WO2009119428A1 - 色素増感太陽電池用色素および色素増感太陽電池 - Google Patents
色素増感太陽電池用色素および色素増感太陽電池 Download PDFInfo
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- WO2009119428A1 WO2009119428A1 PCT/JP2009/055396 JP2009055396W WO2009119428A1 WO 2009119428 A1 WO2009119428 A1 WO 2009119428A1 JP 2009055396 W JP2009055396 W JP 2009055396W WO 2009119428 A1 WO2009119428 A1 WO 2009119428A1
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- WIPO (PCT)
- Prior art keywords
- group
- anthranyl
- dye
- naphthyl
- carbon atoms
- Prior art date
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- -1 phosphorylthiophene compound Chemical class 0.000 claims abstract description 480
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 239000004065 semiconductor Substances 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
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- 125000005843 halogen group Chemical group 0.000 claims description 12
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- 125000003277 amino group Chemical group 0.000 claims description 5
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- 125000004185 ester group Chemical group 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
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- 125000005372 silanol group Chemical group 0.000 claims description 5
- 125000001174 sulfone group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000005427 anthranyl group Chemical group 0.000 claims description 4
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
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- 238000001228 spectrum Methods 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
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- 238000010168 coupling process Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
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- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- OQZAQBGJENJMHT-UHFFFAOYSA-N 1,3-dibromo-5-methoxybenzene Chemical compound COC1=CC(Br)=CC(Br)=C1 OQZAQBGJENJMHT-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
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- GWOGSJALVLHACY-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical class [Ru].N1=CC=CC=C1C1=CC=CC=N1 GWOGSJALVLHACY-UHFFFAOYSA-N 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
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- JGNMMLAOWXJCGJ-UHFFFAOYSA-N 3-diphenylphosphanylpropyl(diphenyl)phosphane;nickel(2+) Chemical class [Ni+2].C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 JGNMMLAOWXJCGJ-UHFFFAOYSA-N 0.000 description 1
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- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 0 C*c1cc(P(*)(*)=O)c(C(C)C(C)c2ccc(C(C)C)[s]2)[s]1 Chemical compound C*c1cc(P(*)(*)=O)c(C(C)C(C)c2ccc(C(C)C)[s]2)[s]1 0.000 description 1
- PGJUTVLURLTNPG-UHFFFAOYSA-N CCC(C)(C)c1ccc(C(C)C(C)c([s]c(C)c2)c2P(O)(O)=O)[s]1 Chemical compound CCC(C)(C)c1ccc(C(C)C(C)c([s]c(C)c2)c2P(O)(O)=O)[s]1 PGJUTVLURLTNPG-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 241001422033 Thestylus Species 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
- 238000006887 Ullmann reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- IJRVQAXSAHHCNH-UHFFFAOYSA-M butyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(C)C IJRVQAXSAHHCNH-UHFFFAOYSA-M 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([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
- 238000000151 deposition Methods 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- XXECWTBMGGXMKP-UHFFFAOYSA-L dichloronickel;2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 XXECWTBMGGXMKP-UHFFFAOYSA-L 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- LYYFCMKDHSQLMB-UHFFFAOYSA-M hexyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCC[N+](C)(C)C LYYFCMKDHSQLMB-UHFFFAOYSA-M 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 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
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- WHZGZTQCUNTYJR-UHFFFAOYSA-L nickel(2+) 2-pyridin-2-ylpyridine dibromide Chemical compound [Ni++].[Br-].[Br-].c1ccc(nc1)-c1ccccn1.c1ccc(nc1)-c1ccccn1.c1ccc(nc1)-c1ccccn1 WHZGZTQCUNTYJR-UHFFFAOYSA-L 0.000 description 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 1
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 1
- 230000035699 permeability Effects 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
- 125000004351 phenylcyclohexyl group Chemical group C1(=CC=CC=C1)C1(CCCCC1)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- IFQMTQSXPWHEEG-UHFFFAOYSA-N thiophen-2-ylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CS1 IFQMTQSXPWHEEG-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
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- STYCVOUVPXOARC-UHFFFAOYSA-M trimethyl(octyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](C)(C)C STYCVOUVPXOARC-UHFFFAOYSA-M 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a dye for a dye-sensitized solar cell and a dye-sensitized solar cell using the dye.
- a semiconductor electrode having a light absorption effect in which a dye is adsorbed on a semiconductor electrode made of a porous metal oxide is used. Since the photoelectric conversion efficiency of a solar cell is proportional to the amount of electrons generated by the absorption of sunlight, it is necessary to increase the dye adsorption amount on the semiconductor electrode in order to improve the conversion efficiency. For this reason, it is calculated
- Non-Patent Document 1 As a dye for a dye-sensitized solar cell, an example in which a carboxylic acid is introduced into an oligothiophene compound to improve affinity and adhesion to a porous metal oxide has been reported (see Non-Patent Document 1). .
- oligothiophene compounds there are no examples of dyes that have improved affinity and adhesion by methods other than the introduction of carboxylic acid, and polythiophene compounds having a wide absorption wavelength are currently similar dyes. Is not designed.
- the present invention has been made in view of such circumstances, and has a high affinity and adhesiveness with a porous metal oxide, and has excellent solubility in an organic solvent, and is a dye-sensitized solar cell. It is an object to provide a dye for use, and a dye-sensitized solar cell using the same.
- poly or oligothiophene compounds having a phosphoric acid (ester) group have an affinity and adhesion on a porous semiconductor made of a metal oxide.
- the present invention was completed by finding that it can be suitably used as a dye for a dye-sensitized solar cell because it has excellent solubility and solubility in an organic solvent.
- a dye for a dye-sensitized solar cell comprising a phosphorylthiophene compound represented by the formula (1): (Wherein R 1 to R 4 and R 13 to R 16 are each independently —OR 5 , —SR 6 , —NR 7 2 , or —O — N + R 8 R 9 R 10 R 11 .
- R 5 to R 11 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with W;
- R 12 and R 17 each independently , Hydrogen atom, halogen atom, hydroxyl group, amino group, silanol group, thiol group, carboxyl group, ester group, thioester group, amide group, cyano group, nitro group, monovalent hydrocarbon group, organooxy group, organoamino group, Represents an organosilyl group, an organothio group, an acyl group, a sulfone group, or a phenyl group optionally substituted by W;
- W is a halogen atom, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, an ester Represents a thioester group, an amide group, a cyano group,
- R 41 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
- a phenyl group which may be substituted with W, and W represents the same meaning as described above.
- both ends of the phosphorylthiophene compound may be independently substituted with a hydrogen atom, a halogen atom, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, or W.
- a composition comprising one phosphorylthiophene compound, 3.
- a varnish comprising one phosphorylthiophene compound, 4).
- An organic thin film comprising one phosphorylthiophene compound, 5).
- a substrate having light permeability, a transparent conductive film laminated on the substrate, and a porous semiconductor made of a metal oxide laminated on the transparent conductive film, and one dye on the surface of the porous semiconductor A semiconductor electrode characterized in that a dye for a sensitized solar cell is adsorbed; 7).
- a dye-sensitized solar cell dye having high affinity and adhesion to a porous metal oxide and having excellent solubility in an organic solvent, and dye sensitization using the same A solar cell can be provided.
- FIG. 1 is a schematic cross-sectional view of a dye-sensitized solar cell produced in Example 1.
- FIG. 2 is a graph showing an absorption spectrum of polythiophene derivative A obtained in Synthesis Example 1.
- FIG. 6 is a graph showing an absorption spectrum of polythiophene derivative B obtained in Synthesis Example 2.
- FIG. 6 is a graph showing an absorption spectrum of polythiophene derivative C obtained in Synthesis Example 3.
- FIG. 6 is a graph showing an absorption spectrum of a polythiophene derivative D obtained in Synthesis Example 4.
- FIG. 3 is a diagram showing an IPCE spectrum of a dye-sensitized solar cell produced in Example 1.
- FIG. 4 is a diagram showing an IPCE spectrum of a dye-sensitized solar cell produced in Example 2.
- FIG. 4 is a diagram showing an IPCE spectrum of a dye-sensitized solar cell produced in Example 3. It is a figure which shows the IPCE spectrum of the dye-sensitized solar cell
- n is normal, “i” is iso, “s” is secondary, “t” is tertiary, “c” is cyclo, “o” is ortho, “M” means meta, “p” means para, “Me” means methyl group, “Et” means ethyl group, “Pr” means propyl group, “Bu” means butyl group, “Pen” "” Means a pentyl group, “Hex” means a hexyl group, “Hep” means a heptyl group, “Oct” means an octyl group, "Dec” means a decyl group, and “Ph” means a phenyl group.
- dye for dye-sensitized solar cells in this invention contains the phosphoryl thiophene compound shown by the said Formula (1).
- the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, c-propyl group, n-butyl group, i-butyl group, s -Butyl group, t-butyl group, c-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1- Dimethyl-n-propyl group, c-pentyl group, 2-methyl-c-butyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl- n-butyl group, 1-ethyl-
- Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, and a decyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; A bicycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-methyl-2-propenyl group, a 1 or 2 or 3-butenyl group, a hexenyl group; Examples thereof include aryl groups such as phenyl group, xylyl group, tolyl group, biphenyl group and naphthyl group; aralkyl
- Some or all of the hydrogen atoms of these monovalent hydrocarbon groups are hydroxyl groups, halogen atoms, amino groups, silanol groups, thiol groups, carboxyl groups, sulfone groups, phosphate groups, phosphate ester groups, ester groups. Substituted with thioester group, amide group, nitro group, organooxy group, organoamino group, organosilyl group, organothio group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group, etc. May be.
- organooxy group examples include an alkoxy group, an alkenyloxy group, and an aryloxy group.
- alkyl group, alkenyl group, and aryl group examples include the same monovalent hydrocarbon groups as those described above.
- organoamino group phenylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, laurylamino group
- Alkylamino groups such as groups; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinony
- organosilyl group examples include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, and decyldimethylsilyl group. Groups and the like.
- organothio group examples include alkylthio groups such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, and laurylthio group.
- Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, and benzoyl group.
- Examples of the ester group include —C (O) OQ 1 and —OC (O) Q 1 .
- Examples of the thioester group include —C (S) OQ 1 and —OC (S) Q 1 .
- Examples of the amide group include —C (O) NHQ 1 , —NHC (O) Q 1 , —C (O) NQ 1 Q 2 , and —NQ 1 C (O) Q 2 .
- Q 1 and Q 2 represent an alkyl group, an alkenyl group, or an aryl group, and these can be exemplified by the same groups as the monovalent hydrocarbon group.
- haloalkyl group having 1 to 20 carbon atoms include CH 2 F, CHF 2 , CF 3 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CH 2 CH 2 CH 2 F, and CH 2 CH.
- alkoxy group having 1 to 20 carbon atoms include OMe, OEt, OPr-n, OPr-i, OBu-n, OBu-i, OBu-s, OBu-t, OPen-n, OCHEt 2 , OHex- n, OCHMe (Pr-n) , OCHMe (Bu-n), OCHEt (Pr-n), OCH 2 CH 2 CHMe 2, OHep-n, OOct-n, include ODec-n, and the like.
- alkylthio group having 1 to 20 carbon atoms include SMe, SEt, SPr-n, SPr-i, SBu-n, SBu-i, SBu-s, SBu-t, SPen-n, SCHEt 2 and SHex- n, SCHMe (Pr-n), SCHMe (Bu-n), SCHEt (Pr-n), SCH 2 CH 2 CHMe 2 , SHep-n, SOCt-n, SDec-n and the like.
- C 1-20 dialkylamino group examples include NMe 2 , NEt 2 , N (Pr-n) 2 , N (Pr-i) 2 , N (Bu-n) 2 , N (Bu-i). 2 , N (Bu-s) 2 , N (Bu-t) 2 , N (Pen-n) 2 , N (CHEt 2 ) 2 , N (Hex-n) 2 , N (Hep-n) 2 , N (Oct-n) 2 , N (Dec-n) 2 , N (Me) (Bu-n), N (Me) (Pen-n), N (Me) (Hex-n), N (Me) ( Hep-n), N (Me) (Oct-n), N (Me) (Dec-n) and the like.
- phenyl group which may be substituted with W include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-trifluoromethylphenyl, m-trifluoromethylphenyl, p-triphenyl.
- R 5 to R 11 in consideration of further improving the adsorptivity to the metal oxide constituting the semiconductor electrode and the solubility in the organic solvent during varnish preparation, A hydrogen atom and an alkyl group having 1 to 10 carbon atoms are preferred.
- R 1 to R 4 and R 13 to R 16 are preferably —OH or —O — N + R 8 R 9 R 10 R 11 for the same reason as described above.
- R 12 and R 17 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom.
- Z in the formula (1) is at least one divalent organic group selected from the above formulas (2) to (10), and a divalent organic group represented by the formula (3) is particularly preferable. In particular, unsubstituted thiophenyl in which R 22 and R 23 are both hydrogen atoms is preferred.
- M, n, o, and p each independently represent an integer of 0 or 1 or more, and are integers that satisfy 1 ⁇ m + n + o and 2 ⁇ m + n + o + p ⁇ 1,000, but 2 ⁇ m + n + o + p ⁇ 200 Is preferable, and 5 ⁇ m + n + o + p ⁇ 200 is more preferable.
- a compound in which any two of n, m, o, and p are 0, and a compound in which any two of n, m, and o are 0 are preferable.
- This compound may be an oligomer satisfying 2 ⁇ m + n + o + p ⁇ 20 or a polymer satisfying 20 ⁇ m + n + o + p ⁇ 1,000.
- the molecular weight of the phosphorylthiophene compound is not particularly limited, but in the case of a polymer, the weight average molecular weight is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
- a weight average molecular weight is a polystyrene conversion value by gel filtration chromatography.
- Both ends of the phosphorylthiophene compound are independently a hydrogen atom, a halogen atom, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with W.
- specific examples of the monoalkylamino group having 1 to 20 carbon atoms include NHMe, NHEt, NHPr-n, NHPr-i, NHBu-n, NHBu-i, NHBu-s, NHBu-t, NHPen-n, NHCHEt 2 , NHHex-n, NHHep-n, NHOct-n, NHDec-n and the like can be mentioned.
- trialkylstannyl group having 1 to 10 carbon atoms include SnMe 3 , SnEt 3 , Sn (Pr-n) 3 , Sn (Pr-i) 3 , Sn (Bu-n) 3 , Sn (Bu— i) 3 , Sn (Bu-s) 3 , Sn (Bu-t) 3 and the like.
- C1-C10 trialkylsilyl group include SiMe 3 , SiEt 3 , Si (Pr—n) 3 , Si (Pr—i) 3 , Si (Bu—n) 3 , Si (Bu—i). ) 3 , Si (Bu-s) 3 , Si (Bu-t) 3 and the like.
- naphthyl group which may be substituted with W include 1-naphthyl, 2-naphthyl, 2-butyl-1-naphthyl, 3-butyl-1-naphthyl, 4-butyl-1-naphthyl, 5- Butyl-1-naphthyl, 6-butyl-1-naphthyl, 7-butyl-1-naphthyl, 8-butyl-1-naphthyl, 1-butyl-2-naphthyl, 3-butyl-2-naphthyl, 4-butyl- 2-naphthyl, 5-butyl-2-naphthyl, 6-butyl-2-naphthyl, 7-butyl-2-naphthyl, 8-butyl-2-naphthyl, 2-hexyl-1-naphthyl, 3-hexyl-1-
- anthranyl group which may be substituted with W include 1-anthranyl, 2-anthranyl, 9-anthranyl, 2-butyl-1-anthranyl, 3-butyl-1-anthranyl and 4-butyl- 1-anthranyl, 5-butyl-1-anthranyl, 6-butyl-1-anthranyl, 7-butyl-1-anthranyl, 8-butyl-1-anthranyl, 9-butyl-1-anthranyl, 10-butyl-1- Anthranyl, 1-butyl-2-anthranyl, 3-butyl-2-anthranyl, 4-butyl-2-anthranyl, 5-butyl-2-anthranyl, 6-butyl-2-anthranyl, 7-butyl-2-anthranyl, 8-butyl-2-anthranyl, 9-butyl-2-anthranyl, 10-butyl-2
- the phosphorylthiophene compound represented by the formula (1) used as the dye for the dye-sensitized solar cell of the present invention is a phosphorylthiophene monomer compound obtained by the method described in International Publication No. 2006/109895 pamphlet. Can be produced by coupling, polymerization, and functional group conversion as necessary.
- the coupling method is not particularly limited, and for example, biaryl coupling, Stille coupling, Suzuki coupling, Ullmann coupling, Heck reaction, Sonogashira coupling, Grignard reaction and the like can be used.
- the polymerization method is not particularly limited as long as it is a method capable of polymerizing a phosphorylthiophene compound.
- the polymerization method may be appropriately selected from known polymerization methods such as chemical oxidation polymerization, electrolytic oxidation polymerization, and catalytic polymerization. In the present invention, catalytic polymerization is preferred.
- the catalytic polymerization is carried out by reacting a phosphorylthiophene monomer compound and a monomer corresponding to Z used as necessary in the presence of a metal catalyst, and a phosphorylthiophene oligomer or polymer represented by the formula (1) It is a method to make a compound.
- a phosphorylthiophene monomer compound used for the catalytic polymerization and the monomer that gives Z a phosphorylthiophene compound having a halogen atom at the terminal (polymerization site) substituent is preferable. Of these, a bromine atom is preferred.
- the metal catalyst examples include nickel complexes, and specific examples include nickel (0) represented by bis (1,5-cyclooctadiene) nickel (0), tetrakis (triphenylphosphine) nickel (0), and the like.
- ) Complex, or nickel chloride bis (triphenylphosphine) nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane ]
- the amount of the metal catalyst used is preferably 0.05 to 2.0 moles, and particularly preferably 0.5 to 0.8 moles, relative to the halogen atoms contained in all monomer compounds of the substrate.
- the amount of the ligand used is preferably 0.05 to 2.0 moles, particularly preferably 0.5 to 0.8 moles, relative to the halogen atoms contained in all monomer compounds of the substrate.
- reaction solvent examples include amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as benzene, toluene and xylene; tetrahydrofuran (THF), 1,4-dioxane, Ether compounds such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether are preferred.
- THF tetrahydrofuran
- Ether compounds such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether are preferred.
- the polymer formed from 1,4-dioxane is preferable in that the degree of polymerization is high.
- the reaction temperature may be not higher than the boiling point of the solvent used, and is usually about 20 to 200 ° C.
- the reaction time is not particularly limited, but is usually about 1 to 48 hours.
- phosphorylthiophene compound of the present invention as a method for solvolysis of the phosphate ester group with water or alcohol, for example, Journal of Chemical Society (J. Chem. Soc.), 1959 3950, Journal of American Chemical Society (J. Am. Chem. Soc.), 1953, page 3379.
- a method for converting a phosphate ester group into an amide or a thioester for example, Organic Phosphorus Compounds, Vol. 4, Willy-Interscience, 1972, 9th.
- a technique for converting a phosphate group to —O ⁇ N + R 8 R 9 R 10 R 11 a technique in which a thiophenephosphonic acid compound is mixed with a quaternary ammonium salt in a reaction solvent can be mentioned.
- the quaternary ammonium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexylammonium hydroxide, trimethyloctylammonium hydroxide, And trimethylphenylammonium hydroxide.
- tetrabutylammonium hydroxide is preferable in that the solubility of the resulting polymer in alcohol solvents such as methanol and ethanol is increased.
- alcohol solvent water, methanol, and ethanol are preferable, and methanol is preferable in that the solubility of thiophenephosphonic acid is high.
- the reaction temperature may be not higher than the boiling point of the solvent used, and is usually about 10 to 40 ° C.
- the reaction time is not particularly limited, but is usually about 5 minutes to 2 hours.
- the dye-sensitized solar cell according to the present invention uses the phosphorylthiophene compound represented by the above-described formula (1) as a dye.
- the substrate has a light transmitting property and the substrate. It has a laminated transparent conductive film and a porous semiconductor made of a metal oxide laminated on the transparent conductive film, and the dye for dye-sensitized solar cell of the present invention is adsorbed on the surface of the porous semiconductor A semiconductor electrode, a counter electrode, and an electrolyte interposed between these electrodes are provided.
- the phosphorylthiophene compound represented by the above formula (1) is used as a pigment, the other solar cell constituent members are particularly limited. It can be used by appropriately selecting from known ones.
- the light-transmitting substrate is not particularly limited as long as it has a light-transmitting property and can be a conductive layer substrate, and includes a glass substrate, a transparent polymer film, and a laminate thereof. Etc. can be used.
- the material for the transparent polymer film include triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), and polyarylate.
- TAC triacetyl cellulose
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- SPS syndiotactic polystyrene
- PPS polyphenylene sulfide
- PC polycarbonate
- the transparent conductive film for example, platinum, gold, silver, copper, zinc, titanium, aluminum, indium, alloys such as these alloys, indium-tin composite oxide, tin oxide doped with fluorine or antimony In particular, it is preferable to use tin dioxide or indium-tin oxide doped with fluorine or antimony.
- This transparent conductive layer can be formed by applying or vapor-depositing on the surface of the transparent substrate.
- the metal oxide constituting the semiconductor examples include TiO 2 , SnO 2 , Fe 2 O 3 , WO 3 , ZnO, Nb 2 O 5 and the like.
- the counter electrode is not particularly limited as long as it acts as a positive electrode of the dye-sensitized solar cell.
- electrolyte salts such as metal iodides such as LiI, NaI, KI, CsI, and CaI 2 , quaternary pyridinium or imidazolium compound iodine salts, tetraalkylammonium compound iodine salts, and the like I ⁇ And an organic solvent containing iodine capable of forming a redox pair.
- Organic solvents include carbonates such as ethylene carbonate and propylene carbonate; ethers such as dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether; methanol, ethanol, ethylene glycol Monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin; acetonitrile, propionitrile, benzonitrile, etc. Nitrile And the like.
- the dye-sensitized solar cell of the present invention may be provided with a functional layer such as a protective layer or an antireflection layer at an appropriate position.
- a method for adsorbing the dye-sensitized solar cell dye of the present invention on the surface of the porous semiconductor a method of preparing a solution (varnish) containing the dye and immersing the substrate having the porous semiconductor in this, a dye
- substrate which has a porous semiconductor can be used.
- the solvent for preparing the solution containing the pigment (varnish) is not particularly limited as long as it has the ability to dissolve the pigment, and examples thereof include methanol and ethanol.
- the concentration of the dye in the solution (varnish) is not particularly limited, but can be about 0.01 to 10 mmol / L.
- the total adsorption amount of the dye can be, for example, about 0.01 to 100 mmol per unit surface area (1 m 2 ) of the semiconductor.
- dyes such as metal complex dyes, methine dyes, porphyrin dyes, and phthalocyanine dyes may be used in combination with the dye of the present invention.
- ruthenium-bipyridine complexes particularly cis-di (thiocyanato) -N, N′-bis (2,) have high optical activity and are excellent in adsorptivity and durability to semiconductors. 2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II) is preferred.
- 2,56-dibromo-3-diethoxyphosphorylthiophene 0.756 g (2.00 mmol) and 2,2′-bipyridyl 0.937 g (6.00 mmol, 1.2 equivalents) were added to the reaction vessel, and the reaction After replacing the vessel with nitrogen, 0.726 g (3.00 mmol) of 2,5-dibromothiophene, 0.541 g (5.00 mmol, 1.0 equivalent) of 1,5-cyclooctadiene, and 50 mL of 1,4-dioxane was added with a syringe.
- Polythiophene A produced in Synthesis Example 1 was put into a reaction vessel, and acetonitrile was added and dissolved in a nitrogen atmosphere. Iodotrimethylsilane (3 equivalents) was slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 20 hours. After the reaction, methanol was added and stirred for 1 hour to crush excess iodotrimethylsilane, and then the solvent was distilled off. The crude product was dissolved in water, washed 10 times with chloroform, passed through an ion exchange resin (IR-120B, IRA-410), the solvent was distilled off, and the residue was dried with a vacuum pump to give a red solid. Obtained.
- Example 1 Production of photoelectric conversion electrode As shown in FIG. 1, titania paste (Ti) on a glass substrate 11 (size: 15 mm ⁇ 25 mm) with an FTO (F: SnO 2 ) film 12 having a surface resistance of 10 ⁇ / sq. -Nanoxide T / S, manufactured by SOLARONIXS) was applied by screen printing, dried at 120 ° C. for 3 minutes, and then baked at 500 ° C. for 30 minutes to form a titania semiconductor layer 13. It was 20 micrometers when the film thickness of the titania semiconductor layer 13 after baking was measured with the stylus type film thickness meter (ET4000A, Kosaka Laboratory Ltd.).
- FTO F: SnO 2
- the substrate after baking is immersed in a methanol solution (concentration: 0.1 mM) of the polythiophene derivative A obtained in Synthesis Example 1, and the polythiophene derivative A (pigment) (not shown) is applied to the titania semiconductor layer 13. It was made to adsorb
- the electrolyte 30 which consists of an acetonitrile solution containing was inject
- IPCE For the solar cell obtained in Example 1, IPCE was measured in the range of 300 to 1,100 nm. The obtained IPCE spectrum is shown in FIG. As shown in FIG. 6, it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 500 nm. Moreover, the current-voltage characteristic of the obtained photovoltaic cell was measured. The results are shown in Table 2. As shown in Table 2, it can be seen that although there is some variation in data depending on the measurement, a photoelectric conversion efficiency of 0.053% is obtained.
- Example 2 A photoelectric conversion electrode and a solar battery cell were produced in the same manner as in Example 1 except that the polythiophene derivative A was changed to the polythiophene derivative B obtained in Synthesis Example 2.
- IPCE was measured in the range of 300 to 1,100 nm.
- the obtained IPCE spectrum is shown in FIG. As shown in FIG. 7, it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 550 nm.
- the current-voltage characteristic of the obtained photovoltaic cell was measured.
- Table 2 As shown in Table 2, it can be seen that a photoelectric conversion efficiency of 0.064% is obtained.
- Example 3 A photoelectric conversion electrode and a solar battery cell were produced in the same manner as in Example 1 except that the polythiophene derivative A was changed to the polythiophene derivative C obtained in Synthesis Example 3.
- IPCE was measured in the range of 300 to 1,100 nm.
- the obtained IPCE spectrum is shown in FIG. As shown in FIG. 8, it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 600 nm.
- the current-voltage characteristic of the obtained photovoltaic cell was measured.
- Table 2 As shown in Table 2, it can be seen that a photoelectric conversion efficiency of 0.469% is obtained.
- Example 4 A photoelectric conversion electrode and a solar battery cell were produced in the same manner as in Example 1 except that the polythiophene derivative A was changed to the polythiophene derivative D obtained in Synthesis Example 4.
- IPCE was measured in the range of 300 to 1,100 nm.
- the obtained IPCE spectrum is shown in FIG.
- FIG. 9 it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 600 nm.
- the current-voltage characteristic of the obtained photovoltaic cell was measured.
- Table 2 As shown in Table 2, it can be seen that a photoelectric conversion efficiency of 0.568% is obtained.
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Abstract
Description
中でも、太陽光エネルギーを利用する太陽電池は、資源が無限であるのみならず、環境調和型デバイスであるため大きな注目を集めている。
特に、色素増感太陽電池は、使用する材料が安価であること、製造プロセスに真空装置を用いなくても済むことなどの利点から、グレッツェルらにより提案されて以来、実用化に向けた研究が盛んに行われている。
太陽電池の光電変換効率は、太陽光の吸収によって発生した電子量に比例することから、変換効率を向上させるためには、半導体電極上の色素吸着量を大きくする必要がある。
このため、色素増感太陽電池用の色素には、金属酸化物に対する、高い親和性や密着性を有することが求められる。
また、半導体電極への色素の吸着は、一般的に、色素を有機溶媒に溶解してなる溶液に、半導体電極を浸漬することにより行われているため、有機溶媒に対する優れた溶解性も色素に求められる重要な性質である。
しかしながら、オリゴチオフェン化合物について、カルボン酸を導入する以外の方法での親和性、密着性の改善を行った色素の例はなく、広い吸収波長をもつポリチオフェン化合物についても、現在のところ、同様の色素の設計は行われていない。
1. 式(1)で表されるフォスフォリルチオフェン化合物を含むことを特徴とする色素増感太陽電池用色素、
2. 1のフォスフォリルチオフェン化合物を含む組成物、
3. 1のフォスフォリルチオフェン化合物を含むワニス、
4. 1のフォスフォリルチオフェン化合物を含む有機薄膜、
5. 4のワニスから作製される有機薄膜、
6. 光透過性を有する基板と、この基板に積層された透明導電膜と、この透明導電膜に積層された金属酸化物からなる多孔質半導体とを有し、前記多孔質半導体の表面に1の色素増感太陽電池用色素が吸着されていることを特徴とする半導体電極、
7. 3のワニスに多孔質半導体を有する基板を浸漬し、前記色素増感太陽電池用色素を前記多孔質半導体に吸着させてなる半導体電極、
8. 6の半導体電極と、対極と、これら半導体電極および対極間に介在する電解質と、を備えて構成される色素増感太陽電池
を提供する。
10 光電変換電極
11 ガラス基板(光透過性を有する基板)
12 FTO膜(透明導電膜)
13 光増感色素が吸着したチタニア半導体層(多孔質半導体)
14 Pt層
15 ガラス基板
20 対極
30 電解質
なお、本明細書中、「n」はノルマルを、「i」はイソを、「s」はセカンダリーを、「t」はターシャリーを、「c」はシクロを、「o」はオルトを、「m」はメタを、「p」はパラを意味し、「Me」はメチル基を、「Et」はエチル基を、「Pr」はプロピル基を、「Bu」はブチル基を、「Pen」はペンチル基を、「Hex」はヘキシル基を、「Hep」はヘプチル基を、「Oct」はオクチル基を、「Dec」はデシル基を、「Ph」はフェニル基を意味する。
式(1)において、炭素数1~20アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、c-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、t-ブチル基、c-ブチル基、n-ペンチル基、1-メチル-n-ブチル基、2-メチル-n-ブチル基、3-メチル-n-ブチル基、1,1-ジメチル-n-プロピル基、c-ペンチル基、2-メチル-c-ブチル基、n-ヘキシル基、1-メチル-n-ペンチル基、2-メチル-n-ペンチル基、1,1-ジメチル-n-ブチル基、1-エチル-n-ブチル基、1,1,2-トリメチル-n-プロピル基、c-ヘキシル基、1-メチル-c-ペンチル基、1-エチル-c-ブチル基、1,2-ジメチル-c-ブチル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基、n-ウンデシル基、n-ドデシル基、n-トリデシル基、n-テトラデシル基、n-ペンタデシル基、n-ヘキサデシル基、n-ヘプタデシル基、n-オクタデシル基、n-ノナデシル基、n-エイコシル基等が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
なお、これらの一価炭化水素基の水素原子の一部または全部は、水酸基、ハロゲン原子、アミノ基、シラノール基、チオール基、カルボキシル基、スルホン基、リン酸基、リン酸エステル基、エステル基、チオエステル基、アミド基、ニトロ基、オルガノオキシ基、オルガノアミノ基、オルガノシリル基、オルガノチオ基、アシル基、アルキル基、シクロアルキル基、ビシクロアルキル基、アルケニル基、アリール基、アラルキル基などで置換されていてもよい。
オルガノアミノ基としては、フェニルアミノ基、メチルアミノ基、エチルアミノ基、プロピルアミノ基、ブチルアミノ基、ペンチルアミノ基、ヘキシルアミノ基、ヘプチルアミノ基、オクチルアミノ基、ノニルアミノ基、デシルアミノ基、ラウリルアミノ基等のアルキルアミノ基;ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、ジペンチルアミノ基、ジヘキシルアミノ基、ジヘプチルアミノ基、ジオクチルアミノ基、ジノニルアミノ基、ジデシルアミノ基等のジアルキルアミノ基;シクロヘキシルアミノ基、モルホリノ基などが挙げられる。
オルガノチオ基としては、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、オクチルチオ基、ノニルチオ基、デシルチオ基、ラウリルチオ基などのアルキルチオ基が挙げられる。
エステル基としては、-C(O)OQ1、-OC(O)Q1が挙げられる。
チオエステル基としては、-C(S)OQ1、-OC(S)Q1が挙げられる。
アミド基としては、-C(O)NHQ1、-NHC(O)Q1、-C(O)NQ1Q2、-NQ1C(O)Q2が挙げられる。
ここで、上記Q1およびQ2は、アルキル基、アルケニル基またはアリール基を示し、これらは上記一価炭化水素基と同様のものを例示することができる。
炭素数1~20アルコキシ基の具体例としては、OMe、OEt、OPr-n、OPr-i、OBu-n、OBu-i、OBu-s、OBu-t、OPen-n、OCHEt2、OHex-n、OCHMe(Pr-n)、OCHMe(Bu-n)、OCHEt(Pr-n)、OCH2CH2CHMe2、OHep-n、OOct-n、ODec-n等が挙げられる。
炭素数1~20ジアルキルアミノ基の具体例としては、NMe2、NEt2、N(Pr-n)2、N(Pr-i)2、N(Bu-n)2、N(Bu-i)2、N(Bu-s)2、N(Bu-t)2、N(Pen-n)2、N(CHEt2)2、N(Hex-n)2、N(Hep-n)2、N(Oct-n)2、N(Dec-n)2、N(Me)(Bu-n)、N(Me)(Pen-n)、N(Me)(Hex-n)、N(Me)(Hep-n)、N(Me)(Oct-n)、N(Me)(Dec-n)等が挙げられる。
また、R12およびR17としては、水素原子、炭素数1~10アルキル基が好ましく、水素原子がより好ましい。
式(1)におけるZは、上記式(2)~(10)から選ばれる少なくとも1種の2価の有機基であるが、特に、式(3)で表される2価の有機基が好適であり、特に、R22およびR23が共に水素原子である非置換チオフェニルが好適である。
なお、この化合物は、2≦m+n+o+p≦20を満たす程度のオリゴマーでも、20≦m+n+o+p≦1,000を満たすポリマーでもよい。
フォスフォリルチオフェン化合物の分子量は特に限定されるものではないが、ポリマーの場合、重量平均分子量1,000~100,000が好ましく、1,000~50,000がより好ましい。なお、重量平均分子量は、ゲル濾過クロマトグラフィーによるポリスチレン換算値である。
炭素数1~10トリアルキルスタニル基の具体例としては、SnMe3、SnEt3、Sn(Pr-n)3、Sn(Pr-i)3、Sn(Bu-n)3、Sn(Bu-i)3、Sn(Bu-s)3、Sn(Bu-t)3等が挙げられる。
炭素数1~10トリアルキルシリル基の具体例としては、SiMe3、SiEt3、Si(Pr-n)3、Si(Pr-i)3、Si(Bu-n)3、Si(Bu-i)3、Si(Bu-s)3、Si(Bu-t)3等が挙げられる。
カップリング法としては、特に限定されるものではなく、例えば、ビアリールカップリング、Stilleカップリング、Suzukiカップリング、Ullmannカップリング、Heck反応、、薗頭カップリング、Grignard反応等を用いることができる。
重合法としては、フォスフォリルチオフェン化合物を重合できる手法であれば特に限定されるものではなく、例えば、化学酸化重合、電解酸化重合、触媒重合等の公知の重合法から適宜選択すればよいが、本発明においては、触媒重合が好適である。
触媒重合に用いられるフォスフォリルチオフェンモノマー化合物や、Zを与えるモノマーとしては、末端(重合部位)置換基がハロゲン原子のフォスフォリルチオフェン化合物が好ましい。中でも、臭素原子が好適である。
配位子の使用量は、基質の全モノマー化合物が有するハロゲン原子に対して0.05~2.0モル倍が好ましく、特に0.5~0.8モル倍が好ましい。
反応溶媒としては、例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド化合物類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類;テトラヒドロフラン(THF)、1,4-ジオキサン、1,2-ジメトキシエタン、ジエチレングリコールジメチルエーテル等のエーテル化合物類が好ましい。中でも、1,4-ジオキサンが生成したポリマーの重合度が高いという点で好適である。
反応温度は、使用溶媒の沸点以下であればよく、通常、20~200℃程度である。
反応時間は、特に限定されるものではないが、通常、1~48時間程度である。
また、リン酸エステル基を、アミドやチオエステルに変換する方法としては、例えば、オーガニック フォスフォラス カンパウンド(Organic Phosphorus Compounds),4巻,ウィリー-インターサイエンス社(Wiley-Interscience),1972年,第9章,155~253頁や、オーガニック フォスフォラス カンパウンド(Organic Phosphorus Compounds),6巻,ウィリー-インターサイエンス社(Wiley-Interscience),1973年,第14章,1~209頁や、オーガニック フォスフォラス カンパウンド(Organic Phosphorus Compounds),7巻,ウィリー-インターサイエンス社(Wiley-Interscience),1976年,第18章,1~486頁に記載されている方法を基本にすればよい。
4級アンモニウム塩としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、テトラヘキシルアンモニウムヒドロキシド、トリメチルブチルアンモニウムヒドロキシド、トリメチルヘキシルアンモニウムヒドロキシド、トリメチルオクチルアンモニウムヒドロキシド、トリメチルフェニルアンモニウムヒドロキシド等が挙げられる。
これらの中でも、得られるポリマーのメタノール、エタノール等のアルコール溶媒への溶解性が高くなるという点で、テトラブチルアンモニウムヒドロキシドが好ましい。
反応溶媒としては、水、メタノール、エタノールが好ましく、中でもメタノールがチオフェンホスホン酸の溶解度が高いという点で好適である。
反応温度は、使用溶媒の沸点以下であればよく、通常、10~40℃程度である。
反応時間は、特に限定させるものではないが、通常、5分~2時間程度である。
なお、テトラアルキルアンモニウム塩等の疎水性の4級アンモニウム塩を有する誘導体に変換することで、メタノール,エタノール等のアルコール溶媒をはじめ各種有機溶媒に対する溶解性が向上する。
本発明の色素増感太陽電池においては、上述した式(1)で表されるフォスフォリルチオフェン化合物を色素として用いることにその特徴があるため、その他の太陽電池構成部材としては特に限定されるものではなく、公知のものから適宜選択して用いることができる。
上記透明ポリマーフィルムの材料としては、トリアセチルセルロース(TAC)、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、シンジオタクチックポリスチレン(SPS)、ポリフェニレンスルフィド(PPS)、ポリカーボネート(PC)、ポリアリレート、ポリスルフォン、ポリエステルスルフォン(PES)、ポリイミド(PI)、ポリエーテルイミド(PEI)、環状ポリオレフィン、ブロム化フェノキシ等を用いることができる。
対極としては、色素増感太陽電池の正極として作用するものであれば、特に限定はなく、例えば、ガラス基板やプラスチックフィルム等に、白金、金、銀、銅、アルミニウム、およびマグネシウムから選ばれる少なくとも1種の金属を塗布または蒸着させた電極等が挙げられる。
有機溶媒としては、エチレンカーボネート、プロピレンカーボネート等のカーボネート類;ジオキサン、ジエチルエーテル、エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテル等のエーテル類;メタノール、エタノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、ポリプロピレングリコールモノアルキルエーテル、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン等のアルコール類;アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル類などが挙げられる。
その他、本発明の色素増感太陽電池には、保護層や反射防止層などの機能層を適宜な位置に設けてもよい。
色素を含む溶液(ワニス)を調製する際の溶媒は、色素の溶解能を有するものであれば特に限定はなく、メタノール、エタノールなどが挙げられる。溶液(ワニス)中の色素濃度は、特に限定されるものではないが、0.01~10mmol/L程度とすることができる。
色素の全吸着量は、例えば、半導体の単位表面積(1m2)あたり、0.01~100mmol程度とすることができる。
これらの中でも、高い光学活性を有し、半導体への吸着性および耐久性に優れているということから、ルテニウム-ビピリジン錯体、中でも、シス-ジ(チオシアナト)-N,N’-ビス(2,2’-ビピリジル-4,4’-ジカルボン酸)ルテニウム(II)が好適である。
なお、実施例にて使用した分析装置および条件は、下記のとおりである。
機種:JNM-A500(JEOL Ltd.)、またはAVANCE 400S(Bruker)
[2]ゲル濾過クロマトグラフィー(GPC)
機種:TOSOH:HLC-8220GPC,カラム:SHODEX GPC KF-804L+GPC KF-805L,カラム温度:40℃,検出器:UV検出器(254nm)およびRI検出器,溶離液:THF,カラム流速:1.0mL/min.
[3]吸収スペクトル
機種:UV-3600、島津製作所(株)製
[4]IPCE(incident-photon conversion efficiency)スペクトル
500WのXeランプを、分光器(SM-250、分光計器(株)製)を用いて300nm~1100nmの範囲で分光し、10nm間隔で単色光を照射し、セルからの光電流を電流計(6487、Keithley製)で検出し、この光電流スペクトルを基準シリコン受光素子で計測したスペクトルを分光感度で補正し、測定した。
[5]電流電圧測定
ソーラーシミュレーター(YSS-80、山下電装(株)製)を用い、擬似太陽光源(AM1.5,100mW/cm2)を照射し、太陽電池セルの電流電圧特性(HSV-100、HOKUTO DENKO製)を測定した。
Mw(GPC): 9,700
1H-NMR(CDCl3): 1.20-1.29(6H, m), 4.02-4.18(4H, m), 6.91(1H, s)
反応終了後、反応液をセライトでろ過し、クロロホルムで残渣を洗浄した。ろ液を10質量%塩酸水溶液で1回、10質量%食塩水で3回洗浄し、有機層に無水硫酸ナトリウムを加えて乾燥し、ろ過後、溶媒を留去した。留去後の残渣にクロロホルムを加えて溶解し、n-ヘキサンに滴下し、析出した固体をろ過で回収し、n-ヘキサンで洗浄した。これを真空ポンプで減圧して乾燥させ、赤色固体を0.351g得た。
Mw(GPC): 9,232
1H-NMR(CDCl3): 1.29-1.35(br), 4.11-4.21(br), 7.13-7.22(br), 7.50-7.83(br)
1H-NMR(D2O): 7.14(1H, s)
13C-NMR(D2O): 112.7(d, J=21.9Hz), 117.9(s, J=7.6Hz), 135.1(d, J=13.4Hz), 138.8(d, 187.5Hz)
31P-NMR(D2O):4.06(s)
1H-NMR(CD3OD): 1.14-1.32(br), 3.82-4.16(br), 7.22-7.78(br)
1H-NMR(CD3OD): 1.00-1.05(t), 1.14-1.32(br), 1.35-1.48(m), 1.61-1.71(m), 3.21-3.27(m), 3.82-4.16(br), 7.22-7.78(br)
[1]光電変換電極の作製
図1に示されるように、表面抵抗値10Ω/sqのFTO(F:SnO2)膜12付きガラス基板11(サイズ:15mm×25mm)上に、チタニアペースト(Ti-Nanoxide T/S,SOLARONIXS社製)をスクリーン印刷法により塗布し、120℃で3分間乾燥させた後、500℃で30分間焼成し、チタニア半導体層13を形成した。焼成後のチタニア半導体層13の膜厚を触針式膜厚計(ET4000A、(株)小阪研究所製)で計測したところ、20μmであった。
次に、合成例1で得られたポリチオフェン誘導体Aのメタノール溶液(濃度:0.1mM)に、上記焼成後の基板を浸漬し、ポリチオフェン誘導体A(色素)(図示省略)をチタニア半導体層13に吸着させ、光電変換電極10を作製した。
直径0.7mmの電解液注入孔を2つ有するFTO膜付きガラス基板15上に、Pt層14を成膜(膜厚:1nm)した対極20の周囲にエチレン-メタクリル酸共重合体アイオノマー樹脂膜(ハイミラン、三井・デュポンポリケミカル(株)製)(膜厚:30nm)を配置し、上記で得られた光電変換電極10と貼り合わせた。その後、電解液注入孔から、0.1mol/Lのヨウ化リチウム、0.025mol/Lのヨウ素、0.5mol/Lのジメチルプロピルイミダゾリウムアイオダイド、および0.5mol/Lのt-ブチルピリジンを含むアセトニトリル溶液からなる電解質30を注入し、色素増感太陽電池セル1を作製した。
また、得られた太陽電池セルの電流電圧特性を測定した。その結果を表2に示す。表2に示されるように、測定時によってデータに多少のばらつきはあるものの、0.053%の光電変換効率が得られていることがわかる。
ポリチオフェン誘導体Aを、合成例2で得られたポリチオフェン誘導体Bに変更した以外は、実施例1と同様にして、光電変換電極および太陽電池セルを作製した。
実施例2で得られた太陽電池セルについて、300~1,100nmの範囲でIPCEを計測した。得られたIPCEスペクトルを図7に示す。図7に示されるように、紫外から550nmにわたって光吸収に対応した領域でIPCEが得られていることがわかる。
また、得られた太陽電池セルの電流電圧特性を測定した。その結果を表2に示す。表2に示されるように、0.064%の光電変換効率が得られていることがわかる。
ポリチオフェン誘導体Aを、合成例3で得られたポリチオフェン誘導体Cに変更した以外は、実施例1と同様にして、光電変換電極および太陽電池セルを作製した。
実施例3で得られた太陽電池セルについて、300~1,100nmの範囲でIPCEを計測した。得られたIPCEスペクトルを図8に示す。図8に示されるように、紫外から600nmにわたって光吸収に対応した領域でIPCEが得られていることがわかる。
また、得られた太陽電池セルの電流電圧特性を測定した。その結果を表2に示す。表2に示されるように、0.469%の光電変換効率が得られていることがわかる。
ポリチオフェン誘導体Aを、合成例4で得られたポリチオフェン誘導体Dに変更した以外は、実施例1と同様にして、光電変換電極および太陽電池セルを作製した。
実施例4で得られた太陽電池セルについて、300~1,100nmの範囲でIPCEを計測した。得られたIPCEスペクトルを図9に示す。図9に示されるように、紫外から600nmにわたって光吸収に対応した領域でIPCEが得られていることがわかる。
また、得られた太陽電池セルの電流電圧特性を測定した。その結果を表2に示す。表2に示されるように、0.568%の光電変換効率が得られていることがわかる。
Claims (8)
- 式(1)で表されるフォスフォリルチオフェン化合物を含むことを特徴とする色素増感太陽電池用色素。
R12およびR17は、それぞれ独立して、水素原子、ハロゲン原子、水酸基、アミノ基、シラノール基、チオール基、カルボキシル基、エステル基、チオエステル基、アミド基、シアノ基、ニトロ基、一価炭化水素基、オルガノオキシ基、オルガノアミノ基、オルガノシリル基、オルガノチオ基、アシル基、スルホン基、またはWで置換されていてもよいフェニル基を表し、
Wは、ハロゲン原子、水酸基、アミノ基、シラノール基、チオール基、カルボキシル基、エステル基、チオエステル基、アミド基、シアノ基、ニトロ基、一価炭化水素基、オルガノオキシ基、オルガノアミノ基、オルガノシリル基、オルガノチオ基、アシル基、またはスルホン基を表し、
m、n、oおよびpは、それぞれ独立して、0または1以上の整数を表し、1≦m+n+o、かつ、2≦m+n+o+p≦1,000を満足し、
Zは、下記式[2]~[10]から選ばれる2価の有機基であり、
ただし、当該フォスフォリルチオフェン化合物の両末端は、互いに独立して、水素原子、ハロゲン原子、炭素数1~20モノアルキルアミノ基、炭素数1~20ジアルキルアミノ基、Wで置換されてもよいフェニル基、Wで置換されてもよいナフチル基、Wで置換されてもよいアントラニル基、炭素数1~10トリアルキルスタニル基、または炭素数1~10トリアルキルシリル基であり、Wは前記と同じ意味を表す。) - 請求項1記載のフォスフォリルチオフェン化合物を含む組成物。
- 請求項1記載のフォスフォリルチオフェン化合物を含むワニス。
- 請求項1記載のフォスフォリルチオフェン化合物を含む有機薄膜。
- 請求項4記載のワニスから作製される有機薄膜。
- 光透過性を有する基板と、この基板に積層された透明導電膜と、この透明導電膜に積層された金属酸化物からなる多孔質半導体とを有し、
前記多孔質半導体の表面には請求項1記載の色素増感太陽電池用色素が吸着されていることを特徴とする半導体電極。 - 請求項3記載のワニスに多孔質半導体を有する基板を浸漬し、前記色素増感太陽電池用色素を前記多孔質半導体に吸着させてなる半導体電極。
- 請求項6記載の半導体電極と、対極と、これら半導体電極および対極間に介在する電解質と、を備えて構成される色素増感太陽電池。
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WO2011118715A1 (ja) * | 2010-03-26 | 2011-09-29 | 日産化学工業株式会社 | 色素増感太陽電池用色素および色素増感太陽電池 |
JP2011204545A (ja) * | 2010-03-26 | 2011-10-13 | Koji Segawa | 色素増感太陽電池用色素および色素増感太陽電池 |
JP2012174348A (ja) * | 2011-02-17 | 2012-09-10 | Nissan Chem Ind Ltd | 色素増感太陽電池用色素及び色素増感太陽電池 |
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WO2007007735A1 (ja) * | 2005-07-12 | 2007-01-18 | Osaka University | 光照射による金属酸化物表面上への有機導電性重合性材料の合成 |
JP2007026994A (ja) * | 2005-07-20 | 2007-02-01 | Sumitomo Osaka Cement Co Ltd | スクリーン印刷用の酸化物光半導体ペースト、そのペーストを用いた酸化物光半導体多孔質薄膜電極及び光電変換素子、並びにスクリーン印刷用の酸化物光半導体ペーストの製造方法 |
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WO2006109895A1 (ja) * | 2005-05-19 | 2006-10-19 | Nissan Chemical Industries, Ltd. | リン酸エステルを有するチオフェン化合物及びその製造法 |
WO2007007735A1 (ja) * | 2005-07-12 | 2007-01-18 | Osaka University | 光照射による金属酸化物表面上への有機導電性重合性材料の合成 |
JP2007026994A (ja) * | 2005-07-20 | 2007-02-01 | Sumitomo Osaka Cement Co Ltd | スクリーン印刷用の酸化物光半導体ペースト、そのペーストを用いた酸化物光半導体多孔質薄膜電極及び光電変換素子、並びにスクリーン印刷用の酸化物光半導体ペーストの製造方法 |
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WO2011118715A1 (ja) * | 2010-03-26 | 2011-09-29 | 日産化学工業株式会社 | 色素増感太陽電池用色素および色素増感太陽電池 |
JP2011204545A (ja) * | 2010-03-26 | 2011-10-13 | Koji Segawa | 色素増感太陽電池用色素および色素増感太陽電池 |
JP5713005B2 (ja) * | 2010-03-26 | 2015-05-07 | 浩司 瀬川 | 色素増感太陽電池用色素および色素増感太陽電池 |
JP2012174348A (ja) * | 2011-02-17 | 2012-09-10 | Nissan Chem Ind Ltd | 色素増感太陽電池用色素及び色素増感太陽電池 |
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