JP3680094B2 - Organic dye-sensitized porous oxide semiconductor electrode and solar cell using the same - Google Patents
Organic dye-sensitized porous oxide semiconductor electrode and solar cell using the same Download PDFInfo
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- JP3680094B2 JP3680094B2 JP2000069561A JP2000069561A JP3680094B2 JP 3680094 B2 JP3680094 B2 JP 3680094B2 JP 2000069561 A JP2000069561 A JP 2000069561A JP 2000069561 A JP2000069561 A JP 2000069561A JP 3680094 B2 JP3680094 B2 JP 3680094B2
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- 239000004065 semiconductor Substances 0.000 title claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000004693 imidazolium salts Chemical class 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 description 33
- -1 sulfoxy group Chemical group 0.000 description 18
- 239000000243 solution Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- GEBYOCJZLPJAJK-UHFFFAOYSA-N [I+].C[N+]1=C(N(C=C1)CCC)C Chemical compound [I+].C[N+]1=C(N(C=C1)CCC)C GEBYOCJZLPJAJK-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 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 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical group C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical group C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- USYCQABRSUEURP-UHFFFAOYSA-N 1h-benzo[f]benzimidazole Chemical group C1=CC=C2C=C(NC=N3)C3=CC2=C1 USYCQABRSUEURP-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical group C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical group C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical group C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical group NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- PIHPSKJRLDSJPX-UHFFFAOYSA-N ethyl n-carbamoylcarbamate Chemical group CCOC(=O)NC(N)=O PIHPSKJRLDSJPX-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 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
- 150000002496 iodine Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl 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])[H] 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 239000002245 particle Substances 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
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 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
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Hybrid Cells (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、有機色素増感型多孔質酸化物半導体電極及びそれを含む湿式太陽電池に関するものである。
【０００２】
【従来の技術】
有機色素増感型酸化物半導体電極を用いた湿式太陽電池は、その製造コストやリサイクルの面ですぐれていることが知られている。有機色素に関しては、従来、数多くのものが知られているが、有機色素であればどのようなものでも酸化物半導体を増感し得るものではない。例えば、アゾ系の有機色素は酸化物半導体に対しては実質的な増感作用を示さない。従って、酸化物半導体に対して増感作用を示す色素の探索は、数多くの実験によらざるを得ないのが実状である。
これまでも、酸化物半導体に対して増感作用を示す有機色素としては各種のものが提案されている（特開平１１−７４００３号公報、特開平１１−１２６９１７号公報、特開昭５６−１３０９７６号公報、特開平１１−２３８９０５号公報）。
しかしながら、従来のものはその増感作用において未だ満足し得るものではない。
【０００３】
【発明が解決しようとする課題】
本発明は、有機色素増感型多孔質酸化物半導体電極において、実用性ある電流−電圧曲線を与える電極及びそれを含む太陽電池を提供することをその課題とする。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに至った。
即ち、本発明によれば、有機色素を厚さが２００〜２０，０００ｎｍの多孔質酸化物半導体膜の表面に吸着させて形成した電極であって、該有機色素が下記一般式（１）で表される化合物であることを特徴とする有機色素増感型多孔質酸化物半導体電極。
【化２】
また、本発明によれば、有機色素を吸着させた多孔質酸化物半導体電極とその対電極とそれらの電極に接触するレドックス電解液とから構成される太陽電池において、該多孔質酸化物半導体電極が、前期特定の有機色素増感型多孔質酸化物半導体電極からなることを特徴とする太陽電池が提供される。
【０００５】
【発明の実施の形態】
前記一般式（１）において、環Ａは、置換もしくは無置換の縮合環を有していてもよい含窒素５員環又は６員環（以下、これらの環を単に複素環とも言う）を示し、環Ｂは縮合環を有しない含窒素の５員環又は６員環を示す。この場合、縮合環としては、置換もしくは無置換のベンゼン環、ナフタレン環、ピリジン環やシクロヘキサン環等が挙げられる。前記縮合環を有してもよい複素環を示すと、オキサゾリン環、オキサゾール環、ベンゾオキサゾール環、ナフトオキサゾール環、チアゾリン環、チアゾール環、ベンゾチアゾール環、ナフトチアゾール環、セレナゾール環、ベンゾセレナゾール環、ナフトセレナゾール環、イミダゾリン環、イミダゾール環、ベンゾイミダゾール環、ナフトイミダゾール環、インドレニン環、ベンゾインドレニン環、ピリジン環、キノリン環、バルビツール酸等が挙げられる。
【０００６】
前記複素環及び縮合環は置換基を有していもよい。この場合の置換基としては、例えば、アルキル基、アルケニル基、アルキニル基、アルコキシ基、カルボキシル基、アルキルカルボニルオキシ基、アルコキシカルボニル基、スルホキシ基、アルキルスルホニル基、ヒドロキシ基、ヒドロキシスルホニル基、アリール基、アリールオキシ基、アシルオキシ基、ガルバモイル基、スルホン酸基、スルファモイル基、シクロアルキル基、シアノ基、ニトロ基、アミノ基、アルキルアミノ基、複素環基、アミノスルホニル基、ハロゲン原子、２−ブトキシエチル基、６−ブロモヘキシル基、２−カルボキシエチル基、３−スルホキシプロピル基、４−スルホキジブチル基、２−ヒドロキシエチル基、フェニルメチル基、４−ブトキシフェニルメチル基等が挙げられる。
【０００７】
前記一般式（１）において、Ｘ1及びＸ2は炭素原子又はヘテロ原子を示すが、少なくともその一方、好ましくはＸ2はヘテロ原子であるのが好ましい。ヘテロ原子には、酸素原子、硫黄原子、セレン原子又は置換基（Ｒ）を有する窒素原子が包含される。この場合、Ｒとしては、水素又は前記複素環及び縮合環に関して示した各種のもの及びフェニル基等のアリール基を挙げることができる。
前記一般式（１）におけるＲ1及びＲ2は、アンカー基又は炭素数１６〜３０の置換基を有していてもよいアルキル基を示すが、それらの一方はアンカー基であり、他方はアルキル基であり、２つの基が同時にアンカー基又はアルキル基であることはない。
アンカー基は、半導体表面に結合性を有する基であり、各種アニオン基であることができるが、下記一般式（２）又は（３）で表される基であることが好ましい。
【化３】
【０００８】
アルキル基の炭素数は、１６以上、好ましくは１６〜３０である。このようなアルキル基には、鎖状の飽和もしくは不飽和のものが包含される。その具体例としては、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコサニル、ドコサニル、ヘキサコサニル、トリアコンタニル等の飽和アルキル基；ヘキサデセニル、ヘプタデセニル、オクタデセニル、ノナデセニル、イコセニル、ドコセニル、ヘキサコセニル、トリアコンテニル等の不飽和アルキル基を示すことができる。
前記アルキル基は、置換基を有することができる。この場合、置換基には、炭素数１〜６のアルコキシ基、炭素数６〜１０のアリール基又はアリールアルキル基、ハロゲン原子（塩素、臭素、フッ素等）、窒素原子やイオウ原子、酸素原子等のヘテロ原子を含む５員環〜６員環の複素環等が包含される。
前記置換基の具体例を以下に示す。
フェニル基、ナフチル基、トリル基等のアリール基、イミダゾリル基、ベンズイミダゾリル基、ピリジル基、チエニル基、フリル基、アキサゾリル基、チアゾリル基、キノリル基等の複素環残基、ヨウ素、臭素、塩素、フッ素等のハロゲン原子、メトキシ基、エトキシ基、ベンジルオキシ基等のアルコキシ基、フェノキシ基等のアリールオキシ基、メチルチオ基、エチルチオ基等のアルキルチオ基、フェニルチオ基等のアリールチオ基、アセチルアミノ基、ベンジルアミノ基等のアミド基、ヒドロキシ基、ニトロ基、シアノ基、アセチル基、ベンゾイル基等のアシル基、ベンゾイルオキシ基、エトキシカルボニル基等のエステル基、メタンスルホニルアミド基、ベンゼンスルホニルアミノ基等のスルホンアミド基、３−フェニルウレイド基等のウレイド基、イソブトキシカルボニルアミド基、カルバモイルオキシ基等のウレタン基、Ｎ−メチルカルバモイル基等のカルバモイル基、メチルアミノ基、アニリノ基等のアミノ基、メチルスルホニル基等のスルホニル基等。
【０００９】
前記一般式（１）で表される色素メロシアニン色素の具体例を以下に示す。
【化５】
【００１０】
本発明の有機色素増感型多孔質酸化物半導体電極は、所定の多孔質酸化物半導体に、特定の有機色素を吸着させることによって製造される。高性能の電池を得る点からは、酸化物半導体の表面積は高い方が好ましいが、高表面積を得るためには、酸化物半導体の１次粒子径が小さいことが好ましい。酸化物半導体の１次粒子径は、１〜２００ｎｍ、好ましくは５０ｎｍ以下である。その比表面積は、５〜１００ｍ2／ｇ程度である。酸化物半導体を電極とするには、その粉末をそれだけでペレット化して焼結してもよいが、導電性基板上に固定化して用いるのが取扱い上好ましい。この場合の基板としては、チタンやタンタルなどの安定な金属や、導電性ガラス、カーボン等でもよい。基板上の酸化物半導体の厚さは２００〜２０，０００ｎｍ、好ましくは１０００ｎｍ以上が望ましい。
酸化物半導体としては、従来公知の各種のものを用いることができる。このようなものには、例えば、酸化チタン（ＴｉＯ2）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ2）、酸化インジウム（Ｉｎ2Ｏ3）、酸化ニオブ（Ｎｂ2Ｏ3）等が包含される。
【００１１】
酸化物半導体粒子は、純粋な金属前駆体の分解によって調製する。できるだけ不純物の少ない水酸化物や、硝酸塩、塩化物、アルコキシドを充分精製してから加水分解して純粋な水酸化物を調製しても良い。また不純物が少なく表面積の大きな酸化物半導体微粒子が市販であるときはそれを利用しても良い。
多孔質酸化物半導体電極が充分に機能するためには酸化物又は低温で加水分解した酸化物は前焼成するのが望ましい。この前焼成は、空気中で３００〜９００℃、好ましくは５００〜８００℃にゆっくり昇温し、約１時間保ち、またゆっくり温度を下げることによって実施される。
前焼成して形成した酸化物は上述した厚さで基板に固定される。これには酸化物の懸濁液に基板をディッピングしてもいいし、酸化物のスラリーを塗布してもよい。酸化物スラリーは水または界面活性剤水溶液を用いたり、ポリエチレングリコールなどを添加して粘性を高めてもよい。その後基板上でゆっくり乾燥させる。次に基板ごと空気中又は不活性雰囲気下で焼成を行う。焼成温度は３００〜９００℃、好ましくは４００〜８００℃で１時間行う。ただし、焼成温度は基板が損傷しない温度以下で行なわなければいけない。
【００１２】
次に、有機色素の多孔質酸化物半導体電極への吸着について説明する。
色素を多孔質酸化物半導体電極に単分子吸着させる、このためには、まず、色素をメタノール、エタノール、アセトニトリル、ジメチルホルムアミドなどの溶媒に溶かす。溶媒の種類は、色素に対しある程度の溶解度を持ち、かつ色素の半導体への吸着を阻害しないものを選ぶ。
次に、半導体電極をこの溶液に浸す。溶液温度は室温でもよい。また、溶液を多孔質な電極の内部までしみ込ませるために、減圧、または温度を上げて電極内部の気泡を除去することもできる。温度は溶媒の沸点または色素の分解温度のいずれか低い温度以下にあわせる。吸着時間は３０分を基準にするが、数分から１晩行っても良い。濃度は１００ｍｇ／１００ｍｌを基準にするが、その１００倍程度濃度が高くても問題ない。色素の溶解度が低い場合は、吸着を繰り返す。色素の吸着がうまくいかないときは、促進剤を添加する。例えば、色素を半導体表面とエステル結合させるには脱水剤を入れると良い。
【００１３】
本発明の場合、吸収領域の異なる２種類以上の有機色素を同時に半導体に吸着させるのが好ましく、この場合には光を効率よく利用できる。２種類以上の色素を半導体電極に吸着させるには、色素の混合溶液に電極を浸す。または低濃度の色素溶液に短時間電極を浸し、色素を一部分だけ吸着させた後、次々と別の色素溶液に電極を浸すことで数種類の色素を少しずつ吸着させる方法もある。
異なる色素の同時吸着で問題になるのは、色素間の電子移動やエネルギー移動が優先して起きることで色素から半導体への電子移動や色素−レドックス間の電子移動の効率が低下してしまうことである。それを防ぐ手段としては、まず第一に、２種類の色素の構造ができるだけ異なるもの同士を用いれば会合が形成しにくくなる。また、大きな官能基をつけたり、色素以上に会合体を作りやすい化合物を同時に加えることでも問題の解決になる。
【００１４】
本発明の太陽電池は、前記のようにして得られる有機色素増感型多孔質酸化物半導体電極と、その対電極と、それらの電極に接触するレドックス電解液とから構成される。
この場合の電解液の溶媒としては、電気化学的に不活性で、かつ電解質を充分な量溶解できる物質が望まれる、例えば、アセトニトリルや炭酸プロピレンなどがある。
電解質については安定なイオンのレドックス対で電荷を充分な速度で電極間を輸送できる物質が望まれる、レドックス対としてはＩ-／Ｉ3 -やＢｒ-／Ｂｒ3 -、キノン／ヒドロキノン対がある、例えばＩ-／Ｉ3 -対をつくるときには沃素のアンモニウム塩と沃素を混合する。陽イオンは電解質が溶媒に溶解しやすいものを選択する。また、レドックス電解液には、イミダゾリウム塩及びピリジン系化合物を添加するのが好ましい。イミダゾリウム塩としては、トリアルキルイミダゾリウムヨウ素や１，２−ジメチル−３−プロピルイミダゾリウムヨウ素等のヨウ素塩等が挙げられる。その添加量は、電解液中０．０１〜２モル／Ｌ、好ましくは０．１〜１モル／Ｌである。ピリジン系化合物としては、ピリジン系化合物としては、ピリジンの他、炭素数１〜６のアルキル基を有するアルキルピリジン等が挙げられる。その添加量は、電解液中、０．０１〜５モル／Ｌ、好ましくは０．１〜３モル／Ｌである。
対電極についてはＩ3 -イオンなどの酸化型レドックスの還元反応を充分な早さでおこなわせる触媒能を持った材料が望まれる、例えば白金又はこれを導電性材料に把持した電極などがある。最終的に電池を作成するときには有機色素を吸着させた電極と対極との間にレドックスを含む電界溶液をはさみ、シール剤で射止する。以上の作業は空気中の水分や酸素を完全に触れさせないような条件下でおこなわなければいけない。
【００１５】
【実施例】
次に、本発明を実施例によりさらに詳細に説明する。
【００１６】
実施例１
ＴｉＯ2酸化物半導体粉末として、チタンイソプロポキシドを加水分解し、オートクレーブ中で２１０℃で１晩結晶化したものを用いた。このチタン酸化物粉末は、これを水、アセチルアセトン、界面活性剤と混合しスラリー状にした。このスラリーを導電性ガラス（Ｆ−ＳｎＯ2、１０Ω／ｓｑ）上に焼成後に所定の膜厚になるように塗布した。焼成はいずれも５００℃、１時間空気中でおこないＴｉ酸化物半導体電極を作成した。
次に、下記式で表されるメロシアニン色素を、エタノール中に１００ｍｇ／１００ｍｌの濃度で溶解し、この溶液に前記チタン酸化物半導体電極を入れて、８０℃、１時間還流して色素を電極に吸着させた。その後、室温で乾燥し、色素吸着した電極を得た。
前記電極の対極としては、白金を２０ｎｍの厚さで蒸着した導電性ガラスを用いた。
【化６】
前記の半導体電極、対極及びレドックス電解液を用いて太陽電池を構成し、光源としてソーラーシュミレーターによる光照射（ＡＭ１５，１００ｍＷ／ｃｍ2）を用いて、その性能を判定し、その結果を表１に示す。
【表１】
【発明の効果】
本発明の電極を用いることにより、高い光／電気変換効率を有する太陽電池を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic dye-sensitized porous oxide semiconductor electrode and a wet solar cell including the same.
[0002]
[Prior art]
It is known that a wet solar cell using an organic dye-sensitized oxide semiconductor electrode is excellent in terms of manufacturing cost and recycling. Many organic dyes are conventionally known, but any organic dye cannot sensitize an oxide semiconductor. For example, an azo organic dye does not exhibit a substantial sensitizing action on an oxide semiconductor. Therefore, in reality, the search for dyes that exhibit a sensitizing action on oxide semiconductors must be carried out through numerous experiments.
In the past, various organic dyes that have a sensitizing action on oxide semiconductors have been proposed (Japanese Patent Laid-Open Nos. 11-74003, 11-126917, and 56-130976). No., JP-A-11-238905).
However, the conventional one is not yet satisfactory in its sensitizing action.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an electrode that gives a practical current-voltage curve in an organic dye-sensitized porous oxide semiconductor electrode and a solar cell including the electrode.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, according to the present invention, an electrode is formed by adsorbing an organic dye on the surface of a porous oxide semiconductor film having a thickness of 200 to 20,000 nm, and the organic dye is represented by the following general formula (1). An organic dye-sensitized porous oxide semiconductor electrode, which is a compound represented by
[Chemical formula 2]
Further, according to the present invention, in a solar cell composed of a porous oxide semiconductor electrode adsorbing an organic dye, a counter electrode thereof, and a redox electrolyte in contact with the electrode, the porous oxide semiconductor electrode Is provided with a specific organic dye-sensitized porous oxide semiconductor electrode in the previous period.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (1), ring A represents a nitrogen-containing 5-membered ring or 6-membered ring (hereinafter, these rings are also simply referred to as a heterocyclic ring) which may have a substituted or unsubstituted condensed ring. and ring B shows the 5- or 6-membered ring nitrogen-containing no fused rings. In this case, examples of the condensed ring include a substituted or unsubstituted benzene ring, naphthalene ring, pyridine ring, and cyclohexane ring. Examples of the heterocyclic ring that may have the condensed ring include oxazoline ring, oxazole ring, benzoxazole ring, naphthoxazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring Naphthoselenazole ring, imidazoline ring, imidazole ring, benzimidazole ring, naphthimidazole ring, indolenine ring, benzoindolenine ring, pyridine ring, quinoline ring, barbituric acid and the like.
[0006]
The heterocyclic ring and the condensed ring may have a substituent. Examples of the substituent in this case include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a carboxyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a sulfoxy group, an alkylsulfonyl group, a hydroxy group, a hydroxysulfonyl group, and an aryl group. , Aryloxy group, acyloxy group, galvamoyl group, sulfonic acid group, sulfamoyl group, cycloalkyl group, cyano group, nitro group, amino group, alkylamino group, heterocyclic group, aminosulfonyl group, halogen atom, 2-butoxyethyl Group, 6-bromohexyl group, 2-carboxyethyl group, 3-sulfoxypropyl group, 4-sulfoxydibutyl group, 2-hydroxyethyl group, phenylmethyl group, 4-butoxyphenylmethyl group and the like.
[0007]
In the general formula (1), X 1 and X 2 each represent a carbon atom or a hetero atom, and at least one of them, preferably X 2 is preferably a hetero atom. The hetero atom includes an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent (R). In this case, examples of R include hydrogen or various groups shown for the heterocyclic ring and the condensed ring, and aryl groups such as a phenyl group.
R 1 and R 2 in the general formula (1) represent an anchor group or an alkyl group which may have a substituent having 16 to 30 carbon atoms, one of which is an anchor group and the other is an alkyl group. And the two groups are not simultaneously an anchor group or an alkyl group.
The anchor group is a group having a binding property to the semiconductor surface, and can be various anionic groups, but is preferably a group represented by the following general formula (2) or (3).
[Chemical 3]
[0008]
The alkyl group has 16 or more carbon atoms, preferably 16 to 30 carbon atoms. Such alkyl groups include those that are chain saturated or unsaturated. Specific examples thereof include saturated alkyl groups such as hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl, docosanyl, hexacosanyl, triacontanyl; hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, dococenyl, hexacocenyl, triacontenyl it can show al kill group.
The alkyl group can have a substituent. In this case, the substituent includes an alkoxy group having 1 to 6 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a halogen atom (chlorine, bromine, fluorine, etc.), a nitrogen atom, a sulfur atom, an oxygen atom, etc. 5-membered to 6-membered heterocycles containing the above heteroatoms are included.
Specific examples of the substituent are shown below.
Aryl group such as phenyl group, naphthyl group, tolyl group, imidazolyl group, benzimidazolyl group, pyridyl group, thienyl group, furyl group, heterocyclic residue such as axazolyl group, thiazolyl group, quinolyl group, iodine, bromine, chlorine, Halogen atoms such as fluorine, alkoxy groups such as methoxy group, ethoxy group and benzyloxy group, aryloxy groups such as phenoxy group, alkylthio groups such as methylthio group and ethylthio group, arylthio groups such as phenylthio group, acetylamino group, benzyl Amide groups such as amino groups, acyl groups such as hydroxy groups, nitro groups, cyano groups, acetyl groups and benzoyl groups, ester groups such as benzoyloxy groups and ethoxycarbonyl groups, sulfones such as methanesulfonylamide groups and benzenesulfonylamino groups Amide group, 3-phenylureido group, etc. Ureido group, isobutoxycarbonyl amido group, carbamoyl urethane groups such as oxy group, a carbamoyl group, such as N- methylcarbamoyl group, methylamino group, an amino group such as anilino group, and a sulfonyl group such as a methylsulfonyl group.
[0009]
Specific examples of the merocyanine dye represented by the general formula (1) are shown below.
[Chemical formula 5]
[0010]
The organic dye-sensitized porous oxide semiconductor electrode of the present invention is produced by adsorbing a specific organic dye to a predetermined porous oxide semiconductor. From the viewpoint of obtaining a high-performance battery, the surface area of the oxide semiconductor is preferably high, but in order to obtain a high surface area, it is preferable that the primary particle diameter of the oxide semiconductor is small. The primary particle diameter of the oxide semiconductor is 1 to 200 nm, preferably 50 nm or less. Its specific surface area is about 5 to 100 m 2 / g. In order to use an oxide semiconductor as an electrode, the powder may be pelletized by itself and sintered, but it is preferable to fix the powder on a conductive substrate for handling. In this case, the substrate may be a stable metal such as titanium or tantalum, conductive glass, carbon, or the like. The thickness of the oxide semiconductor on the substrate is 200 to 20,000 nm, preferably 1000 nm or more.
Various conventionally known oxide semiconductors can be used. Such materials include, for example, titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ), indium oxide (In 2 O 3 ), niobium oxide (Nb 2 O 3 ), and the like. The
[0011]
Oxide semiconductor particles are prepared by decomposition of a pure metal precursor. A pure hydroxide may be prepared by sufficiently purifying a hydroxide with as little impurities as possible, nitrates, chlorides, and alkoxides and then hydrolyzing them. Further, when oxide semiconductor fine particles having a small amount of impurities and a large surface area are commercially available, they may be used.
In order for the porous oxide semiconductor electrode to function sufficiently, it is desirable to pre-fire the oxide or the oxide hydrolyzed at a low temperature. This pre-baking is carried out by slowly raising the temperature in air to 300 to 900 ° C., preferably 500 to 800 ° C., keeping it for about 1 hour, and slowly lowering the temperature.
The oxide formed by pre-baking is fixed to the substrate with the thickness described above. For this, the substrate may be dipped into an oxide suspension, or an oxide slurry may be applied. As the oxide slurry, water or a surfactant aqueous solution may be used, or polyethylene glycol or the like may be added to increase the viscosity. Thereafter, it is slowly dried on the substrate. Next, the substrate is baked in air or in an inert atmosphere. The baking temperature is 300 to 900 ° C., preferably 400 to 800 ° C. for 1 hour. However, the firing temperature must be below the temperature at which the substrate is not damaged.
[0012]
Next, adsorption of the organic dye to the porous oxide semiconductor electrode will be described.
In order to adsorb the dye to the porous oxide semiconductor electrode by a single molecule, first, the dye is dissolved in a solvent such as methanol, ethanol, acetonitrile, or dimethylformamide. The type of solvent is selected so that it has a certain degree of solubility in the dye and does not inhibit the adsorption of the dye to the semiconductor.
Next, the semiconductor electrode is immersed in this solution. The solution temperature may be room temperature. Further, in order to soak the solution into the inside of the porous electrode, the bubbles inside the electrode can be removed by reducing the pressure or raising the temperature. The temperature is adjusted to a temperature lower than the boiling point of the solvent or the decomposition temperature of the dye. Although the adsorption time is based on 30 minutes, it may be performed for several minutes to overnight. The concentration is based on 100 mg / 100 ml, but there is no problem even if the concentration is about 100 times higher. If the solubility of the dye is low, the adsorption is repeated. If dye adsorption is not successful, an accelerator is added. For example, a dehydrating agent may be added to esterify the dye with the semiconductor surface.
[0013]
In the case of the present invention, it is preferable that two or more types of organic dyes having different absorption regions are simultaneously adsorbed on the semiconductor, and in this case, light can be used efficiently. In order to adsorb two or more kinds of dyes to the semiconductor electrode, the electrode is immersed in a mixed solution of the dyes. Alternatively, there is a method in which several kinds of dyes are adsorbed little by little by immersing the electrode in a low concentration dye solution for a short time and adsorbing only a part of the dye, and then immersing the electrode in another dye solution one after another.
The problem with simultaneous adsorption of different dyes is that the efficiency of electron transfer from the dye to the semiconductor or between the dye and the redox is reduced because the electron transfer and energy transfer between the dyes take precedence. It is. As a means for preventing this, first of all, it is difficult to form an association if two types of dyes having different structures are used as much as possible. The problem can also be solved by adding a large functional group or adding a compound that more easily forms an aggregate than the dye.
[0014]
The solar cell of the present invention is composed of an organic dye-sensitized porous oxide semiconductor electrode obtained as described above, a counter electrode thereof, and a redox electrolyte solution in contact with these electrodes.
As the solvent of the electrolytic solution in this case, a substance which is electrochemically inert and can dissolve a sufficient amount of the electrolyte is desired, for example, acetonitrile and propylene carbonate.
As for the electrolyte, a substance capable of transporting charges between electrodes at a sufficient rate with a stable ion redox pair is desired. Examples of the redox pair include I − / I 3 − , Br − / Br 3 − , and quinone / hydroquinone pairs. For example, when forming an I − / I 3 − pair, an ammonium salt of iodine and iodine are mixed. The cation is selected so that the electrolyte is easily dissolved in the solvent. Further, it is preferable to add an imidazolium salt and a pyridine-based compound to the redox electrolyte. Examples of the imidazolium salt include iodine salts such as trialkylimidazolium iodine and 1,2-dimethyl-3-propylimidazolium iodine. The amount added is 0.01 to 2 mol / L, preferably 0.1 to 1 mol / L in the electrolytic solution. As the pyridine compound, examples of the pyridine compound include pyridine and alkyl pyridine having an alkyl group having 1 to 6 carbon atoms. The amount added is 0.01 to 5 mol / L, preferably 0.1 to 3 mol / L in the electrolytic solution.
For counterelectrode I 3 - material having a catalytic ability to perform a sufficient fast reduction reaction of oxidized redox ion is desired, for example, a platinum or which grasped conductive material electrodes. When a battery is finally produced, an electric field solution containing redox is sandwiched between an electrode on which an organic dye is adsorbed and a counter electrode, and is shot with a sealant. The above work must be performed under conditions that prevent moisture and oxygen in the air from being completely exposed.
[0015]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0016]
Example 1
As the TiO 2 oxide semiconductor powder, titanium isopropoxide was hydrolyzed and crystallized overnight at 210 ° C. in an autoclave. This titanium oxide powder was mixed with water, acetylacetone and a surfactant to form a slurry. This slurry was applied on conductive glass (F-SnO 2 , 10Ω / sq) so as to have a predetermined film thickness after firing. Both firings were performed in air at 500 ° C. for 1 hour to prepare a Ti oxide semiconductor electrode.
Next, a merocyanine dye represented by the following formula is dissolved in ethanol at a concentration of 100 mg / 100 ml. The titanium oxide semiconductor electrode is placed in this solution, and the dye is refluxed at 80 ° C. for 1 hour. Adsorbed. Then, it dried at room temperature and obtained the dye-adsorbed electrode.
As the counter electrode of the electrode, conductive glass in which platinum was deposited with a thickness of 20 nm was used.
[Chemical 6]
A solar cell is constructed using the semiconductor electrode, the counter electrode and the redox electrolyte, and its performance is determined using light irradiation (AM15, 100 mW / cm 2 ) by a solar simulator as a light source. Show.
[Table 1]
【The invention's effect】
By using the electrode of the present invention, a solar cell having high photo / electric conversion efficiency can be obtained.
Claims (4)
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| JP2000069561A JP3680094B2 (en) | 1999-06-02 | 2000-03-13 | Organic dye-sensitized porous oxide semiconductor electrode and solar cell using the same |
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