JP2015005489A - Pigment for dye-sensitized solar batteries, semiconductor electrode, and dye-sensitized solar battery - Google Patents
Pigment for dye-sensitized solar batteries, semiconductor electrode, and dye-sensitized solar battery Download PDFInfo
- Publication number
- JP2015005489A JP2015005489A JP2013209119A JP2013209119A JP2015005489A JP 2015005489 A JP2015005489 A JP 2015005489A JP 2013209119 A JP2013209119 A JP 2013209119A JP 2013209119 A JP2013209119 A JP 2013209119A JP 2015005489 A JP2015005489 A JP 2015005489A
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- Prior art keywords
- dye
- group
- sensitized solar
- semiconductor
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 66
- 239000000049 pigment Substances 0.000 title claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000035945 sensitivity Effects 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 61
- 238000000034 method Methods 0.000 description 55
- 239000010410 layer Substances 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- -1 sulfeno group Chemical group 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
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- 239000010408 film Substances 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 229910052802 copper Inorganic materials 0.000 description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
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- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 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
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- Y02E10/549—Organic PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、色素増感型太陽電池用色素、半導体電極及び色素増感型太陽電池に関するものである。 The present invention relates to a dye for a dye-sensitized solar cell, a semiconductor electrode, and a dye-sensitized solar cell.
大量の化石燃料の使用で引き起こされる二酸化炭素濃度増加による地球温暖化、さらに、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及びテルル化カドミウムやセレン化インジウム銅などの無機系太陽電池が挙げられる。 Global warming due to the increase in carbon dioxide concentration caused by the use of large amounts of fossil fuels, and the increase in energy demand accompanying population growth are recognized as problems related to the survival of humankind. Therefore, in recent years, the use of sunlight that does not generate infinite and harmful substances has been energetically studied. Examples of solar energy that is a clean energy source that is currently in practical use include 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などの要求もあり、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 terms of long payback to the user, and there has been 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などがあり、利用される有機半導体は、クロロフィル、ペリレンなどの合成色素や顔料、ポリアセチレンなどの導電性高分子材料、または、これらの複合材料などである。これらを真空蒸着法、キャスト法またはディッピング法などにより、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、大面積化が容易などの長所もあるが、光電変換効率は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 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, photoelectric conversion efficiency is often as low as 1% or less, and there is a problem that 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(例えば、非特許文献1参照)。この文献には、電池作製に必要な材料及び製造技術も開示されている。この太陽電池は色素増感型太陽電池またはグレッツェル型太陽電池と呼ばれ、ルテニウム錯体(以下Ru錯体と記す)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などの安価な半導体を高純度まで精製する必要がないために、前述の無機系太陽電池と比較して製造コストが低減できること、また、利用できる光は可視光領域に幅広くいきわたっているため、可視光領域のエネルギー強度が高いとされる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, for example, Non-Patent Document 1). This document also discloses materials and manufacturing techniques necessary for battery fabrication. This solar cell 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 (hereinafter referred to as Ru complex) as a working electrode. The advantage of this method is that it is not necessary to purify inexpensive semiconductors such as titanium oxide to high purity, so that the manufacturing cost can be reduced compared to the inorganic solar cells described above, and the available light is in the visible light region. Because it is widespread, it is possible to effectively convert sunlight, which has a high energy intensity in the visible light region, into electricity.
しかしながら、資源的制約がある貴金属のRuが使われているため、色素増感型太陽電池が実用化された場合には、Ru錯体の安定供給に問題が生じる可能性がある。また、この資源的な制約から、Ru錯体自体が高価であり、大量製造の際にコスト面での問題も生じる可能性がある。このような問題を解決するため、Ru錯体の少なくとも一部をより安価な有機色素へ変更することを目的として、様々な提案がなされてきた。その例として、種々のメロシアニン色素、シアニン色素、9−フェニルキサンテン系色素、クマリン系色素などが開示されているが、これらは、光電変換特性において、Ru錯体よりもかなり劣っており、実用性に乏しいものがほとんどであった(例えば、特許文献1〜4参照)。 However, since noble metal Ru, which has resource limitations, is used, there is a possibility that a problem may occur in the stable supply of the Ru complex when a dye-sensitized solar cell is put into practical use. In addition, due to this resource limitation, the Ru complex itself is expensive, and there may be a problem in terms of cost during mass production. In order to solve such a problem, various proposals have been made for the purpose of changing at least part of the Ru complex to a cheaper organic dye. For example, various merocyanine dyes, cyanine dyes, 9-phenylxanthene dyes, coumarin dyes, and the like have been disclosed. However, these are considerably inferior to Ru complexes in photoelectric conversion characteristics, and are practical. Most of them were poor (see, for example, Patent Documents 1 to 4).
一方、最近、色素増感型太陽電池用色素として、Ru錯体に匹敵する高性能を有する有機色素が開示されつつあるが(例えば、特許文献5〜16参照)、実用的な太陽電池を製造する観点からは、さらなる改良が求められている。 Recently, organic dyes having high performance comparable to Ru complexes are being disclosed as dye-sensitized solar cell dyes (see, for example, Patent Documents 5 to 16), but practical solar cells are manufactured. From the viewpoint, further improvement is required.
本発明の課題は、優れた光電変換特性を有し、かつ耐久性も向上した色素増感型太陽電池用色素と、この色素増感型太陽電池用色素により増感された優れた光電変換効率を有し、かつ耐久性も向上した半導体電極及びその半導体電極を用いてなる色素増感型太陽電池を提供することである。 An object of the present invention is to provide a dye-sensitized solar cell dye having excellent photoelectric conversion characteristics and improved durability, and an excellent photoelectric conversion efficiency sensitized by the dye-sensitized solar cell dye And a dye-sensitized solar cell using the semiconductor electrode with improved durability.
本発明者らは、上記課題を解決すべく鋭意検討した結果、一般式(1)で示される色素増感型太陽電池用色素(以下、「色素」という)、この色素により増感された半導体電極及びこの半導体電極を用いてなる色素増感型太陽電池によって、これらの目標を達成することができた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a dye for a dye-sensitized solar cell represented by the general formula (1) (hereinafter referred to as “dye”), a semiconductor sensitized by this dye These goals could be achieved by an electrode and a dye-sensitized solar cell using this semiconductor electrode.
一般式(1)において、R1、R2は炭素数4以上の脂肪族基を示す。R3、R4は水素原子または脂肪族基を示し、両者が連結してシクロペンタン環またはシクロヘキサン環を形成しても良い。Lはメチン基ユニットを示す。R5はpKaが6未満の酸性基を少なくとも一つ有する炭素数4以下の脂肪族基を示す。R6はpKaが6未満の酸性基を少なくとも一つ有する炭素数4以上の脂肪族基を示す。 In the general formula (1), R 1 and R 2 represent an aliphatic group having 4 or more carbon atoms. R 3 and R 4 represent a hydrogen atom or an aliphatic group, and they may be linked to form a cyclopentane ring or a cyclohexane ring. L represents a methine group unit. R 5 represents an aliphatic group having 4 or less carbon atoms having at least one acidic group having a pKa of less than 6. R 6 represents an aliphatic group having 4 or more carbon atoms having at least one acidic group having a pKa of less than 6.
上記一般式(1)で示される色素は優れた光電変換特性を有し、かつ耐久性も向上しており、この色素で増感することによって、優れた光電変換効率を有し、かつ耐久性も向上した半導体電極及び色素増感型太陽電池を得ることができる。 The dye represented by the general formula (1) has excellent photoelectric conversion characteristics and improved durability. By sensitizing with this dye, the dye has excellent photoelectric conversion efficiency and durability. Further improved semiconductor electrodes and dye-sensitized solar cells can be obtained.
以下に本発明の色素について詳細に述べる。前記一般式(1)において、一般式(1)において、R1、R2は炭素数4以上の脂肪族基(例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、テトラコシル基、ヘキサコシル基、オクタコシル基、トリアコンチル基などのアルキル基、ベンジル基、フェネチル基、ナフチルメチル基などのアラルキル基など)を示す。これらは同じでも異なっていても良く、また互いに連結して環状となっていても良い。うち好ましいものは、R1、R2がともに炭素数6以上のアルキル基のものであり、より好ましいものは、R1、R2がともに炭素数16以上のアルキル基のものである。そして中でも特に好ましいものは、R1、R2がともに炭素数18〜24のアルキル基のものである。 The dye of the present invention is described in detail below. In the general formula (1), in the general formula (1), R 1 and R 2 are aliphatic groups having 4 or more carbon atoms (for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracosyl group, hexacosyl group, octacosyl group, triacontyl group and other alkyl groups, benzyl group, phenethyl group, naphthyl group An aralkyl group such as a methyl group). These may be the same or different, and may be connected to each other to form a ring. Among them, preferred are those in which R 1 and R 2 are both alkyl groups having 6 or more carbon atoms, and more preferred are those in which both R 1 and R 2 are alkyl groups having 16 or more carbon atoms. Among them, particularly preferred are those in which R 1 and R 2 are both alkyl groups having 18 to 24 carbon atoms.
R3、R4は水素原子または脂肪族基(例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などのアルキル基、ベンジル基、フェネチル基、ナフチルメチル基などのアラルキル基など)を示し、両者が連結してシクロペンタン環またはシクロヘキサン環を形成しても良い。うち好ましいものは両者が連結してシクロペンタン環またはシクロヘキサン環を形成しているものであり、中でも両者が連結してシクロペンタン環を形成しているものが特に好ましい。 R 3 and R 4 are each a hydrogen atom or an aliphatic group (for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, an aralkyl group such as a benzyl group, a phenethyl group or a naphthylmethyl group). And the like may be linked to form a cyclopentane ring or a cyclohexane ring. Among them, preferred are those in which they are linked to form a cyclopentane ring or a cyclohexane ring, and particularly preferred are those in which both are linked to form a cyclopentane ring.
Lはメチン基ユニットを示す。このメチン基ユニットは、詳しくは奇数炭素数のメチン鎖から構成されているが、その炭素数は1または3が好ましく、炭素数1のモノメチン基が特に好ましい。 L represents a methine group unit. The methine group unit is specifically composed of a methine chain having an odd number of carbon atoms, and the number of carbon atoms is preferably 1 or 3, and a monomethine group having 1 carbon atom is particularly preferable.
R5はpKaが6未満の酸性基を少なくとも一つ有する炭素数4以下の脂肪族基(例えば、メチル基、エチル基、プロピル基、ブチル基などのアルキル基、アリル基、ブテニル基などのアルケニル基、プロパルギル基などのアルキニル基など)を示す。またpKaが6未満の酸性基の例としては、カルボキシ基、スルホ基、スルフィノ基、スルフェノ基、フォスフォノ基、フォスフィニコ基などが挙げられる。また、これらpKaが6未満の酸性基は、遊離酸であっても良く、また塩(例えば、アンモニウム塩、トリメチルアンモニウム塩、トリエチルアンモニウム塩、テトラ−n−ブチルアンモニウム塩などのアンモニウム塩、リチウム塩、ナトリウム塩、カリウム塩などのアルカリ金属塩)であっても良い。そして以上述べたうち好ましい組み合わせのものは、上述のpKaが6未満の酸性基を置換基として有する炭素数2以下のアルキル基であり、中でもカルボキシ基を置換基として有する炭素数2個以下のアルキル基がより好ましく、さらにカルボキシメチル基が特に好ましい。なおこのカルボキシ基は、前述の通り遊離酸もしくは塩のいずれであっても良い。 R 5 is an aliphatic group having 4 or less carbon atoms having at least one acidic group having a pKa of less than 6 (for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as an allyl group or a butenyl group). Group, an alkynyl group such as a propargyl group). Examples of acidic groups having a pKa of less than 6 include carboxy group, sulfo group, sulfino group, sulfeno group, phosphono group, and phosphinico group. These acidic groups having a pKa of less than 6 may be free acids, and salts (for example, ammonium salts such as ammonium salt, trimethylammonium salt, triethylammonium salt, tetra-n-butylammonium salt, lithium salt) , Alkali metal salts such as sodium salts and potassium salts). Of the above-described combinations, the preferred combination is an alkyl group having 2 or less carbon atoms having an acidic group having a pKa of less than 6 as a substituent, and an alkyl having 2 or less carbon atoms having a carboxy group as a substituent. A group is more preferable, and a carboxymethyl group is particularly preferable. This carboxy group may be either a free acid or a salt as described above.
R6はpKaが6未満の酸性基を少なくとも一つ有する炭素数4以上の脂肪族基(例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ペンタデシル基などのアルキル基、ベンジル基、フェネチル基、ナフチルメチル基などのアラルキル基など)を示す。またpKaが6未満の酸性基の例としては、前述のR5と同様の置換基が挙げられる。また、これらの酸性基は前述のR5と同様に遊離酸もしくは塩のいずれであっても良い。以上述べたうち好ましい組み合わせのものは、上述のpKaが6未満の酸性基を置換基として有する炭素数4以上のアルキル基であり、中でもカルボキシ基を置換基として有する炭素数5個以上のアルキル基がより好ましく、末端がカルボキシ基で置換された炭素数5〜15のアルキル基が特に好ましい。なおこのカルボキシ基は、前述の通り遊離酸もしくは塩のいずれであっても良い。 R 6 is an aliphatic group having 4 or more carbon atoms having at least one acidic group having a pKa of less than 6, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an undecyl group, a dodecyl group, An alkyl group such as a tetradecyl group or a pentadecyl group, an aralkyl group such as a benzyl group, a phenethyl group, or a naphthylmethyl group). Examples of the acidic group having a pKa of less than 6 include the same substituent as R 5 described above. Further, these acidic groups may be either free acids or salts as in the case of R 5 described above. Of the above-described combinations, preferred combinations are alkyl groups having 4 or more carbon atoms having an acidic group having a pKa of less than 6 as a substituent, and in particular, alkyl groups having 5 or more carbon atoms having a carboxy group as a substituent. Are more preferable, and an alkyl group having 5 to 15 carbon atoms having a terminal substituted with a carboxy group is particularly preferable. This carboxy group may be either a free acid or a salt as described above.
なお以上述べた一般式(1)は、上述の置換基以外にも、可能であるならば当業界で周知の置換基を有していても良い。 The general formula (1) described above may have a substituent well known in the art if possible, in addition to the above-described substituent.
そして一般式(1)におけるLとチアゾリジン環の二重結合連結部位、さらにチアゾリジン環同士の二重結合連結部位においては、それぞれの部位にZ型とE型の幾何異性体が生じる可能性があるが、本発明においては、これらの幾何異性の組み合わせはどのような組み合わせであっても構わない。またLが炭素数3以上のメチン基ユニットである場合は、それぞれの炭素二重結合についての幾何構造の異性体(cis型、trans型)が生じる可能性があるが、本発明においては、これらの幾何異性の組み合わせもどのような組み合わせであっても構わない。 In addition, in the double bond linking site between L and the thiazolidine ring in the general formula (1), and further in the double bond linking site between the thiazolidine rings, there is a possibility that Z-type and E-type geometric isomers are generated at each site. However, in the present invention, any combination of these geometric isomerisms may be used. In addition, when L is a methine group unit having 3 or more carbon atoms, geometrical isomers (cis type, trans type) for each carbon double bond may be generated. Any combination of geometrical isomerisms may be used.
また一般式(1)におけるR3とR4がいずれもアルキル基である組み合わせの場合には、R3とR4がそれぞれ結合するインドリン環2位及び3位の炭素原子が不斉炭素となり、それぞれの部位の光学異性体が生じる可能性があるが、本発明においては、これらの光学異性の組み合わせはどのような組み合わせであっても構わない。 When R 3 and R 4 in the general formula (1) are both alkyl groups, the carbon atoms at the 2-position and 3-position of the indoline ring to which R 3 and R 4 are respectively bonded are asymmetric carbons, There is a possibility that optical isomers of each site may be generated, but in the present invention, any combination of these optical isomers may be used.
以下に、一般式(1)で示される本発明の色素の具体例を挙げるが、本発明はむろんこれらに限定されるものではない。 Specific examples of the dye of the present invention represented by the general formula (1) are given below, but the present invention is not limited to these examples.
これらの化合物は、例えば特開平8−269345号公報、国際公開第2004/011555号パンフレットなどに記載の合成法を参考に容易に合成できる。 These compounds can be easily synthesized with reference to synthesis methods described in, for example, JP-A-8-269345 and WO 2004/011555.
色素増感型太陽電池は、導電性支持体、導電性支持体表面上に設けられた色素によって増感された半導体層(半導体電極)、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など、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もよい。 The dye-sensitized solar cell includes a conductive support, a semiconductor layer (semiconductor electrode) sensitized with a dye provided on the surface of 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 diffuse or mix 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、アルミニウムなどの金属、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などの金属酸化物(以降「FTO」と略記する)などが挙げられる。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. And the like (hereinafter abbreviated as “FTO”). 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、ニッケルなど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、圧着などで設置し、その上にITOやFTOを設ける方法、あるいは表面に導電性を有する透明基板体上に金属リード線を設置する方法がある。 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. A metal lead wire is placed on a transparent conductive support by vapor deposition, sputtering, pressure bonding, etc., and ITO or FTO is provided thereon, or a metal lead wire is placed on a transparent substrate having conductivity on the surface. There is.
半導体層が含有する半導体としては、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などがある。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などが好ましいものとして挙げられる。その他の化合物半導体としては亜鉛、ガリウム、インジウム、カドミウムなどのリン化物やガリウム砒素、銅−インジウム−セレン化物、銅−インジウム−硫化物などが好ましい。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、ニオブ酸カリウムなどが好ましい。 Examples of the semiconductor contained in the semiconductor layer include a single semiconductor such as silicon and germanium, a compound semiconductor typified by a metal chalcogenide, or a compound having a perovskite structure. Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxides, cadmium, zinc, lead, silver, antimony, bismuth. And sulfides, cadmium, selenide of lead, telluride of cadmium, 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。光電変換効率から見ると、単結晶が好ましいが、製造コスト、原材料確保などから見ると、多結晶が好ましい。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. From the viewpoint of photoelectric conversion efficiency, a single crystal is preferable, but from the viewpoint of manufacturing costs, securing raw materials, etc., a polycrystal is preferable. 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−ゲル法などがある。分散液の作製方法としては、ゾル−ゲル法、乳鉢など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、または、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などが挙げられる。 As a method of 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. As a method for producing a dispersion, a sol-gel method, a method of mechanically pulverizing with a mortar, a method of dispersing while pulverizing using a mill, or a fine particle in a solvent when synthesizing a semiconductor, The method of using it as it is is mentioned.
機械的粉砕、または、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または半導体微粒子と樹脂の混合物を、水または有機溶剤に分散して作製される。使用される樹脂としては、ポリアルキレンオキシ化合物、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など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、ポリイミド樹脂などが挙げられる。 In the case of a dispersion prepared by mechanical pulverization or pulverization using a mill, the dispersion is prepared 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 polyalkyleneoxy compounds, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic esters, methacrylic esters, silicone resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, polyvinyls. Formal resin, polyester resin, cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin and the like can be mentioned.
半導体微粒子を分散する媒体としては、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などのアルコール系媒体、アセトン、アセチルアセトン、メチルエチルケトン、あるいはメチルイソブチルケトンなどのケトン系媒体、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチルなどのエステル系媒体、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などのエーテル系媒体、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−ピロリドンなどのアミド系媒体、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−クロロナフタレンなどのハロゲン化炭化水素系媒体、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、あるいはクメンなどの炭化水素系媒体を挙げることができる。これらは、単独または2種以上の混合媒体として用いることができる。 As the medium for dispersing the semiconductor fine particles, alcohol media such as water, methanol, ethanol, or isopropyl alcohol, ketone media such as acetone, acetylacetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or n-acetate Ester media such as butyl, ether media such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl-2-pyrrolidone Medium, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluoro Halogenated hydrocarbon media such as benzene, bromobenzene, iodobenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, Examples thereof include hydrocarbon-based media such as toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or as a mixed medium of two or more.
分散液の塗布方法としては、ローラ法、ディップ法、エアーナイフ法、ブレード法、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、あるいはスプレー法を挙げることができる。 Examples of the dispersion application method include a roller method, a dip method, an air knife method, a blade method, a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method.
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。 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、加熱処理してもよいし、しなくともよい。しかし、微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。さらに、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い。これらの処理は、単独で行っても構わないし、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構わないし、裏側から照射しても構わない。照射時間には特に制限がないが、1時間以内で行うことが好ましい。プレス処理は、9.8×106N/m2以上で行うことが好ましく、9.8×107N/m2以上で行うことがさらに好ましい。プレスする時間は、特に制限がないが、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, heat treatment is preferred from the viewpoints of electronic contact between fine particles, improvement in coating film strength, and improvement in adhesion to the support. Further, microwave irradiation, press treatment, or electron beam irradiation may be performed. 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. 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 performed at 9.8 × 10 6 N / m 2 or more, and more preferably at 9.8 × 10 7 N / m 2 or more. The pressing time is not particularly limited, but is preferably 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.
本発明の一般式(1)で示される色素増感型太陽電池用色素は、単独で使用しても良く、2種以上を併用しても構わない。また、ルテニウム(Ru)錯体も用いた色素増感型太陽電池におけるRuの使用量を減少させる目的から、本発明の色素とRu錯体を併用しても構わない。他のメロシアニン色素、シアニン色素、9−フェニルキサンテン系色素、クマリン系色素、フタロシアニン系色素、ナフタロシアニン系色素等と本発明の色素を併用しても構わない。 The dye-sensitized solar cell dye represented by the general formula (1) of the present invention may be used alone or in combination of two or more. In addition, for the purpose of reducing the amount of Ru used in a dye-sensitized solar cell that also uses a ruthenium (Ru) complex, the dye of the present invention and a Ru complex may be used in combination. Other merocyanine dyes, cyanine dyes, 9-phenylxanthene dyes, coumarin dyes, phthalocyanine dyes, naphthalocyanine dyes and the like may be used in combination.
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、エアーナイフ法など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、スプレー法など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.
色素を吸着する際に、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いずれであってもよい。さらに、縮合助剤としてチオールまた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 catalytically acting that physically or chemically binds the dye to the inorganic surface, or one that acts stoichiometrically to favorably shift the chemical equilibrium. . Further, a thiol or hydroxy compound may be added as a condensation aid.
色素を溶解あるいは分散する媒体は、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などのアルコール系媒体、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などのケトン系媒体、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチルなどのエステル系媒体、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などのエーテル系媒体、アセトニトリル、プロピオニトリルなどのニトリル系媒体、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−ピロリドンなどのアミド系媒体、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−クロロナフタレンなどのハロゲン化炭化水素系媒体、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、あるいはクメンなどの炭化水素系媒体を挙げることができる。これらは、単独または2種以上混合して用いることができる。 The medium for dissolving or dispersing the dye is water, methanol, ethanol, alcohol medium such as isopropyl alcohol, ketone medium such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or n-butyl acetate. Ester media such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, nitrile media such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, or N Amide media such as methyl-2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenze , O-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, or halogenated hydrocarbon media such as 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methyl Examples thereof include hydrocarbon media such as cyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or in admixture of two or more.
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、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、ディスパーザーまたは超音波分散などが挙げられるが、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時間以下がさらに好ましい。 The temperature for adsorbing the dye is preferably -50 ° C or higher and 200 ° C or lower. Further, the 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 from 5 seconds to 1000 hours, more preferably from 10 seconds to 500 hours, and even more preferably from 1 minute to 150 hours.
本発明では、色素を半導体層に吸着させる際に、ステロイド系化合物を併用して、共吸着させても構わない。 In the present invention, when the dye is adsorbed on the semiconductor layer, a steroidal compound may be used in combination and co-adsorbed.
そのステロイド系化合物の具体例としては、下記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 steroidal compound include those shown in E-1 to E-10 below. 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、または、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−ルチジンなどの塩基性化合物、または、リン酸、リン酸エステル、アルキルリン酸、酢酸、プロピオン酸など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, a basic compound such as t-butylpyridine, 2-picoline, 2,6-lutidine, or phosphoric acid, phosphate ester, alkyl You may immerse in the organic solvent containing acidic compounds, such as phosphoric acid, an acetic acid, and propionic acid.
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、無機正孔輸送物質、有機正孔輸送物質などを用いることができる。 As the charge transfer layer, an electrolytic solution in which a redox couple is dissolved in an organic solvent, a gel electrolyte in which a polymer matrix is impregnated with a liquid in which the redox couple is dissolved in an organic solvent, a molten salt containing a redox couple, a solid electrolyte, an inorganic A hole transport material, an organic hole transport material, or the like can be used.
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、ヨウ化カルシウムなどの金属ヨウ化物−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などの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、臭化カルシウムなどの金属臭化物−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などの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などの金属錯体、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などのイオウ化合物、ビオロゲン色素、ヒドロキノン−キノンなどが挙げられる。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 is preferably composed of an electrolyte, a solvent, and an additive. Preferred electrolytes are metal iodide-iodine combinations such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, and calcium iodide, and quaternary compounds such as tetraalkylammonium iodide, pyridinium iodide, and imidazolium iodide. Iodine salt of ammonium compound-iodine combination, metal bromide-bromine combination such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide, quaternary ammonium such as tetraalkylammonium bromide, pyridinium bromide Compound bromine salt-bromine combination, ferrocyanate-ferricyanate, metal complex such as ferrocene-ferricinium ion, sulfur compound such as sodium polysulfide, alkylthiol-alkyl disulfide , Viologen dye, hydroquinone - such as quinone, 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がさらに好ましい。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などのカーボネート系溶媒、3−メチル−2−オキサゾリジノンなどの複素環化合物、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などのエーテル系溶媒、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などのアルコール系溶媒、アセトニトリル、ベンゾニトリルなどのニトリル系溶媒、ジメチルスルホキシド、スルホランなどの非プロトン性極性溶媒などが好ましい。また、t−ブチルピリジン、2−ピコリン、2,6−ルチジンなど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, and aprotic polar solvents such as dimethyl sulfoxide and sulfolane are preferred. Moreover, you may use together basic compounds, such as t-butyl pyridine, 2-picoline, and 2, 6- lutidine.
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などの手法により、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など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、ジベンジリデン−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などを挙げることができる。 The electrolyte can be gelled by techniques such as polymer addition, oil gelling agent addition, polymerization including polyfunctional monomers, and polymer crosslinking reaction. Preferable polymers for gelation by addition of polymer include polyacrylonitrile, polyvinylidene fluoride, and the like. Preferred gelling agents for gelation by adding an oil gelling agent include dibenzylidene-D-sorbitol, cholesterol derivatives, amino acid derivatives, trans- (1R, 2R) -1,2-cyclohexanediamine alkylamide derivatives, alkyl Examples include urea derivatives, N-octyl-D-gluconamidobenzoate, double-headed amino acid derivatives, quaternary ammonium derivatives, and the like.
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などを挙げることができる。さらに、アクリルアミド、メチルアクリレートなどのアクリル酸や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、フマル酸ジエチルなど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などのジエン類、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など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など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 Dienes such as pentadiene, aromatic vinyl compounds such as styrene, p-chlorostyrene, sodium styrenesulfonate, vinyl esters, acrylonitrile, methacrylonitrile, vinyl compounds having a nitrogen-containing heterocyclic ring, vinyls having a quaternary ammonium salt A monofunctional monomer such as a compound, N-vinylformamide, vinyl sulfonic acid, vinylidene fluoride, vinyl alkyl ethers, and 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)などのアゾ系開始剤、ベンゾイルパーオキシドなどの過酸化物系開始剤などが好ましい。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), peroxide initiators such as benzoyl peroxide, and the like 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。架橋反応に必要な反応性基の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、ピペラジンなどの含窒素複素環を挙げることができる。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、イソシアネートなど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 reactive group necessary for the crosslinking reaction include nitrogen-containing heterocycles such as pyridine, imidazole, thiazole, oxazole, triazole, morpholine, piperidine and piperazine. Preferred cross-linking agents include bifunctional or higher functional reagents capable of electrophilic reaction with nitrogen atoms such as alkyl halides, halogenated aralkyls, sulfonic acid esters, acid anhydrides, acid chlorides, and isocyanates.
無機正孔輸送物質を電解質の代わりに用いる場合、ヨウ化銅、チオシアン化銅などをキャスト法、塗布法、スピンコート法、浸漬法、電解メッキなどの手法により電極内部に導入することができる。 When an inorganic hole transport material 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, or electrolytic plating.
また、電解質の代わりに有機電荷輸送物質を用いることも可能である。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号公報などに示されているオキサジアゾール類、特公昭45−555号公報などに示されているトリフェニルメタン類、特公昭52−4188号公報などに示されているピラゾリン類、特公昭55−42380号公報などに示されているヒドラゾン類、特開昭56−123544号公報など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など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。 It is also possible to use an organic charge transport material instead of the electrolyte. Charge transport materials include hole transport materials and electron transport materials. Examples of the former include, for example, oxadiazoles shown in Japanese Patent Publication No. 34-5466, triphenylmethanes shown in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. Pyrazolines shown in JP-A-55-42380, hydrazones shown in JP-B-56-123544, oxadiazoles shown in JP-A-56-123544, etc., JP-A-54-58445 And tetrasylbenzidines disclosed in JP-A-58-65440, and stilbenes disclosed in JP-A-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−ジオキシドなどがある。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, or 1,3,7-trinitrodibenzothiophene-5,5-dioxide . These electron transport materials can be used alone or as a mixture of two or more.
さらに、電荷移動層中の電荷移動効率を向上させる目的として、ある種の電子吸引性化合物を電荷移動層中に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などのキノン類、4−ニトロベンズアルデヒドなどのアルデヒド類、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などのケトン類、無水フタル酸、4−クロロナフタル酸無水物などの酸無水物、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などのシアノ化合物、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などのフタリド類などを挙げることができる。 Furthermore, for the purpose of improving the charge transfer efficiency in the charge transfer layer, a certain kind of electron withdrawing compound can be added to the charge transfer layer. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, phenanthrenequinone, and 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 -p- Nitorobenzaru) phthalide, or 3- (alpha-cyano -p- Nitorobenzaru) -4,5,6,7 such phthalides such as tetrachloro phthalide can be cited.
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、フェノキシ樹脂などが挙げられる。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 a charge transport material, a resin may be used in combination. When the 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 given. 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、色素を吸着した半導体層の上に、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である。もう一つは、色素を吸着した半導体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 bonded onto a semiconductor layer that has adsorbed a dye, and a liquid charge transfer layer is sandwiched in the gap. The other is a method in which a charge transfer layer is provided directly on a semiconductor layer adsorbed with a dye. 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、浸漬など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など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、各種印刷法などが挙げられる。 In the former case, examples of the method for sandwiching the charge transfer layer include a normal pressure process using capillary action 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 electrolytic solution, the organic charge transport material solution and gel electrolyte can be applied in the same manner as the semiconductor layer and pigment application, as well as the immersion method, roller method, dipping method, air knife method, extrusion method, slide Examples include the hopper method, wire bar method, spin method, spray method, casting method, and various printing methods.
対極は、前述の表面に導電性を有する基板と同様に導電層を有する支持体上に用いることができるが、導電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、インジウムなどの金属、炭素系化合物、ITO、FTOなどの導電性金属酸化物などが挙げられる。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 substrate having conductivity on the surface, 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.
半導体層に光が到達するためには、半導体層を保持した表面に導電性を有する基板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表面に導電性を有する基板が透明であり、太陽光を半導体層を保持した導電性基板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、プラスチックまたは金属薄膜が好ましい。 In order for light to reach the semiconductor layer, at least one of the conductive substrate and the counter electrode on the surface holding the semiconductor layer must be substantially transparent. In the photoelectric conversion element of the present invention, a method in which the conductive substrate is transparent on the surface holding the semiconductor fine particle layer and sunlight is incident from the conductive substrate side holding the semiconductor layer 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。いず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、貼り合わせなど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、化学気相蒸着(CVD)など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 conductive material by a method such as coating, vapor deposition, or chemical vapor deposition (CVD).
次に本発明を実施例によりさら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.
(合成例:色素D−4の合成)
中間体A;0.70g、中間体B;0.60g、酢酸アンモニウム0.05g、酢酸20mlを混合し、浴温120℃にて5時間加熱を行った。ついで室温まで冷却、そして析出した固体を濾取し、酢酸30ml、ついで水30ml、さらにメタノール30mlで洗浄後乾燥して、0.89gの粗生成物を得た。これをシリカゲルカラムクロマトグラフィー(展開溶媒:クロロホルム/メタノール=10/1(容量比))で精製して、0.72gの色素D−4を得た。吸収極大:534nm(メタノール溶液)。
(Synthesis Example: Synthesis of Dye D-4)
Intermediate A: 0.70 g, Intermediate B: 0.60 g, ammonium acetate 0.05 g, and acetic acid 20 ml were mixed and heated at a bath temperature of 120 ° C. for 5 hours. Subsequently, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with 30 ml of acetic acid, then 30 ml of water, and further 30 ml of methanol and dried to obtain 0.89 g of a crude product. This was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 10/1 (volume ratio)) to obtain 0.72 g of Dye D-4. Absorption maximum: 534 nm (methanol solution).
(実施例1)
<色素増感型太陽電池の作製>
酸化チタン(日本アエロジル社製、商品名: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、商品名: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。さらに、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10μmになるように塗布し、室温で乾燥後、100℃で1時間、さらに、550℃で1時間焼成し、半導体電極を得た。
Example 1
<Preparation of dye-sensitized solar cell>
Paint conditioner (2 g titanium oxide (Nippon Aerosil Co., Ltd., trade name: P-25), 0.2 g acetylacetone, 0.3 g surfactant (trade name: Triton X-100, made by Aldrich Co.) together with 6.5 g water (Red Devil) for 6 hours. 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 10 μm, dried at room temperature, and then baked at 100 ° C. for 1 hour and further at 550 ° C. for 1 hour to obtain a semiconductor electrode.
表1に示す本発明の色素及び下記比較の色素を、それぞれテトラヒドロフランに溶解し、0.3mMの濃度の色素溶液を作製した。そしてこの色素溶液に、前記ステロイド化合物(E−1)を0.6mMの濃度で溶解した。以上のようにして得た色素溶液に、先に作製した色素未吸着の半導体電極を室温で3時間浸漬して吸着処理を施し、色素により増感された半導体電極(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色素増感型太陽電池を作製した。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、4−t−ブチルピリジン0.05Mの3−メトキシプロピオニトリル溶液を使用した。 The dye of the present invention shown in Table 1 and the dye of the following comparison were each dissolved in tetrahydrofuran 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. In the dye solution obtained as described above, the previously prepared dye-unadsorbed semiconductor electrode was immersed for 3 hours at room temperature to perform adsorption treatment, and a semiconductor electrode (working electrode) sensitized with the dye was prepared. As the counter electrode, a titanium plate on which platinum was sputtered was used. Both electrodes were placed so as to face each other, and an electrolyte was injected between them to produce a dye-sensitized solar cell. The electrolyte was 3-methoxypropionitrile of lithium iodide 0.1M, iodine 0.05M, 1,2-dimethyl-3-n-propylimidazolium iodide 0.5M, 4-t-butylpyridine 0.05M. The solution was used.
<光電変換効率の評価>
このようにして作製した色素増感型太陽電池の作用電極側から、光源としてソーラーシミュレーター(山下電装(株)製、装置名:YSS−40S)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(ソーラートロン社製、装置名:SI−1280B)を用いて光電変換特性を測定した。以上のようにして得られた本発明及び比較の色素を用いて作製した各々の色素増感型太陽電池の光電変換効率について、比較色素C−1の光電変換効率を100とした場合の相対値として評価した。その結果を表1に示す。
<Evaluation of photoelectric conversion efficiency>
Pseudo sunlight (AM1.5G, irradiation intensity) generated from a solar simulator (manufactured by Yamashita Denso Co., Ltd., device name: YSS-40S) as a light source from the working electrode side of the dye-sensitized solar cell thus produced. 100mW / cm < 2 >) was irradiated, and the photoelectric conversion characteristic was measured using the electrochemical measuring device (The solartron company make, apparatus name: SI-1280B). About the photoelectric conversion efficiency of each dye-sensitized solar cell produced using the present invention and the comparative dye obtained as described above, the relative value when the photoelectric conversion efficiency of the comparative dye C-1 is 100 As evaluated. The results are shown in Table 1.
以下の方法にて、色素増感型太陽電池用色素の耐久性評価において極めて重要な因子となる半導体電極に対する色素の吸着安定性を評価した。本発明の色素及び比較の色素をt−ブチルアルコール/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、色素未吸着の半導体電極を室温で3時間浸漬して吸着処理を施した。ついで、この色素吸着半導体電極を電解質の溶媒である3−メトキシアセトニトリル中に浸漬し、遮光、密閉かつ25℃で90日間保存した。保存した後の半導体電極上における色素の担持状態を目視で観察した。その結果を表2に示す。 The adsorption stability of the dye to the semiconductor electrode, which is a very important factor in evaluating the durability of the dye for dye-sensitized solar cells, was evaluated by the following method. The dye of the present invention and the comparative dye were dissolved in a mixed solution of t-butyl alcohol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. The dye solution was adsorbed by immersing the dye-unadsorbed semiconductor electrode at room temperature for 3 hours. Next, this dye-adsorbing semiconductor electrode was immersed in 3-methoxyacetonitrile, which is an electrolyte solvent, shielded from light, sealed and stored at 25 ° C. for 90 days. The state of dye support on the semiconductor electrode after storage was visually observed. The results are shown in Table 2.
表1及び表2の結果から、本発明の色素が、優れた光電変換特性と優れた半導体電極への吸着安定性、すなわち耐久性を併せ持っていることがわかる。また表1におけるD−1、D−2、D−8とその他の本発明の色素との比較より、本発明の好ましい態様の光電変換特性における優位性も明らかである。そして中でもD−11、D−12、D−14、D−15の光電変換特性が特に優れていることも明らかである。 From the results of Tables 1 and 2, it can be seen that the dye of the present invention has both excellent photoelectric conversion characteristics and excellent adsorption stability to semiconductor electrodes, that is, durability. Moreover, the superiority in the photoelectric conversion characteristic of the preferable aspect of this invention is also clear from the comparison with D-1, D-2, D-8 in Table 1 and the other pigment | dye of this invention. And it is also clear that the photoelectric conversion characteristics of D-11, D-12, D-14, and D-15 are particularly excellent.
本発明の色素増感型太陽電池用色素は、色素増感型太陽電池に加えて、特定波長の光に感応する光センサーなどに活用することができる。 The dye for dye-sensitized solar cells of the present invention can be used for an optical sensor sensitive to light of a specific wavelength in addition to the dye-sensitized solar cell.
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