の実施例の記載に限られず、本発明の範囲内で種々変更した実施例とすることができる。例えば、電解質５としては、不揮発性のイミダゾリウム塩等のイオン性液体及びこのイオン性液体をゲル化させたもの、並びにヨウ化銅、チオシアン化銅等の固体などを用いることもできる。また、これらの化合物等を用いた場合、半導体電極３と触媒電極４との間の距離は特に限定されないが、１００μｍ以下、特に２０μｍ以下（通常、１μｍ以上）とすることができる。この距離が１００μｍ以下であれば、光電変換効率を十分に高くすることができる。   It should be noted that the present invention is not limited to the description of the above-described embodiments, and can be variously modified embodiments within the scope of the present invention. For example, as the electrolyte 5, an ionic liquid such as a non-volatile imidazolium salt, a gel obtained by gelling the ionic liquid, a solid such as copper iodide or copper thiocyanide, or the like can also be used. Further, when these compounds are used, the distance between the semiconductor electrode 3 and the catalyst electrode 4 is not particularly limited, but can be 100 μm or less, particularly 20 μm or less (usually 1 μm or more). If this distance is 100 μm or less, the photoelectric conversion efficiency can be sufficiently increased.

金属線状体の表面に設けられた、増感色素を有する半導体層からなる半導体電極、又は金属線状体の表面に設けられた、触媒層からなる触媒電極の各々を斜め方向からみた模式図である。Schematic view of each of a semiconductor electrode made of a semiconductor layer having a sensitizing dye provided on the surface of a metal linear body or a catalyst electrode made of a catalyst layer provided on the surface of the metal linear body, as viewed from an oblique direction. It is. 図１の、金属線状体と、半導体層又は触媒層との間に、更に導電層が設けられた半導体電極又は触媒電極の各々を斜め方向からみた模式図である。It is the schematic diagram which looked at each of the semiconductor electrode or catalyst electrode in which the conductive layer was further provided between the metal linear body of FIG. 1, and the semiconductor layer or the catalyst layer from the diagonal direction. 金属網状体の一例の平面図である。It is a top view of an example of a metal net-like body. 図３の金属網状体の表面に設けられた、増感色素を有する半導体層又は触媒層の一例の外観を示す平面図である。It is a top view which shows the external appearance of an example of the semiconductor layer or catalyst layer which has a sensitizing dye provided in the surface of the metal network of FIG. 図３の金属網状体の表面に設けられた、増感色素を有する半導体層又は触媒層の他例の外観を示す平面図である。It is a top view which shows the external appearance of the other example of the semiconductor layer or catalyst layer which has the sensitizing dye provided in the surface of the metal network of FIG. 金属線状体の表面に設けられた、増感色素を有する半導体層からなる半導体電極を備える本発明の色素増感型太陽電池１０１−１の断面を示す模式図である。It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 101-1 of this invention provided with the semiconductor electrode which is provided in the surface of the metal linear body and consists of a semiconductor layer which has a sensitizing dye. 図６において更に第２集電電極が設けられた色素増感型太陽電池１０１−２の断面を示す模式図である。It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 101-2 in which the 2nd current collection electrode was further provided in FIG. 金属線状体の表面に設けられた、触媒層からなる触媒電極を備える本発明の他の色素増感型太陽電池１０２−１の断面を示す模式図である。It is a schematic diagram which shows the cross section of the other dye-sensitized solar cell 102-1 of this invention provided with the catalyst electrode which consists of a catalyst layer provided in the surface of the metal linear body. 図８において更に第１集電電極が設けられた色素増感型太陽電池１０２−２の断面を示す模式図である。It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 102-2 in which the 1st current collection electrode was further provided in FIG. 金属網状体の表面に設けられた増感色素を有する半導体層からなる半導体電極を備える本発明の他の色素増感型太陽電池１０３−１の断面を示す模式図である。It is a schematic diagram which shows the cross section of the other dye-sensitized solar cell 103-1 of this invention provided with the semiconductor electrode which consists of a semiconductor layer which has the sensitizing dye provided in the surface of the metal network. 図１０において更に第２集電電極が設けられた色素増感型太陽電池１０３−２の断面を示す模式図である。It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 103-2 in which the 2nd current collection electrode was further provided in FIG. 金属網状体の表面に設けられた触媒層からなる触媒電極を備える本発明の他の色素増感型太陽電池１０４−１の断面を示す模式図である。It is a schematic diagram which shows the cross section of the other dye-sensitized solar cell 104-1 of this invention provided with the catalyst electrode which consists of a catalyst layer provided in the surface of the metal network. 図１２において更に第１集電電極が設けられた色素増感型太陽電池１０４−２の断面を示す模式図である。It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 104-2 in which the 1st current collection electrode was further provided in FIG. 金属線状体の表面に設けられた、増感色素を有する半導体層からなる半導体電極と、金属線状体の表面に設けられた触媒層からなる触媒電極とを備える本発明の更に他の色素増感型太陽電池１０５の断面を示す模式図である。Still another dye of the present invention comprising a semiconductor electrode comprising a semiconductor layer having a sensitizing dye provided on the surface of a metal linear body and a catalyst electrode comprising a catalyst layer provided on the surface of the metal linear body 3 is a schematic diagram showing a cross section of a sensitized solar cell 105. FIG. 金属網状体の表面に設けられた、増感色素を有する半導体層からなる半導体電極と、金属網状体の表面に設けられた触媒層からなる触媒電極とを備える本発明の更に他の色素増感型太陽電池１０６の断面を示す模式図である。Still another dye sensitization of the present invention comprising a semiconductor electrode comprising a semiconductor layer having a sensitizing dye provided on the surface of a metal network and a catalyst electrode comprising a catalyst layer provided on the surface of the metal network. 3 is a schematic diagram showing a cross section of a solar cell 106. FIG. 金属網状体の表面に設けられた、増感色素を有する半導体層からなる半導体電極と、金属線状体の表面に設けられた触媒層からなる触媒電極とを備える本発明の更に他の色素増感型太陽電池１０７の断面を示す模式図である。Still another dye sensitization of the present invention comprising a semiconductor electrode comprising a semiconductor layer having a sensitizing dye provided on the surface of a metal network and a catalyst electrode comprising a catalyst layer provided on the surface of the metal wire. 3 is a schematic view showing a cross section of a sensitive solar cell 107. FIG. 金属線状体の表面に設けられた、増感色素を有する半導体層からなる半導体電極と、金属網状体の表面に設けられた触媒層からなる触媒電極とを備える本発明の更に他の色素増感型太陽電池１０８の断面を示す模式図である。Still another dye sensitization of the present invention comprising a semiconductor electrode comprising a semiconductor layer having a sensitizing dye provided on the surface of a metal linear body and a catalyst electrode comprising a catalyst layer provided on the surface of the metal network. 3 is a schematic view showing a cross section of a sensitive solar cell 108. FIG.

符号の説明Explanation of symbols

１；透光性基板、２；基板、３；半導体電極、３１、３２；半導体層、３３；貫通部、４；触媒電極、４１、４２；触媒層、４３；貫通部、５；電解質、６１、６２；金属線状体、７１、７２；金属網状体、８１、８２；導電層、９１；第１集電電極、９２；第２集電電極、Ｓ；シール部、１０１−１、１０１−２、１０２−１、１０２−２、１０３−１、１０３−２、１０４−１、１０４−２、１０５、１０６、１０７、１０８；色素増感型太陽電池。   DESCRIPTION OF SYMBOLS 1; Translucent board | substrate, 2; Board | substrate, 3; Semiconductor electrode, 31, 32; Semiconductor layer, 33; Penetration part, 4: Catalyst electrode, 41, 42; Catalyst layer, 43: Penetration part, 5: Electrolyte, 61 62; Metal linear body, 71, 72; Metal network, 81, 82; Conductive layer, 91; First current collecting electrode, 92; Second current collecting electrode, S; Seal part, 101-1, 101- 2, 102-1, 102-2, 103-1, 103-2, 104-1, 104-2, 105, 106, 107, 108; Dye-sensitized solar cell.

Claims (12)

透光性基板１と、該透光性基板１に対向して配設された基板２と、該透光性基板１と該基板２との間の該透光性基板１の側に配設された、増感色素を有する半導体電極３と、該基板２の表面に設けられた触媒電極４と、該半導体電極３の少なくとも一部に含有され、且つ少なくとも該半導体電極３と該触媒電極４との間に充填された電解質５と、を備え、該半導体電極３は、金属線状体６１の表面の少なくとも一部に設けられた、該増感色素を有する半導体層３１、及び金属網状体７１の表面の少なくとも一部に設けられた、該増感色素を有する半導体層３２のうちの少なくとも一方からなることを特徴とする色素増感型太陽電池。   Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, and disposed on the side of translucent substrate 1 between translucent substrate 1 and substrate 2 The semiconductor electrode 3 having a sensitizing dye, the catalyst electrode 4 provided on the surface of the substrate 2, and at least part of the semiconductor electrode 3, and at least the semiconductor electrode 3 and the catalyst electrode 4 The semiconductor electrode 3 is provided on at least a part of the surface of the metal linear body 61, and the semiconductor layer 31 having the sensitizing dye, and the metal network. 71. A dye-sensitized solar cell comprising at least one of the semiconductor layers 32 having the sensitizing dye provided on at least a part of the surface of 71. 上記金属線状体６１及び上記金属網状体７１のうちの少なくとも一方がタングステンを含有する請求項１に記載の色素増感型太陽電池。   The dye-sensitized solar cell according to claim 1, wherein at least one of the metal linear body 61 and the metal network body 71 contains tungsten. 上記金属線状体６１と上記半導体層３１との間、及び上記金属網状体７１と上記半導体層３２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８１が設けられている請求項１又は２に記載の色素増感型太陽電池。   A conductive layer 81 made of a conductive oxide is provided between at least one of the metal wire 61 and the semiconductor layer 31 and between the metal network 71 and the semiconductor layer 32. The dye-sensitized solar cell according to claim 1 or 2. 透光性基板１と、該透光性基板１に対向して配設された基板２と、該透光性基板１の表面に設けられた、増感色素を有する半導体電極３と、該透光性基板１と該基板２との間に該半導体電極３に対向して配設された触媒電極４と、該半導体電極３の少なくとも一部に含有され、且つ少なくとも該半導体電極３と該触媒電極４との間に充填された電解質５と、を備え、該触媒電極４は、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１、及び金属網状体７２の表面の少なくとも一部に設けられた触媒層４２のうちの少なくとも一方からなることを特徴とする色素増感型太陽電池。   A translucent substrate 1, a substrate 2 disposed opposite the translucent substrate 1, a semiconductor electrode 3 having a sensitizing dye provided on the surface of the translucent substrate 1, and the translucent substrate A catalyst electrode 4 disposed between the optical substrate 1 and the substrate 2 so as to face the semiconductor electrode 3; and at least part of the semiconductor electrode 3; and at least the semiconductor electrode 3 and the catalyst An electrolyte 5 filled between the electrode 4 and the catalyst electrode 4, the catalyst layer 41 provided on at least part of the surface of the metal linear body 62, and at least the surface of the metal network 72. A dye-sensitized solar cell comprising at least one of the catalyst layers 42 provided in part. 上記金属線状体６２及び上記金属網状体７２のうちの少なくとも一方がタングステンを含有する請求項４に記載の色素増感型太陽電池。   The dye-sensitized solar cell according to claim 4, wherein at least one of the metal linear body 62 and the metal net body 72 contains tungsten. 上記金属線状体６２と上記触媒層４１との間、及び上記金属網状体７２と上記触媒層４２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８２が設けられている請求項４又は５に記載の色素増感型太陽電池。   A conductive layer 82 made of a conductive oxide is provided between at least one of the metal wire 62 and the catalyst layer 41 and between the metal network 72 and the catalyst layer 42. The dye-sensitized solar cell according to claim 4 or 5. 透光性基板１と、該透光性基板１に対向して配設された基板２と、該透光性基板１と該基板２との間の該透光性基板１の側に配設された、増感色素を有する半導体電極３と、該透光性基板１と該基板２との間に該半導体電極３に対向して配設された触媒電極４と、該半導体電極３の少なくとも一部に含有され、且つ該半導体電極３と該触媒電極４との間に充填された電解質５と、を備え、該半導体電極３は、金属線状体６１の表面の少なくとも一部に設けられた、該増感色素を有する半導体層３１、及び金属網状体７１の表面の少なくとも一部に設けられた、該増感色素を有する半導体層３２のうちの少なくとも一方からなり、該触媒電極４は、金属線状体６２の表面の少なくとも一部に設けられた触媒層４１、及び金属網状体７２の表面の少なくとも一部に設けられた触媒層４２のうちの少なくとも一方からなることを特徴とする色素増感型太陽電池。   Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, and disposed on the side of translucent substrate 1 between translucent substrate 1 and substrate 2 A semiconductor electrode 3 having a sensitizing dye, a catalyst electrode 4 disposed opposite to the semiconductor electrode 3 between the translucent substrate 1 and the substrate 2, and at least the semiconductor electrode 3. An electrolyte 5 contained in part and filled between the semiconductor electrode 3 and the catalyst electrode 4, and the semiconductor electrode 3 is provided on at least a part of the surface of the metal linear body 61. The catalyst electrode 4 comprises at least one of the semiconductor layer 31 having the sensitizing dye and the semiconductor layer 32 having the sensitizing dye provided on at least part of the surface of the metal network 71. The catalyst layer 41 provided on at least a part of the surface of the metal linear body 62, and the surface of the metal network 72 Dye-sensitized solar cell characterized by comprising at least one of the catalyst layer 42 provided on the least part. 上記金属線状体６１、上記金属網状体７１、上記金属線状体６２及び上記金属網状体７２のうちの少なくとも一つがタングステンを含有する請求項７に記載の色素増感型太陽電池。   The dye-sensitized solar cell according to claim 7, wherein at least one of the metal wire 61, the metal network 71, the metal wire 62, and the metal network 72 contains tungsten. 上記金属線状体６１と上記半導体層３１との間、及び上記金属網状体７１と上記半導体層３２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８１が設けられている請求項７又は８に記載の色素増感型太陽電池。   A conductive layer 81 made of a conductive oxide is provided between at least one of the metal wire 61 and the semiconductor layer 31 and between the metal network 71 and the semiconductor layer 32. The dye-sensitized solar cell according to claim 7 or 8. 上記金属線状体６２と上記触媒層４１との間、及び上記金属網状体７２と上記触媒層４２との間のうちの少なくとも一方に、導電性酸化物からなる導電層８２が設けられている請求項７又は８に記載の色素増感型太陽電池。   A conductive layer 82 made of a conductive oxide is provided between at least one of the metal wire 62 and the catalyst layer 41 and between the metal network 72 and the catalyst layer 42. The dye-sensitized solar cell according to claim 7 or 8. 上記半導体電極３がチタニアを含有する請求項１乃至１０のうちのいずれか１項に記載の色素増感型太陽電池。   The dye-sensitized solar cell according to any one of claims 1 to 10, wherein the semiconductor electrode 3 contains titania. 上記触媒電極４が貴金属及びカーボンのうちの少なくとも一方を含有する請求項１乃至１１のうちのいずれか１項に記載の色素増感型太陽電池。   The dye-sensitized solar cell according to any one of claims 1 to 11, wherein the catalyst electrode 4 contains at least one of a noble metal and carbon.
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