CN102160233A - 染料敏化的光电转换器件 - Google Patents
染料敏化的光电转换器件 Download PDFInfo
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- CN102160233A CN102160233A CN2009801328487A CN200980132848A CN102160233A CN 102160233 A CN102160233 A CN 102160233A CN 2009801328487 A CN2009801328487 A CN 2009801328487A CN 200980132848 A CN200980132848 A CN 200980132848A CN 102160233 A CN102160233 A CN 102160233A
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- electrooptical device
- expression
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- 239000004065 semiconductor Substances 0.000 claims abstract description 61
- 239000000434 metal complex dye Substances 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 52
- -1 metal complex compound Chemical class 0.000 claims description 44
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 239000000975 dye Substances 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004425 isosulfocyanate group Chemical group 0.000 claims description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 abstract description 8
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 abstract 1
- 239000010408 film Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 37
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 26
- 239000010419 fine particle Substances 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000002585 base Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 206010070834 Sensitisation Diseases 0.000 description 10
- 125000003368 amide group Chemical group 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 10
- 230000008313 sensitization Effects 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
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- 238000003786 synthesis reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
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- 239000002253 acid Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical class CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical group 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000005129 aryl carbonyl group Chemical group 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 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 3
- 229960001091 chenodeoxycholic acid Drugs 0.000 description 3
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- 125000001309 chloro group Chemical group Cl* 0.000 description 3
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- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- GRHBQAYDJPGGLF-UHFFFAOYSA-N isothiocyanic acid Chemical compound N=C=S GRHBQAYDJPGGLF-UHFFFAOYSA-N 0.000 description 3
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- 150000003053 piperidines Chemical class 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
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- 239000011701 zinc Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
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- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical class OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 2
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
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- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- MIMSKFFWJBGRNG-UHFFFAOYSA-N naphthalene;1h-pyrrole Chemical class C=1C=CNC=1.C1=CC=CC2=CC=CC=C21 MIMSKFFWJBGRNG-UHFFFAOYSA-N 0.000 description 1
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QCYXGORGJYUYMT-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QCYXGORGJYUYMT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Chemical group 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical class [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- XCXHVVWAGKXDTH-UHFFFAOYSA-N pyridin-1-ium;iodate Chemical compound [O-]I(=O)=O.C1=CC=[NH+]C=C1 XCXHVVWAGKXDTH-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].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 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl 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])C([H])([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
- 150000003431 steroids Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical class [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- DTIFFPXSSXFQCJ-UHFFFAOYSA-N tetrahexylazanium Chemical compound CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC DTIFFPXSSXFQCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 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
- OHOVBSAWJQSRDD-UHFFFAOYSA-N thiophen-2-yloxyboronic acid Chemical compound OB(O)OC1=CC=CS1 OHOVBSAWJQSRDD-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 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
- 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
- 229930195735 unsaturated hydrocarbon Natural products 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Abstract
本发明公开了一种染料敏化的光电转换器件,其中在布置于衬底上的氧化物半导体微粒的薄膜上负载有由下式(1)表示的金属络合物染料或其盐(在式(1)中,m1表示1~2的整数,n1表示1~3的整数。X1表示氧原子或硫原子。Y1和Y2各自独立地表示硫氰酸根基团(-SCN)或异硫氰酸根基团(-NCS)。M1和M2表示氢原子。R1和R2表示氢原子。R3和R4各自独立地表示具有1~6个碳原子的直链烷基。而且,当m1为2从而存在多个各个R3和R4时,各个R3和R4可以相互相同或不同)。
Description
技术领域
本发明涉及光电转换器件和使用所述光电转换器件的太阳能电池,所述光电转换器件具有利用金属络合物染料或其盐敏化的半导体细粒的薄膜,更具体地,本发明涉及光电转换器件和使用所述光电转换器件的太阳能电池,在所述光电转换器件中在氧化物半导体细粒的薄膜上负载具有特定结构的金属络合物化合物(金属络合物染料)。
背景技术
利用太阳光的太阳能电池作为代替化石燃料如石油和煤的能源而引起了人们的关注。目前,正在积极地开发和研究使用晶体或无定形硅的硅太阳能电池,使用镓、砷等的化合物半导体太阳能电池等。然而,它们的问题在于,由于其制造所需要的能量和成本高而难以广泛使用。使用利用染料敏化的半导体细粒的光电转换器件、或使用所述光电转换器件的太阳能电池也是已知的,且公开了用于制造其的材料和制造技术(参见专利文献1、非专利文献1、非专利文献2)。通过使用相对廉价的氧化物半导体如二氧化钛可制造这种光电转换器件。因此,这种光电转换器件引起关注的原因在于,与使用硅等的常规太阳能电池相比可获得更低成本的光电转换器件,并且能够获得彩色的太阳能电池等。然而,仍存在转换效率比硅太阳能电池低的问题,于是期望进一步提高转换效率(参见专利文献1)。
现有技术文献
专利文献
专利文献1:日本特许第2664194号公报
专利文献2:WO 2002/011213
非专利文献
非专利文献1:B.O’Regan等人,Nature,第353卷,737页(1991)
非专利文献2:M.K.Nazeeruddin等人,J,Am.Chem.Soc,第115卷,6382页(1993)
非专利文献3:W,Kubo等人,Chem.Lett.,1241页(1998)
非专利文献4:Marko Hapke等人,Synthesis No.17,2711-2719页(2007)
发明内容
本发明要解决的问题
在使用利用金属络合物染料敏化的氧化物半导体细粒的光电转换器件中,需要开发一种具有高转换效率和高实用性的稳定的光电转换器件。
解决问题的手段
本发明人进行了锐意努力以解决上述问题,结果,发现通过使用具有特定结构的次甲基染料对半导体细粒的薄膜进行敏化并制造光电转换器件能够解决上述问题,且完成了本发明。
即,本发明为:
(1)一种光电转换器件,其中在布置于衬底上的氧化物半导体细粒的薄膜上负载有由下式(1)表示的金属络合物染料或其盐:
其中m1表示1~2的整数,n1表示1~3的整数;X1表示氧原子或硫原子;Y1和Y2各自独立地表示硫氰酸根基团(-SCN)或异硫氰酸根基团(-NCS);M1和M2表示氢原子;R1和R2表示氢原子;R3和R4各自独立地表示1~6个碳原子的直链烷基;另外当m1为2、R3和R4各自存在多个时,各个R3和R4可以相互相同或不同;
(2)如(1)中所述的光电转换器件,其中式(1)中的X1为硫原子;
(3)如(2)中所述的光电转换器件,其中式(1)中的n1为1;
(4)如(3)中所述的光电转换器件,其中式(1)中的Y1和Y2各自为异硫氰酸根基团(-NCS);
(5)如(4)中所述的光电转换器件,其中式(1)中的R3和R4各自独立地为3~5个碳原子的直链烷基;
(6)如(5)中所述的光电转换器件,其中式(1)中的R3和R4各自为正丁基;
(7)如(6)中所述的光电转换器件,其中式(1)中的m1为2;
(8)如(6)中所述的光电转换器件,其中式(1)中的m1为1;
(9)一种光电转换器件,其中在布置于衬底上的氧化物半导体细粒的薄膜上负载有由(1)中所述式(1)表示的金属络合物染料或其盐的一种以上、以及次甲基染料和/或具有不同于式(1)的结构的金属络合物染料;
(10)如(1)~(9)中任一项所述的光电转换器件,其中所述薄膜包含二氧化钛、氧化锌或氧化锡。
(11)如(1)~(10)中任一项所述的光电转换器件,其中在包合化合物的存在下负载金属络合物染料或其盐;
(12)一种使用(1)~(11)中任一项所述的光电转换器件的太阳能电池;
(13)一种由(1)中所述的式(1)表示的金属络合物染料或其盐;以及
(14)一种光电转换器件,其中在布置于衬底上的氧化物半导体细粒的薄膜上负载有由下式(1)表示的金属络合物染料或其盐:
其中m1表示1~2的整数,n1表示1~3的整数;X1表示氧原子、硫原子、硒原子或=NR5,其中R5表示氢原子或可具有取代基的脂族烃残基;Y1和Y2各自独立地表示硫氰酸根基团(-SCN)、卤素原子或异硫氰酸根基团(-NCS);且Y1和Y2可结合在一起而形成一个配体;M1和M2各自独立地表示氢原子或铵离子;R1和R2各自独立地表示氢原子、可具有取代基的脂族烃残基、或可具有取代基的烷氧基;且当n1为2以上、或当m1为2从而R1和R2各自存在多个时,各个R1和R2可以相互相同或不同;且多个R1和/或R2可形成环,且在这种环上还可具有取代基;R3和R4各自独立地表示氢原子、可具有取代基的脂族烃残基、或可具有取代基的芳族烃残基;当m1为2、R3和R4各自存在多个时,各个R3和R4可以相互相同或不同;且R3和R4可以相互结合而形成可具有取代基的环;芳环a、芳环b、芳环c、芳环d和芳环e各自可具有1~3个取代基;且芳环f可具有1~4个取代基。
发明效果
通过使用具有特定结构的本发明的金属络合物染料或其盐,能够提供具有高转换效率和高稳定性的光电转换器件、以及太阳能电池。本发明的金属络合物染料或其盐的特征在于,即使其上要负载染料的氧化物半导体细粒的膜薄,也能够获得足够的转换效率。
具体实施方式
下面将对本发明进行详细说明。
本发明的光电转换器件为在布置于衬底上的氧化物半导体细粒的薄膜上负载有由下式(1)表示的金属络合物染料(包括其盐;下文中相同)的光电转换器件。在本说明书中,除非有其它说明,否则“化合物”表示化合物或其盐。
在式(1)中,m1表示1~2的整数,n1表示1~3的整数、优选1。
在式(1)中,X1表示氧原子、硫原子、硒原子或=NR5,优选氧原子、硫原子或硒原子,更优选氧原子或硫原子,特别优选硫原子。此处,R5表示氢原子或可具有取代基的脂族烃残基。
上述中的“脂族烃残基”的实例包括可具有取代基的饱和或不饱和的直链、支化或环状烷基。优选的脂族烃残基的实例包括可具有取代基的1~36个碳原子的饱和或不饱和的直链或支化烷基,且更优选的脂族烃残基的实例包括可具有取代基的1~18个碳原子的饱和或不饱和的直链或支化烷基。可具有取代基的环烷基的实例包括3~8个碳原子的环烷基。其具体实例分别包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、辛基、十八烷基、异丙基、环己基、乙烯基、丙烯基、戊烯基、丁烯基、己烯基、己二烯基、异丙烯基、异己烯基、环己烯基、环戊二烯基、乙炔基、丙炔基、戊炔基、己炔基、异己炔基和环己炔基。它们可具有如上所述的取代基。
取代基的实例包括可具有取代基的芳族残基、可具有取代基的脂族烃残基、羟基、磷酸基、氰基、硝基、卤素原子、羧基、碳酰胺基、烷氧基羰基、芳基羰基、烷氧基、芳氧基、取代的酰胺基、酰基、以及取代或未取代的氨基。
上述中的“芳族残基”是指通过从芳环上除去一个氢原子而得到的基团。所述芳环的具体实例包括芳族烃环如苯、萘、蒽、菲、芘、二萘嵌苯和涤纶;杂芳环如茚、薁、吡啶、吡嗪、嘧啶、吡唑、吡唑烷、噻唑烷、唑烷、吡喃、苯并吡喃、吡咯、吡咯烷、苯并咪唑、咪唑啉、咪唑烷、咪唑、吡唑、三唑、三嗪、二唑、二氢吲哚、噻吩、噻吩并噻吩、呋喃、唑、二唑、噻嗪、噻唑、吲哚、苯并噻唑、苯并噻二唑、萘噻唑、苯并唑、萘唑、假吲哚、苯并假吲哚、吡嗪、喹啉和喹唑啉;以及稠合芳环如芴和咔唑。优选的是具有5~16个碳原子的芳环(芳环以及包含芳环的稠环)的芳族残基。
上述中的“脂族烃残基”可以与X1项中所述的那些相同。
上述中“卤素原子”的实例包括氟原子、氯原子、溴和碘原子。“卤素原子”优选为氟原子或氯原子,更优选氯原子。
上述中“烷氧基羰基”的实例包括1~10个碳原子的烷氧基羰基。“烷氧基羰基”的具体实例包括甲氧基羰基、乙氧基羰基、正丙氧基羰基、异丙氧基羰基、正丁氧基羰基、异丁氧基羰基、仲丁氧基羰基、叔丁氧基羰基、正戊氧基羰基、正己氧基羰基、正庚氧基羰基、正壬氧基羰基和正癸氧基羰基。
上述中“芳基羰基”的实例包括其中芳基如二苯甲酮和二萘甲酮与羰基连接在一起的基团。
烷氧基的实例包括甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基。它们可还具有取代基。
上述中“芳氧基”的实例包括苯氧基和萘氧基,其可具有苯基和甲基作为取代基。
上述中“取代的酰胺基”的具体实例包括如酰胺基、乙酰胺基、N-甲基酰胺基、N-乙基酰胺基、N-(正丙基)酰胺基、N-(正丁基)酰胺基、N-异丁基酰胺基、N-(仲丁基酰胺)基、N-(叔丁基)酰胺基、N,N-二甲基酰胺基、N,N-二乙基酰胺基、N,N-二(正丙基)酰胺基、N,N-二(正丁基)酰胺基、N,N-二异丁基酰胺基、N-甲基乙酰胺基、N-乙基乙酰胺基、N-(正丙基)乙酰胺基、N-(正丁基)乙酰胺基、N-异丁基乙酰胺基、N-(仲丁基)乙酰胺基、N-(叔丁基)乙酰胺基、N,N-二甲基乙酰胺基、N,N-二乙基乙酰胺基、N,N-二(正丙基)乙酰胺基、N,N-二(正丁基)乙酰胺基和N,N-二异丁基乙酰胺基等的酰胺基,乙酰胺基和烷基酰胺基;或芳基酰胺基如苯基酰胺基、萘基酰胺基、苯基乙酰胺基和萘基乙酰胺基。
上述中“酰基”的实例包括1~10个碳原子的烷基羰基、和芳基羰基。“酰基”优选为1~4个碳原子的烷基羰基,且“酰基”的具体实例包括乙酰基、丙酰基、三氟甲基羰基、五氟乙基羰基、苯甲酰基和萘甲酰基。
上述中“取代或未取代的氨基”的实例包括氨基;烷基取代的氨基如单或二甲基氨基、单或二乙基氨基、单或二(正丙基)氨基、单或二(正丁基)氨基和单或二(正己基)氨基;芳族取代的氨基如单或二苯基氨基和单或二萘基氨基;利用一个烷基和一个芳族烃残基取代的氨基或苯甲基氨基如单烷基单苯基氨基;以及乙酰基氨基和苯基乙酰基氨基。
在式(1)中,Y1和Y2各自独立地表示硫氰酸根基(-SCN)、卤素原子或异硫氰酸根基(-NCS),优选硫氰酸根基(-SCN)或异硫氰酸根基(-NCS),更优选异硫氰酸根基(-NCS)。此外,可将Y1和Y2结合在一起而形成一个配体。所述“卤素原子”可以与X1项中所述的那些相同。
在式(1)中,M1和M2各自独立地表示氢原子或铵离子,优选氢原子。铵离子的实例包括烷基铵离子如四甲基铵离子、四丁基铵离子和四己基铵离子;以及环状铵离子如1,3-二甲基咪唑离子、1,1-二正丁基吡咯离子、哌啶离子和哌嗪离子。
在式(1)中,R1和R2各自独立地表示氢原子、可具有取代基的脂族烃残基或可具有取代基的烷氧基;且当n1为2以上、或者m1为2从而R1和R2各自存在多个时,则各个R1和R2可以相互相同或不同;且多个R1和/或R2可形成环,且在这种环上还可具有取代基。R1和R2的优选实例包括氢原子或可具有取代基的脂族烃残基。R1和R2更优选为氢原子。“可具有取代基的脂族烃残基”和“烷氧基”可与上述X1项中所述的那些相同。
在式(1)中,R3和R4各自独立地表示氢原子、可具有取代基的脂族烃残基或可具有取代基的芳族烃残基,优选可具有取代基的脂族烃残基,更优选可具有取代基的饱和烷基,进一步优选1~6个碳原子的直链烷基,特别优选3~5个碳原子的直链烷基,最优选正丁基。当m1为2、R3和R4各自存在多个时,各个R3和R4可以相互相同或不同;且可将R3和R4相互结合在一起而形成可具有取代基的环。通过将R3和R4结合在一起而形成的环的实例包括可具有取代基的脂族烃环、和可具有取代基的杂环。“可具有取代基的脂族烃残基”和“可具有取代基的芳族烃残基”可以与X1项中所述的那些相同。
对于式(1)中的R1、R2、R3和R4,考虑在氧化物半导体细粒上负载有染料时对所用溶剂的溶解度、对分子间聚集的抑制效果等来适当选择。
上述“脂族烃环”的实例包括饱和烃环如环丁烷环、环戊烷环、环己烷环和环庚烷环;以及不饱和烃环如环丁烯环、环戊烯环和环己烯环,其可还具有取代基。
在式(1)中,分别地,芳环a、芳环b和芳环e可还具有与式(1)中明确描述的取代基不同的1~3个取代基,芳环f可还具有与式(1)中明确描述的取代基不同的1~4个取代基。当式(1)中的m1为1时,则分别地,芳环c或芳环d中的任意一个可还具有与式(1)中明确描述的取代基不同的1~3个取代基,其它芳环可还具有与式(1)中明确描述的取代基不同的1~4个取代基。当m1为2时,芳环c和芳环d可分别还具有与式(1)中明确描述的取代基不同的1~3个取代基。芳环a、b、c、d和e与芳环f还可具有的所述取代基可以与X1项中所述的那些相同。
在由式(1)表示的金属络合物染料中,优选由下式(2)或式(3)表示的金属络合物染料。
式(2)和式(3)中的Y1、Y2、R3和R4可分别与式(1)中的Y1、Y2、R3和R4相同。芳环a至芳环f可具有式(1)的说明中所述的取代基。
当由式(1)中表示的金属络合物染料具有酸性基团如羧基、磷酸基、羟基和磺酸基作为取代基时,它们可分别形成盐。所述盐的实例包括与碱金属或碱土金属等如锂、钠、钾、镁和钙的盐;或与有机碱如季铵如四甲基铵、四丁基铵、吡啶咪唑哌嗪和哌啶的盐。优选四丁基铵盐和哌啶盐。
由式(1)表示的金属络合物染料可以为结构异构体如顺式异构体、反式异构体和其混合物、光学活性物质和外消旋物,但未特别限制于任意一种异构体,且能够良好地用作本发明中的光敏染料。
通过例如下面所示的反应图式,能够制造由式(1)表示的金属络合物染料。即,通过烷基化试剂等将由下式(4)表示的溴芴体转化成式(5)的取代体,再然后利用与硼酸体(6)的偶联反应,能够获得式(7)的化合物。通过NBS(N-溴代琥珀酰亚胺)对式(7)的化合物进行溴代而得到式(8)的化合物。通过将式(8)的这种化合物与吡啶衍生物(9)和(10)反应能够得到由式(11)和(12)表示的化合物。根据非专利文献4中所述的方法,能够将式(11)的化合物与式(12)的化合物缩合而得到式(13)的化合物。将式(13)的化合物与钌-对甲基异丙基苯二聚体(14)反应而获得式(15)的化合物,而且,将式(15)的化合物与由式(16)表示的联吡啶体和式(17)的硫氰酸铵反应而得到由式(1)表示的金属络合物染料。
在下述中,由下式(18)例示了由式(1)表示的金属络合物染料的优选具体实例。将式(18)中的取代基等的优选组合示于表1~2中。
表1
表2
下面显示了其它具体实例。
本发明的染料敏化的光电转换器件为例如通过使用氧化物半导体细粒在衬底上布置氧化物半导体细粒的薄膜并然后在这种薄膜上负载式(1)的金属络合物染料的器件。
在本发明中,优选将具有导电表面的衬底作为在其上布置氧化物半导体细粒的薄膜的衬底。这种衬底易于商购获得。具体地,例如,能够使用通过在玻璃表面上或透明聚合物材料如聚对苯二甲酸乙二醇酯或聚醚砜的表面上布置导电金属氧化物如掺杂铟、氟或锑的氧化锡的薄膜或者铜、银或金的金属薄膜而形成的衬底。电导率通常可以为1000Ω以下,特别优选100Ω以下。优选将金属氧化物作为氧化物半导体的细粒。金属氧化物的实例包括钛、锡、锌、钨、锆、镓、铟、钇、铌、钽和钒等的氧化物。其中,优选钛、锡、锌、铌、铟等的氧化物,更优选二氧化钛、氧化锌和氧化锡。这些氧化物半导体可以单独使用,但也可以以混合物的形式使用或通过被涂布在半导体的表面上使用。作为平均粒径,所述氧化物半导体细粒的粒径通常为1~500nm,优选1~100nm。通过将大粒径的粒子和小粒径的粒子混合,或以多层的形式,能够使用这种氧化物半导体细粒。
通过喷雾等直接在衬底上涂布氧化物半导体细粒的方法,在作为电极的衬底上以薄膜形式电沉积半导体细粒的方法,将半导体细粒的浆体、或含有通过对半导体细粒的前体如半导体醇盐进行水解而得到的细粒的糊料涂布在衬底上然后进行干燥、硬化或煅烧的方法等,能够在衬底上形成氧化物半导体细粒的薄膜。考虑到使用氧化物半导体的电极的性能,优选使用浆体的方法。在这种方法中,通过以平均初始粒径为1~200nm的方式将二次凝结的氧化物半导体细粒常规地分散在分散介质中,能够得到所述浆体。
其中分散浆体的分散介质没有特别限制,只要其能够将半导体细粒分散在其中即可。可使用水、醇如乙醇、酮如丙酮和乙酰丙酮、烃如己烷等。可以以混合物的形式使用它们,且优选使用水,因为会降低浆体的粘度变化。为了稳定氧化物半导体细粒的分散状况,可以使用分散稳定剂。能够使用的分散稳定剂的实例包括酸如乙酸、盐酸和硝酸,或有机溶剂如乙酰丙酮、丙烯酸、聚乙二醇和聚乙烯醇。
可以对在其上可以涂布浆体的衬底进行煅烧,煅烧温度通常为100℃以上,优选200℃以上,且上限约为衬底的熔点(软化点)以下,通常上限为900℃,优选600℃以下。煅烧时间没有特别限制,但优选大约在4小时以内。在衬底上氧化物半导体细粒薄膜的厚度通常为1~200μm,优选1~50um。
可以对氧化物半导体细粒的薄膜进行二次处理。例如,可以将在其上布置了氧化物半导体细粒薄膜的整个衬底直接浸入与半导体相同的金属的醇盐、金属酰基化物、氯化物、氮化物、硫化物等的溶液中,接着进行干燥或再煅烧以提高半导体细粒薄膜的性能。金属醇盐的实例包括乙醇钛、异丙醇钛和叔丁醇钛,所述金属酰基化物的实例包括正二丁基-二乙酰基锡。当使用它们时,通常使用它们的醇溶液。氯化物的实例包括四氯化钛、四氯化锡和氯化锌。当使用它们时,通常使用它们的水溶液。
由此得到的氧化物半导体薄膜由氧化物半导体的细粒构成。
然后,下面将对在氧化物半导体细粒薄膜上负载由本发明式(1)表示的金属络合物染料的方法进行描述。
作为负载式(1)的金属络合物染料的方法,能够提及在通过将金属络合物染料溶于能够溶解金属络合物染料的溶剂中而得到的溶液中,或者在低溶性金属络合物染料的情况下、通过将金属络合物染料分散在其中而获得的分散液中,将在其上布置了氧化物半导体细粒的薄膜的衬底进行浸渍的方法。浸渍温度大约为从室温至溶剂的沸点,且浸渍时间为约1分钟至48小时。能够用于溶解金属络合物染料的溶剂的具体实例包括甲醇、乙醇、乙腈、二甲亚砜、二甲基甲酰胺、丙酮和叔丁醇。可通过将这些溶剂中的两种以上以任选比率进行混合来使用。当式(1)的金属络合物染料在这些溶剂中不能显示足够的溶解度时,可以添加铵盐如四丁基碘化铵以促进染料的溶解。可根据金属络合物染料来合适地确定金属络合物染料在溶液或分散液中的浓度,但通常所述浓度为1×10-6M~1M,优选1×10-5M~1×10-1M。以这种方法,能够获得具有利用式(1)的金属络合物染料敏化的氧化物半导体细粒薄膜的本发明光电转换器件。
待负载的式(1)的金属络合物染料可以为一种物质或几种的混合物。当其为混合物时,可通过将本发明式(1)的一种金属络合物染料与本发明式(1)的另一种金属络合物染料进行混合而得到所述混合物,或者可以将其它金属络合物染料或有机染料混合。特别地,具有不同吸收波长的金属络合物染料的混合物能够利用宽范围的吸收波长,从而制造高转换效率的太阳能电池。作为能够与由本发明式(1)表示的金属络合物染料进行混合的金属络合物染料,无特殊限制,优选在非专利文献2中所示的钌络合物及其季盐、酞菁、卟啉等。用于混合物中的有机染料的实例包括染料如不含金属的酞菁、卟啉和花青、部花青、oxonol、三苯基甲烷型、次甲基染料如非专利文献2中所示的丙烯酸染料、呫吨型、唑型、蒽醌型和二萘嵌苯型。优选地,包括钌络合物、部花青或次甲基染料如丙烯酸染料等。当使用两种以上染料时,可以在半导体细粒的薄膜上顺序吸附这些染料或在将其混合和溶解之后进行吸附。
这些染料的混合比没有特别限制,且可根据各种染料适当选择最佳条件,优选从等摩尔比至每一种染料至少不少于约10mol%。当使用溶解或分散了两种以上染料的溶液在氧化物半导体细粒的膜上对染料进行吸附时,溶液中染料的总浓度可以与仅负载有一种时的类似。作为用于混合物中的染料的溶剂,可以使用如上所述的这种溶剂且用于各种染料的溶剂可以相同或不同。
当在氧化物半导体细粒的薄膜上负载金属络合物染料时,为了防止金属络合物染料自身发生聚集,可在包合化合物的存在下有效地负载金属络合物染料。在这种情况下,包合化合物的实例包括甾族型化合物如胆酸、冠醚、环糊精、杯芳烃和聚环氧乙烷,优选包括胆酸衍生物如脱氧胆酸、脱氢脱氧胆酸、鹅脱氧胆酸、胆酸甲酯和胆酸钠盐;聚环氧乙烷等。在负载金属络合物染料之后,可利用胺化合物如4-叔丁基吡啶(TBP)对半导体细粒的薄膜进行处理。处理方法包括例如将利用负载有金属络合物染料的半导体细粒薄膜形成的衬底浸在胺的乙醇溶液中的方法。
本发明的太阳能电池由光电转换器件的电极、对电极、氧化还原电解质或空穴输送材料或p型半导体等构成,在所述光电转换器件中在上述氧化物半导体细粒的薄膜上负载有金属络合物染料。氧化还原电解质、空穴输送材料、p型半导体等的形态包括液体、凝固体(凝胶或凝胶状物质)、固体等。液体状形态包括氧化还原电解质、熔融盐、空穴输送材料、p型半导体等在溶剂中的溶液;在常温下的熔融盐等。凝固体的形态(凝胶或凝胶状物质)包括在聚合物基质或低分子量胶凝剂等中含有这些的那些形态。作为固体形态,可以使用氧化还原电解质、熔融盐、空穴输送材料、p型半导体等。空穴输送材料包括胺类衍生物;导电聚合物如聚乙炔、聚苯胺和聚噻吩;和用于盘状液晶的那些物质如苯并[9,10]菲型化合物。所述p型半导体包括CuI、CuSCN等。
作为对电极,优选具有导电性并可催化氧化还原电解质的还原反应的这种对电极。可以使用在玻璃或聚合物膜上气相沉积铂、碳、铑、钌等或施加导电细粒而得到的物质。
用于本发明太阳能电池的氧化还原电解质包括包含卤素化合物和卤素分子的卤素氧化还原型电解质,所述卤素化合物具有卤素离子作为反离子;金属络合物等如氰亚铁酸盐-氰铁酸盐或二茂铁-二茂铁离子和钴络合物的金属氧化还原型电解质;有机氧化还原型电解质如烷基硫醇-烷基二硫化物、紫精(viologen)染料、氢醌-醌,优选为卤素氧化还原型电解质。在包含卤素化合物和卤素分子的卤素氧化还原型电解质中,卤素分子的实例包括诸如碘分子和溴分子,且优选碘分子。具有卤素离子作为反离子的卤素化合物的实例包括金属卤化物如LiBr、NaBr、KBr、LiI、NaI、KI、CsI、CaI2、MgI2、CuI的盐;或有机季铵盐如四烷基碘化铵、碘化咪唑和碘化吡啶优选具有碘离子作为反离子的盐。除了上述碘离子之外,还优选使用具有酰亚胺离子如二(三氟甲烷磺酰基)酰亚胺离子和二氰基酰亚胺离子作为反离子的电解质。
当氧化还原电解质采用含有其的溶液形式时,使用电化学惰性的溶剂。所述溶剂包括例如乙腈、碳酸亚丙酯、碳酸亚乙酯、3-甲氧基丙腈、甲氧基乙腈、乙二醇、丙二醇、二乙二醇、三乙二醇、γ-丁内酯、二甲氧基乙烷、碳酸二乙酯、二乙醚、碳酸二乙酯、碳酸二甲酯、1,2-二甲氧基乙烷、二甲基甲酰胺、二甲亚砜、1,3-二烷、甲酸甲酯、2-甲基四氢呋喃、3-甲基-唑烷-2-酮、环丁砜、四氢呋喃和水,其中,特别优选乙腈、碳酸亚丙酯、碳酸亚乙酯、3-甲氧基丙腈、甲氧基乙腈、乙二醇、3-甲基-唑烷-2-酮和γ-丁内酯。这些溶剂可单独使用或以其两种以上组合的方式使用。所述凝胶状电解质包括基质如含有电解质或电解质溶液的低聚物和聚合物;在非专利文献3中所述的低分子量胶凝剂等,类似于含有电解质或电解质溶液;等等。所述氧化还原电解质的浓度通常为0.01~99质量%,优选0.1~90质量%。
通过在光电转换器件的电极上放置对电极以将薄膜夹在对电极和电极之间,并利用含有氧化还原电解质等的溶液对其间的空间进行填充,能够制备本发明的太阳能电池,所述光电转换器件在衬底上的氧化物半导体细粒的薄膜上负载有本发明式(1)的金属络合物染料。
实施例
参考下列实施例对本发明进行更详细地说明,但不应将本发明的范围限制于此。在实施例中,除非有其它说明,否则“份”是指“质量份”。
分别通过使用分光光度计UV-3150(源自岛津制作所株式会社(Shimadzu Corporation))、Gemini 300(源自瓦里安公司(Varian Inc.))和高效液相色谱-质谱仪LCMS-2010EV(源自岛津制作所株式会社)来进行吸附、核磁共振分析和质量分析。
合成例1
在氮气气氛下,向通过将20.8份叔丁醇钾溶于102份二甲亚砜(DMSO)中而得到的溶液中滴加通过将15.4份2-溴芴溶于153份二甲亚砜(DMSO)中而得到的溶液。在搅拌30分钟之后,在将反应溶液温度保持为40~45℃的同时,滴加27.8份碘代丁烷。在40℃下搅拌40分钟之后,将反应溶液添加至冰水中。利用氯仿-水对反应混合物进行萃取,并以硫酸镁对氯仿相进行干燥,然后将氯仿蒸出而得到褐色焦油状固体。将这种褐色焦油状固体溶于少量氯仿中,并通过柱色谱法(己烷)进行分离和提纯,从而得到12.6份2-溴-9,9-二丁基芴,其为无色晶体。
合成例2
在将2.7份2-噻吩硼酸和6份2-溴-9,9-二丁基芴溶于78份1,2-二甲氧基乙烷中之后,添加0.59份四(三苯基膦)钯(O)和47份20%的碳酸钠水溶液,并在回流下将混合物反应5小时。利用甲苯对反应混合物进行萃取,并以硫酸镁对甲苯相进行干燥,然后将甲苯蒸出而得到褐色焦油状混合物。通过柱色谱法(己烷-乙酸乙酯)对所得褐色焦油状混合物进行分离和提纯,从而得到5.9份下列化合物(1001),其为无色晶体。
合成例3
在将5.9份上述化合物(1001)溶于635份氯仿与乙酸1∶1的混合溶液中之后,添加1.9份N-溴代琥珀酰亚胺,并在回流下将混合物反应1小时。在进一步添加0.94份N-溴代琥珀酰亚胺之后,使混合物在回流下反应1小时。利用5%的碳酸氢钠水溶液-氯仿对反应混合物进行萃取,并以硫酸镁对氯仿相进行干燥,然后将氯仿蒸出。通过柱色谱法(己烷-乙酸乙酯)对所得混合物进行分离和提纯,从而得到6.8份下列化合物(1002),其为无色晶体。
合成例4
在将5.0份上述化合物(1002)和2.2份2-氯-4-吡啶硼酸溶于40份1,2-二甲氧基乙烷中之后,添加0.38份四(三苯基膦)钯(O)和25份20%的碳酸钠水溶液,并在回流下将混合物反应5小时。利用氯仿对反应混合物进行萃取,并以硫酸镁对氯仿相进行干燥,然后将氯仿蒸出。通过柱色谱法(氯仿)对所得混合物进行分离和提纯,从而得到5.0份下列化合物(1003),其为淡黄色固体。
合成例5
在氮气气氛下,将1.6份二溴二(三苯基膦)镍(II)、1.2份锌粉、0.78份氯化锂和2.7份四乙基碘化铵添加至39份四氢呋喃中,并对混合物进行搅拌。滴加通过将5.0份上述化合物(1003)溶于20份四氢呋喃中而得到的溶液,并在回流下将混合物反应20小时。在将反应溶液冷却至室温之后,添加44份30%的氨水、32份水、178份二氯甲烷,并将混合物搅拌15分钟。利用二氯甲烷对反应混合物进行萃取,并以硫酸镁对二氯甲烷相进行干燥,然后将二氯甲烷蒸出。通过柱色谱法(氯仿)对所得混合物进行分离和提纯,从而得到3.3份下列化合物(1004),其为淡黄色固体。
合成例6
在氮气气氛下,在75份氯仿中,对1份上述化合物(1004)和0.35份钌-对甲基异丙基苯二聚体进行加热回流。在反应完成之后,将氯仿蒸出,然后在60℃下干燥14小时,从而得到1.35份下列化合物(1005),其为褐色晶体。
源自这种化合物(1005)的核磁共振分析的测量值如下。
源自核磁共振分析的测量值:
1H-NMR(PPM:d6-DMSO):0.515-0.562(m,6H),0.614-0.663(t,12H),1.012-1.098(m,16H),2.086(m,8H),2.233(s,3H),2.634-2.728(m,1H),6.020-6.040(d,2H),6.259-6.279(d,2H),7.364-7.392(m,4H),7.479-7.508(m,2H),7.821-7.953(m,10H),7.988-8.008(d,2H),8.371-8.384(d,2H),9.045(s,2H),9.454-9.475(d,2H)。
实施例1
在遮光和氮气气氛下,将0.521份上述化合物(1005)和0.099份2,2′-联吡啶-4,4′-二羧酸在20份无水二甲基甲酰胺(DMF)中于140℃下搅拌4小时。添加0.65份硫氰酸铵,并将混合物搅拌另外4小时。在反应完成之后,将混合物冷却至室温,并静置36小时。其后,对反应溶液进行过滤,并将滤液倒入100份水中,将沉淀的晶体滤出。利用2份水将所得晶体洗涤两次,然后在70℃下干燥14小时,从而得到0.522份上表1中化合物编号(6)的化合物(金属络合物染料),其为黑褐色晶体。
这种化合物编号(6)的吸光度、核磁共振分析和质量分析的测量值如下。
吸光度的测量
最大吸收波长(λmax)=388nm,分子消光系数(ε)=56625(溶剂:N,N-二甲基甲酰胺)
这种化合物在553nm处显示最大吸收波长。
源自核磁共振分析的测量值:
1H-NMR(PPM:d6-DMSO):0.534-0.670(m,16H),0.989-1.083(m,12H),2.081(m,8H),7.089-7.102(d,2H),7.361-7.461(m,8H),7.656-7.744(dd,2H),7.843-7.950(m,8H),8.155-8.384(m,4H),8.967-9.018(d,2H),9.123-9.171(d,2H),9.216-9.235(d,1H),9.459-9.478(d,1H)
质量分析测量值:
质量(M-1)=1334
实施例2和比较例1
将二氧化钛分散液PASOL HPW-18NR(源自触媒化成工业株式会社(Shokubai Kasei Kogyo K.K.))制成糊膏,并将其涂布到透明导电玻璃电极上而形成二氧化钛膜。向通过在450℃下对二氧化钛膜烧结30分钟而得到的半导体薄膜滴加约1cc的0.04M的四氯化钛水溶液,接着在60℃下静置30分钟并进行水洗,然后再次在450℃下煅烧30分钟,从而得到具有四氯化钛处理的半导体薄膜(膜厚度:7μm,通过源自东京精密株式会社(Tokyo Seimitu Co.,Ltd.)的表面粗糙度/形状测量仪Surfcom 570A测得)的多孔衬底。
将在实施例1中得到的化合物编号(6)的金属络合物染料溶于叔丁醇∶乙腈(1∶1)的混合溶剂中使其为3.0×10-4M,再添加鹅脱氧胆酸而使其为40mM。向这种溶液中浸入通过上述方法得到的多孔衬底并在室温(20℃)下保持12小时,从而使得衬底负载有染料,然后,利用混合溶剂进行洗涤,接着进行干燥,从而得到本发明的光电转换器件,其包含染料敏化的半导体细粒的薄膜。以相同的方式,通过使用由下式(2001)表示的化合物得到了作为比较的光电转换器件(参见日本专利3731752的实施例2)。
通过以其间空隙空间为20微米的方式,将由此得到的本发明光电转换器件和作为比较的光电转换器件的半导体细粒薄膜与利用铂溅射的导电玻璃的溅射表面对置地固定,并通过倒入含电解质的溶液来填充所述空隙空间,分别获得了本发明的太阳能电池和作为比较的太阳能电池。作为电解质,使用(1,2-二甲基-3-丙基咪唑碘化物0.6M)+(LiI0.1M)+(I2 0.1M)+(叔丁基吡啶0.5M)的3-甲氧基丙腈溶液。
待测量的电池有效部分的尺寸为0.25cm2。光源通过AM(空气质量)1.5滤波器后为100mW/cm2。通过使用太阳模拟器YSS-50A(源自山下电装株式会社(Yamashita Denso Co.Ltd.))测量了短路电流、开路电压、转换效率。
表3评价结果
根据表3的结果,从化合物编号(6)的化合物获得了优异的光电转换效率,其效率比已知的染料(2001)更好。特别地,确认即使当二氧化钛的膜厚度薄时,化合物编号(6)的化合物仍显示了足够高的转换效率。
在纯化过程期间或当吸附在二氧化钛电极上时,本发明的金属络合物染料极易溶于有机溶剂中,因此也具有优异的操作性。
合成例7
在氮气气氛下,将4.7份上述化合物(1003)和0.1份二(三叔丁基膦)钯(O)添加至27份四氢呋喃中,接着进行搅拌。滴加2-吡啶基溴化锌的四氢呋喃(0.5mol/L)溶液30份,并将混合物在回流下反应1小时。此外,添加0.1份二(三叔丁基膦)钯(O)并回流2小时,将所述操作重复两次。在将反应溶液冷却至室温之后,利用氯仿对反应混合物进行萃取,并以硫酸镁对氯仿相进行干燥,然后将氯仿蒸出。利用氯仿/己烷混合溶液对所得混合物进行重结晶,从而得到4.5份下列化合物(1006),其为淡黄色固体。
源自这种化合物(1006)的核磁共振分析的测量值如下。
源自核磁共振分析的测量值:
1H-NMR(PPM:CD2Cl2):0.65(m.10H),1.15(m.4H),2.10(t.4H),7.41(m.4H),7.53(d.1H),7.62(dd.1H),7.78(m.5H),7.91(m.1H),8.53(d.1H),8.71(d.1H),8.76(m.2H)
合成例8
在氮气气氛下,在200ml氯仿中,将2.00份上述化合物(1006)和1.19份钌-对甲基异丙基苯二聚体加热回流4小时。在反应完成之后,将氯仿蒸出,然后在60℃下干燥14小时,从而得到3.18份下列化合物(1007),其为褐色晶体。
源自这种化合物(1007)的核磁共振分析的测量值如下。
源自核磁共振分析的测量值:
1H-NMR(PPM:d-DMSO):0.58(m.10H),1.03(m.10H),2.06(m.4H),2.21(s.3H),2.61(m.1H),6.01(d.2H),6.26(t.2H),7.37(m.2H),7.48(m.1H),7.88(m.7H),8.35(m.2H),8.93(m.2H),9.51(dd.2H)
实施例3
在遮光和氮气气氛下,将3.00份上述化合物(1007)和0.82份2,2′-联吡啶-4,4′-二羧酸在166ml无水二甲基甲酰胺(DMF)中于140℃下搅拌4小时。添加5.38份硫氰酸铵,并将混合物搅拌另外4小时。在反应完成之后,将混合物冷却至室温,并静置36小时。其后,对反应溶液进行过滤,并将滤液倒入830份水中,将析出的晶体滤出。利用2份水对所得晶体洗涤两次,然后在70℃下干燥14小时,从而得到2.78份化合物编号(46)的化合物(金属络合物染料),其为黑褐色晶体。
化合物编号(46)的吸光度分析的测量值如下。
吸光度的测量
最大吸收波长(λmax)=387nm,分子消光系数(ε)=40563(溶剂:二甲亚砜∶乙醇=1∶9的混合溶液)
这种化合物也在530nm处具有最大吸收波长,且在530nm处的分子消光系数(ε)为17750。
实施例4和实施例5
将二氧化钛分散液PASOL HPW-18NR(源自触媒化成工业株式会社)制成糊膏,并将其涂布到透明导电玻璃电极上而形成二氧化钛膜。向通过在450℃下对二氧化钛膜烧结30分钟而得到的半导体薄膜滴加约1cc的0.04M的四氯化钛水溶液,接着在60℃下静置30分钟并进行水洗,然后再次在450℃下煅烧30分钟,从而得到具有四氯化钛处理的半导体薄膜(膜厚度:7μm,通过源自东京精密株式会社的表面粗糙度/形状测量仪Surfcom 570A测得)的多孔衬底。
将在实施例1中得到的化合物编号(6)的金属络合物染料和在实施例3中得到的化合物编号(46)的金属络合物染料分别溶于叔丁醇∶乙腈(1∶1)的混合溶剂中使其为3.0×10-4M,分别地,对于化合物编号(6)添加鹅脱氧胆酸而使其为10mM,并对于化合物编号(46)添加乌索脱氧胆酸而使其为10mM。向这些溶液中浸入通过上述方法得到的多孔衬底并在室温(20℃)下保持12小时,从而使得各种衬底负载有各自的染料,然后,利用混合溶剂进行洗涤,接着进行干燥,从而得到本发明的光电转换器件,其包含染料敏化的半导体细粒的薄膜。
通过以其间空隙空间为20微米的方式,将由此获得的本发明光电转换器件的半导体细粒薄膜与利用铂溅射的导电玻璃的溅射表面对置地固定,并通过倒入含电解质的溶液来填充所述空隙空间,分别获得了本发明的太阳能电池。作为电解质,使用(1,2-二甲基-3-丙基咪唑碘化物0.6M)+(LiI0.1M)+(I2 0.1M)+(叔丁基吡啶0.5M)的3-甲氧基丙腈溶液。
待测量的电池有效部分的尺寸为0.25cm2。光源通过AM(空气质量)1.5滤波器后为100mW/cm2。通过使用太阳模拟器WXS-155S-10AM1.5G(源自Wacom电装株式会社(Wacom Electric Co.Ltd.))测量了短路电流、开路电压、转换效率。
表4
根据表4的结果可确认,从化合物编号(6)和(46)的化合物获得了优异的光电转换效率,且即使当二氧化钛的膜厚度薄时,也能够获得足够高的转换效率。
在纯化过程期间或当吸附在二氧化钛电极上时,本发明的金属络合物染料极易溶于有机溶剂中,因此也具有这些优异的操作性。
工业实用性
通过使用本发明具有特定结构的金属络合物染料或其盐作为用于染料敏化的光电转换器件的敏化染料,即使当负载染料的氧化物半导体细粒的膜较薄时,也能够获得具有高转换效率和高稳定性的光电转换器件和太阳能电池。
Claims (14)
2.如权利要求1中所述的光电转换器件,其中式(1)中的X1为硫原子。
3.如权利要求2中所述的光电转换器件,其中式(1)中的n1为1。
4.如权利要求3中所述的光电转换器件,其中式(1)中的Y1和Y2各自为异硫氰酸根基团(-NCS)。
5.如权利要求4中所述的光电转换器件,其中式(1)中的R3和R4各自独立地为3~5个碳原子的直链烷基。
6.如权利要求5中所述的光电转换器件,其中式(1)中的R3和R4各自为正丁基。
7.如权利要求6中所述的光电转换器件,其中式(1)中的m1为2。
8.如权利要求6中所述的光电转换器件,其中式(1)中的m1为1。
9.一种光电转换器件,其中在布置于衬底上的氧化物半导体细粒的薄膜上负载有由权利要求1的式(1)表示的金属络合物染料或其盐的一种以上、以及次甲基染料和/或具有不同于所述式(1)的结构的金属络合物染料。
10.如权利要求1~9中任一项所述的光电转换器件,其中所述薄膜包含二氧化钛、氧化锌或氧化锡。
11.如权利要求1~10中任一项所述的光电转换器件,其中在包合化合物的存在下负载金属络合物染料或其盐。
12.一种使用权利要求1~11中任一项所述的光电转换器件的太阳能电池。
13.一种由权利要求1的式(1)表示的金属络合物染料或其盐。
14.一种光电转换器件,其中在布置于衬底上的氧化物半导体细粒的薄膜上负载有由下式(1)表示的金属络合物染料或其盐:
其中m1表示1~2的整数,n1表示1~3的整数;X1表示氧原子、硫原子、硒原子或=NR5,其中R5表示氢原子或可具有取代基的脂族烃残基;Y1和Y2各自独立地表示硫氰酸根基团(-SCN)、卤素原子或异硫氰酸根基团(-NCS);且Y1和Y2可结合在一起而形成一种配体;M1和M2各自独立地表示氢原子或铵离子;R1和R2各自独立地表示氢原子、可具有取代基的脂族烃残基、或可具有取代基的烷氧基;且当n1为2以上、或m1为2从而R1和R2各自存在多个时,各个R1和R2可以相互相同或不同;且多个R1和/或R2可形成环,且在这种环上还可具有取代基;R3和R4各自独立地表示氢原子、可具有取代基的脂族烃残基、或可具有取代基的芳族烃残基;当m1为2、R3和R4各自存在多个时,各个R3和R4可以相互相同或不同;且R3和R4可以相互结合在一起而形成可具有取代基的环;芳环a、芳环b、芳环c、芳环d和芳环e各自可具有1~3个取代基;且芳环f可具有1~4个取代基。
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