JP2007048680A - Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using it - Google Patents
Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using it Download PDFInfo
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- JP2007048680A JP2007048680A JP2005233938A JP2005233938A JP2007048680A JP 2007048680 A JP2007048680 A JP 2007048680A JP 2005233938 A JP2005233938 A JP 2005233938A JP 2005233938 A JP2005233938 A JP 2005233938A JP 2007048680 A JP2007048680 A JP 2007048680A
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- 150000001350 alkyl halides Chemical class 0.000 description 1
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- 125000000304 alkynyl group Chemical group 0.000 description 1
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- 150000004053 quinones Chemical class 0.000 description 1
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- 230000006798 recombination Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
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- 150000003431 steroids Chemical class 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、光電変換素子に関するものである。 The present invention relates to a photoelectric conversion element.
大量の化石燃料の使用で引き起こされるCO2濃度増加による地球温暖化、更に人口増加に伴うエネルギー需要の増大は、人類の存亡にまで関わる問題と認識されている。そのため近年、無限で有害物質を発生しない太陽光の利用が精力的に検討されている。このクリーンエネルギー源である太陽光利用として現在実用化されているものは住宅用の単結晶シリコン、多結晶シリコン、アモルファスシリコンおよびテルル化カドミウムやセレン化インジウム銅等の無機系太陽電池が挙げられる。 Global warming due to the increase in CO 2 concentration caused by the use of a large amount of fossil fuel, and the increase in energy demand accompanying population increase are recognized as problems related to the existence of human beings. For this reason, in recent years, the use of sunlight that is infinite and does not generate harmful substances has been energetically studied. What is currently put into practical use as sunlight, which is a clean energy source, includes residential single crystal silicon, polycrystalline silicon, amorphous silicon, and inorganic solar cells such as cadmium telluride and indium copper selenide.
しかしながら、これらの無機系太陽電池にも欠点がある。例えばシリコン系では、非常に純度の高いものが要求され、当然精製の工程は複雑でプロセス数が多く、製造コストが高い。それ以外にも軽量化等の要求もあり、特に、ユーザーへのペイバックが長い点でも不利であり、普及には問題があった。 However, these inorganic solar cells also have drawbacks. For example, a silicon system is required to have a very high purity. Naturally, the purification process is complicated, the number of processes is large, and the manufacturing cost is high. In addition, there is a demand for weight reduction and the like, and in particular, it is disadvantageous in that payback to the user is long, and there is a problem in the spread.
その一方で、有機材料を使う太陽電池も多く提案されている。有機太陽電池としては、p型有機半導体と仕事関数の小さい金属を接合させるショットキー型光電変換素子、p型有機半導体とn型無機半導体、あるいはp型有機半導体と電子受容性有機化合物を接合させるヘテロ接合型光電変換素子等があり、利用される有機半導体は、クロロフィル、ペリレン等の合成色素や顔料、ポリアセチレン等の導電性高分子材料、またはそれらの複合材料等である。これらを真空蒸着法、キャスト法、またはディッピング法等により、薄膜化し電池材料が構成されている。有機材料は低コスト、大面積化が容易等の長所もあるが、変換効率は1%以下と低いものが多く、また耐久性も悪いという問題もあった。 On the other hand, many solar cells using organic materials have been proposed. As an organic solar cell, a Schottky photoelectric conversion element that joins a p-type organic semiconductor and a metal having a low work function, a p-type organic semiconductor and an n-type inorganic semiconductor, or a p-type organic semiconductor and an electron-accepting organic compound are joined. There are heterojunction photoelectric conversion elements and the like, and organic semiconductors used are synthetic dyes and pigments such as chlorophyll and perylene, conductive polymer materials such as polyacetylene, or composite materials thereof. These are thinned by a vacuum deposition method, a casting method, a dipping method, or the like to form a battery material. Although organic materials have advantages such as low cost and easy area enlargement, there are many problems in that conversion efficiency is low at 1% or less, and durability is poor.
こうした状況の中で、良好な特性を示す太陽電池がスイスのグレッツェル博士らによって報告された(非特許文献1参照)。この文献には電池作製に必要な材料および製造技術も開示されている。提案された電池は色素増感型太陽電池、あるいはグレッツェル型太陽電池と呼ばれ、ルテニウム錯体で分光増感された酸化チタン多孔質薄膜を作用電極とする湿式太陽電池である。この方式の利点は酸化チタン等の安価な酸化物半導体を高純度まで精製する必要がないこと、従って安価で、更に利用できる光は広い可視光領域にまでわたっており、可視光成分の多い太陽光を有効に電気へ変換できることである。 Under such circumstances, a solar cell exhibiting good characteristics has been reported by Dr. Gretzell of Switzerland (see Non-Patent Document 1). This document also discloses materials and manufacturing techniques necessary for battery fabrication. The proposed battery is called a dye-sensitized solar cell or a Gretzel solar cell, and is a wet solar cell using a titanium oxide porous thin film spectrally sensitized with a ruthenium complex as a working electrode. The advantage of this method is that it is not necessary to purify an inexpensive oxide semiconductor such as titanium oxide to high purity, and therefore, it is inexpensive and more usable light extends over a wide visible light region, so that a solar with a large amount of visible light components is used. It is that light can be effectively converted into electricity.
反面、資源的制約があるルテニウム錯体が使われているため、この太陽電池が実用化された場合に、ルテニウム錯体の供給が危ぶまれている。また、このルテニウム錯体は高価なため、安価な有機色素へ変更することが出来れば、この問題は解決出来る。この電池の色素としてメロシアニン色素、シアニン色素、9−フェニルキサンテン系色素が報告されている(例えば、特許文献1〜3参照)。しかしながら、これらの色素は酸化チタンへの吸着性が悪く、高い増感効果を得る事ができない。また、酸化チタンに担持された色素自体の経時安定性も低いという問題があった。酸化チタンの分光増感色素として高性能な物が開示されているが、やはり酸化チタンに担持された色素自体の経時安定性に問題がある(例えば、特許文献4〜5参照)。 On the other hand, ruthenium complexes with limited resources are used, so when this solar cell is put to practical use, the supply of ruthenium complexes is in danger. Moreover, since this ruthenium complex is expensive, this problem can be solved if it can be changed to an inexpensive organic dye. Merocyanine dyes, cyanine dyes, and 9-phenylxanthene dyes have been reported as dyes for this battery (see, for example, Patent Documents 1 to 3). However, these dyes have poor adsorptivity to titanium oxide, and a high sensitization effect cannot be obtained. Further, there is a problem that the dye itself supported on titanium oxide has low stability over time. Although high-performance products have been disclosed as spectral sensitizing dyes for titanium oxide, there is still a problem in the temporal stability of the dye itself supported on titanium oxide (see, for example, Patent Documents 4 to 5).
最近、酸化物半導体の分光増感色素として高性能を有し、さらに経時安定性にも優れた有機色素が開示された(例えば、特許文献6〜7参照)が、実用的な耐久性を備えた太陽電池を製造する観点からは、未だ経時安定性の面で性能が不十分であった。
本発明の課題は高性能で耐久性に優れた光電変換素子を提供することである。 An object of the present invention is to provide a photoelectric conversion element having high performance and excellent durability.
本発明者らは上記課題を達成すべく鋭意検討した結果、前記一般式[I]〜[IV]で示される色素の少なくとも1種を光電変換材料として用いることで目標達成する事が出来た。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have achieved the goal by using at least one of the dyes represented by the general formulas [I] to [IV] as a photoelectric conversion material.
光電変換材料とは、例えば導電性支持体を構成する材料、半導体電極を構成する材料、電解質、対極を構成する材料等、光を電気エネルギーに変換する素子を構成する全ての部材の事を意味する。可視領域に光電変換能を持たない半導体電極上に可視領域の光を吸収する色素を吸着担持させる事により、半導体電極の光電変換能を可視領域にまで拡大する事ができるが、このような目的で使用される色素は増感色素と呼ばれる。本発明の色素は、この増感色素の事を意味する。 The photoelectric conversion material means all members constituting an element that converts light into electric energy, such as a material constituting a conductive support, a material constituting a semiconductor electrode, an electrolyte, and a material constituting a counter electrode. To do. By adsorbing and supporting a dye that absorbs light in the visible region on a semiconductor electrode that does not have photoelectric conversion capability in the visible region, the photoelectric conversion capability of the semiconductor electrode can be expanded to the visible region. The dye used in is called a sensitizing dye. The dye of the present invention means this sensitizing dye.
一般式[I]において、R1は酸性基を置換基として有するアルキル基、アラルキル基、アルケニル基、アリール基、あるいはヘテロ環を示す。R2、R3はアルキル基、アラルキル基、アリール基、あるいはヘテロ環置換基を示し、R2とR3で結合して環状構造を形成してもよい。R4は芳香環上の置換基であって、水素原子、アルキル基、アルコキシ基、アリール基、ヘテロ環、あるいはハロゲン原子を示す。L1は二価の連結基を示し、lは0あるいは1を示す。A1は、メチン炭素とカルボニル炭素に連結してヘテロ環を形成する残基であり、少なくとも1個の酸性基を置換基として有する。 In the general formula [I], R 1 represents an alkyl group having an acidic group as a substituent, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic ring. R 2 and R 3 each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic substituent, and may combine with R 2 and R 3 to form a cyclic structure. R 4 is a substituent on the aromatic ring and represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic ring, or a halogen atom. L 1 represents a divalent linking group, and l represents 0 or 1. A1 is a residue that forms a heterocycle by linking to a methine carbon and a carbonyl carbon, and has at least one acidic group as a substituent.
一般式[II]において、R5は酸性基を置換基として有するアルキル基、アラルキル基、アルケニル基、アリール基、あるいはヘテロ環を示す。R6、R7はアルキル基、アラルキル基、アリール基、あるいはヘテロ環置換基を示し、R6とR7で結合して環状構造を形成してもよい。R8は芳香環上の置換基であって、水素原子、アルキル基、アルコキシ基、アリール基、ヘテロ環、あるいはハロゲン原子を示す。L2は二価の連結基を示し、mは0あるいは1を示す。R9は水素原子、アルキル基、アラルキル基、アリール基、あるいはヘテロ環を示し、Zは電子吸引性の置換基を示す。 In the general formula [II], R 5 represents an alkyl group having an acidic group as a substituent, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic ring. R 6 and R 7 each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic substituent, and may be bonded to each other at R 6 and R 7 to form a cyclic structure. R 8 is a substituent on the aromatic ring and represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic ring, or a halogen atom. L 2 represents a divalent linking group, and m represents 0 or 1. R 9 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic ring, and Z represents an electron-withdrawing substituent.
一般式[III]において、R10は酸性基を置換基として有するアルキル基、アラルキル基、アルケニル基、アリール基、あるいはヘテロ環を示す。R11、R12はアルキル基、アラルキル基、アリール基、あるいはヘテロ環置換基を示し、R11とR12で結合して環状構造を形成してもよい。R13は芳香環上の置換基であって、水素原子、アルキル基、アルコキシ基、アリール基、ヘテロ環、あるいはハロゲン原子を示す。L3は二価の連結基を示し、nは0あるいは1を示す。R14、R15、R16はアルキル基、アラルキル基、あるいはアリール基を示し、これらの中、少なくとも一つは酸性基を置換基として有する。pは0あるいは1を示す。 In the general formula [III], R 10 represents an alkyl group having an acidic group as a substituent, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic ring. R 11 and R 12 represent an alkyl group, an aralkyl group, an aryl group, or a heterocyclic substituent, and may combine with R 11 and R 12 to form a cyclic structure. R 13 is a substituent on the aromatic ring and represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic ring, or a halogen atom. L 3 represents a divalent linking group, and n represents 0 or 1. R 14 , R 15 and R 16 represent an alkyl group, an aralkyl group or an aryl group, and at least one of them has an acidic group as a substituent. p represents 0 or 1;
一般式[IV]において、R17は酸性基を置換基として有するアルキル基、アラルキル基、アルケニル基、アリール基、あるいはヘテロ環を示す。R18、R19はアルキル基、アラルキル基、アリール基、あるいはヘテロ環置換基を示し、R18とR19で結合して環状構造を形成してもよい。R20は芳香環上の置換基であって、水素原子、アルキル基、アルコキシ基、アリール基、ヘテロ環、あるいはハロゲン原子を示す。L4は二価の連結基を示し、qは0あるいは1を示す。R21は水素原子、アルキル基、アラルキル基、あるいはアリール基を示し、R22は、酸性基を置換基として有するアルキル基、酸性基を置換基として有するアラルキル基、あるいは酸性基を置換基として有するアリール基を示す。A2は、メチン炭素と四級窒素原子と連結してヘテロ環を形成する残基であり、X-は対アニオンである。 In the general formula [IV], R 17 represents an alkyl group having an acidic group as a substituent, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic ring. R 18 and R 19 represent an alkyl group, an aralkyl group, an aryl group, or a heterocyclic substituent, and may be bonded to each other at R 18 and R 19 to form a cyclic structure. R 20 is a substituent on the aromatic ring and represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a hetero ring, or a halogen atom. L 4 represents a divalent linking group, and q represents 0 or 1. R 21 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R 22 has an alkyl group having an acidic group as a substituent, an aralkyl group having an acidic group as a substituent, or an acidic group as a substituent. An aryl group is shown. A2 is a residue that forms a heterocycle by linking the methine carbon and a quaternary nitrogen atom, and X − is a counter anion.
本発明で使用される一般式[I]〜[IV]の色素を用いることにより、優れた変換効率を示し、かつ耐久性に優れた光電変換素子を得ることが出来る。 By using the dyes of the general formulas [I] to [IV] used in the present invention, a photoelectric conversion element that exhibits excellent conversion efficiency and excellent durability can be obtained.
一般式[I]〜[IV]の色素の詳細について説明する。 Details of the dyes of the general formulas [I] to [IV] will be described.
R1、R5、R10、およびR17の具体例としては以下に示される置換基が挙げられる。カルボキシメチル基、2−カルボキシエチル基、3−カルボキシプロピル基、1,3−ジカルボキシプロピル基等のカルボキシアルキル基、4−カルボキシベンジル基、2−(4−カルボキシフェニル)エチル基等の酸性基を置換基として有するアラルキル基、2−カルボキシエテニル基等の酸性基を置換基として有するアルキニル基が挙げられる。酸性の置換基の具体例としてはカルボキシル基の他に、スルホ基、スルフィノ基、スルフェノ基、フォスフォノ基、フォスフィニコ基等が挙げられるが、これらの中でもカルボキシル基が特に好ましい。 Specific examples of R 1 , R 5 , R 10 , and R 17 include the substituents shown below. Carboxyalkyl groups such as carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group and 1,3-dicarboxypropyl group, acidic groups such as 4-carboxybenzyl group and 2- (4-carboxyphenyl) ethyl group And an alkynyl group having an acidic group such as a 2-carboxyethenyl group as a substituent. Specific examples of the acidic substituent include a sulfo group, a sulfino group, a sulfeno group, a phosphono group, a phosphinico group and the like in addition to a carboxyl group, and among these, a carboxyl group is particularly preferable.
酸性基を置換基として有するアリール基としては次に示されるような物が挙げられるが、これらに限定されるものではない。 Examples of the aryl group having an acidic group as a substituent include the following, but are not limited thereto.
酸性基を置換基として有するヘテロ環置換基としては次に示されるような置換基が挙げられるが、これらに限定されるものではない。 Examples of the heterocyclic substituent having an acidic group as a substituent include, but are not limited to, the following substituents.
R2とR3、R6とR7、R11とR12、R18とR19の具体例としては、メチル基、エチル基、シキロヘキシル等のアルキル基、ベンジル基、フェネチル基等のアラルキル基、フェニル基、ビフェニル基、1−ナフチル基等のアリール基、フリル基、チエニル基、インドリル基等のヘテロ環、あるいはハロゲン原子が挙げられる。その中でも好ましい物は、R2とR3、R6とR7、R11とR12、R18とR19の間で結合して環状構造を形成する残基であり、中でも特に好ましい物は、R2とR3、R6とR7、R11とR12、R18とR19の間で結合してシクロペンタン環、あるいはシクロヘキサン環を形成するアルキレン基残基である。 Specific examples of R 2 and R 3 , R 6 and R 7 , R 11 and R 12 , R 18 and R 19 include alkyl groups such as methyl, ethyl, and cyclohexyl, and aralkyl groups such as benzyl and phenethyl. Aryl groups such as phenyl group, biphenyl group and 1-naphthyl group, hetero rings such as furyl group, thienyl group and indolyl group, and halogen atoms. Among them, preferred are R 2 and R 3 , R 6 and R 7 , R 11 and R 12 , and a residue that forms a cyclic structure by bonding between R 18 and R 19. , R 2 and R 3 , R 6 and R 7 , R 11 and R 12 , and R 18 and R 19 are bonded together to form a cyclopentane ring or a cyclohexane ring.
R4、R8、R13およびR20の具体例は水素原子、メチル基、エチル基、シキロヘキシル基等のアルキル基、メトキシ基、エトキシ基等のアルコキシ基、フェニル基、ビフェニル基、1−ナフチル基等のアリール基、フリル基、チエニル基、インドリル基等のヘテロ環、あるいはハロゲン原子を示し、それらはさらに置換基を有していてもよい。その置換基の具体例としては、アルキルチオ基、アリールオキシ基、アリールチオ基、ハロゲン原子、ジ置換アミノ基、アリール基、ヘテロ環を挙げることができる。 Specific examples of R 4 , R 8 , R 13 and R 20 are hydrogen atom, methyl group, ethyl group, alkyl group such as cyclohexyl group, alkoxy group such as methoxy group, ethoxy group, phenyl group, biphenyl group, 1-naphthyl. An aryl group such as a group, a hetero ring such as a furyl group, a thienyl group, or an indolyl group, or a halogen atom, which may further have a substituent. Specific examples of the substituent include an alkylthio group, an aryloxy group, an arylthio group, a halogen atom, a disubstituted amino group, an aryl group, and a heterocyclic ring.
L1、L2、L3、およびL4の具体例は、ビニレン基、1,4−フェニレン基、4−置換スチリル基、2,5−チエニレン基等の二価の共役炭化水素残基、二価の芳香族炭化水素残基、二価の芳香族ヘテロ環残基であり、これらはさらに置換基を有しても良い。 Specific examples of L 1 , L 2 , L 3 and L 4 are divalent conjugated hydrocarbon residues such as vinylene group, 1,4-phenylene group, 4-substituted styryl group and 2,5-thienylene group, These are a divalent aromatic hydrocarbon residue and a divalent aromatic heterocyclic residue, and these may further have a substituent.
A1で示されるヘテロ環の具体例としては次に示されるような物が挙げられるが、これらに限定されるものではない。 Specific examples of the heterocycle represented by A1 include, but are not limited to, the following.
R9の具体例は水素原子の他に、メチル基、エチル基等のアルキル基、ベンジル基、フェネチル基等のアラルキル基、フェニル基、ビフェニル基、1−ナフチル基等のアリール基、フリル基、チエニル基、インドリル基等のヘテロ環が挙げられる。 Specific examples of R 9 include hydrogen atom, alkyl group such as methyl group and ethyl group, aralkyl group such as benzyl group and phenethyl group, aryl group such as phenyl group, biphenyl group and 1-naphthyl group, furyl group, Heterocycles such as thienyl group and indolyl group can be mentioned.
Zの具体例としては、シアノ基、アシル基、パーフルオロアルキル基、ニトロ基、トリフルオロアセチル基、置換スルホニル基等が挙げられるが、その中でも特にシアノ基が好ましい。 Specific examples of Z include a cyano group, an acyl group, a perfluoroalkyl group, a nitro group, a trifluoroacetyl group, a substituted sulfonyl group, etc. Among them, a cyano group is particularly preferable.
R14、R15、R16の具体例は、メチル基、エチル基、プロピル基、n−ブチル基等のアルキル基、ベンジル基、フェネチル基等のアラルキル基、フェニル基、2−ナフチル基等のアリール基が挙げられる。酸性の置換基としては、カルボキシル基、スルホ基、スルフィノ基、スルフェノ基、フォスフォノ基、フォスフィニコ基等が挙げられるが、その中でも、カルボキシル基が特に好ましい。また、酸性の置換基はR14〜R16の中のいずれに存在しても良いが、中でもR14が酸性の置換基を有し、R15とR16には酸性置換基を有しない物が特に好ましい。 Specific examples of R 14 , R 15 and R 16 include alkyl groups such as methyl group, ethyl group, propyl group and n-butyl group, aralkyl groups such as benzyl group and phenethyl group, phenyl group and 2-naphthyl group. An aryl group is mentioned. Examples of the acidic substituent include a carboxyl group, a sulfo group, a sulfino group, a sulfeno group, a phosphono group, and a phosphinico group, among which a carboxyl group is particularly preferable. An acidic substituent may be present in any of R 14 to R 16 , and among them, R 14 has an acidic substituent, and R 15 and R 16 do not have an acidic substituent. Is particularly preferred.
R21の具体例は水素原子の他に、メチル基、エチル基等のアルキル基、ベンジル基、フェネチル基等のアラルキル基、フェニル基、ビフェニル基、1−ナフチル基等のアリール基が挙げられる。 Specific examples of R 21 include a hydrogen atom, an alkyl group such as a methyl group and an ethyl group, an aralkyl group such as a benzyl group and a phenethyl group, and an aryl group such as a phenyl group, a biphenyl group, and a 1-naphthyl group.
R22の具体例は、メチル基、エチル基、プロピル基、n−ブチル基等のアルキル基、ベンジル基、フェネチル基等のアラルキル基、フェニル基、2−ナフチル基等のアリール基が挙げられ、さらにこれらは酸性の置換基を有する。酸性の置換基としては、カルボキシル基、スルホ基、スルフィノ基、スルフェノ基、フォスフォノ基、フォスフィニコ基等が挙げられるが、その中でも、カルボキシル基が特に好ましい。 Specific examples of R 22 include alkyl groups such as methyl group, ethyl group, propyl group and n-butyl group, aralkyl groups such as benzyl group and phenethyl group, aryl groups such as phenyl group and 2-naphthyl group, Furthermore, they have an acidic substituent. Examples of the acidic substituent include a carboxyl group, a sulfo group, a sulfino group, a sulfeno group, a phosphono group, and a phosphinico group, among which a carboxyl group is particularly preferable.
A2で示されるヘテロ環の具体例としては次に示されるような物が挙げられるが、これらに限定されるものではない。 Specific examples of the heterocycle represented by A2 include, but are not limited to, the following.
X-の具体例としては、塩素アニオン、臭素アニオン、ヨウ素アニオン等のハライドアニオン、p−トルエンスルホン酸アニオン等のアリールスルホン酸アニオン、メチル硫酸アニオン等のアルキル硫酸アニオン、硫酸アニオン、過塩素酸アニオン、テトラフルオロホウ酸アニオン、ヘキサフルオロリン酸アニオン等が挙げられる。 X - include Examples of the chloride anion, a bromine anion, halide anions such as iodine anion, p- toluenesulfonate anion and aryl sulfonate anion, an alkyl sulfate anion such as methyl sulfate anion, a sulfate anion, a perchlorate anion , Tetrafluoroborate anion, hexafluorophosphate anion and the like.
本発明の色素は、メロシアニン色素に分類される色素である。メロシアニン色素は、分子内にドナー性の置換基を有するユニットと、アクセプター性の置換基を有するユニットとを共役二重結合で連結した構造を有する。メロシアニン色素を半導体の分光増感剤として使用する場合には、色素のアクセプターユニット上に半導体との吸着性を促進する酸性基を導入する事が一般的である。色素は、吸着性を促進する酸性基を介して半導体上に吸着する。しかし、その吸着性は実用的見地からみて不十分であり、光電変換素子の加熱保存時に電解液中に色素が再溶解する問題があった。本発明で示されるように、アクセプターユニットだけでなく、ドナーユニットにも酸性基を導入した色素を使用する事により、加熱保存時における電解液への色素の再溶出を効果的に防止する事ができる事が判明した。特定構造のドナーユニットと酸性基を組み合わせる事により、加熱保存時の色素の再溶出軽減と高変換効率を兼ね備えたセルを製造する事ができる。 The dye of the present invention is a dye classified as a merocyanine dye. The merocyanine dye has a structure in which a unit having a donor substituent in a molecule and a unit having an acceptor substituent are connected by a conjugated double bond. When a merocyanine dye is used as a spectral sensitizer for a semiconductor, it is common to introduce an acidic group that promotes the adsorptivity with the semiconductor onto the acceptor unit of the dye. The dye is adsorbed onto the semiconductor via an acidic group that promotes adsorptivity. However, the adsorptivity is insufficient from a practical point of view, and there is a problem that the dye is re-dissolved in the electrolytic solution when the photoelectric conversion element is stored under heating. As shown in the present invention, by using a dye having an acidic group introduced not only in the acceptor unit but also in the donor unit, re-elution of the dye into the electrolytic solution during heat storage can be effectively prevented. It turns out that you can. By combining a donor unit having a specific structure and an acidic group, it is possible to produce a cell having both reduced re-elution of dye during heat storage and high conversion efficiency.
ドナーユニット上の酸性基は、色素の発色を支配する共役二重結合系の原子上にあっても良く、色素の発色を支配する共役二重結合系からSP3炭素原子を介して独立した残基上にあっても良いが、色素の色をよりレッドシフトさせる目的からは、色素の発色を支配する共役二重結合系から独立した残基上に酸性基を導入する事が好ましい。 The acidic group on the donor unit may be on an atom of a conjugated double bond system that governs the color development of the dye, and remains independent from the conjugated double bond system that governs the color development of the dye via the SP 3 carbon atom. Although it may be on the group, for the purpose of red-shifting the color of the dye, it is preferable to introduce an acidic group on a residue independent of the conjugated double bond system that governs the color development of the dye.
次に、本発明の一般式[I]の色素の具体例を挙げるが、これらに限定されるものではない。 Next, specific examples of the dye of the general formula [I] of the present invention will be given, but the invention is not limited thereto.
次に、本発明の一般式[II]の色素の具体例を挙げるが、これらに限定されるものではない。 Next, specific examples of the dye of the general formula [II] of the present invention will be given, but the invention is not limited thereto.
次に、本発明の一般式[III]の色素の具体例を挙げるが、これらに限定されるものではない。 Next, specific examples of the dye of the general formula [III] of the present invention will be given, but the invention is not limited thereto.
次に、本発明の一般式[IV]の色素の具体例を挙げるが、これらに限定されるものではない。 Next, specific examples of the dye of the general formula [IV] of the present invention will be given, but the invention is not limited to these.
本発明の光電変換素子は、導電性支持体、導電性支持体上に設置した色素によって増感された半導体層、電荷移動層及び対極からなる。半導体層は単層構成でも積層構成でもよく、目的に応じて設計される。また、導電性支持体の導電層と半導体層の境界、半導体層と移動層の境界等、この素子における境界においては、各層の構成成分は相互に拡散、または混合していてもよい。 The photoelectric conversion element of the present invention comprises a conductive support, a semiconductor layer sensitized by a dye placed on the conductive support, a charge transfer layer, and a counter electrode. The semiconductor layer may be a single layer structure or a stacked structure, and is designed according to the purpose. In addition, at the boundary of this element such as the boundary between the conductive layer and the semiconductor layer of the conductive support, the boundary between the semiconductor layer and the moving layer, the constituent components of each layer may be diffused or mixed with each other.
導電性支持体は、金属のように支持体そのものに導電性があるもの、または表面に導電剤を含む導電層を有するガラスあるいはプラスチックの支持体を用いることができる。後者の場合、導電剤としては白金、金、銀、銅、アルミニウム等の金属、炭素、あるいはインジウム−スズ複合酸化物(以降「ITO」と略記する)、フッ素をドーピングした酸化スズ等の金属酸化物(以降「FTO」と略記する)等が挙げられる。導電性支持体は、光を10%以上透過する透明性を有していることが好ましく、50%以上透過することがより好ましい。この中でも、ITOやFTOからなる導電層をガラス上に堆積した導電性ガラスが特に好ましい。 As the conductive support, there can be used a support made of glass or plastic having a conductive layer containing a conductive agent on its surface, such as a metal having a conductive property in itself. In the latter case, the conductive agent is a metal oxide such as platinum, gold, silver, copper, aluminum or the like, carbon or indium-tin composite oxide (hereinafter abbreviated as “ITO”), fluorine-doped tin oxide or the like. (Hereinafter abbreviated as “FTO”) and the like. The conductive support preferably has a transparency that transmits light of 10% or more, and more preferably transmits 50% or more. Among these, conductive glass in which a conductive layer made of ITO or FTO is deposited on glass is particularly preferable.
透明導電性支持体の抵抗を下げる目的で、金属リード線を用いてもよい。金属リード線の材質はアルミニウム、銅、銀、金、白金、ニッケル等の金属が挙げられる。金属リード線は、透明導電性支持体に蒸着、スパッタリング、圧着等で設置し、その上にITOやFTOを設ける方法、あるいは透明導電性支持体上に金属リード線を設置する。 For the purpose of reducing the resistance of the transparent conductive support, a metal lead wire may be used. Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. The metal lead wire is installed on the transparent conductive support by vapor deposition, sputtering, pressure bonding, etc., and ITO or FTO is provided thereon, or the metal lead wire is set on the transparent conductive support.
半導体としては、シリコン、ゲルマニウムのような単体半導体、あるいは金属のカルコゲニドに代表される化合物半導体、またはペロブスカイト構造を有する化合物等を使用することができる。金属のカルコゲニドとしてはチタン、スズ、亜鉛、鉄、タングステン、ジルコニウム、ハフニウム、ストロンチウム、インジウム、セリウム、イットリウム、ランタン、バナジウム、ニオブ、あるいはタンタルの酸化物、カドミウム、亜鉛、鉛、銀、アンチモン、ビスマスの硫化物、カドミウム、鉛のセレン化物、カドミウムのテルル化物等が挙げられる。他の化合物半導体としては亜鉛、ガリウム、インジウム、カドミウム、等のリン化物、ガリウム砒素、銅−インジウム−セレン化物、銅−インジウム−硫化物等が好ましい。また、ペロブスカイト構造を有する化合物としては、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸ナトリウム、チタン酸バリウム、ニオブ酸カリウム等が好ましい。 As the semiconductor, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, a compound having a perovskite structure, or the like can be used. Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver, antimony, bismuth. Sulfide, cadmium, lead selenide, cadmium telluride and the like. Other compound semiconductors are preferably phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like. As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable.
本発明に用いられる半導体は、単結晶でも多結晶でもよい。変換効率としては単結晶が好ましいが、製造コスト、原材料確保等の点では多結晶が好ましく、その半導体の粒径は2nm以上、1μm以下であることが好ましい。 The semiconductor used in the present invention may be single crystal or polycrystalline. As the conversion efficiency, a single crystal is preferable, but a polycrystal is preferable in terms of manufacturing cost, securing raw materials, and the like, and the particle size of the semiconductor is preferably 2 nm or more and 1 μm or less.
導電性支持体上に半導体層を形成する方法としては、半導体微粒子の分散液またはコロイド溶液を導電性支持体上に塗布する方法、ゾル−ゲル法等がある。その分散液の作製方法としては、前述のゾル−ゲル法、乳鉢等で機械的に粉砕する方法、ミルを使って粉砕しながら分散する方法、あるいは半導体を合成する際に溶媒中で微粒子として析出させ、そのまま使用する方法等が挙げられる。 As a method for forming a semiconductor layer on a conductive support, there are a method of applying a dispersion or colloidal solution of semiconductor fine particles on a conductive support, a sol-gel method, and the like. The dispersion can be prepared by the above-mentioned sol-gel method, a method of mechanically pulverizing with a mortar, etc., a method of dispersing while pulverizing using a mill, or a fine particle in a solvent when synthesizing a semiconductor. And a method of using it as it is.
機械的粉砕、あるいはミルを使用して粉砕して作製する分散液の場合、少なくとも半導体微粒子単独、あるいは半導体微粒子と樹脂の混合物を水あるいは有機溶剤に分散して形成される。使用される樹脂としては、スチレン、酢酸ビニル、アクリル酸エステル、メタクリル酸エステル等によるビニル化合物の重合体や共重合体、シリコーン樹脂、フェノキシ樹脂、ポリスルホン樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリエステル樹脂、セルロースエステル樹脂、セルロースエーテル樹脂、ウレタン樹脂、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリアミド樹脂、ポリイミド樹脂等が挙げられる。 In the case of a dispersion prepared by mechanical pulverization or pulverization using a mill, it is formed by dispersing at least semiconductor fine particles alone or a mixture of semiconductor fine particles and a resin in water or an organic solvent. Resins used include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid esters, methacrylic acid esters, silicone resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, polyvinyl formal resins, polyester resins. , Cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin and the like.
半導体微粒子を分散する溶媒としては、水、メタノール、エタノール、あるいはイソプロピルアルコール等のアルコール系溶媒、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒を挙げることができる。これらは単独、あるいは2種以上の混合溶媒として用いることができる。 Solvents for dispersing the semiconductor fine particles include alcohol solvents such as water, methanol, ethanol, and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl formate, ethyl acetate, and n-butyl acetate. Ester solvents, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or ether solvents such as dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, or amide solvents such as N-methyl-2-pyrrolidone , Dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodine Halogenated hydrocarbon solvents such as debenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, Examples thereof include hydrocarbon solvents such as m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or as a mixed solvent of two or more.
得られた分散液の塗布方法としては、ローラ法、ディップ法、エアナイフ法、ブレード法、ワイヤーバー等、スライドホッパ法、エクストルージョン法、カーテン法、スピン法、あるいはスプレー法を挙げることができる。 Examples of a method for applying the obtained dispersion include a roller method, a dip method, an air knife method, a blade method, a wire bar, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method.
更に半導体層は、単層であっても多層であってもよい。多層の場合、粒径の異なる半導体微粒子の分散液を多層塗布したり、種類の異なる半導体や、樹脂、添加剤の組成が異なる塗布層を多層塗布することもできる。また、一度の塗布で膜厚が不足する場合には多層塗布は有効な手段である。 Furthermore, the semiconductor layer may be a single layer or multiple layers. In the case of multiple layers, a dispersion of semiconductor fine particles having different particle diameters can be applied in multiple layers, or different types of semiconductors, and application layers having different compositions of resins and additives can be applied in multiple layers. In addition, when the film thickness is insufficient with a single coating, the multilayer coating is an effective means.
一般的に、半導体層の膜厚が増大するほど単位投影面積当たりの担持色素量も増えるため光の捕獲率が高くなるが、生成した電子の拡散距離も増えるために電荷の再結合も多くなってしまう。従って、半導体層の膜厚は0.1〜100μmが好ましく、1〜30μmがより好ましい。 In general, as the thickness of the semiconductor layer increases, the amount of supported dye increases per unit projected area and the light capture rate increases. However, the diffusion distance of the generated electrons also increases, and the recombination of charges also increases. End up. Therefore, the film thickness of the semiconductor layer is preferably 0.1 to 100 μm, and more preferably 1 to 30 μm.
半導体微粒子は導電性支持体上に塗布した後、加熱処理してもしなくともよいが、粒子同士の電子的コンタクト及び塗膜強度の向上や支持体との密着性向上の点から、加熱処理をした方が好ましい。更に、マイクロ波照射、プレス処理あるいは電子線照射を行ってもよく、これらの処理は単独で行っても二種類以上行っても構わない。加熱処理の際、加熱温度は40〜700℃が好ましく、80〜600℃がより好ましい。また、加熱時間は5分〜50時間が好ましく、10分〜20時間がより好ましい。マイクロ波照射は、半導体電極の半導体層形成側から照射しても、裏側から照射しても構わない。照射時間には特に制限が無いが、1時間以内で行うことが好ましい。プレス処理は、100kg/cm2以上が好ましく、1000kg/cm2が更に好ましい。プレスする時間は特に制限が無いが、1時間以内で行うことが好ましい。 The semiconductor fine particles may or may not be heat-treated after being coated on the conductive support. However, from the viewpoint of improving the electronic contact between the particles and the strength of the coating film and the adhesion to the support, the heat treatment is performed. Is preferable. Furthermore, microwave irradiation, press treatment, or electron beam irradiation may be performed, and these treatments may be performed alone or in combination of two or more. In the heat treatment, the heating temperature is preferably 40 to 700 ° C, more preferably 80 to 600 ° C. The heating time is preferably 5 minutes to 50 hours, and more preferably 10 minutes to 20 hours. The microwave irradiation may be performed from the semiconductor layer forming side of the semiconductor electrode or from the back side. Although there is no restriction | limiting in particular in irradiation time, It is preferable to carry out within 1 hour. The press treatment is preferably 100 kg / cm 2 or more, more preferably 1000 kg / cm 2 . There is no particular limitation on the pressing time, but it is preferably performed within 1 hour.
半導体微粒子は多くの色素を吸着できるように表面積の大きなものが好ましい。このため半導体層を支持体上に塗設した状態での表面積は、投影面積に対して10倍以上であることが好ましく、100倍以上であることがより好ましい。 The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For this reason, it is preferable that the surface area in the state which coated the semiconductor layer on the support body is 10 times or more with respect to a projection area, and it is more preferable that it is 100 times or more.
本発明の光電変換素子における色素は、一般式[I]、一般式[II]、一般式[III]、一般式[IV]で示される色素の何れかを光電変換材料として用いる。また、これらを併用しても構わない。 As the dye in the photoelectric conversion element of the present invention, any one of the dyes represented by the general formula [I], the general formula [II], the general formula [III], and the general formula [IV] is used as the photoelectric conversion material. Moreover, you may use these together.
半導体層に色素を吸着させる方法としては、色素溶液中あるいは色素分散液中に半導体微粒子を含有する作用電極を浸漬する方法、色素溶液あるいは分散液を半導体層に塗布して吸着させる方法を用いることができる。前者の場合、浸漬法、ディップ法、ローラ法、エアーナイフ法等を用いることができ、後者の場合は、ワイヤーバー法、スライドホッパー法、エクストルージョン法、カーテン法、スピン法、スプレー法等を用いることができる。 As a method of adsorbing the dye to the semiconductor layer, a method of immersing a working electrode containing semiconductor fine particles in a dye solution or a dye dispersion, or a method of applying a dye solution or a dispersion to the semiconductor layer and adsorbing it is used. Can do. In the former case, dipping method, dipping method, roller method, air knife method, etc. can be used, and in the latter case, wire bar method, slide hopper method, extrusion method, curtain method, spin method, spray method, etc. Can be used.
色素を吸着する際、縮合剤を併用してもよい。縮合剤は、無機物表面に物理的あるいは化学的に色素を結合すると思われる触媒的作用をするもの、または化学量論的に作用し、化学平衡を有利に移動させるものの何れであってもよい。更に、縮合助剤としてチオール、あるいはヒドロキシ化合物を添加してもよい。 When adsorbing the dye, a condensing agent may be used in combination. The condensing agent may be either one that has a catalytic action that is supposed to physically or chemically bind the dye to the inorganic surface, or one that acts stoichiometrically to favorably shift the chemical equilibrium. Furthermore, a thiol or a hydroxy compound may be added as a condensation aid.
色素を溶解、あるいは分散する溶媒は、水、メタノール、エタノール、あるいはイソプロピルアルコール等のアルコール系溶媒、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、アセトニトリル、プロピオニトリル等のニトリル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒を挙げることができ、これらは単独、あるいは2種以上の混合として用いることができる。 Solvents for dissolving or dispersing the dye are water, methanol, ethanol, alcohol solvents such as isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or n-butyl acetate. Ester solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, nitrile solvents such as acetonitrile, propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, or Amide solvents such as N-methyl-2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-di Halogenated hydrocarbon solvents such as lolobenzene, fluorobenzene, bromobenzene, iodobenzene, or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene , Hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, or cumene, and these can be used alone or as a mixture of two or more.
これらを用い、色素を吸着する際の温度としては、−50℃以上、200℃以下が好ましい。また、この吸着は攪拌しながら行っても構わない。攪拌する場合の方法としては、スターラー、ボールミル、ペイントコンディショナー、サンドミル、アトライター、ディスパーザー、あるいは超音波分散等が挙げられるが、これらに限定されるものではない。吸着に要する時間は、5秒以上、1000時間以下が好ましく、10秒以上、500時間以下がより好ましく、1分以上、150時間が更に好ましい。 The temperature at which these are used and the dye is adsorbed is preferably -50 ° C or higher and 200 ° C or lower. Further, this adsorption may be performed while stirring. Examples of the stirring method include, but are not limited to, a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, and ultrasonic dispersion. The time required for adsorption is preferably 5 seconds or more and 1000 hours or less, more preferably 10 seconds or more and 500 hours or less, and further preferably 1 minute or more and 150 hours.
本発明では、一般式[I]、一般式[II]、一般式[III]、あるいは一般式[IV]で示される色素を吸着する際、ステロイド系化合物を併用しても構わない。 In the present invention, a steroidal compound may be used in combination when adsorbing the dye represented by the general formula [I], the general formula [II], the general formula [III], or the general formula [IV].
そのステロイド化合物の具体例としては、(E−1)〜(E−10)に示すものが挙げられる。ステロイド系化合物の量は、色素1質量部に対して0.01〜1000質量部が好ましく、0.1〜100質量部がより好ましい。 Specific examples of the steroid compound include those shown in (E-1) to (E-10). 0.01-1000 mass parts is preferable with respect to 1 mass part of pigment | dyes, and, as for the quantity of a steroid type compound, 0.1-100 mass parts is more preferable.
色素を吸着した後、あるいは色素と上記ステロイド系化合物を共吸着した後、t−ブチルピリジン、2−ピコリン、2,6−ルチジン等の塩基性化合物、あるいはリン酸、リン酸エステル、アルキルリン酸、酢酸、プロピオン酸等の酸性化合物を含有する有機溶媒に浸漬処理しても構わない。 After adsorbing the dye, or after co-adsorbing the dye and the steroidal compound, basic compounds such as t-butylpyridine, 2-picoline, 2,6-lutidine, or phosphoric acid, phosphate ester, alkyl phosphoric acid Further, it may be dipped in an organic solvent containing an acidic compound such as acetic acid or propionic acid.
本発明の電荷移動層としては、酸化還元対を有機溶媒に溶解した電解液、酸化還元対を有機溶媒に溶解した液体をポリマーマトリックスに含浸したゲル電解質、酸化還元対を含有する溶融塩、固体電解質、有機正孔輸送材料等を用いることができる。 As the charge transfer layer of the present invention, an electrolytic solution in which a redox couple is dissolved in an organic solvent, a gel electrolyte in which a liquid in which the redox couple is dissolved in an organic solvent is impregnated in a polymer matrix, a molten salt containing the redox couple, a solid An electrolyte, an organic hole transport material, or the like can be used.
本発明で使用される電解液は、電解質、溶媒、及び添加物から構成されることが好ましい。好ましい電解質はヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化セシウム、ヨウ化カルシウム等の金属ヨウ化物−ヨウ素の組み合わせ、テトラアルキルアンモニウムヨ−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−ヨウ素の組み合わせ、臭化リチウム、臭化ナトリウム、臭化カリウム、臭化セシウム、臭化カルシウム等の金属臭化物−臭素の組み合わせ、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−臭素の組み合わせ、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、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、ビオロゲン色素、ヒドロキノン−キノン等が挙げられる。上述の電解質は単独の組み合わせであっても混合であってもよい。また、電解質として、室温で溶融状態の溶融塩を用いることもできる。この溶融塩を用いた場合は、特に溶媒を用いなくても構わない。 The electrolytic solution used in the present invention is preferably composed of an electrolyte, a solvent, and an additive. Preferred electrolytes include metal iodide-iodine combinations such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, and the like. Iodine salts of quaternary ammonium compounds-iodine combinations, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide-bromine combinations, quaternary compounds such as tetraalkylammonium bromide, pyridinium bromide Bromine-bromine combinations of ammonium compounds, metal complexes such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion, sulfur compounds such as sodium polysulfide, alkylthiol-alkyldisulfide, viologen Dye, hydroquinone - quinones, and the like. The above-mentioned electrolytes may be a single combination or a mixture. Further, a molten salt in a molten state at room temperature can also be used as the electrolyte. When this molten salt is used, it is not necessary to use a solvent.
電解液における電解質濃度は、0.05〜20Mが好ましく、0.1〜15Mが更に好ましい。電解液に用いる溶媒としては、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系溶媒、3−メチル−2−オキサゾリジノン等の複素環化合物、ジオキサン、ジエチルエーテル、エチレングリコールジアルキルエーテル等のエーテル系溶媒、メタノール、エタノール、ポリプロピレングリコールモノアルキルエーテル等のアルコール系溶媒、アセトニトリル、ベンゾニトリル等のニトリル系溶媒、ジメチルスルホキシド、スルホラン等の非プロトン性極性溶媒等が好ましい。また、t−ブチルピリジン、2−ピコリン、2,6−ルチジン等の塩基性化合物を併用しても構わない。 The electrolyte concentration in the electrolytic solution is preferably 0.05 to 20M, and more preferably 0.1 to 15M. Solvents used for the electrolyte include carbonate solvents such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether solvents such as dioxane, diethyl ether and ethylene glycol dialkyl ether, methanol, ethanol Alcohol solvents such as polypropylene glycol monoalkyl ether, nitrile solvents such as acetonitrile and benzonitrile, aprotic polar solvents such as dimethyl sulfoxide and sulfolane are preferred. Further, basic compounds such as t-butylpyridine, 2-picoline, and 2,6-lutidine may be used in combination.
本発明では、電解質はポリマー添加、オイルゲル化剤添加、多官能モノマー類を含む重合、ポリマーの架橋反応等の手法によりゲル化させることもできる。ポリマー添加によりゲル化させる場合の好ましいポリマーとしては、ポリアクリロニトリル、ポリフッ化ビニリデン等を挙げることができる。オイルゲル化剤添加によりゲル化させる場合の好ましいゲル化剤としては、ジベンジルデン−D−ソルビトール、コレステロール誘導体、アミノ酸誘導体、トランス−(1R,2R)−1,2−シクロヘキサンジアミンのアルキルアミド誘導体、アルキル尿素誘導体、N−オクチル−D−グルコンアミドベンゾエート、双頭型アミノ酸誘導体、4級アンモニウム誘導体等を挙げることができる。 In the present invention, the electrolyte can be gelled by a technique such as addition of a polymer, addition of an oil gelling agent, polymerization including polyfunctional monomers, or a crosslinking reaction of the polymer. Preferable polymers in the case of gelation by polymer addition include polyacrylonitrile, polyvinylidene fluoride and the like. Preferred gelling agents for gelation by adding an oil gelling agent include dibenzylden-D-sorbitol, cholesterol derivatives, amino acid derivatives, alkylamide derivatives of trans- (1R, 2R) -1,2-cyclohexanediamine, alkylureas Derivatives, N-octyl-D-gluconamide benzoate, double-headed amino acid derivatives, quaternary ammonium derivatives and the like can be mentioned.
多官能モノマーによって重合する場合の好ましいモノマーとしては、ジビニルベンゼン、エチレングルコールジメタクリレート、エチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート等を挙げることができる。更に、アクリルアミド、メチルアクリレート等のアクリル酸やα−アルキルアクリル酸から誘導されるエステル類やアミド類、マレイン酸ジメチル、フマル酸ジエチル等のマレイン酸やフマル酸から誘導されるエステル類、ブタジエン、シクロペンタジエン等のジエン類、スチレン、p−クロロスチレン、スチレンスルホン酸ナトリウム等の芳香族ビニル化合物、ビニルエステル類、アクリロニトリル、メタクリロニトリル、含窒素複素環を有するビニル化合物、4級アンモニウム塩を有するビニル化合物、N−ビニルホルムアミド、ビニルスルホン酸、ビニリデンフルオライド、ビニルアルキルエーテル類、N−フェニルマレイミド等の単官能モノマーを含有してもよい。モノマー全量に占める多官能性モノマーは、0.5〜70質量%が好ましく、1.0〜50質量%がより好ましい。 Preferred monomers for polymerization with a polyfunctional monomer include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and the like. be able to. Furthermore, esters and amides derived from acrylic acid such as acrylamide and methyl acrylate and α-alkyl acrylic acid, esters derived from maleic acid and fumaric acid such as dimethyl maleate and diethyl fumarate, butadiene, cyclohexane and the like. Dienes such as pentadiene, aromatic vinyl compounds such as styrene, p-chlorostyrene and sodium styrene sulfonate, vinyl esters, acrylonitrile, methacrylonitrile, vinyl compounds having a nitrogen-containing heterocyclic ring, vinyl having a quaternary ammonium salt A monofunctional monomer such as a compound, N-vinylformamide, vinylsulfonic acid, vinylidene fluoride, vinyl alkyl ethers, N-phenylmaleimide may be contained. 0.5-70 mass% is preferable and the polyfunctional monomer which occupies for the monomer whole quantity has more preferable 1.0-50 mass%.
上述のモノマーは、ラジカル重合によって重合することができる。本発明で使用できるゲル電解質用モノマーは、加熱、光、電子線あるいは電気化学的にラジカル重合することができる。架橋高分子が加熱によって形成される場合に使用される重合開始剤は、2,2´−アゾビスイソブチロニトリル、2,2´−アゾビス(2,4−ジメチルバレロニトリル)、ジメチル−2,2´−アゾビス(2−メチルプロピオネート)等のアゾ系開始剤、ベンゾイルパーオキシド等の過酸化物系開始剤等が好ましい。これらの重合開始剤の添加量は、モノマー総量に対して、0.01〜20質量%が好ましく、0.1〜10質量%がより好ましい。 The above-mentioned monomers can be polymerized by radical polymerization. The monomer for gel electrolyte that can be used in the present invention can be radically polymerized by heating, light, electron beam or electrochemical. The polymerization initiator used when the crosslinked polymer is formed by heating is 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2. Azo initiators such as 2,2′-azobis (2-methylpropionate) and peroxide initiators such as benzoyl peroxide are preferable. The addition amount of these polymerization initiators is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total amount of monomers.
ポリマーの架橋反応により電解質をゲル化させる場合、架橋反応に必要な反応性基を含有するポリマー及び架橋剤を併用することが望ましい。架橋可能な反応性基に好ましい例としては、ピリジン、イミダゾール、チアゾール、オキサゾール、トリアゾール、モルフォリン、ピペリジン、ピペラジン等の含窒素複素環を挙げることができ、好ましい架橋剤は、ハロゲン化アルキル、ハロゲン化アラルキル、スルホン酸エステル、酸無水物、酸クロリド、イソシアネート等の窒素原子に対して求電子反応可能な2官能以上の試薬を挙げることができる。 When the electrolyte is gelled by a polymer crosslinking reaction, it is desirable to use a polymer containing a reactive group necessary for the crosslinking reaction and a crosslinking agent in combination. Preferable examples of the crosslinkable reactive group include nitrogen-containing heterocycles such as pyridine, imidazole, thiazole, oxazole, triazole, morpholine, piperidine, piperazine, etc. Preferred crosslinking agents include alkyl halides, halogens Bifunctional or higher functional reagents capable of electrophilic reaction with nitrogen atoms such as aralkyl fluoride, sulfonic acid ester, acid anhydride, acid chloride, and isocyanate can be exemplified.
無機固体化合物を電解質の代わりに用いる場合、ヨウ化銅、チオシアン化銅等をキャスト法、塗布法、スピンコート法、浸漬法、電解メッキ等の手法により電極内部に導入することができる。 When an inorganic solid compound is used instead of the electrolyte, copper iodide, copper thiocyanide, or the like can be introduced into the electrode by a casting method, a coating method, a spin coating method, a dipping method, electrolytic plating, or the like.
また、本発明では電解質の代わりに有機電荷輸送物質を用いることができる。電荷輸送物質には正孔輸送物質と電子輸送物質がある。前者の例としては、例えば特公昭34−5466号公報等に示されているオキサジアゾール類、特公昭45−555号公報等に示されているトリフェニルメタン類、特公昭52−4188号公報等に示されているピラゾリン類、特公昭55−42380号公報等に示されているヒドラゾン類、特開昭56−123544号公報等に示されているオキサジアゾール類、特開昭54−58445号公報に示されているテトラアリールベンジジン類、特開昭58−65440号公報、あるいは特開昭60−98437号公報に示されているスチルベン類等を挙げることができる。その中でも、本発明に使用される電荷輸送物質としては、特開昭60−24553号公報、特開平2−96767号公報、特開平2−183260号公報、並びに特開平2−226160号公報に示されているヒドラゾン類、特開平2−51162号公報、並びに特開平3−75660号公報に示されているスチルベン類が特に好ましい。また、これらは単独、あるいは2種以上の混合物として用いることができる。 In the present invention, an organic charge transport material can be used instead of the electrolyte. Charge transport materials include hole transport materials and electron transport materials. Examples of the former include, for example, oxadiazoles disclosed in Japanese Patent Publication No. 34-5466, triphenylmethanes disclosed in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. Pyrazolines shown in the above, hydrazones shown in JP-B-55-42380, oxadiazoles shown in JP-A-56-123544, etc., JP-A-54-58445 And tetrasylbenzidines disclosed in JP-A No. 58-65440, and stilbenes disclosed in JP-A No. 60-98437. Among them, examples of the charge transport material used in the present invention are shown in JP-A-60-24553, JP-A-2-96767, JP-A-2-183260, and JP-A-2-226160. Particularly preferred are the hydrazones described, and the stilbenes shown in JP-A-2-51162 and JP-A-3-75660. Moreover, these can be used individually or in mixture of 2 or more types.
一方、電子輸送物質としては、例えばクロラニル、テトラシアノエチレン、テトラシアノキノジメタン、2,4,7−トリニトロ−9−フルオレノン、2,4,5,7−テトラニトロ−9−フルオレノン、2,4,5,7−テトラニトロキサントン、2,4,8−トリニトロチオキサントン、1,3,7−トリニトロジベンゾチオフェン、あるいは1,3,7−トリニトロジベンゾチオフェン−5,5−ジオキシド等がある。これらの電子輸送物質は単独、あるいは2種以上の混合物として用いることができる。 On the other hand, examples of the electron transport material include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, etc. . These electron transport materials can be used alone or as a mixture of two or more.
また、更に増感効果を増大させる増感剤として、ある種の電子吸引性化合物を添加することもできる。この電子吸引性化合物としては例えば、2,3−ジクロロ−1,4−ナフトキノン、1−ニトロアントラキノン、1−クロロ−5−ニトロアントラキノン、2−クロロアントラキノン、フェナントレンキノン等のキノン類、4−ニトロベンズアルデヒド等のアルデヒド類、9−ベンゾイルアントラセン、インダンジオン、3,5−ジニトロベンゾフェノン、あるいは3,3′,5,5′−テトラニトロベンゾフェノン等のケトン類、無水フタル酸、4−クロロナフタル酸無水物等の酸無水物、テレフタラルマロノニトリル、9−アントリルメチリデンマロノニトリル、4−ニトロベンザルマロノニトリル、あるいは4−(p−ニトロベンゾイルオキシ)ベンザルマロノニトリル等のシアノ化合物、3−ベンザルフタリド、3−(α−シアノ−p−ニトロベンザル)フタリド、あるいは3−(α−シアノ−p−ニトロベンザル)−4,5,6,7−テトラクロロフタリド等のフタリド類等を挙げることができる。 Further, as a sensitizer that further increases the sensitizing effect, a certain kind of electron-withdrawing compound can be added. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, and phenanthrenequinone, 4-nitro Aldehydes such as benzaldehyde, ketones such as 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, or 3,3 ', 5,5'-tetranitrobenzophenone, phthalic anhydride, 4-chloronaphthalic anhydride Acid anhydrides such as terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalononitrile, or cyano compounds such as 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide , 3- (α-cyano- - Nitorobenzaru) phthalide, or 3- (alpha-cyano -p- Nitorobenzaru) -4,5,6,7 can be mentioned phthalides such as tetrachloro phthalide like.
これらの電荷輸送材料を用いて電荷移動層を形成する場合、樹脂を併用しても構わない。樹脂を併用する場合にはポリスチレン樹脂、ポリビニルアセタール樹脂、ポリスルホン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリフェニレンオキサイド樹脂、ポリアリレート樹脂、アクリル樹脂、メタクリル樹脂、フェノキシ樹脂等が挙げられる。これらの中でも、ポリスチレン樹脂、ポリビニルアセタール樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂が好ましい。これらの樹脂は、単独あるいは共重合体として2種以上を混合しても構わない。 When forming a charge transfer layer using these charge transport materials, a resin may be used in combination. When resin is used in combination, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, polyester resin, polyphenylene oxide resin, polyarylate resin, acrylic resin, methacrylic resin, phenoxy resin and the like can be mentioned. Among these, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, and polyarylate resin are preferable. These resins may be used alone or as a copolymer in combination of two or more.
電荷移動層の形成方法は大きく2通りの方法が挙げられる。1つは増感色素を担持した半導体微粒子含有層の上に、先に対極を貼り合わせ、その隙間に液状の電荷移動層を挟み込む方法、もう一つは、半導体微粒子含有層の上に直接電荷移動層を付与する方法である。後者の場合、電荷移動層の上に対極を新たに付与することになる。 There are two main methods for forming the charge transfer layer. One is a method in which a counter electrode is first pasted on a semiconductor fine particle-containing layer carrying a sensitizing dye, and a liquid charge transfer layer is sandwiched between the opposite electrodes, and the other is a method in which a charge is directly applied on the semiconductor fine particle-containing layer. This is a method of providing a moving layer. In the latter case, a counter electrode is newly provided on the charge transfer layer.
前者の場合、電荷移動層の挟み込み方法として、浸漬等による毛管現象を利用する常圧プロセスと常圧より低い圧力にして気相を液相に置換する真空プロセスが挙げられる。後者の場合、湿式の電荷移動層においては未乾燥のまま対極を付与し、エッジ部の液漏洩防止を施す必要がある。また、ゲル電解液の場合においては、湿式で塗布して重合等の方法により固体化する方法もある。その場合、乾燥、固定化した後に対極を付与してもよい。電解液の他、有機電荷輸送材料の溶解液やゲル電解質を付与する方法としては、半導体微粒子含有層や色素の付与と同様に、浸漬法、ローラ法、ディップ法、エアーナイフ法、エクストルージョン法、スライドホッパー法、ワイヤーバー法、スピン法、スプレー法、キャスト法、各種印刷法等が挙げられる。 In the former case, examples of the method for sandwiching the charge transfer layer include a normal pressure process using a capillary phenomenon due to immersion and a vacuum process in which the gas phase is replaced with a liquid phase at a pressure lower than normal pressure. In the latter case, in the wet charge transfer layer, it is necessary to provide a counter electrode without being dried to prevent liquid leakage at the edge portion. In the case of a gel electrolyte, there is a method in which it is applied in a wet manner and solidified by a method such as polymerization. In that case, you may provide a counter electrode after drying and fixing. In addition to the electrolyte solution, the organic charge transport material solution and the gel electrolyte can be applied in the same manner as the semiconductor fine particle-containing layer and the dye, as in the immersion method, roller method, dipping method, air knife method, and extrusion method. , Slide hopper method, wire bar method, spin method, spray method, casting method, various printing methods, and the like.
対極は、前述の導電性支持体と同様に導電性層を有する支持体上に用いることができるが、導電性層自体が強度や密封性を十分有する場合は必ずしも支持体は必要ではない。対極に用いる材料の具体例としては、白金、金、銀、銅、アルミニウム、ロジウム、インジウム等の金属、炭素系化合物、ITO、FTO等の導電性金属酸化物等が挙げられる。対極の厚さには特に制限はない。 The counter electrode can be used on a support having a conductive layer in the same manner as the conductive support described above, but the support is not necessarily required when the conductive layer itself has sufficient strength and sealing properties. Specific examples of the material used for the counter electrode include metals such as platinum, gold, silver, copper, aluminum, rhodium and indium, carbon compounds, and conductive metal oxides such as ITO and FTO. There is no particular limitation on the thickness of the counter electrode.
感光層に光が到達するためには、半導体層を保持した導電性支持体と対極の少なくとも一方は実質的に透明でなければならない。本発明の光電変換素子においては、半導体微粒子層を保持した導電性支持体が透明であり、太陽光を導電性支持体側から入射させる方法が好ましい。この場合、対極には光を反射させる材料を使用することが好ましく、金属、導電性酸化物を蒸着したガラス、プラスチック、あるいは金属薄膜が好ましい。 In order for light to reach the photosensitive layer, at least one of the conductive support holding the semiconductor layer and the counter electrode must be substantially transparent. In the photoelectric conversion element of the present invention, a method in which the conductive support holding the semiconductor fine particle layer is transparent and sunlight is incident from the conductive support side is preferable. In this case, a material that reflects light is preferably used for the counter electrode, and a metal, glass, plastic, or metal thin film on which a conductive oxide is deposited is preferable.
対極の塗設については前述の通り、電荷移動層の上に付与する場合と半導体層上に付与する場合の2通りがある。何れの場合も対極材料の種類や電荷移動層の種類により、適宜、電荷移動層上または半導体層上に対極材料を塗布、ラミネート、蒸着、貼り合わせ等の手法により形成可能である。また、電荷移動層が固体の場合には、その上に直接、前述の導電性材料を塗布、蒸着、CVD等の手法で対極を形成することができる。 As described above, there are two types of coating of the counter electrode: when applied on the charge transfer layer and when applied on the semiconductor layer. In any case, the counter electrode material can be appropriately formed on the charge transfer layer or the semiconductor layer by a technique such as coating, laminating, vapor deposition, or bonding depending on the type of the counter electrode material or the type of the charge transfer layer. When the charge transfer layer is solid, the counter electrode can be formed directly on the charge transfer layer by a technique such as coating, vapor deposition, or CVD.
次に本発明を実施例により更に詳細に説明するが、本発明はこれらに何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these at all.
(実施例1)
酸化チタン(日本アエロジル社製P−25)2g、アセチルアセトン0.2g、界面活性剤(アルドリッチ社製Triton X−100)0.3gを水6.5gと共にペイントコンディショナー(レッドデビル社製)で6時間分散処理を施した。更に、この分散液4.0gに対して濃硝酸0.2ml、エタノール0.4ml、ポリエチレングリコール(#20,000)1.2gを加えてペーストを作製した。このペーストをFTOガラス基板上に膜厚12μmになるように塗布し、室温で乾燥後、100℃で1時間、更に550℃で1時間焼成した。
Example 1
2 hours of titanium oxide (P-25 manufactured by Nippon Aerosil Co., Ltd.), 0.2 g of acetylacetone, and 0.3 g of surfactant (Triton X-100 manufactured by Aldrich) together with 6.5 g of water in a paint conditioner (manufactured by Red Devil) for 6 hours. Dispersion treatment was performed. Further, 0.2 g of concentrated nitric acid, 0.4 ml of ethanol, and 1.2 g of polyethylene glycol (# 20,000) were added to 4.0 g of this dispersion to prepare a paste. This paste was applied onto an FTO glass substrate so as to have a film thickness of 12 μm, dried at room temperature, and then fired at 100 ° C. for 1 hour and further at 550 ° C. for 1 hour.
例示色素(A−13)で示した色素をt−ブタノール/アセトニトリル(1/1)の混合溶液に溶解し、0.3mMの濃度の色素溶液を作製した。この色素溶液に、先に作製した半導体電極を室温で15時間浸漬して吸着処理を施し、作用電極を作製した。対極にはチタニウム板上に白金をスパッタリングしたものを使用した。両電極を互いに向かい合うように配置し、それらの間に電解液を注入して光電変換素子を作製した。電解液はヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシアセトニトリル溶液を使用した。 The dye shown in the exemplified dye (A-13) was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. The semiconductor electrode prepared earlier was immersed in this dye solution at room temperature for 15 hours to perform an adsorption treatment, thereby preparing a working electrode. As the counter electrode, a titanium plate on which platinum was sputtered was used. Both electrodes were arranged so as to face each other, and an electrolytic solution was injected between them to produce a photoelectric conversion element. As the electrolytic solution, a 3-methoxyacetonitrile solution of lithium iodide 0.1 M, iodine 0.05 M, and 1,2-dimethyl-3-n-propylimidazolium iodide 0.5 M was used.
このようにして作製した光電変換素子の作用極側から、光源としてソーラーシミュレーター(YSS−40S、山下電装(株)製)から発生した擬似太陽光(AM1.5G、照射強度100mW/cm2)を照射し、電気化学測定装置(SI−1280B、ソーラートロン社製)を用いて光電変換特性を評価した。その結果、開放電圧0.62V、短絡電流密度13.2mA/cm2、形状因子0.58、変換効率4.75%と良好な値を示した。 Pseudo sunlight (AM1.5G, irradiation intensity 100 mW / cm 2 ) generated from a solar simulator (YSS-40S, manufactured by Yamashita Denso Co., Ltd.) as a light source from the working electrode side of the photoelectric conversion element thus manufactured. The photoelectric conversion characteristics were evaluated using an electrochemical measurement device (SI-1280B, manufactured by Solartron). As a result, the open circuit voltage was 0.62 V, the short circuit current density was 13.2 mA / cm 2 , the shape factor was 0.58, and the conversion efficiency was 4.75%.
さらに、この光電変換素子を60℃環境下で10日間保存した後、上記と同じ光電変換特性を評価した。その結果、開放電圧0.61V、短絡電流密度12.8mA/cm2、形状因子0.58、変換効率4.53%と良好な値を示した。次いで、光電変換効率の維持率を求めた。維持率は保存前の光電変換効率に対する、保存後の光電変換効率の百分率として算出した。その結果、維持率は95%であった。 Furthermore, after storing this photoelectric conversion element in a 60 ° C. environment for 10 days, the same photoelectric conversion characteristics as described above were evaluated. As a result, an open circuit voltage of 0.61 V, a short-circuit current density of 12.8 mA / cm 2 , a shape factor of 0.58, and a conversion efficiency of 4.53% were shown. Subsequently, the maintenance rate of photoelectric conversion efficiency was calculated | required. The maintenance rate was calculated as a percentage of the photoelectric conversion efficiency after storage with respect to the photoelectric conversion efficiency before storage. As a result, the maintenance rate was 95%.
(実施例2〜20)
例示色素(A−13)を、表1に示す例示色素に変更した以外は実施例1と同様にして素子を作製し評価した。その結果を表1に示す。
(Examples 2 to 20)
A device was prepared and evaluated in the same manner as in Example 1 except that the exemplified dye (A-13) was changed to the exemplified dye shown in Table 1. The results are shown in Table 1.
(実施例21)
例示色素(B−5)で示した色素をt−ブタノール/アセトニトリル(1/1)の混合溶液に溶解し、0.3mMの濃度の色素溶液を作製した。この色素溶液に、実施例1に記載した方法に従って作製した半導体電極を室温で15時間浸漬して吸着処理を施し、作用電極を作製した。対極にはチタニウム板上に白金をスパッタリングしたものを使用した。両電極を互いに向かい合うように配置し、それらの間に電解液を注入して光電変換素子を作製した。電解液はヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシアセトニトリル溶液を使用した。
(Example 21)
The dye shown in the exemplified dye (B-5) was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. A semiconductor electrode produced according to the method described in Example 1 was immersed in this dye solution at room temperature for 15 hours to perform an adsorption treatment, thereby producing a working electrode. As the counter electrode, a titanium plate on which platinum was sputtered was used. Both electrodes were arranged so as to face each other, and an electrolytic solution was injected between them to produce a photoelectric conversion element. As the electrolytic solution, a 3-methoxyacetonitrile solution of lithium iodide 0.1 M, iodine 0.05 M, and 1,2-dimethyl-3-n-propylimidazolium iodide 0.5 M was used.
このようにして作製した光電変換素子の作用極側から、光源としてソーラーシミュレーター(YSS−40S、山下電装(株)製)から発生した擬似太陽光(AM1.5G、照射強度100mW/cm2)を照射し、電気化学測定装置(SI−1280B、ソーラートロン社製)を用いて光電変換特性を評価した。その結果、開放電圧0.65V、短絡電流密度10.4mA/cm2、形状因子0.60、変換効率4.06%と良好な値を示した。 Pseudo sunlight (AM1.5G, irradiation intensity 100 mW / cm 2 ) generated from a solar simulator (YSS-40S, manufactured by Yamashita Denso Co., Ltd.) as a light source from the working electrode side of the photoelectric conversion element thus manufactured. The photoelectric conversion characteristics were evaluated using an electrochemical measurement device (SI-1280B, manufactured by Solartron). As a result, the open circuit voltage was 0.65 V, the short-circuit current density was 10.4 mA / cm 2 , the shape factor was 0.60, and the conversion efficiency was 4.06%.
さらに、この光電変換素子を60℃環境下で10日間保存した後、上記と同じ光電変換特性を評価した。その結果、開放電圧0.65V、短絡電流密度9.9mA/cm2、形状因子0.60、変換効率3.86%と良好な値を示した。次いで、光電変換効率の維持率を求めた。維持率は保存前の光電変換効率に対する、保存後の光電変換効率の百分率として算出した。その結果、維持率は95%であった。 Furthermore, after storing this photoelectric conversion element in a 60 ° C. environment for 10 days, the same photoelectric conversion characteristics as described above were evaluated. As a result, an open circuit voltage of 0.65 V, a short circuit current density of 9.9 mA / cm 2 , a shape factor of 0.60, and a conversion efficiency of 3.86% were shown. Subsequently, the maintenance rate of photoelectric conversion efficiency was calculated | required. The maintenance rate was calculated as a percentage of the photoelectric conversion efficiency after storage with respect to the photoelectric conversion efficiency before storage. As a result, the maintenance rate was 95%.
(実施例22〜33)
例示色素(B−5)を、表2に示す例示色素に変更した以外は実施例21と同様にして素子を作製し評価した。その結果を表2に示す。
(Examples 22 to 33)
A device was prepared and evaluated in the same manner as in Example 21 except that the exemplified dye (B-5) was changed to the exemplified dye shown in Table 2. The results are shown in Table 2.
(実施例34)
例示色素(C−5)で示した色素をt−ブタノール/アセトニトリル(1/1)の混合溶液に溶解し、0.3mMの濃度の色素溶液を作製した。この色素溶液に、実施例1に記載した方法に従って作製した半導体電極を室温で15時間浸漬して吸着処理を施し、作用電極を作製した。対極にはチタニウム板上に白金をスパッタリングしたものを使用した。両電極を互いに向かい合うように配置し、それらの間に電解液を注入して光電変換素子を作製した。電解液はヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシアセトニトリル溶液を使用した。
(Example 34)
The dye shown in the exemplified dye (C-5) was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. A semiconductor electrode produced according to the method described in Example 1 was immersed in this dye solution at room temperature for 15 hours to perform an adsorption treatment, thereby producing a working electrode. As the counter electrode, a titanium plate on which platinum was sputtered was used. Both electrodes were arranged so as to face each other, and an electrolytic solution was injected between them to produce a photoelectric conversion element. As the electrolytic solution, a 3-methoxyacetonitrile solution of lithium iodide 0.1 M, iodine 0.05 M, and 1,2-dimethyl-3-n-propylimidazolium iodide 0.5 M was used.
このようにして作製した光電変換素子の作用極側から、光源としてソーラーシミュレーター(YSS−40S、山下電装(株)製)から発生した擬似太陽光(AM1.5G、照射強度100mW/cm2)を照射し、電気化学測定装置(SI−1280B、ソーラートロン社製)を用いて光電変換特性を評価した。その結果、開放電圧0.70V、短絡電流密度13.7mA/cm2、形状因子0.62、変換効率5.95%と良好な値を示した。 Pseudo sunlight (AM1.5G, irradiation intensity 100 mW / cm 2 ) generated from a solar simulator (YSS-40S, manufactured by Yamashita Denso Co., Ltd.) as a light source from the working electrode side of the photoelectric conversion element thus manufactured. The photoelectric conversion characteristics were evaluated using an electrochemical measurement device (SI-1280B, manufactured by Solartron). As a result, the open circuit voltage was 0.70 V, the short-circuit current density was 13.7 mA / cm 2 , the shape factor was 0.62, and the conversion efficiency was 5.95%.
さらに、この光電変換素子を60℃環境下で10日間保存した後、上記と同じ光電変換特性を評価した。その結果、開放電圧0.70V、短絡電流密度12.9mA/cm2、形状因子0.62、変換効率5.60%と良好な値を示した。次いで、光電変換効率の維持率を求めた。維持率は保存前の光電変換効率に対する、保存後の光電変換効率の百分率として算出した。その結果、維持率は94%であった。 Furthermore, after storing this photoelectric conversion element in a 60 ° C. environment for 10 days, the same photoelectric conversion characteristics as described above were evaluated. As a result, the open circuit voltage was 0.70 V, the short-circuit current density was 12.9 mA / cm 2 , the shape factor was 0.62, and the conversion efficiency was 5.60%. Subsequently, the maintenance rate of photoelectric conversion efficiency was calculated | required. The maintenance rate was calculated as a percentage of the photoelectric conversion efficiency after storage with respect to the photoelectric conversion efficiency before storage. As a result, the maintenance rate was 94%.
(実施例35〜46)
例示色素(C−5)を、表3に示す例示色素に変更した以外は実施例34と同様にして素子を作製し評価した。その結果を表3に示す。
(Examples 35 to 46)
A device was prepared and evaluated in the same manner as in Example 34 except that the exemplified dye (C-5) was changed to the exemplified dye shown in Table 3. The results are shown in Table 3.
(実施例47)
例示色素(D−5)で示した色素をt−ブタノール/アセトニトリル(1/1)の混合溶液に溶解し、0.3mMの濃度の色素溶液を作製した。この色素溶液に、実施例1に記載した方法に従って作製した半導体電極を室温で15時間浸漬して吸着処理を施し、作用電極を作製した。対極にはチタニウム板上に白金をスパッタリングしたものを使用した。両電極を互いに向かい合うように配置し、それらの間に電解液を注入して光電変換素子を作製した。電解液はヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシアセトニトリル溶液を使用した。
(Example 47)
The dye shown in the exemplified dye (D-5) was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. A semiconductor electrode produced according to the method described in Example 1 was immersed in this dye solution at room temperature for 15 hours to perform an adsorption treatment, thereby producing a working electrode. As the counter electrode, a titanium plate on which platinum was sputtered was used. Both electrodes were arranged so as to face each other, and an electrolytic solution was injected between them to produce a photoelectric conversion element. As the electrolytic solution, a 3-methoxyacetonitrile solution of lithium iodide 0.1 M, iodine 0.05 M, and 1,2-dimethyl-3-n-propylimidazolium iodide 0.5 M was used.
このようにして作製した光電変換素子の作用極側から、光源としてソーラーシミュレーター(YSS−40S、山下電装(株)製)から発生した擬似太陽光(AM1.5G、照射強度100mW/cm2)を照射し、電気化学測定装置(SI−1280B、ソーラートロン社製)を用いて光電変換特性を評価した。その結果、開放電圧0.68V、短絡電流密度10.4mA/cm2、形状因子0.62、変換効率4.38%と良好な値を示した。 Pseudo sunlight (AM1.5G, irradiation intensity 100 mW / cm 2 ) generated from a solar simulator (YSS-40S, manufactured by Yamashita Denso Co., Ltd.) as a light source from the working electrode side of the photoelectric conversion element thus manufactured. The photoelectric conversion characteristics were evaluated using an electrochemical measurement device (SI-1280B, manufactured by Solartron). As a result, the open circuit voltage was 0.68 V, the short circuit current density was 10.4 mA / cm 2 , the shape factor was 0.62, and the conversion efficiency was 4.38%.
さらに、この光電変換素子を60℃環境下で10日間保存した後、上記と同じ光電変換特性を評価した。その結果、開放電圧0.68V、短絡電流密度9.9mA/cm2、形状因子0.62、変換効率4.17%と良好な値を示した。次いで、光電変換効率の維持率を求めた。維持率は保存前の光電変換効率に対する、保存後の光電変換効率の百分率として算出した。その結果、維持率は95%であった。 Furthermore, after storing this photoelectric conversion element in a 60 ° C. environment for 10 days, the same photoelectric conversion characteristics as described above were evaluated. As a result, the open circuit voltage was 0.68 V, the short-circuit current density was 9.9 mA / cm 2 , the shape factor was 0.62, and the conversion efficiency was 4.17%. Subsequently, the maintenance rate of photoelectric conversion efficiency was calculated | required. The maintenance rate was calculated as a percentage of the photoelectric conversion efficiency after storage with respect to the photoelectric conversion efficiency before storage. As a result, the maintenance rate was 95%.
(実施例48〜56)
例示色素(D−5)を、表4に示す例示色素に変更した以外は実施例47と同様にして素子を作製し評価した。その結果を表4に示す。
(Examples 48 to 56)
A device was prepared and evaluated in the same manner as in Example 47 except that the exemplified dye (D-5) was changed to the exemplified dye shown in Table 4. The results are shown in Table 4.
(実施例57)
例示色素(C−5)で示した色素をt−ブタノール/アセトニトリル(1/1)の混合溶液に溶解し、0.3mMの濃度の色素溶液を作製した。この色素溶液に、ステロイド化合物(E−1)を0.6mMの濃度で溶解した。次いで、この色素溶液に、実施例1で作製した半導体電極を室温で15時間浸漬して吸着処理を施した。電解液はヨウ化リチウム0.1M、ヨウ素0.05M、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリウム0.5Mの3−メトキシアセトニトリル溶液、対極にはチタニウム板上に白金をスパッタリングしたものを使用した。
(Example 57)
The dye shown in the exemplified dye (C-5) was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. The steroid compound (E-1) was dissolved in this dye solution at a concentration of 0.6 mM. Subsequently, the semiconductor electrode produced in Example 1 was immersed in this dye solution at room temperature for 15 hours to perform an adsorption treatment. The electrolyte is a lithium iodide 0.1M, iodine 0.05M, 1,2-dimethyl-3-n-propylimidazolium iodide 0.5M 3-methoxyacetonitrile solution, and the counter electrode is sputtered with platinum on a titanium plate. We used what we did.
このようにして作製した光電変換素子の作用極側から、光源としてソーラーシミュレーター(YSS−40S、山下電装(株)製)から発生した擬似太陽光(AM1.5G、照射強度100mW/cm2)を照射し、電気化学測定装置(SI−1280B、ソーラートロン社製)を用いて光電変換特性を評価した。その結果、開放電圧0.73V、短絡電流密度14.2mA/cm2、形状因子0.64、変換効率6.63%と良好な値を示した。 Pseudo sunlight (AM1.5G, irradiation intensity 100 mW / cm 2 ) generated from a solar simulator (YSS-40S, manufactured by Yamashita Denso Co., Ltd.) as a light source from the working electrode side of the photoelectric conversion element thus manufactured. The photoelectric conversion characteristics were evaluated using an electrochemical measurement device (SI-1280B, manufactured by Solartron). As a result, the open circuit voltage was 0.73 V, the short-circuit current density was 14.2 mA / cm 2 , the shape factor was 0.64, and the conversion efficiency was 6.63%.
さらに、この光電変換素子を60℃環境下で10日間保存した後、上記と同じ光電変換特性を評価した。その結果、開放電圧0.73V、短絡電流密度13.7mA/cm2、形状因子0.63、変換効率6.30%と良好な値を示した。次いで、光電変換効率の維持率を求めた。維持率は保存前の光電変換効率に対する、保存後の光電変換効率の百分率として算出した。その結果、維持率は95%であった。 Furthermore, after storing this photoelectric conversion element in a 60 ° C. environment for 10 days, the same photoelectric conversion characteristics as described above were evaluated. As a result, the open circuit voltage was 0.73 V, the short-circuit current density was 13.7 mA / cm 2 , the shape factor was 0.63, and the conversion efficiency was 6.30%. Subsequently, the maintenance rate of photoelectric conversion efficiency was calculated | required. The maintenance rate was calculated as a percentage of the photoelectric conversion efficiency after storage with respect to the photoelectric conversion efficiency before storage. As a result, the maintenance rate was 95%.
(実施例58〜64)
例示色素(C−5)を、表5に示す例示色素に変更し、ステロイド化合物(E−1)を表5に示す例示化合物に変更した以外は以外は実施例57と同様にして素子を作製し評価した。その結果を表5に示す。
(Examples 58 to 64)
A device was fabricated in the same manner as in Example 57 except that the exemplified dye (C-5) was changed to the exemplified dye shown in Table 5 and the steroid compound (E-1) was changed to the exemplified compound shown in Table 5. And evaluated. The results are shown in Table 5.
(比較例1)
例示色素(A−13)を、(F−1)に示す比較色素に変更した以外は実施例1と同様にして素子を作製し、評価した。その結果、開放電圧0.61V、短絡電流密度13.0mA/cm2、形状因子0.61、変換効率4.84%と良好な値を示した。
(Comparative Example 1)
A device was prepared and evaluated in the same manner as in Example 1 except that the exemplified dye (A-13) was changed to the comparative dye shown in (F-1). As a result, the open circuit voltage was 0.61 V, the short-circuit current density was 13.0 mA / cm 2 , the shape factor was 0.61, and the conversion efficiency was 4.84%.
さらに、この光電変換素子を60℃環境下で10日間保存した後、上記と同じ光電変換特性を評価した。その結果、開放電圧0.58V、短絡電流密度10.3mA/cm2、形状因子0.60、変換効率3.58%と性能低下が観察された。光電変換効率の維持率を求めると、74%である。 Furthermore, after storing this photoelectric conversion element in a 60 ° C. environment for 10 days, the same photoelectric conversion characteristics as described above were evaluated. As a result, an open circuit voltage of 0.58 V, a short circuit current density of 10.3 mA / cm 2 , a form factor of 0.60, and a conversion efficiency of 3.58% were observed. When the maintenance rate of the photoelectric conversion efficiency is obtained, it is 74%.
(比較例2〜5)
比較色素(F−1)を表6に示す色素に変更した以外は、比較例1と同様にして素子を作製し、評価した。その結果を表6に示す。すべて、初期性能は良好であるが、加熱保存後の性能が低下しており、本発明の色素が優れている事がわかる。
(Comparative Examples 2 to 5)
A device was prepared and evaluated in the same manner as in Comparative Example 1 except that the comparative dye (F-1) was changed to the dye shown in Table 6. The results are shown in Table 6. In all cases, the initial performance is good, but the performance after heat storage is lowered, indicating that the dye of the present invention is excellent.
(比較例6〜7)
比較色素(F−1)を表7に示す色素に変更した以外は、比較例1と同様にして素子を作製し、評価した。その結果を表7に示す。初期性能も悪く、加熱保存後の性能低下も大きい事から、本発明の色素が優れている事がわかる。
(Comparative Examples 6-7)
A device was prepared and evaluated in the same manner as in Comparative Example 1 except that the comparative dye (F-1) was changed to the dye shown in Table 7. The results are shown in Table 7. Since the initial performance is poor and the performance degradation after heat storage is large, it can be seen that the dye of the present invention is excellent.
本発明の活用例として、太陽電池等の光電変換素子に加えて、特定波長の光に感応する光センサー等が挙げられる。 Examples of utilization of the present invention include photosensors that are sensitive to light of a specific wavelength, in addition to photoelectric conversion elements such as solar cells.
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