JP2013258110A - Photoelectrode for photoelectric conversion element, and method of manufacturing the same - Google Patents
Photoelectrode for photoelectric conversion element, and method of manufacturing the same Download PDFInfo
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- JP2013258110A JP2013258110A JP2012134931A JP2012134931A JP2013258110A JP 2013258110 A JP2013258110 A JP 2013258110A JP 2012134931 A JP2012134931 A JP 2012134931A JP 2012134931 A JP2012134931 A JP 2012134931A JP 2013258110 A JP2013258110 A JP 2013258110A
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- Prior art keywords
- acid
- dye
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- photoelectric conversion
- coadsorbent
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 1
- 229960001091 chenodeoxycholic acid Drugs 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 229960002471 cholic acid Drugs 0.000 description 1
- 235000019416 cholic acid Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 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 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- DGABKXLVXPYZII-SIBKNCMHSA-N hyodeoxycholic acid Chemical compound C([C@H]1[C@@H](O)C2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 DGABKXLVXPYZII-SIBKNCMHSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002476 indolines Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- SMEROWZSTRWXGI-HVATVPOCSA-N lithocholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 SMEROWZSTRWXGI-HVATVPOCSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004963 sulfonylalkyl group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RUDATBOHQWOJDD-UZVSRGJWSA-N ursodeoxycholic acid Chemical compound C([C@H]1C[C@@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-UZVSRGJWSA-N 0.000 description 1
- 229960001661 ursodiol Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc 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
- 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
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
Description
本発明は、光電変換素子用光電極及びその製造方法に関する。 The present invention relates to a photoelectrode for a photoelectric conversion element and a method for producing the same.
色素増感太陽電池の色素として用いられる金属錯体色素、有機色素、天然色素等はカルボキシル基等を有しており、酸化チタンや酸化スズ等の半導体金属酸化物（以下、光電極という）表面に存在する水酸基と反応して、エステル結合等により光電極表面に吸着される。光電極表面の色素が光を吸収することで発生した電子は、エステル結合等を経由して酸化チタンや酸化スズ等の半導体金属酸化物に注入される。これにより、色素増感太陽電池は光エネルギーを電気エネルギーに変換することを可能としている。 Metal complex dyes, organic dyes, natural dyes, and the like used as dyes for dye-sensitized solar cells have a carboxyl group, etc., on the surface of semiconductor metal oxides (hereinafter referred to as photoelectrodes) such as titanium oxide and tin oxide. It reacts with the existing hydroxyl group and is adsorbed on the surface of the photoelectrode by an ester bond or the like. Electrons generated when the dye on the surface of the photoelectrode absorbs light are injected into a semiconductor metal oxide such as titanium oxide or tin oxide via an ester bond or the like. Thereby, the dye-sensitized solar cell can convert light energy into electric energy.
色素増感太陽電池の変換効率向上のために、色素が光を吸収して発生した電子が効率よく半導体金属酸化物に注入されることが求められる。光電極表面に色素が会合や凝集することなく吸着されていることで効率的な電子注入が達成される。即ち、色素同士が会合又は凝集することで、結合されていないカルボキシル基等が生じるため、ここから電子が漏れて光電極に注入される電子が減少する。その結果、短絡電流密度が低下し、変換効率も低下する。 In order to improve the conversion efficiency of the dye-sensitized solar cell, it is required that electrons generated by the dye absorbing light are efficiently injected into the semiconductor metal oxide. Efficient electron injection is achieved because the dye is adsorbed on the surface of the photoelectrode without association or aggregation. That is, when the dyes associate or aggregate with each other, an unbound carboxyl group or the like is generated, so that electrons leak from here and electrons injected into the photoelectrode are reduced. As a result, the short circuit current density is lowered and the conversion efficiency is also lowered.
電子の漏れによる光電極に注入される電子の減少を防ぐために、光電極を色素溶媒に浸漬して色素を固定する際、色素溶液に共吸着剤を添加して色素同士の会合や凝集を抑制する試みがなされている。共吸着剤としては、例えば、ステアリン酸、１−デシルホスホン酸、ヘキサデシルマロン酸、３―フェニルプロピオン酸等（特許文献１）が知られている。 In order to prevent a decrease in electrons injected into the photoelectrode due to electron leakage, when the photoelectrode is immersed in a dye solvent to fix the dye, a co-adsorbent is added to the dye solution to suppress association and aggregation of the dyes. Attempts have been made. As co-adsorbents, for example, stearic acid, 1-decylphosphonic acid, hexadecylmalonic acid, 3-phenylpropionic acid and the like (Patent Document 1) are known.
特許文献１では、共吸着剤としてのカルボン酸やマロン酸誘導体としては、カルボキシル基にメチレン基（−ＣＨ２−）を３個はさんでから、水素、フェニル基、炭素数１〜２０のアルキル基を有する炭素がある構造を規定している。例えば、直鎖脂肪族カルボン酸では炭素数５以上のカルボン酸を規定している。 In Patent Document 1, as a carboxylic acid or malonic acid derivative as a co-adsorbent, a methylene group (—CH 2 —) is sandwiched between three carboxyl groups, hydrogen, a phenyl group, and an alkyl having 1 to 20 carbon atoms. Defines the structure in which the carbon having a group is present. For example, a linear aliphatic carboxylic acid defines a carboxylic acid having 5 or more carbon atoms.
そのため、長いアルキル基を有する共吸着剤をアルキル基等の疎水基を有する色素（例えば、炭素数９のノニル基を有するＺ−９０７色素、Ｄ−９０８色素等）と同時に使用する際には、色素のアルキル基と共吸着剤のアルキル基が立体障害となり、光電極への色素の吸着と競合し、色素の吸着を妨げる可能性がある。色素の吸着量が低下すると、色素が光を吸収して発生する電子の量も減少するため、短絡電流密度の低下に繋がる。また、長いアルキル基を有する共吸着剤は、色素が吸着していない半導体金属酸化物表面の水酸基に立体障害により、吸着しにくく、半導体金属酸化物からの電子の漏れを防止する効果が低いため、開放電圧の低下に繋がる。また、特許文献１に開示されたヘキサデシルマロン酸は、試薬においても日本国内での入手は困難であり、価格も１ｇで約１０万円と非常に高価である。 Therefore, when using a coadsorbent having a long alkyl group simultaneously with a dye having a hydrophobic group such as an alkyl group (for example, a Z-907 dye having a nonyl group having 9 carbon atoms, a D-908 dye, etc.) There is a possibility that the alkyl group of the dye and the alkyl group of the co-adsorbent are sterically hindered and compete with the adsorption of the dye to the photoelectrode, thereby hindering the adsorption of the dye. When the amount of dye adsorbed decreases, the amount of electrons generated by the dye absorbing light also decreases, leading to a decrease in short circuit current density. In addition, a co-adsorbent having a long alkyl group is difficult to adsorb due to steric hindrance to the hydroxyl group on the surface of the semiconductor metal oxide to which no dye is adsorbed, and has a low effect of preventing electron leakage from the semiconductor metal oxide. , Leading to a decrease in the open circuit voltage. Moreover, the hexadecylmalonic acid disclosed in Patent Document 1 is difficult to obtain in Japan as a reagent, and the price is very expensive at about 100,000 yen per gram.
これらの理由から、アルキル基等の疎水基を有する色素と同時に使用し、変換効率の向上が達成できる、安価な共吸着剤の開発が求められており、このような共吸着剤を用いた光電極を提供することを目的とする。 For these reasons, there is a demand for the development of an inexpensive coadsorbent that can be used simultaneously with a dye having a hydrophobic group such as an alkyl group to improve the conversion efficiency, and light using such a coadsorbent is required. An object is to provide an electrode.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、共吸着剤として特定のカルボン酸やマロン酸誘導体を用いることで上記目的が達成できることを見出し、さらに研究を重ね、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using a specific carboxylic acid or malonic acid derivative as a co-adsorbent. It came to complete.
即ち、本発明は、以下の構成を包含する。
項１．共吸着剤と色素とが吸着した半導体金属酸化物膜からなる光電変換素子用光電極であって、
前記共吸着剤は、
一般式（１）：
Ｒ１−ＣＨ（ＣＯＯＨ）２ （１）
［式中、Ｒ１はフェニル基、ベンジル基、ナフチル基、ターシャリーブチル基又は炭素数３〜７の環状アルキル基である。］
で示される化合物、
一般式（２）：
Ｒ２−ＣＯＯＨ （２）
［式中、Ｒ２はフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３〜５若しくは７の環状アルキル基である。］
で示される化合物、
一般式（３）：
Ｒ３−ＣＨ２ＣＯＯＨ （３）
［式中、Ｒ３はナフチル基、ターシャリーブチル基、又は炭素数３〜７の環状アルキル基である。］
で示される化合物、及び
一般式（４）：
Ｒ４−ＣＨ２ＣＨ２ＣＯＯＨ （４）
［式中、Ｒ４は炭素数３〜７の環状アルキル基である。］
で示される化合物
よりなる群から選ばれる少なくとも１種を含有する、光電変換素子用光電極。
項２．共吸着剤と色素とのモル比が１：２０〜２０：１である、項１に記載の光電変換素子用光電極。
項３．前記共吸着剤がフェニルマロン酸、ベンジルマロン酸、ナフチルマロン酸、ターシャリーブチルマロン酸、シクロプロピルマロン酸、シクロブチルマロン酸、シクロペンチルマロン酸、シクロヘキシルマロン酸、シクロヘプチルマロン酸、安息香酸、１−ナフタレンカルボン酸、２−ナフタレンカルボン酸、２，２−ジメチルプロパン酸、シクロプロパンカルボン酸、シクロブタンカルボン酸、シクロペンタンカルボン酸、シクロヘプタンカルボン酸、１−ナフチル酢酸、２−ナフチル酢酸、ターシャリーブチル酢酸、シクロプロピル酢酸、シクロブチル酢酸、シクロペンチル酢酸、シクロヘキシル酢酸、シクロヘプチル酢酸、シクロプロピルプロピオン酸、シクロブチルプロピオン酸、シクロペンチルプロピオン酸、シクロヘキシルプロピオン酸及びシクロヘプチルプロピオン酸よりなる群から選ばれる少なくとも１種である、項１又は２に記載の光電変換素子用光電極。
項４．（Ａ１）共吸着剤を含む溶液を半導体金属酸化物膜に塗布及び乾燥した後、前記処理を施した半導体金属酸化物膜に色素を含む溶液を塗布及び乾燥する工程、
（Ａ２）半導体金属酸化物膜に色素を含む溶液を塗布及び乾燥した後、前記処理を施した半導体金属酸化物膜に共吸着剤を含む溶液を塗布及び乾燥する工程、
（Ａ３）半導体金属酸化物膜に、共吸着剤及び色素を含む溶液を塗布及び乾燥する工程、
（Ｂ１）共吸着剤を含む溶液に半導体金属酸化物膜を浸漬した後、色素を含む溶液に前記処理を施した半導体金属酸化物膜を浸漬する工程、
（Ｂ２）色素を含む溶液に半導体金属酸化物膜を浸漬した後、共吸着剤を含む溶液に前記処理を施した半導体金属酸化物膜を浸漬する工程、又は
（Ｂ３）共吸着剤及び色素を含む溶液に、半導体金属酸化物を浸漬する工程
を備え、且つ、前記共吸着剤は、一般式（１）：
Ｒ１−ＣＨ（ＣＯＯＨ）２ （１）
［式中、Ｒ１はフェニル基、ベンジル基、ナフチル基、ターシャリーブチル基又は炭素数３〜７の環状アルキル基である。］
で示される化合物、
一般式（２）：
Ｒ２−ＣＯＯＨ （２）
［式中、Ｒ２はフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３〜５若しくは７の環状アルキル基である。］
で示される化合物、
一般式（３）：
Ｒ３−ＣＨ２ＣＯＯＨ （３）
［式中、Ｒ３はナフチル基、ターシャリーブチル基、又は炭素数３〜７の環状アルキル基である。］
で示される化合物、及び
一般式（４）：
Ｒ４−ＣＨ２ＣＨ２ＣＯＯＨ （４）
［式中、Ｒ４は炭素数３〜７の環状アルキル基である。］
で示される化合物
よりなる群から選ばれる少なくとも１種を含有する、光電変換素子用光電極の製造方法。
項５．前記工程（Ａ３）及び（Ｂ３）において、前記共吸着剤及び色素を含む溶液中の共吸着剤と色素とのモル比が１：２０〜２０：１である、項４に記載の製造方法。
項６．項１〜３のいずれかに記載の光電変換素子用光電極、又は項４若しくは５に記載の製造方法により得られた光電変換素子用光電極を備える光電変換素子。
項７．項６に記載の光電変換素子を備える色素増感太陽電池。
That is, the present invention includes the following configurations.
Item 1. A photoelectric conversion element photoelectrode comprising a semiconductor metal oxide film in which a coadsorbent and a dye are adsorbed,
The co-adsorbent is
General formula (1):
R 1 —CH (COOH) 2 (1)
[Wherein, R 1 represents a phenyl group, a benzyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
A compound represented by
General formula (2):
R 2 —COOH (2)
[Wherein, R 2 represents a phenyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 5 or 7 carbon atoms. ]
A compound represented by
General formula (3):
R 3 —CH 2 COOH (3)
[Wherein, R 3 represents a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
And a compound represented by the general formula (4):
R 4 —CH 2 CH 2 COOH (4)
[Wherein R 4 is a cyclic alkyl group having 3 to 7 carbon atoms. ]
The photoelectrode for photoelectric conversion elements containing at least 1 sort (s) chosen from the group which consists of a compound shown by these.
Item 2. Item 2. The photoelectric conversion element photoelectrode according to Item 1, wherein the molar ratio of the coadsorbent to the dye is 1:20 to 20: 1.
Item 3. The coadsorbent is phenylmalonic acid, benzylmalonic acid, naphthylmalonic acid, tertiary butylmalonic acid, cyclopropylmalonic acid, cyclobutylmalonic acid, cyclopentylmalonic acid, cyclohexylmalonic acid, cycloheptylmalonic acid, benzoic acid, 1 -Naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 2,2-dimethylpropanoic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 1-naphthylacetic acid, 2-naphthylacetic acid, tertiary Butylacetic acid, cyclopropylacetic acid, cyclobutylacetic acid, cyclopentylacetic acid, cyclohexylacetic acid, cycloheptylacetic acid, cyclopropylpropionic acid, cyclobutylpropionic acid, cyclopentylpropionic acid, cyclohexylpropionic acid It is at least one selected from phosphate and the group consisting of cycloheptyl propionic acid, claim 1 or 2 for a photoelectric conversion element photoelectrode described.
Item 4. (A1) A step of applying and drying a solution containing a co-adsorbent on a semiconductor metal oxide film, and then applying and drying a solution containing a dye on the semiconductor metal oxide film subjected to the treatment.
(A2) applying and drying a solution containing a co-adsorbent on the semiconductor metal oxide film subjected to the treatment after applying and drying the solution containing the dye on the semiconductor metal oxide film;
(A3) A step of applying and drying a solution containing a coadsorbent and a dye on the semiconductor metal oxide film,
(B1) a step of immersing the semiconductor metal oxide film subjected to the treatment in a solution containing a dye after immersing the semiconductor metal oxide film in a solution containing the coadsorbent;
(B2) a step of immersing the semiconductor metal oxide film in the solution containing the co-adsorbent after immersing the semiconductor metal oxide film in the solution containing the dye, or (B3) adding the co-adsorbent and the dye A step of immersing a semiconductor metal oxide in a solution containing the coadsorbent, wherein the coadsorbent is represented by the general formula (1):
R 1 —CH (COOH) 2 (1)
[Wherein, R 1 represents a phenyl group, a benzyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
A compound represented by
General formula (2):
R 2 —COOH (2)
[Wherein, R 2 represents a phenyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 5 or 7 carbon atoms. ]
A compound represented by
General formula (3):
R 3 —CH 2 COOH (3)
[Wherein, R 3 represents a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
And a compound represented by the general formula (4):
R 4 —CH 2 CH 2 COOH (4)
[Wherein R 4 is a cyclic alkyl group having 3 to 7 carbon atoms. ]
The manufacturing method of the photoelectrode for photoelectric conversion elements containing at least 1 sort (s) chosen from the group which consists of a compound shown by these.
Item 5. Item 5. The production method according to Item 4, wherein in the steps (A3) and (B3), the molar ratio of the coadsorbent and the dye in the solution containing the coadsorbent and the dye is 1:20 to 20: 1.
Item 6. Item 6. A photoelectric conversion element comprising the photoelectric electrode for a photoelectric conversion element according to any one of Items 1 to 3, or the photoelectric electrode for a photoelectric conversion element obtained by the production method according to Item 4 or 5.
Item 7. A dye-sensitized solar cell comprising the photoelectric conversion element according to Item 6.
本発明の光電極は、使用する特定の共吸着剤を添加することで色素の吸着時に色素同士の会合や凝集を防ぐことができるため、本発明の光電変換素子用光電極を光電変換素子に用いれば、変換効率の値を向上させることができる。 Since the photoelectrode of the present invention can prevent the association or aggregation of the dyes during adsorption of the dye by adding the specific co-adsorbent used, the photoelectrode for the photoelectric conversion element of the present invention is used as a photoelectric conversion element. If used, the value of conversion efficiency can be improved.
１．共吸着剤
本発明で使用する共吸着剤は、一般式（１）：
Ｒ１−ＣＨ（ＣＯＯＨ）２ （１）
［式中、Ｒ１はフェニル基、ベンジル基、ナフチル基、ターシャリーブチル基又は炭素数３〜７の環状アルキル基である。］
で示される化合物、
一般式（２）：
Ｒ２−ＣＯＯＨ （２）
［式中、Ｒ２はフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３〜５若しくは７の環状アルキル基である。］
で示される化合物、
一般式（３）：
Ｒ３−ＣＨ２ＣＯＯＨ （３）
［式中、Ｒ３はナフチル基、ターシャリーブチル基、又は炭素数３〜７の環状アルキル基である。］
で示される化合物、及び
一般式（４）：
Ｒ４−ＣＨ２ＣＨ２ＣＯＯＨ （４）
［式中、Ｒ４は炭素数３〜７の環状アルキル基である。］
で示される化合物
よりなる群から選ばれる少なくとも１種を含有する。
1. Coadsorbent The coadsorbent used in the present invention has the general formula (1):
R 1 —CH (COOH) 2 (1)
[Wherein, R 1 represents a phenyl group, a benzyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
A compound represented by
General formula (2):
R 2 —COOH (2)
[Wherein, R 2 represents a phenyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 5 or 7 carbon atoms. ]
A compound represented by
General formula (3):
R 3 —CH 2 COOH (3)
[Wherein, R 3 represents a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
And a compound represented by the general formula (4):
R 4 —CH 2 CH 2 COOH (4)
[Wherein R 4 is a cyclic alkyl group having 3 to 7 carbon atoms. ]
Containing at least one selected from the group consisting of compounds represented by:
化学式（１）において、Ｒ１はフェニル基、ベンジル基、ナフチル基、ターシャリーブチル基又は炭素数３〜７の環状アルキル基であり、好ましくはフェニル基、ベンジル基、又は炭素数３〜７の環状アルキル基であり、より好ましくはフェニル基又はシクロペンチル基である。 In the chemical formula (1), R 1 is a phenyl group, a benzyl group, a naphthyl group, a tertiary butyl group or a cyclic alkyl group having 3 to 7 carbon atoms, preferably a phenyl group, a benzyl group or a carbon atom having 3 to 7 carbon atoms. A cyclic alkyl group, more preferably a phenyl group or a cyclopentyl group.
このような化学式（１）で示される化合物としては、具体的には、フェニルマロン酸、ベンジルマロン酸、ターシャリーブチルマロン酸、シクロプロピルマロン酸、シクロブチルマロン酸、シクロペンチルマロン酸、シクロヘキシルマロン酸、シクロヘプチルマロン酸等が挙げられ、なかでも、フェニルマロン酸、シクロペンチルマロン酸等が好ましく、フェニルマロン酸がより好ましい。 Specific examples of the compound represented by the chemical formula (1) include phenylmalonic acid, benzylmalonic acid, tertiary butylmalonic acid, cyclopropylmalonic acid, cyclobutylmalonic acid, cyclopentylmalonic acid, and cyclohexylmalonic acid. And cycloheptylmalonic acid, among which phenylmalonic acid and cyclopentylmalonic acid are preferred, and phenylmalonic acid is more preferred.
化学式（２）において、Ｒ２はフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３〜５若しくは７の環状アルキル基であり、好ましくはフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３、５若しくは７の環状アルキル基であり、より好ましくは炭素数３、５又は７の環状アルキル基である。 In the chemical formula (2), R 2 is a phenyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 5 or 7 carbon atoms, preferably a phenyl group, a naphthyl group, a tertiary butyl group, or carbon. A cyclic alkyl group having 3, 5, or 7 carbon atoms, more preferably a cyclic alkyl group having 3, 5, or 7 carbon atoms.
このような化学式（２）で示される化合物としては、具体的には、シクロプロパンカルボン酸、シクロブタンカルボン酸、シクロペンタンカルボン酸、シクロヘプタンカルボン酸等が挙げられ、シクロプロパンカルボン酸、シクロペンタンカルボン酸、シクロヘプタンカルボン酸等が好ましい。 Specific examples of the compound represented by the chemical formula (2) include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, and the like. Acid, cycloheptanecarboxylic acid and the like are preferable.
化学式（３）において、Ｒ３はナフチル基、ターシャリーブチル基、又は炭素数３〜７の環状アルキル基であり、好ましくはターシャリーブチル基、又は炭素数３〜７の環状アルキル基であり、より好ましくはターシャリーブチル基、シクロプロピル基、シクロペンチル基又はシクロヘキシル基である。 In the chemical formula (3), R 3 is a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms, preferably a tertiary butyl group or a cyclic alkyl group having 3 to 7 carbon atoms, More preferred is a tertiary butyl group, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.
このような化学式（３）で示される化合物としては、具体的には、ターシャリーブチル酢酸、シクロプロピル酢酸、シクロブチル酢酸、シクロペンチル酢酸、シクロヘキシル酢酸、シクロヘプチル酢酸等が挙げられ、ターシャリーブチル酢酸、シクロプロピル酢酸、シクロペンチル酢酸、シクロヘキシル酢酸等が好ましい。 Specific examples of the compound represented by the chemical formula (3) include tertiary butyl acetic acid, cyclopropyl acetic acid, cyclobutyl acetic acid, cyclopentyl acetic acid, cyclohexyl acetic acid, cycloheptyl acetic acid, and the like. Cyclopropylacetic acid, cyclopentylacetic acid, cyclohexylacetic acid and the like are preferred.
化学式（４）において、Ｒ４は炭素数３〜７の環状アルキル基であり、好ましくは炭素数３〜５の環状アルキル基である。 In the chemical formula (4), R 4 is a cyclic alkyl group having 3 to 7 carbon atoms, preferably a cyclic alkyl group having 3 to 5 carbon atoms.
このような化学式（４）で示される化合物としては、具体的には、シクロプロピルプロピオン酸、シクロブチルプロピオン酸、シクロペンチルプロピオン酸等が好ましい。 Specifically, the compound represented by the chemical formula (4) is preferably cyclopropylpropionic acid, cyclobutylpropionic acid, cyclopentylpropionic acid, or the like.
これら化学式（１）〜（４）で示される共吸着剤は、後述の色素とともに吸着させることで色素の会合や凝集を抑制し、色素が吸着していない半導体金属酸化物表面の水酸基に共吸着剤を吸着させて、半導体金属酸化物からの電子の漏れを防止して開放電圧を向上させることができることができる点で好ましい。 The co-adsorbents represented by these chemical formulas (1) to (4) suppress the association and aggregation of the dye by adsorbing together with the dye described later, and co-adsorb to the hydroxyl group on the surface of the semiconductor metal oxide to which the dye is not adsorbed. It is preferable in that the agent can be adsorbed to prevent leakage of electrons from the semiconductor metal oxide and improve the open circuit voltage.
本発明において、共吸着剤としては、上記した化学式（１）〜（４）で示される共吸着剤を単独で用いてもよいし、２種以上を組合せて用いてもよい。 In the present invention, as the coadsorbent, the coadsorbents represented by the above chemical formulas (1) to (4) may be used singly or in combination of two or more.
また、本発明において、共吸着剤としては、上記した化学式（１）〜（４）で示される共吸着剤以外にも、従来から共吸着剤として知られる化合物を併用することもできる。このような化合物としては、具体的には、コール酸、デオキシコール酸、ケノデオキシコール酸、ヒオデオキシコール酸、ウルソデオキシコール酸、リトコール酸等が挙げられる。これらの従来から知られている共吸着剤を使用する場合は、使用する共吸着剤中の化学式（１）〜（４）で示される共吸着剤の量は、７０〜１００モル％、特に８０〜１００モル％とすることが好ましい。 In the present invention, as the coadsorbent, in addition to the coadsorbents represented by the above chemical formulas (1) to (4), compounds conventionally known as coadsorbents can be used in combination. Specific examples of such compounds include cholic acid, deoxycholic acid, chenodeoxycholic acid, hyodeoxycholic acid, ursodeoxycholic acid, lithocholic acid and the like. When these conventionally known coadsorbents are used, the amount of the coadsorbent represented by the chemical formulas (1) to (4) in the coadsorbent used is 70 to 100 mol%, particularly 80. It is preferable to set it to -100 mol%.
２．色素
色素は、可視域又は近赤外域に吸収特性を有し、光電極の光吸収効率を向上（増感）させる色素であれば特に限定されないが、金属錯体色素、有機色素、天然色素、半導体等が好ましく、金属錯体色素、有機色素、天然色素がさらに好ましい。また、多孔質チタニア膜への吸着性を付与するために、色素の分子中にカルボキシル基、ヒドロキシル基、スルホニル基、ホスホニル基、カルボキシルアルキル基、ヒドロキシアルキル基、スルホニルアルキル基、ホスホニルアルキル基等の官能基を有するものが好適に用いられる。
2. The dye dye is not particularly limited as long as it has absorption characteristics in the visible region or near infrared region and improves (sensitizes) the light absorption efficiency of the photoelectrode, but is not limited to metal complex dyes, organic dyes, natural dyes, semiconductors. Are preferable, and metal complex dyes, organic dyes, and natural dyes are more preferable. In addition, in order to impart adsorptivity to the porous titania film, a carboxyl group, hydroxyl group, sulfonyl group, phosphonyl group, carboxylalkyl group, hydroxyalkyl group, sulfonylalkyl group, phosphonylalkyl group, etc. in the dye molecule Those having the functional group are preferably used.
金属錯体色素としては、例えば、ルテニウム、オスミウム、鉄、コバルト、亜鉛、水銀等の錯体；金属ポルフィリン；金属フタロシアニン；クロロフィル等を用いることができる。また、有機色素としては、例えば、シアニン系色素、ヘミシアニン系色素、メロシアニン系色素、キサンテン系色素、トリフェニルメタン系色素、金属フリーフタロシアニン系色素、ペリレン系色素、クマリン系色素、ポリエン系色素、インドリン系色素、カルバゾール系色素等が挙げられるが、これらに限定されるものではない。 As a metal complex dye, for example, a complex of ruthenium, osmium, iron, cobalt, zinc, mercury or the like; metal porphyrin; metal phthalocyanine; chlorophyll or the like can be used. Examples of organic dyes include cyanine dyes, hemicyanine dyes, merocyanine dyes, xanthene dyes, triphenylmethane dyes, metal-free phthalocyanine dyes, perylene dyes, coumarin dyes, polyene dyes, indolines. System dyes, carbazole dyes and the like, but are not limited thereto.
色素として用いることができる半導体としては、ｉ型の光吸収係数が大きなアモルファス半導体、直接遷移型半導体、量子サイズ効果を示し、可視光を効率よく吸収する微粒子半導体等が好ましい。 As a semiconductor that can be used as a dye, an amorphous semiconductor having a large i-type light absorption coefficient, a direct transition semiconductor, a fine particle semiconductor that exhibits a quantum size effect and efficiently absorbs visible light, and the like are preferable.
通常、各種の半導体、金属錯体色素、有機色素の一種、又は光電変換の波長域をできるだけ広くし、かつ変換効率を上げるため、二種類以上の色素を混合することができる。また、目的とする光源の波長域と強度分布に合わせるように、混合する色素とその割合を選ぶことができる。 Usually, two or more kinds of dyes can be mixed in order to widen the wavelength range of various semiconductors, metal complex dyes, organic dyes, or photoelectric conversion as much as possible and increase the conversion efficiency. Moreover, the pigment | dye to mix and its ratio can be selected so that it may match with the wavelength range and intensity distribution of the target light source.
３．光電極
本発明の光電変換素子用光電極は上記した共吸着剤と色素とが吸着した半導体金属酸化物からなる。例えば、樹脂基板又はガラス基板上に上記の共吸着剤と色素とが吸着した半導体金属酸化物膜が形成されていることが好ましい。
3. Photoelectrode The photoelectrode for a photoelectric conversion element of the present invention comprises a semiconductor metal oxide in which the coadsorbent and the dye are adsorbed. For example, it is preferable that a semiconductor metal oxide film in which the coadsorbent and the dye are adsorbed is formed on a resin substrate or a glass substrate.
樹脂基板としては、導電性の樹脂基板であれば特に制限されないが、例えば、ポリエチレンナフタレート樹脂基板（ＰＥＮ樹脂基板）、ポリエチレンテレフタレート樹脂基板（ＰＥＴ樹脂基板）等のポリエステル；ポリアミド；ポリスルホン；ポリエーテルサルホン；ポリエーテルエーテルケトン；ポリフェニレンサルファイド；ポリカーボネート；ポリイミド；ポリメチルメタクリレート；ポリスチレン；トリ酢酸セルロース；ポリメチルペンテン等が挙げられる。 The resin substrate is not particularly limited as long as it is a conductive resin substrate. For example, polyester such as polyethylene naphthalate resin substrate (PEN resin substrate) and polyethylene terephthalate resin substrate (PET resin substrate); polyamide; polysulfone; polyether Examples include sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, and polymethylpentene.
ガラス基板としても特に制限はなく、公知又は市販のものを使用すればよく、無色又は有色ガラス、網入りガラス、ガラスブロック等のいずれでもよい。 There is no restriction | limiting in particular also as a glass substrate, What is necessary is just to use a well-known or commercially available thing, and any of colorless or colored glass, meshed glass, a glass block etc. may be sufficient.
この樹脂基板又はガラス基板としては、板厚が０．０５〜１０ｍｍ程度のものを使用することができる。 As this resin substrate or glass substrate, a substrate having a thickness of about 0.05 to 10 mm can be used.
本発明では、半導体金属酸化物膜は、樹脂基板又はガラス基板の表面上に直接形成されていてもよいが、透明導電膜を介して形成されていてもよい。 In the present invention, the semiconductor metal oxide film may be formed directly on the surface of the resin substrate or the glass substrate, but may be formed via a transparent conductive film.
透明導電膜としては、例えば、スズドープ酸化インジウム膜（ＩＴＯ膜）、フッ素ドープ酸化スズ膜（ＦＴＯ膜）、アンチモンドープ酸化スズ膜（ＡＴＯ膜）アルミニウムドープ酸化亜鉛膜（ＡＺＯ膜）、ガリウムドープ酸化亜鉛膜（ＧＺＯ膜）等が挙げられる。これらの透明導電膜を介することで、発生した電流を外部にとりだすことが容易となる。これらの透明導電膜の膜厚は、０．０２〜１０μｍ程度とするのが好ましい。 Examples of the transparent conductive film include a tin-doped indium oxide film (ITO film), a fluorine-doped tin oxide film (FTO film), an antimony-doped tin oxide film (ATO film), an aluminum-doped zinc oxide film (AZO film), and a gallium-doped zinc oxide. Examples include a film (GZO film). By passing through these transparent conductive films, it becomes easy to take out the generated current to the outside. The film thickness of these transparent conductive films is preferably about 0.02 to 10 μm.
樹脂基板又はガラス基板上に半導体金属酸化物膜を形成する方法としては、特に制限されるわけではないが、例えば、上述した半導体金属酸化物を含む膜形成用組成物を作製し、樹脂基板又はガラス基板上に当該膜形成用組成物を塗布及び乾燥させればよい。また、乾燥させた後、得られた膜に、必要に応じて加熱処理を施して焼成させてもよい。 The method for forming the semiconductor metal oxide film on the resin substrate or the glass substrate is not particularly limited. For example, a film forming composition containing the semiconductor metal oxide described above is prepared, and the resin substrate or What is necessary is just to apply | coat and dry the said composition for film formation on a glass substrate. Further, after drying, the obtained film may be subjected to a heat treatment as necessary to be baked.
塗布方法は特に制限はなく、スクリーン印刷、ディップコート、スプレーコート、スピンコート、スキージ法等の常法を採用することができる。 The coating method is not particularly limited, and conventional methods such as screen printing, dip coating, spray coating, spin coating, and squeegee method can be employed.
また、乾燥条件及び焼成条件は特に制限はなく、乾燥温度を６０〜２５０℃程度、焼成温度を２５０〜８００℃程度とすることが好ましい。 Moreover, there is no restriction | limiting in particular in drying conditions and baking conditions, It is preferable that drying temperature shall be about 60-250 degreeC and baking temperature shall be about 250-800 degreeC.
半導体金属酸化物膜の作製に当たっては、得られる膜の膜厚が０．５〜５０μｍ程度となるように塗布することが好ましい。 In producing the semiconductor metal oxide film, it is preferable to apply so that the thickness of the obtained film is about 0.5 to 50 μm.
前記半導体金属酸化物としては、例えば、酸化チタン、酸化スズ、酸化亜鉛等が例示できるが、酸化チタンが好ましく、多孔質酸化チタンがより好ましい。 Examples of the semiconductor metal oxide include titanium oxide, tin oxide, and zinc oxide. Titanium oxide is preferable, and porous titanium oxide is more preferable.
本明細書中において「酸化チタン」とは、二酸化チタンのみを指すものではなく、三酸化二チタン（Ｔｉ２Ｏ３）；一酸化チタン（ＴｉＯ）；Ｔｉ４Ｏ７、Ｔｉ５Ｏ９等に代表される二酸化チタンから酸素欠損した組成のもの等も含むものである。また、末端ＯＨ基に代表されるように一部酸化チタンの合成に起因するＴｉ−Ｏ−Ｔｉ以外の基を含んでいてもよい。同様に「酸化スズ」、「酸化亜鉛」も酸素欠損した組成のもの等も含むものであり、末端ＯＨ基に代表されるようなＳｎ−Ｏ−ＳｎやＺｎ−Ｏ−Ｚｎ以外の基を含んでいてもよい。 In this specification, “titanium oxide” does not refer to only titanium dioxide, but includes dititanium trioxide (Ti 2 O 3 ); titanium monoxide (TiO); Ti 4 O 7 , Ti 5 O 9 and the like. It also includes a composition having oxygen deficiency from a representative titanium dioxide. Further, as represented by the terminal OH group, a group other than Ti—O—Ti resulting from the synthesis of titanium oxide may be included. Similarly, “tin oxide” and “zinc oxide” include those having an oxygen-deficient composition, and include groups other than Sn—O—Sn and Zn—O—Zn as represented by terminal OH groups. You may go out.
前記多孔質酸化チタンに使用される酸化チタンとしては、例えば、公知又は市販の酸化チタンナノ粒子；公知又は市販の酸化チタンナノチューブ；酸化チタンナノロッド；酸化チタンナノファイバー；酸化チタンナノ粒子のチューブ状集合体（特開２０１０−２４１３２号公報等）等を１種単独で用いてもよいし、２種以上を組合せて用いてもよい。 Examples of the titanium oxide used in the porous titanium oxide include known or commercially available titanium oxide nanoparticles; known or commercially available titanium oxide nanotubes; titanium oxide nanorods; titanium oxide nanofibers; No. 2010-24132 etc.) may be used alone or in combination of two or more.
本発明の光電変換素子用光電極に前記共吸着剤と色素を吸着させる順序としては、特に制限されない。具体的には、前記共吸着剤と色素を同時に吸着させてもよく、色素を吸着させてから共吸着剤を吸着させてもよく、共吸着剤を吸着させてから色素を吸着させてもよい。色素の会合及び凝集をより抑制するためには、前記共吸着剤と色素を同時に吸着させることが好ましく、また同時に行うのが簡便である。 The order in which the coadsorbent and the dye are adsorbed to the photoelectrode for photoelectric conversion element of the present invention is not particularly limited. Specifically, the coadsorbent and the dye may be adsorbed simultaneously, the coadsorbent may be adsorbed after the dye is adsorbed, or the dye may be adsorbed after the coadsorbent is adsorbed. . In order to further suppress the association and aggregation of the dye, it is preferable to adsorb the co-adsorbent and the dye at the same time, and it is easy to carry out at the same time.
色素を半導体金属酸化物膜に吸着させる方法としては、例えば、溶媒に色素を溶解させた溶液を、半導体金属酸化物膜上にスプレーコートやスピンコート等により塗布した後、乾燥する方法により形成することができる。この場合、適当な温度（例えば２５〜６０℃程度）に基板を加熱してもよい。また、半導体金属酸化物膜を前記溶液に浸漬して吸着させる方法を用いることもできる。浸漬する時間は色素が充分に吸着すれば特に制限されることはないが、好ましくは１０分〜３０時間、より好ましくは１〜２０時間である。また、必要に応じて浸漬する際に溶媒や基板を２５〜６０℃程度に加熱してもよい。溶液にする場合の色素の濃度としては、０．０１〜１００ｍｍｏｌ／Ｌ、好ましくは０．１〜１０ｍｍｏｌ／Ｌ程度である。 As a method for adsorbing the dye to the semiconductor metal oxide film, for example, a solution in which the dye is dissolved in a solvent is applied on the semiconductor metal oxide film by spray coating or spin coating and then dried. be able to. In this case, the substrate may be heated to an appropriate temperature (for example, about 25 to 60 ° C.). Alternatively, a method in which a semiconductor metal oxide film is immersed and adsorbed in the solution can be used. The immersion time is not particularly limited as long as the dye is sufficiently adsorbed, but is preferably 10 minutes to 30 hours, more preferably 1 to 20 hours. Moreover, you may heat a solvent and a board | substrate at about 25-60 degreeC, when immersing as needed. The concentration of the dye in the case of a solution is about 0.01 to 100 mmol / L, preferably about 0.1 to 10 mmol / L.
前記共吸着剤を半導体金属酸化物膜に吸着させる方法としては、例えば、溶媒に共吸着剤を溶解させた溶液を、半導体金属酸化物膜上にスプレーコートやスピンコート等により塗布した後、乾燥する方法により形成することができる。この場合、適当な温度（例えば２５〜６０℃程度）に基板を加熱してもよい。また、半導体金属酸化物膜を前記溶液に浸漬して吸着させる方法を用いることもできる。浸漬する時間は共吸着剤が充分に吸着すれば特に制限されることはないが、好ましくは１０分〜３０時間、より好ましくは１〜２０時間である。また、必要に応じて浸漬する際に溶媒や基板を２５〜６０℃程度に加熱してもよい。溶液にする場合の共吸着剤の濃度としては０．１μｍｏｌ／Ｌ〜３３ｍｍｏｌ／Ｌが好ましく、０．１μｍｏｌ／Ｌ〜１０ｍｍｏｌ／Ｌ程度が特に好ましい。 As a method for adsorbing the coadsorbent on the semiconductor metal oxide film, for example, a solution in which the coadsorbent is dissolved in a solvent is applied on the semiconductor metal oxide film by spray coating, spin coating, or the like, and then dried. It can form by the method to do. In this case, the substrate may be heated to an appropriate temperature (for example, about 25 to 60 ° C.). Alternatively, a method in which a semiconductor metal oxide film is immersed and adsorbed in the solution can be used. The immersion time is not particularly limited as long as the co-adsorbent is sufficiently adsorbed, but is preferably 10 minutes to 30 hours, more preferably 1 to 20 hours. Moreover, you may heat a solvent and a board | substrate at about 25-60 degreeC, when immersing as needed. The concentration of the co-adsorbent in the case of a solution is preferably from 0.1 μmol / L to 33 mmol / L, particularly preferably from about 0.1 μmol / L to 10 mmol / L.
前記共吸着剤を色素と共に吸着させる場合は、共吸着剤と色素の双方を溶解させた溶液を用いて塗布及び乾燥、又は浸漬を行うことが好ましい。この際の濃度や時間等の条件は上記したものを採用できる。共吸着剤を色素吸着後に吸着させる場合は、色素を吸着させた光電極を共吸着剤の溶液に浸漬して吸着させることが好ましい。 In the case of adsorbing the coadsorbent together with the dye, it is preferable to perform application and drying or immersion using a solution in which both the coadsorbent and the dye are dissolved. The above-mentioned conditions such as concentration and time can be employed. When the coadsorbent is adsorbed after the dye adsorption, it is preferable that the photoelectrode on which the dye is adsorbed is immersed in a solution of the coadsorbent.
未吸着の色素及び共吸着剤は、吸着工程後、速やかに洗浄により除去するのが好ましい。洗浄は色素及び共吸着剤ともに、湿式洗浄槽中でアセトニトリル、アルコール系溶媒等を用いて行うのが好ましい。 The unadsorbed dye and coadsorbent are preferably removed by washing immediately after the adsorption step. Washing is preferably carried out using acetonitrile, an alcohol solvent or the like in a wet washing tank together with the dye and the co-adsorbent.
用いる共吸着剤と色素とのモル比は、共吸着剤：色素で１：２０〜２０：１が好ましく、１：１５〜１５：１がより好ましく、１：１０〜１０：１が特に好ましい。ただし、共吸着剤の使用量は、本発明の効果が達成できるものであれば、共吸着剤が色素の吸着を阻害しない観点から、色素に対するモル比で少量であることが好ましい。 The molar ratio of the coadsorbent to the dye used is preferably from 1:20 to 20: 1, more preferably from 1:15 to 15: 1, and particularly preferably from 1:10 to 10: 1. However, the amount of the coadsorbent used is preferably a small amount in terms of a molar ratio to the dye from the viewpoint that the coadsorbent does not inhibit the adsorption of the dye as long as the effect of the present invention can be achieved.
ここで、共吸着剤と色素とのモル比は使用する共吸着剤の総モル量と色素の総モル量との比で表される。共吸着剤と色素の双方を溶かした溶液を用いて吸着を行う場合、該溶液における双方のモル濃度の比でも表すことができる。この共吸着剤と色素とのモル比が、そのまま本発明の光電極における共吸着剤と色素とのモル比になる。 Here, the molar ratio between the coadsorbent and the dye is represented by the ratio between the total molar amount of the coadsorbent used and the total molar amount of the dye. When adsorption is performed using a solution in which both the co-adsorbent and the dye are dissolved, it can also be expressed by the ratio of the molar concentrations of both in the solution. The molar ratio between the co-adsorbent and the dye becomes the molar ratio between the co-adsorbent and the dye in the photoelectrode of the present invention as it is.
４．光電変換素子及び色素増感太陽電池
本発明の光電変換素子は、本発明の光電変換素子用光電極を用いたものであれば特に制限はないが、例えば、本発明の光電変換素子用光電極の半導体金属酸化物膜の上に対向電極（対極）を形成し、これら電極間を電解液で満たすことにより得ることができる。
4). Photoelectric Conversion Element and Dye-Sensitized Solar Cell The photoelectric conversion element of the present invention is not particularly limited as long as it uses the photoelectrode for photoelectric conversion element of the present invention. For example, the photoelectrode for photoelectric conversion element of the present invention A counter electrode (counter electrode) is formed on the semiconductor metal oxide film, and the gap between these electrodes is filled with an electrolytic solution.
対極は、導電性材料からなる単層構造でもよいし、導電層と基板とから構成されていてもよい。基板としては、特に限定されず、材質、厚さ、寸法、形状等は目的に応じて適宜選択することができ、例えば、金属、無色又は有色ガラス、網入りガラス、ガラスブロック等が用いられる他、樹脂でも良い。かかる樹脂としては、ポリエチレンテレフタレート等のポリエステル、ポリアミド、ポリスルホン、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリフェニレンサルファイド、ポリカーボネート、ポリイミド、ポリメチルメタクリレート、ポリスチレン、トリ酢酸セルロース、ポリメチルペンテン等が挙げられる。また、電荷輸送層上に直接導電性材料を塗布、メッキ又は蒸着（ＰＶＤ、ＣＶＤ）して対極を形成しても良い。 The counter electrode may have a single layer structure made of a conductive material, or may be composed of a conductive layer and a substrate. The substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like can be appropriately selected according to the purpose. For example, metal, colorless or colored glass, meshed glass, glass block, etc. are used. Resin may be used. Examples of such resins include polyesters such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, and polymethylpentene. Alternatively, the counter electrode may be formed by applying, plating, or vapor-depositing (PVD, CVD) a conductive material directly on the charge transport layer.
導電性材料としては、白金、金、ニッケル、チタン、アルミニウム、銅、銀、タングステン等の金属；炭素材料；導電性有機物等の比抵抗の小さな材料が用いられる。 As the conductive material, a metal having a small specific resistance, such as a metal such as platinum, gold, nickel, titanium, aluminum, copper, silver, or tungsten; a carbon material; or a conductive organic material is used.
また、対極の抵抗を下げる目的で金属リードを用いても良い。金属リードは白金、金、ニッケル、チタン、アルミニウム、銅、銀、タングステン等の金属からなるのが好ましく、アルミニウム又は銀からなるのが特に好ましい。 A metal lead may be used for the purpose of reducing the resistance of the counter electrode. The metal lead is preferably made of a metal such as platinum, gold, nickel, titanium, aluminum, copper, silver or tungsten, and particularly preferably made of aluminum or silver.
電解液の電解質としては、特に制限はない。電解質の例としては、ヨウ素とヨウ化物（ＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＣａＩ２等の金属ヨウ化物、ヨウ化４級アンモニウム化合物等）の組合せ、臭素と臭化物（ＬｉＢｒ、ＢａＢｒ、ＫＢｒ、ＣｓＢｒ、ＣａＢｒ、ＣａＢｒ２等の金属臭化物、臭化４級アンモニウム化合物等）の組合せ、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。これらの電解質は混合して用いてもよい。中でも、酸化還元対を形成しやすい点からヨウ素とヨウ化物を含むことが好ましい。具体的には、ヨウ素、並びにヨウ化リチウム及び／又はヨウ化４級アンモニウムを含むことが好ましい。特に、ヨウ素、ヨウ化リチウム及びヨウ化４級アンモニウムを全て使用することが好ましい。 There is no restriction | limiting in particular as electrolyte of electrolyte solution. Examples of electrolytes include iodine and iodide (LiI, NaI, KI, CsI , CaI 2 , etc. of a metal iodide, iodide quaternary ammonium compounds) combinations, bromine and bromide (LiBr, BaBr, KBr, CsBr, CaBr, CaBr 2 or the like of metal bromide, a combination of bromide quaternary ammonium compounds, etc.), ferrocyanide - ferricyanate, ferrocene - metal complexes such as ferricinium ion, sodium polysulfide, alkylthiol - alkyl disulfide, etc. And sulfur compounds, viologen dyes, hydroquinone-quinones, and the like. These electrolytes may be used as a mixture. Among these, iodine and iodide are preferably included from the viewpoint of easy formation of a redox pair. Specifically, it is preferable to contain iodine and lithium iodide and / or quaternary ammonium iodide. In particular, it is preferable to use all of iodine, lithium iodide and quaternary ammonium iodide.
ヨウ素、並びにヨウ化リチウム及び／又はヨウ化４級アンモニウムを使用する場合、ヨウ素と、ヨウ化リチウム及びヨウ化４級アンモニウムは、本発明の電解液中で酸化還元対であるＩ−／Ｉ３ −を形成する（Ｉ−存在下にＩ２を添加することでＩ３ −が生成する）。なお、ヨウ化リチウムの添加により生成するリチウムイオンは、色素増感太陽電池のチタニア負極等に用いられる多孔質チタニアに吸着する。そのため、チタニア伝導帯をより下げて色素からチタニアへの電子注入速度をより向上させることも可能である。また、チタニアに注入された電子の輸送をより促進させ、短絡電流密度をより向上させ、光電変換効率をより向上させることも可能である。 When iodine and lithium iodide and / or quaternary ammonium iodide are used, iodine and lithium iodide and quaternary ammonium iodide are redox couples in the electrolyte of the present invention, I − / I 3. - forming a (I - to produce - I 3 by the addition of I 2 in the presence). In addition, the lithium ion produced | generated by addition of lithium iodide adsorb | sucks to the porous titania used for the titania negative electrode etc. of a dye-sensitized solar cell. Therefore, it is possible to further improve the electron injection rate from the dye to titania by lowering the titania conduction band. It is also possible to further promote the transport of electrons injected into titania, further improve the short-circuit current density, and further improve the photoelectric conversion efficiency.
ヨウ化４級アンモニウムとしては、ヨウ化テトラアルキルアンモニウム、ヨウ化１，３−ジアルキルイミダゾリウム、ヨウ化１−アルキルピリジニウム、ヨウ化１，１−ジアルキルピロリジニウム等（これらの化合物において、アルキルとしては、メチル、エチル、プロピル、ブチル等の低級アルキル基等が挙げられる）が使用できる。 Examples of the quaternary ammonium iodide include tetraalkylammonium iodide, 1,3-dialkylimidazolium iodide, 1-alkylpyridinium iodide, 1,1-dialkylpyrrolidinium iodide, etc. (in these compounds, as alkyl May be a lower alkyl group such as methyl, ethyl, propyl and butyl).
各々の電解質の濃度としては、より充分な光電変換効率を得る観点から、ヨウ化物イオンＩ−の供給源としてはヨウ化４級アンモニウムを主成分とするのが好ましい。 As the concentration of each electrolyte, it is preferable that quaternary ammonium iodide is a main component as a supply source of iodide ion I − from the viewpoint of obtaining a sufficient photoelectric conversion efficiency.
各成分の具体的な濃度としては、ヨウ化物イオン（Ｉ−）と三ヨウ化物イオン（Ｉ３ −）の拡散速度をより向上させ、より色素が光励起しやすくすることで、短絡電流密度をより向上させ、光電変換効率をより向上させる観点から、ヨウ素は０．０１〜０．５ｍｏｌ／Ｌ程度（好ましくは０．０５〜０．３ｍｏｌ／Ｌ程度）が好ましい。また、ヨウ化リチウムは０．０１〜０．５ｍｏｌ／Ｌ程度（好ましくは０．０５〜０．３ｍｏｌ／Ｌ程度）が好ましい。さらに、ヨウ化４級アンモニウムは０．１〜２．０ｍｏｌ／Ｌ程度（好ましくは０．３〜１．５ｍｏｌ／Ｌ程度）が好ましい。 The specific concentration of each component is such that the diffusion rate of iodide ions (I − ) and triiodide ions (I 3 − ) is further improved, and the dye is more easily photoexcited, so that the short-circuit current density is further increased. From the viewpoint of improving and further improving the photoelectric conversion efficiency, iodine is preferably about 0.01 to 0.5 mol / L (preferably about 0.05 to 0.3 mol / L). Further, the lithium iodide is preferably about 0.01 to 0.5 mol / L (preferably about 0.05 to 0.3 mol / L). Furthermore, the quaternary ammonium iodide is preferably about 0.1 to 2.0 mol / L (preferably about 0.3 to 1.5 mol / L).
上記した成分以外にも、塩基性物質、例えば、４−ターシャリーブチルピリジン、Ｎ−メチルベンズイミダゾール、Ｎ−ｎ−ブチルベンズイミダゾール等を含有させることもできる。これらの塩基性物質を含有させれば、光電変換素子を作製した際に、チタニア電極のチタニア表面に吸着することで、チタニア電極からの逆電子移動をより防ぐことができ、開放電圧をより向上させるとともに、光電変換効率をより向上させることができる。 In addition to the above-described components, basic substances such as 4-tertiarybutylpyridine, N-methylbenzimidazole, Nn-butylbenzimidazole, and the like can also be contained. If these basic substances are contained, when a photoelectric conversion element is produced, it is adsorbed on the titania surface of the titania electrode, so that reverse electron transfer from the titania electrode can be further prevented, and the open-circuit voltage is further improved. In addition, the photoelectric conversion efficiency can be further improved.
このように光電変換効率をより向上させるとともに、チタニアに吸着した色素がより脱離しにくくする観点から、塩基性物質の添加量は、０．１〜１．０ｍｏｌ／Ｌ程度、特に０．３〜０．８ｍｏｌ／Ｌ程度が好ましい。 Thus, from the viewpoint of further improving the photoelectric conversion efficiency and making the dye adsorbed to titania more difficult to desorb, the addition amount of the basic substance is about 0.1 to 1.0 mol / L, particularly 0.3 to About 0.8 mol / L is preferable.
他にも、本発明の電解液には、上述のヨウ化リチウムと同様に、チタニアの伝導帯をより下げて色素からチタニアへの電子注入速度をより向上させることができるグアニジンチオシアネート等も添加することができる。この場合、これらの添加量は、０．０１〜１．０ｍｏｌ／Ｌ程度、特に０．０５〜０．５ｍｏｌ／Ｌが好ましい。 In addition, guanidine thiocyanate, which can lower the conduction band of titania and further improve the electron injection rate from the dye to titania, is added to the electrolytic solution of the present invention, similarly to the above-described lithium iodide. be able to. In this case, the amount of these added is preferably about 0.01 to 1.0 mol / L, and particularly preferably 0.05 to 0.5 mol / L.
なお、本発明の電解液においては、上記成分以外にも、粘度調整剤（ポリエチレングリコール等）、脱水剤（ゼオライト、シリカゲル等）等を、本発明の効果を損なわない範囲内で含ませることも可能である。 In addition, in the electrolytic solution of the present invention, in addition to the above components, a viscosity modifier (polyethylene glycol, etc.), a dehydrating agent (zeolite, silica gel, etc.) and the like may be included within a range not impairing the effects of the present invention. Is possible.
電解液の溶媒としては特に制限はない。電解液の例としては、アセトニトリル、３−メトキシプロピオニトリル等のニトリル化合物、γ−ブチロラクトン等の環状エステル化合物、１−メチル−２−ピロリドン等の環状アミド化合物、１−エチル−３−メチルイミダゾリウム・ビスフルオロスルホニルイミド等のイオン液体が使用できる。 There is no restriction | limiting in particular as a solvent of electrolyte solution. Examples of the electrolyte include nitrile compounds such as acetonitrile and 3-methoxypropionitrile, cyclic ester compounds such as γ-butyrolactone, cyclic amide compounds such as 1-methyl-2-pyrrolidone, 1-ethyl-3-methylimidazo An ionic liquid such as lithium bisfluorosulfonylimide can be used.
本発明の色素増感太陽電池は、本発明の光電変換素子をモジュール化するとともに、所定の電気配線を設けることによって製造することができる。 The dye-sensitized solar cell of the present invention can be manufactured by modularizing the photoelectric conversion element of the present invention and providing predetermined electrical wiring.
以下、実施例に基づいて、本発明を具体的に説明するが、本発明は、これらのみに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these.
［チタニアを含む膜形成用組成物の作成］
チタンイソプロポキシド０．０５ｍｏｌに酢酸０．０５ｍｏｌを加えて１５分撹拌した。蒸留水７３ｍＬを加えて１時間撹拌した。さらに濃硝酸１ｍＬを加えて８０℃で７５分間加熱及び撹拌を行った。蒸留水を加えて全量を９３ｍＬとしてチタニアゾル水溶液を得た。このチタニアゾル水溶液４０ｍＬを内容積１２５ｍＬの圧力反応容器に入れて２５０℃で１２時間加熱した。得られた白色沈殿物（チタニア）をエタノールで溶媒置換した後、１００ｍＬエタノール分散液とした。これにα−テルピネオール７ｇとエチルセルロースの１０重量％エタノール溶液８．６５ｇを加えて撹拌した。十分に撹拌した後、エバポレーターを用いてエタノールを留去してチタニアを含む膜形成用組成物１０ｇを得た。
[Preparation of a film-forming composition containing titania]
Acetic acid 0.05 mol was added to titanium isopropoxide 0.05 mol and stirred for 15 minutes. Distilled water 73mL was added and it stirred for 1 hour. Further, 1 mL of concentrated nitric acid was added, and the mixture was heated and stirred at 80 ° C. for 75 minutes. Distilled water was added to make a total volume of 93 mL to obtain an aqueous titania sol solution. 40 mL of this titania sol aqueous solution was placed in a pressure reaction vessel having an internal volume of 125 mL and heated at 250 ° C. for 12 hours. The obtained white precipitate (titania) was subjected to solvent substitution with ethanol, and then made into a 100 mL ethanol dispersion. To this, 7 g of α-terpineol and 8.65 g of a 10 wt% ethanol solution of ethyl cellulose were added and stirred. After sufficiently stirring, ethanol was distilled off using an evaporator to obtain 10 g of a film forming composition containing titania.
［チタニア負極の作成］
フッ素ドープ酸化スズ（ＦＴＯ）膜付きガラス（日本板硝子（株）製；４ｍｍ厚）にポリエステル製スクリーン印刷版（２２５メッシュ）を用いて、上記で作製したチタニアを含む膜形成用組成物を、５ミリ角の大きさに膜厚１４μｍになるまで繰り返しスクリーン印刷を行った。さらに電気炉に入れて５００℃にて１時間焼成を行った。
[Creation of titania negative electrode]
A film-forming composition containing titania prepared as described above was prepared using a polyester screen printing plate (225 mesh) on a glass with fluorine-doped tin oxide (FTO) film (manufactured by Nippon Sheet Glass Co., Ltd .; 4 mm thickness). Screen printing was repeatedly performed until the film thickness was 14 μm in the size of millimeter square. Furthermore, it put into the electric furnace and baked at 500 degreeC for 1 hour.
［増感色素の固定］
台湾・エバーライト社製のＤ−９０８色素をアセトニトリルとターシャリーブチルアルコールの容量比１：１混合溶媒に０．５ｍｍｏｌ／Ｌの濃度で溶解したものに、共吸着剤を所定量添加して後述する実施例１〜６又は比較例１〜２の色素溶液を得た。得られた色素溶液に上記５００℃で焼成したチタニア負極を２５℃で２０時間浸漬して色素を固定した。
[Immobilization of sensitizing dye]
A predetermined amount of a co-adsorbent was added to a solution obtained by dissolving D-908 dye, manufactured by Everlite, Taiwan, in a mixed solvent of acetonitrile and tertiary butyl alcohol in a volume ratio of 1: 1 at a concentration of 0.5 mmol / L. The dye solutions of Examples 1 to 6 or Comparative Examples 1 and 2 to be obtained were obtained. The titania negative electrode fired at 500 ° C. was immersed in the obtained dye solution at 25 ° C. for 20 hours to fix the dye.
［小型セルの組み立て］
色素を固定した上記チタニア負極に、スペーサー兼シール剤として厚さ５０μｍの低密度ポリエチレンフィルム（デュポン社製バイネル）を用いて、白金をスパッタしたフッ素ドープ酸化スズ（ＦＴＯ）膜付きガラス（ピルキントン社製：２．２ｍｍ厚）を貼り合わせた。ヨウ素０．０６ｍｏｌ／Ｌ、ヨウ化リチウム０．１ｍｏｌ／Ｌ、ヨウ化１−エチル−３−メチルイミダゾリウム０．５ｍｏｌ／Ｌ、４−ターシャリーブチルピリジン０．５ｍｏｌ／Ｌをアセトニトリルに溶解した電解液を注入して封止を行い、光電変換素子を作製した。
[Assembly of small cells]
Glass with fluorine-doped tin oxide (FTO) film sputtered with platinum using a low-density polyethylene film (Bunel made by DuPont) having a thickness of 50 μm as a spacer and sealant on the above-mentioned titania negative electrode on which the dye is fixed (Pilkinton) : 2.2 mm thickness). Electrolysis in which 0.06 mol / L of iodine, 0.1 mol / L of lithium iodide, 0.5 mol / L of 1-ethyl-3-methylimidazolium iodide, and 0.5 mol / L of 4-tertiarybutylpyridine were dissolved in acetonitrile. The liquid was injected and sealed to prepare a photoelectric conversion element.
［小型セルの性能評価］
作製した小型セルに（株）三永電気製作所製のソーラーシミュレータでＡＭ１．５（ＪＩＳＣ８９１２Ａランク）の条件下の１００ｍＷ／ｃｍ２の強度の光を照射して上記小型セルの光電変換特性を２５℃にて評価した。なお、測定は４回行い、その平均値を採用した。
[Performance evaluation of small cells]
The produced small cell was irradiated with light having an intensity of 100 mW / cm 2 under the condition of AM1.5 (JISC8912A rank) with a solar simulator manufactured by Mitsunaga Electric Co., Ltd., and the photoelectric conversion characteristic of the small cell was measured at 25 ° C. Evaluated. In addition, the measurement was performed 4 times and the average value was adopted.
実施例１
色素溶液の組成を以下のようにして、小型セルの評価を行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：フェニルマロン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．４ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６５Ｖ、フィルファクターＦＦが０．６９、光電変換効率が７．８％であった。
Example 1
The composition of the dye solution was evaluated as follows for small cells.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: Phenylmalonic acid 0.5mmol / L
Short-circuit current density J SC is 17.4 mA / cm 2 for small cells, open circuit voltage V OC is 0.65V, fill factor FF is 0.69, the photoelectric conversion efficiency was 7.8%.
実施例２
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：フェニルマロン酸 ５．０ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．１ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６５Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．６％であった。
Example 2
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: Phenylmalonic acid 5.0 mmol / L
Short-circuit current density J SC of the small cell is 17.1mA / cm 2, the open circuit voltage V OC is 0.65V, fill factor FF is 0.68, the photoelectric conversion efficiency was 7.6%.
実施例３
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：フェニルマロン酸 ０．０５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．５ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６５Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．３％であった。
Example 3
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: Phenylmalonic acid 0.05mmol / L
Short-circuit current density J SC of the small cell is 16.5 mA / cm 2, the open circuit voltage V OC is 0.65V, fill factor FF is 0.68, the photoelectric conversion efficiency was 7.3%.
実施例４
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロペンチルマロン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．５ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６５Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．３％であった。
Example 4
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclopentylmalonic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 16.5 mA / cm 2, the open circuit voltage V OC is 0.65V, fill factor FF is 0.68, the photoelectric conversion efficiency was 7.3%.
実施例５
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：ベンジルマロン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．８ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６４Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．３％であった。
Example 5
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: benzylmalonic acid 0.5mmol / L
Short-circuit current density J SC of the small cell is 16.8mA / cm 2, the open circuit voltage V OC is 0.64 V, the fill factor FF is 0.68, the photoelectric conversion efficiency was 7.3%.
実施例６
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロプロパンカルボン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．５ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６４Ｖ、フィルファクターＦＦが０．６９、光電変換効率が７．３％であった。
Example 6
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclopropanecarboxylic acid 0.5 mmol / L
Short-circuit current density J SC is 16.5 mA / cm 2 for small cells, open circuit voltage V OC is 0.64 V, the fill factor FF is 0.69, the photoelectric conversion efficiency was 7.3%.
実施例７
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロペンタンカルボン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．１ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６４Ｖ、フィルファクターＦＦが０．６７、光電変換効率が７．３％であった。
Example 7
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclopentanecarboxylic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 17.1mA / cm 2, the open circuit voltage V OC is 0.64 V, the fill factor FF is 0.67, the photoelectric conversion efficiency was 7.3%.
実施例８
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロヘプタンカルボン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．０ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６３Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．３％であった。
Example 8
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cycloheptanecarboxylic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 17.0mA / cm 2, the open circuit voltage V OC is 0.63V, fill factor FF is 0.68, the photoelectric conversion efficiency was 7.3%.
実施例９
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：ターシャリーブチル酢酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．１ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６３Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．３％であった。
Example 9
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: Tertiary butyl acetate 0.5mmol / L
Short-circuit current density J SC of the small cell is 17.1mA / cm 2, the open circuit voltage V OC is 0.63V, fill factor FF is 0.68, the photoelectric conversion efficiency was 7.3%.
実施例１０
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロプロピル酢酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．９ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６４Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．４％であった。
Example 10
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclopropylacetic acid 0.5mmol / L
Short-circuit current density J SC of the small cell is 16.9mA / cm 2, the open circuit voltage V OC is 0.64 V, the fill factor FF is 0.68, the photoelectric conversion efficiency was 7.4%.
実施例１１
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロペンチル酢酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．１ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６５Ｖ、フィルファクターＦＦが０．６９、光電変換効率が７．７％であった。
Example 11
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclopentylacetic acid 0.5 mmol / L
Short-circuit current density J SC is 17.1mA / cm 2 of the small cell, the open circuit voltage V OC is 0.65V, fill factor FF is 0.69, the photoelectric conversion efficiency was 7.7%.
実施例１２
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロヘキシル酢酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．０ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６４Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．４％であった。
Example 12
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclohexyl acetic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 17.0mA / cm 2, the open circuit voltage V OC is 0.64 V, the fill factor FF is 0.68, the photoelectric conversion efficiency was 7.4%.
実施例１３
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロペンチルプロピオン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１７．４ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６４Ｖ、フィルファクターＦＦが０．６８、光電変換効率が７．６％であった。
Example 13
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclopentylpropionic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 17.4 mA / cm 2, the open circuit voltage V OC is 0.64 V, the fill factor FF is 0.68, the photoelectric conversion efficiency was 7.6%.
比較例１
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：共吸着剤の添加なし
小型セルの短絡電流密度ＪＳＣが１６．４ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６３Ｖ、フィルファクターＦＦが０．６６、光電変換効率が６．８％であった。
Comparative Example 1
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: short-circuit current density J SC is 16.4mA / cm 2 without small cells the addition of a co-adsorbent, open circuit voltage V OC is 0.63V, fill factor FF is 0.66, the photoelectric conversion efficiency 6.8 %Met.
比較例２
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：シクロヘキサンカルボン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．０ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６０Ｖ、フィルファクターＦＦが０．６８、光電変換効率が６．８％であった。
Comparative Example 2
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: cyclohexanecarboxylic acid 0.5mmol / L
Short-circuit current density J SC of the small cell is 16.0mA / cm 2, the open circuit voltage V OC is 0.60 V, the fill factor FF is 0.68, the photoelectric conversion efficiency was 6.8%.
比較例３
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：３−フェニルプロピオン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１６．１ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．６２Ｖ、フィルファクターＦＦが０．６８、光電変換効率が６．８％であった。
Comparative Example 3
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: 3-phenylpropionic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 16.1mA / cm 2, the open circuit voltage V OC is 0.62 V, the fill factor FF is 0.68, the photoelectric conversion efficiency was 6.8%.
比較例４
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：１−デシルホスホン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１４．９ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．７０Ｖ、フィルファクターＦＦが０．６５、光電変換効率が６．８％であった。
Comparative Example 4
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: 1-decylphosphonic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 14.9mA / cm 2, the open circuit voltage V OC is 0.70 V, the fill factor FF of 0.65, the photoelectric conversion efficiency was 6.8%.
比較例５
色素溶液の組成を以下のようにして、小型セルを行った。
色素：Ｄ９０８色素 ０．５ｍｍｏｌ／Ｌ
共吸着剤：ヘキサデシルマロン酸 ０．５ｍｍｏｌ／Ｌ
小型セルの短絡電流密度ＪＳＣが１４．６ｍＡ／ｃｍ２、開放電圧ＶＯＣが０．７０Ｖ、フィルファクターＦＦが０．６５、光電変換効率が６．６％であった。
Comparative Example 5
A small cell was made with the composition of the dye solution as follows.
Dye: D908 dye 0.5 mmol / L
Coadsorbent: hexadecylmalonic acid 0.5 mmol / L
Short-circuit current density J SC of the small cell is 14.6mA / cm 2, the open circuit voltage V OC is 0.70 V, the fill factor FF of 0.65, the photoelectric conversion efficiency was 6.6%.
以上の結果を表１に示す。 The results are shown in Table 1.
Claims (7)
前記共吸着剤は、
一般式（１）：
Ｒ１−ＣＨ（ＣＯＯＨ）２ （１）
［式中、Ｒ１はフェニル基、ベンジル基、ナフチル基、ターシャリーブチル基又は炭素数３〜７の環状アルキル基である。］
で示される化合物、
一般式（２）：
Ｒ２−ＣＯＯＨ （２）
［式中、Ｒ２はフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３〜５若しくは７の環状アルキル基である。］
で示される化合物、
一般式（３）：
Ｒ３−ＣＨ２ＣＯＯＨ （３）
［式中、Ｒ３はナフチル基、ターシャリーブチル基、又は炭素数３〜７の環状アルキル基である。］
で示される化合物、及び
一般式（４）：
Ｒ４−ＣＨ２ＣＨ２ＣＯＯＨ （４）
［式中、Ｒ４は炭素数３〜７の環状アルキル基である。］
で示される化合物
よりなる群から選ばれる少なくとも１種を含有する、光電変換素子用光電極。 A photoelectric conversion element photoelectrode comprising a semiconductor metal oxide film in which a coadsorbent and a dye are adsorbed,
The co-adsorbent is
General formula (1):
R 1 —CH (COOH) 2 (1)
[Wherein, R 1 represents a phenyl group, a benzyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
A compound represented by
General formula (2):
R 2 —COOH (2)
[Wherein, R 2 represents a phenyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 5 or 7 carbon atoms. ]
A compound represented by
General formula (3):
R 3 —CH 2 COOH (3)
[Wherein, R 3 represents a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
And a compound represented by the general formula (4):
R 4 —CH 2 CH 2 COOH (4)
[Wherein R 4 is a cyclic alkyl group having 3 to 7 carbon atoms. ]
The photoelectrode for photoelectric conversion elements containing at least 1 sort (s) chosen from the group which consists of a compound shown by these.
（Ａ２）半導体金属酸化物膜に色素を含む溶液を塗布及び乾燥した後、前記処理を施した半導体金属酸化物膜に共吸着剤を含む溶液を塗布及び乾燥する工程、
（Ａ３）半導体金属酸化物膜に、共吸着剤及び色素を含む溶液を塗布及び乾燥する工程、
（Ｂ１）共吸着剤を含む溶液に半導体金属酸化物膜を浸漬した後、色素を含む溶液に前記処理を施した半導体金属酸化物膜を浸漬する工程、
（Ｂ２）色素を含む溶液に半導体金属酸化物膜を浸漬した後、共吸着剤を含む溶液に前記処理を施した半導体金属酸化物膜を浸漬する工程、又は
（Ｂ３）共吸着剤及び色素を含む溶液に、半導体金属酸化物を浸漬する工程
を備え、且つ、前記共吸着剤は、一般式（１）：
Ｒ１−ＣＨ（ＣＯＯＨ）２ （１）
［式中、Ｒ１はフェニル基、ベンジル基、ナフチル基、ターシャリーブチル基又は炭素数３〜７の環状アルキル基である。］
で示される化合物、
一般式（２）：
Ｒ２−ＣＯＯＨ （２）
［式中、Ｒ２はフェニル基、ナフチル基、ターシャリーブチル基、又は炭素数３〜５若しくは７の環状アルキル基である。］
で示される化合物、
一般式（３）：
Ｒ３−ＣＨ２ＣＯＯＨ （３）
［式中、Ｒ３はナフチル基、ターシャリーブチル基、又は炭素数３〜７の環状アルキル基である。］
で示される化合物、及び
一般式（４）：
Ｒ４−ＣＨ２ＣＨ２ＣＯＯＨ （４）
［式中、Ｒ４は炭素数３〜７の環状アルキル基である。］
で示される化合物
よりなる群から選ばれる少なくとも１種を含有する、光電変換素子用光電極の製造方法。 (A1) A step of applying and drying a solution containing a co-adsorbent on a semiconductor metal oxide film, and then applying and drying a solution containing a dye on the semiconductor metal oxide film subjected to the treatment.
(A2) applying and drying a solution containing a co-adsorbent on the semiconductor metal oxide film subjected to the treatment after applying and drying the solution containing the dye on the semiconductor metal oxide film;
(A3) A step of applying and drying a solution containing a coadsorbent and a dye on the semiconductor metal oxide film,
(B1) a step of immersing the semiconductor metal oxide film subjected to the treatment in a solution containing a dye after immersing the semiconductor metal oxide film in a solution containing the coadsorbent;
(B2) a step of immersing the semiconductor metal oxide film in the solution containing the co-adsorbent after immersing the semiconductor metal oxide film in the solution containing the dye, or (B3) adding the co-adsorbent and the dye A step of immersing a semiconductor metal oxide in a solution containing the coadsorbent, wherein the coadsorbent is represented by the general formula (1):
R 1 —CH (COOH) 2 (1)
[Wherein, R 1 represents a phenyl group, a benzyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
A compound represented by
General formula (2):
R 2 —COOH (2)
[Wherein, R 2 represents a phenyl group, a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 5 or 7 carbon atoms. ]
A compound represented by
General formula (3):
R 3 —CH 2 COOH (3)
[Wherein, R 3 represents a naphthyl group, a tertiary butyl group, or a cyclic alkyl group having 3 to 7 carbon atoms. ]
And a compound represented by the general formula (4):
R 4 —CH 2 CH 2 COOH (4)
[Wherein R 4 is a cyclic alkyl group having 3 to 7 carbon atoms. ]
The manufacturing method of the photoelectrode for photoelectric conversion elements containing at least 1 sort (s) chosen from the group which consists of a compound shown by these.
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