WO2006080384A1 - 修飾酸化チタン微粒子及びそれを用いた光電変換素子 - Google Patents
修飾酸化チタン微粒子及びそれを用いた光電変換素子 Download PDFInfo
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- WO2006080384A1 WO2006080384A1 PCT/JP2006/301199 JP2006301199W WO2006080384A1 WO 2006080384 A1 WO2006080384 A1 WO 2006080384A1 JP 2006301199 W JP2006301199 W JP 2006301199W WO 2006080384 A1 WO2006080384 A1 WO 2006080384A1
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- WIPO (PCT)
- Prior art keywords
- dye
- oxides
- oxide
- titanium
- group
- Prior art date
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011859 microparticle Substances 0.000 title abstract 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 13
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 5
- 239000010419 fine particle Substances 0.000 claims description 104
- 229910052719 titanium Inorganic materials 0.000 claims description 81
- 239000010936 titanium Substances 0.000 claims description 81
- 239000000975 dye Substances 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000004065 semiconductor Substances 0.000 claims description 51
- -1 titanium metal oxides Chemical class 0.000 claims description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 238000012546 transfer Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 150000004703 alkoxides Chemical class 0.000 claims description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000434 metal complex dye Substances 0.000 claims description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical group [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 210000000689 upper leg Anatomy 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 62
- 239000000725 suspension Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 230000001235 sensitizing effect Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000565 sealant Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- MAZJFWHKKPFVND-UHFFFAOYSA-N aluminum propan-2-ol propan-2-olate Chemical compound [Al+3].CC(C)O.CC(C)[O-].CC(C)[O-].CC(C)[O-] MAZJFWHKKPFVND-UHFFFAOYSA-N 0.000 description 4
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 4
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
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- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DLYVTEULDNMQAR-SRNOMOOLSA-N Cholic Acid Methyl Ester Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCC(=O)OC)[C@@]2(C)[C@@H](O)C1 DLYVTEULDNMQAR-SRNOMOOLSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- DLYVTEULDNMQAR-UHFFFAOYSA-N Methylallocholat Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(=O)OC)C1(C)C(O)C2 DLYVTEULDNMQAR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XKGMHABTFTUWDV-UHFFFAOYSA-N [W+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [W+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] XKGMHABTFTUWDV-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 150000001842 cholic acids Chemical class 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BFAXWWIZHJPOJD-UHFFFAOYSA-O ethyl 1H-imidazol-1-ium-1-sulfonate Chemical compound [NH+]1(C=NC=C1)S(=O)(=O)OCC BFAXWWIZHJPOJD-UHFFFAOYSA-O 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical class O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002362 hafnium Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical class [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- IZSFVWCXDBEUQK-UHFFFAOYSA-N propan-2-ol;zinc Chemical compound [Zn].CC(C)O.CC(C)O IZSFVWCXDBEUQK-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- OHULXNKDWPTSBI-UHFFFAOYSA-N strontium;propan-2-olate Chemical compound [Sr+2].CC(C)[O-].CC(C)[O-] OHULXNKDWPTSBI-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OVZUSPADPSOQQN-UHFFFAOYSA-N tri(propan-2-yloxy)indigane Chemical compound [In+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] OVZUSPADPSOQQN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CURCMGVZNYCRNY-UHFFFAOYSA-N trimethylazanium;iodide Chemical compound I.CN(C)C CURCMGVZNYCRNY-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
- H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- 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
- H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to modified titanium oxide fine particles, a method for producing the same, and a photoelectric conversion element using the same.
- the single crystal electrode has the disadvantage that the conversion efficiency is very low and the cost is high due to the small adsorption capacity of the dye.
- a method using a high surface area semiconductor with sintered fine particles and a large number of pores as an electrode was used by Tsubomura et al. It has been reported that the performance of an electrode using high quality zinc oxide is very high (Patent Document 1).
- the main factors that affect the conversion efficiency of dye-sensitized solar cells include short-circuit current, open-circuit voltage, and shape factor.
- the short-circuit current and form factor are the sensitizing dyes used.
- Various improvements have been proposed to improve the conversion efficiency by expanding the absorption wavelength region by reducing the internal resistance of the battery and reducing the internal resistance of the battery.
- open-circuit voltage there is little research on open-circuit voltage, and it is no exaggeration to say that improvement has hardly progressed.
- Patent Document 2 is a force-single metal oxide that uses niobium oxide as a semiconductor electrode for the purpose of improving the open-circuit voltage, so its effect is insufficient.
- Patent Document 1 Japanese Patent No. 2664194
- Patent Document 2 Japanese Patent No. 2945955
- Non-Patent Document 1 J. Am. Chem. Soc. 115 (1993) 6382
- the main object of the present invention is to provide metal oxide fine particles useful for dye-sensitized solar cells and a solar cell capable of developing a high open-circuit voltage using the same.
- modified acid titanium fine particles can solve the above-mentioned problems and have completed the present invention.
- the present invention provides: (1) Periodic table Group IB oxides, Group oxides, Group oxides, Group oxides, Group oxides, Group IVA oxides other than titanium oxides, Group IVB oxides, Group VIA oxides, Group VIII oxide and vanadate strength Group strength: One or more selected non-titanium metal oxides (including silicon oxide) and modified titanium oxide fine particles composed of titanium oxide,
- Non-titanium metal oxides are magnesium oxide, calcium oxide, strontium oxide, zirconium oxide, tantalum oxide, chromium oxide, molybdate oxide, niobium oxide , Scandium oxide, vanadium oxide, iron oxide, nickel oxide, tungstic oxide, zinc oxide, aluminum oxide, indium oxide, silicon acid And modified stannic acid titanium fine particles as described in (1), which are one or two kinds of selected group forces,
- the ratio of non-titanium metal oxides (including silicon oxide) other than titanium oxide to titanium oxide is the atomic ratio of titanium Z non-titanium metal atoms (including silicon atoms).
- Periodic table Group metal consisting of Group I metal, Group X metal, Group X metal, Group X metal, Group IVA metal other than Titanium, Group IVB metal and Group VA metal
- One or more types selected Production of modified titanium oxide fine particles composed of titanium oxide and non-titanium metal oxide (including silicon oxide), characterized by reacting titanium metal (including silicon) alkoxide with titanium alkoxide in an organic solvent.
- Alcohol solvating power is a monohydric alcohol or a polyhydric alcohol, The method for producing modified titanium oxide fine particles according to (6),
- modified titanium oxide fine particles characterized in that it is polyhydric alcohol power 1, 4 butanediol or octanol,
- a conductive support having a semiconductor-containing layer sensitized by a dye and a conductive support having a counter electrode are arranged to face each other at a predetermined interval, and a charge transfer layer is provided in the gap between the two supports.
- Dye power A dye-sensitized photoelectric conversion element according to (9) or (10), which is an S-methine dye or a metal complex dye,
- a conductive support having a semiconductor-containing layer sensitized by a dye and a conductive support having a counter electrode are arranged to face each other at a predetermined interval, and a charge transfer layer is sandwiched between the two supports.
- a dye-sensitized photoelectric conversion element comprising modified titanium oxide fine particles made of titanium
- the solar cell using the modified titanium oxide titanium fine particles of the present invention has a high open circuit voltage. Therefore, it is useful as a power source for electrical products that function with only a certain voltage and minimum current, such as a calculator. In addition, since the voltage is high, the number of batteries in series can be reduced, and there is an advantage that the manufacturing cost of electrical products and the like is reduced.
- modified titanium oxide fine particles of the present invention are excellent in photocatalytic activity, they are useful as a catalyst for oxidation reaction utilizing light or for semiconductor electrodes.
- modified titanium oxide fine particles of the present invention will be described.
- the modified oxide titanium fine particles of the present invention can also be referred to as titanium-based composite oxide fine particles.
- the ratio of non-titanium metal oxides (including silicon oxides) combined with titanium, and the composite method, are also characteristic.
- Types of non-titanium metal oxides (including silicon oxides) compounded with modified titanium oxide fine particles include periodic table group IB oxides, group oxides, group oxides, group oxides, One type selected from the group consisting of Group IIIB oxides, Group IVA oxides other than titanium oxides, Group IVB oxides, Group VIA oxides, Group VIII oxides and vanadium oxides, or Two or more types of non-titanium metal oxides (including silicon oxides) are used.
- Preferred examples of non-titanium metal oxides (including silicon oxides) include vanadium oxides, periodic table group oxides such as magnesium oxide, calcium oxide, strontium oxide, and group oxides.
- Certain zinc oxides scandium oxides, group oxides, aluminum oxides, group oxides, indium oxides, zirconium oxides, group IVA oxides, hafnium Acids, IVB group silicon oxides, stannates, VIA group chromium oxides, molybdates, tungsten oxides VIII group oxides such as iron oxides, nickel oxides, and group IB oxides such as silver oxides.
- magnesium, zirconium, and silicon oxides are preferred. Is one type or two or more types It may be.
- tantalum oxide or niobium oxide may be used as the metal oxide.
- the proportion of non-titanium metal oxide (including silicon oxide) other than acid / titanium combined with acid / titanium is titanium Z non-titanium metal.
- I / O. 005-20 force S is preferable, 1ZO. 01-3 is more preferable, and I / O. 02-0.5 force is more preferable.
- the semiconductor-containing layer made of the modified titanium oxide fine particles preferably has a high surface area for the purpose of adsorbing sensitizing dyes and the like.
- the modified acid titanium fine particles of the present invention have a high surface area. It is preferable that the primary particle size of the sugure be small. Specifically, 1 to 3000 nm, preferably 5 to 500 nm is more preferable.
- the primary particle diameter of the modified titanium oxide fine particles can be calculated from the specific surface area, and the specific surface area is usually 0.5 to 1500 m 2 Zg, preferably 3 to 300 m 2 Zg.
- the pore volume of the modified acid titanium fine particles is preferably 0.05 to 0.8 ml / g, and the average pore diameter is preferably in the range of 1 to 250 nm.
- the modified titanium oxide fine particles obtained by the production method as described below are usually obtained as fine particles having the above-mentioned physical properties. If desired, the physical properties of the fine particles are adjusted to the above-mentioned range by sieving. It's pretty cute.
- the method for producing the modified titanium oxide fine particles of the present invention includes a material that is a raw material for the modified titanium oxide fine particles, each of the non-titanium metal oxides other than titanium alkoxide and titanium (including silicon oxide).
- Alkoxide can be obtained by reaction in a reaction vessel in a solvent. It can also be obtained by reacting a mixture of titanium alkoxide and the above-mentioned metal other than titanium, such as chloride, sulfide, nitrate, acetate, etc. in a reaction vessel in a solvent.
- a method using an alkoxide of a non-titanium metal (including silicon) is preferable.
- an organic solvent such as alcohol, hexane, toluene, or a mixture thereof can be used.
- an organic solvent such as alcohol, hexane, toluene, or a mixture thereof
- modified titanium oxide fine particles having high crystallinity can be obtained.
- the raw material is a metal alkoxide
- the organic solvent which does not add water is preferable.
- an organic solvent to which water is not added means an organic solvent in a natural state.
- Organic solvents having a water content of 10% or less, 5% or less, and 3% or less are preferable in this order.
- the reaction temperature is preferably about 110 ° C to 400 ° C.
- the reaction may be performed under nitrogen substitution.
- the desired fine particles may be obtained by an operation such as centrifugation.
- the valve attached to the reaction vessel is opened while maintaining the temperature in the vicinity of the reaction temperature, and the internal pressure is required. Depending on the conditions, fine particles can be obtained by removing the solvent such as alcohol used in the vaporized state under heating.
- the modified acid oxide titanium fine particles of the present invention are excellent in photocatalytic activity, the Hyundai-Fujishima effect It can be used as a catalyst for photo-oxidation reaction typified by, and a catalyst carrier utilizing its heat resistance, but a preferred application is as a semiconductor-containing layer (semiconductor electrode) in a dye-sensitized photoelectric conversion element. It is a use.
- the use of the modified oxide-titanium fine particles of the present invention in a photoelectric conversion element exhibits a remarkable effect in improving the open-circuit voltage.
- the modified titanium oxide fine particles of the present invention are obtained by devising the types and ratios of titanium oxide and non-titanium metal oxides (including silicon oxides) compounded therewith, as well as the composite method.
- the photocatalytic ability of titanium fine particles can be increased by, for example, sensitizing with a photocatalytic substance having high catalytic activity or a specific sensitizing dye. That is, at least one of a conductive support having a semiconductor-containing layer in which a sensitizing dye is adsorbed on a conductive support such as transparent conductive glass, and a conductive support having a counter electrode.
- a photoelectric conversion element that is arranged to face each other at a predetermined interval and has a charge transfer layer sandwiched between the two supports, the modified titanium oxide fine particles are formed as the semiconductor-containing layer using the modified titanium oxide fine particles.
- a solar cell is a closed circuit in which lead wires are arranged so that a current generated from the photoelectric conversion element can be taken out.
- examples of the conductive support include conductive materials typified by FTO (fluorine-doped tin oxide), ATO (antimony-doped tin oxide), and ITO (indium-doped tin oxide).
- Is obtained by forming a thin film on the surface of a stable inorganic or organic substrate such as glass, plastic, polymer film, titanium, tantalum, or bonbon. Its conductivity is usually 1000 ⁇ / cm 2 or less, preferably 100 ⁇ / cm 2 or less.
- a semiconductor electrode is obtained by disposing a semiconductor-containing layer sensitized with a dye on the surface of a conductive support.
- the conductive support is also simply referred to as a conductive support.
- Such a conductive support may be prepared by a method known per se or obtained from a factory.
- a slurry or paste of modified titanium oxide fine particles is applied or coated on the conductive support, and then dried, cured, or cured.
- Other preferred methods include a method in which a thin film made of an oxide semiconductor is directly formed on a substrate by vapor deposition, a method in which the substrate is used as an electrode, and the like. The method using a slurry of modified oxide titanium fine particles is most preferable in terms of the performance of the oxide semiconductor electrode.
- the oxide semiconductor fine particles that may be secondary agglomerated are dispersed in a dispersion medium using a dispersing agent so that the average primary particle diameter force becomes ⁇ 3000 nm, or in the present invention, Preparation of suspension strength of titanium oxide fine particles modified by hydrolysis of alkoxides, etc., precursors of acid semiconductors by hydrolysis of alkoxide in alcohol (glycothermal method) I can do it.
- a dispersion medium for obtaining a slurry water, alcohol such as ethanol, ketone such as acetone or acetylacetone, hexane, etc. may be used as long as it can disperse modified acid titanium fine particles.
- Organic solvents such as hydrocarbons may be used, and these may be used as a mixture. The use of water is preferred from the viewpoint of reducing the change in viscosity of the slurry.
- a dispersion stabilizer or the like may be added to the slurry for the purpose of obtaining stable primary fine particles.
- the dispersion stabilizer that can be used include polyhydric alcohols such as polyethylene glycol, condensates of these polyhydric alcohols with phenol, octyl alcohol, etc., hydroxypropinoremethinoresenorelose, hydroxymethinoresenole.
- Cellulose cellulose derivatives such as hydroxyethylenocellulose, carboxymethylcellulose, polyacrylamide, poly (meth) acrylic acid and its salts, poly (meth) acrylic acid and its salts, acrylamide and (meth) acrylic acid Or a copolymer with an alkali metal salt thereof, or (A) an acrylamide and an alkali metal salt of Z or (meth) acrylic acid and (B) methyl (meth) acrylate, (meth
- Salts of (meth) acrylic acid esters such as ethyl acrylate, or polyacrylic acid derivatives that are copolymers with hydrophobic monomers such as styrene, ethylene, propylene, and water-soluble polyacrylic acid derivatives, melamine sulfonic acid formaldehyde condensates
- Examples include salts of naphthalene sulfonic acid formaldehyde condensates, high molecular weight lignin sulfonates, acids such as hydrochloric acid, nitric acid, and acetic acid. These are not limited to these dispersion stabilizers. These dispersion stabilizers can be used alone or in combination of two or more.
- polyhydric alcohols such as polyethylene glycol, or condensates with phenol, octyl alcohol, etc., and carboxyl groups and z or sulfone groups in the molecule.
- Poly (meth) acrylic acid, poly (meth) acrylic acid sodium, poly (meth) acrylic acid sodium salt, poly (meth) acrylic acid potassium salt, poly (meth) acrylic acid lithium and the like are preferred.
- Acrylic acid and its salts, and acids such as carboxymethylcellulose, hydrochloric acid, nitric acid and acetic acid are preferred.
- the concentration of the modified acid titanium fine particles in the slurry is usually 1 to 90% by weight, preferably 5 to 80% by weight.
- the firing temperature of the conductive support coated with the slurry is generally below the melting point (or softening point) of the substrate used, and is usually 100 to 900 ° C, preferably 100 to 600 ° C.
- the firing time is not particularly limited, but is preferably within 4 hours.
- the film thickness after firing is preferably about 1 to about 3 to 50 ⁇ m, more preferably about 5 to 30 ⁇ m, and more preferably about LOO ⁇ m.
- Secondary treatment may be performed for the purpose of improving the surface smoothness of the semiconductor-containing layer thus obtained! /! (See Non-Patent Document 1).
- non-titanium metal oxides (including silicon) alkoxides, chlorides, nitrides, and sulfides that are the same as the non-titanium metal oxides (including silicon oxides) used to prepare the modified oxide titanium fine particles.
- Smoothness can be improved by immersing the conductive support having a semiconductor-containing layer directly in a solution of acetate or the like and drying or refiring.
- metal alkoxide examples include titanium ethoxide, titanium isopropoxide, titanium tertoxide, n-dibutyldiacetyltin and the like, and an alcohol solution thereof is used.
- a salted product for example, tetrasalt-titanium, tetrasalt-titanium, zinc chloride, etc. are mentioned, and an aqueous solution thereof is appropriately used.
- the sensitizing dye When the sensitizing dye is adsorbed (supported) on the modified titanium oxide fine particles of the present invention, light energy can be absorbed and converted into electric energy.
- a dye for sensitization a metal complex dye, a non-metal organic dye, or the like is used, and there is no particular limitation as long as it can enhance light absorption in combination with modified titanium oxide fine particles. You may mix and use a pigment
- dyes may be sufficient and an organic pigment
- by mixing dyes having different absorption wavelengths a wide range of absorption wavelengths can be used, and a dye-sensitized photoelectric conversion element and a solar cell with high conversion efficiency can be obtained.
- metal complex dyes examples include Ruthenium complexes, phthalocyanines, porphyrins, and the like.
- organic dyes include methine dyes such as non-metallic phthalocyanines, porphyrinsyanine, merocyanine, oxonol, trifluoromethane, and acrylic acid dyes, and xanthene.
- dyes such as azo-type, azo-type, anthraquinone-type and perylene-type.
- Preferred examples include ruthenium complexes, merocyanine, and methine dyes such as acrylic acid.
- Preferable examples include International Patent Publication No. WO2002011213, International Patent Publication No.
- the ratio of each dye in the case of using a mixture of dyes is not particularly limited, and the optimum condition is selected according to each dye. Generally, from the equimolar mixture, 10% mol per dye. It is preferable to use more than about.
- the total concentration of the dyes in the solution may be the same as when only one kind is supported.
- Solvents as described below can be used, and the solvent for each dye used may be the same or different.
- the above-described dye is dissolved in a solvent as described below, or in a dispersion obtained by dispersing the dye in the case of a poorly soluble dye.
- a method of immersing a conductive support provided with a semiconductor-containing layer made of modified titanium oxide fine particles or modified titanium oxide fine particles is preferred.
- the immersion temperature is generally from room temperature to the boiling point of the solvent, and the immersion time is about 1 to 48 hours.
- the solvent that can be used for dissolving the dye examples include methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, and t-butanol.
- Dye concentration of the solution is usually 1 X 10- 6 M ⁇ 1M goodness tool preferably 1 X 10- 5 M ⁇ 1 X is 10.
- the conductive support on which the semiconductor-containing layer sensitized with the dye is arranged as a semiconductor electrode.
- the dye When the dye is supported on the semiconductor-containing layer, it is effective to support the dye in the presence of the inclusion compound in order to prevent the association between the dyes.
- clathrate compounds include steroidal compounds such as cholic acid, crown ether, cyclodextrin, calixarene, and polyethylene oxide.
- Preferred examples include cholic acid, deoxycholic acid, and chenodeoxyl. These include cholic acid, cholic acid methyl ester, and cholic acids such as sodium cholate, polyethylene oxide, and the like.
- the surface of the semiconductor electrode may be treated with an amine compound such as tert-butyl pyridine.
- a treatment method for example, a method of immersing a substrate provided with a semiconductor-containing layer carrying a dye in an ethanol solution of amine is employed.
- the photoelectric conversion element of the present invention includes a semiconductor electrode obtained by supporting a sensitizing dye on the semiconductor-containing layer, a counter electrode provided to face the semiconductor electrode, and a charge transfer layer provided between the electrodes. Configured as the main element.
- a solution in which a redox electrolyte, a hole transport material, or the like is dissolved in a solvent or a room temperature molten salt (ionic liquid) is used.
- Examples of usable acid-reducing electrolytes include halogen molecules and halogen ions.
- Halogen oxidation-reduction electrolytes composed of halogen compounds, ferrocyanates, ferricyanates, metal complexes such as ferricium ions, cobalt complexes, etc., alkyl thiol alkyl disulfides
- Examples thereof include organic acid-reducing electrolytes such as piorogen dye and hydroquinone-quinone, but halogen redox electrolytes are preferred.
- Examples of the halogen molecule in the halogenate-reducing electrolyte, which is the halogen compound power include iodine molecules and bromine molecules, and iodine molecules are preferred.
- Examples of the halogen compound having a halogen ion as a counter ion include halogenated metal salts such as Lil, Nal, KI, Csl, Cal, and Cul.
- a salt having a counter ion as a counter ion is preferred.
- the salt having iodine ion as a counter ion include lithium iodide, sodium iodide, trimethylammonium iodide salt and the like.
- an electrochemically inert solvent is used as the solvent.
- acetonitrile, propylene carbonate, ethylene carbonate are particularly preferable.
- DOO, 3-methoxypropionate - tolyl, methoxy ⁇ Seth nitrile, E Ji glycol, 3-methoxy-O hexa-di-lysine one 2-one, y- butylate port Rataton are particularly preferred. These may be used alone or in combination of two or more.
- the concentration of the redox electrolyte is usually 0.01 to 99% by weight, preferably 0.1 to 90% by weight.
- a method in which a room temperature melt (ionic liquid) is used as a solvent for the redox electrolyte can be employed.
- room temperature melts include 1 —Methyl-1-alkyl imidazolium iodide, buryu imidazolium tetrafluoride, 1-ethyl imidazolium sulfonate, alkyl imidazolium trifluoromethanesulamide, 1 methylpyrrolidi-umioiodide, 1 -Methyl-3 alkyl imidazolium bis (trifluoromethanesulfol) amide and the like.
- a low molecular gelling agent is dissolved in the charge transfer layer to increase the viscosity, or a reactive component is used in combination to cause a reaction after injection of the charge transfer layer. I will do it.
- a hole transport material or a P-type semiconductor can be used as a solid type instead of the redox electrolyte.
- the hole transport material examples include conductive polymers such as amamine derivatives, polyacetylene, polyaline, and polythiophene, and discotic liquid crystals.
- P-type semiconductors include, for example, Cul and CuSCN. Can be mentioned.
- the surface of the conductive support such as the FTO conductive glass has a platinum, carbon, or rhodium that catalytically acts on the reduction reaction of the redox electrolyte.
- platinum, carbon, or rhodium that catalytically acts on the reduction reaction of the redox electrolyte.
- those known per se such as those obtained by vapor-depositing ruthenium or the like, or applying and firing conductive fine particle precursors are used.
- the thickness of platinum, carbon, rhodium, ruthenium, etc. after coating and firing is preferably 10 to 50 ⁇ .
- a counter electrode is disposed opposite to a semiconductor electrode in which a semiconductor-containing layer sensitized with a dye is disposed on the surface of a conductive support at a predetermined interval, and the periphery is sealed with a sealant.
- the charge transfer layer is sealed in the gap.
- a semiconductor-containing layer sensitized with a dye is arranged around a conductive support in consideration of a seal portion to form a semiconductor electrode.
- the injection hole of the charge transfer layer is left around the semiconductor electrode, and the sheet is sealed by screen printing or a dispenser.
- the coating agent for example, the solvent is evaporated by heating at 100 ° C for 10 minutes, and then the other conductive support with platinum or the like is superposed so that the conductive surfaces face each other, The gap is made with a press, and UV light is irradiated with a high-pressure mercury lamp, for example, 3000 mJ Zcm 2 and cured.
- Post-curing if necessary, for example at 120 ° C for 10 minutes Chisaru
- the charge transfer layer injection port is sealed with a sealant to obtain a photoelectric conversion element.
- the sealant is prepared using epoxy resin, epoxy (meth) acrylate resin, crosslinking agent, polymerization initiator and the like as main components.
- the sealant is prepared using polyisobutylene-based resin as a main component. Each of these can be used as it is on the market.
- the photoelectric conversion element of the present invention thus obtained has excellent durability such as adhesion and heat-and-moisture resistance. Lead wires are arranged between the positive electrode and the negative electrode, and a resistance component is inserted between them. A dye-sensitized solar cell can be obtained.
- FIG. 1 is a schematic cross-sectional view of the relevant part for explaining the structure of a dye-sensitized solar cell using a photoelectric conversion element prepared from modified titanium oxide fine particles according to the present invention.
- Conductive material, 2 indicates a semiconductor-containing layer sensitized by a dye.
- 1 and 2 are collectively referred to as a semiconductor electrode.
- 3 is a counter electrode in which platinum or the like is disposed on a conductive surface inside the substrate
- 4 is a charge transfer layer disposed so as to be sandwiched between opposing conductive supports
- 5 is a sealant
- 6 is a substrate.
- Respectively. 1 and 6 are collectively referred to as a conductive support.
- Titanium isopropoxide 7.32g as titanium alkoxide and 24.23g zircoyu isopropoxide as zircaure alkoxide, 1,4-butanediol 130ml with the mixture (TiZZr atomic ratio 1Z3) as solvent It was suspended in and placed in a 300 ml autoclave and sealed. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 300 ° C and heat treatment was performed for 2 hours. After completion of the reaction, the autoclave valve was opened while maintaining the temperature at 300 ° C., and the solvent was removed, whereby the reaction product was recovered as xerogel to obtain 11.4 g of modified titanium oxide fine particles.
- Titanium isopropoxide 25g as titanium alkoxide and 18.2g zirco-isopropoxide as zircoure alkoxide, and their mixture (TiZZr atomic ratio 1 /0.3) was suspended in 130 ml of 1,4 butanediol as a solvent and sealed in an autoclave having a capacity of 300 ml. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 300 ° C and heat treatment was performed for 2 hours. After completion of the reaction, the mixture was naturally cooled to obtain 150 ml of a suspension containing 13.7 g of modified titanium oxide fine particles.
- Titanium isopropoxide and tetraethyl orthokeate were used in the atomic ratios shown in Table 2, and 150 ml of a suspension containing modified acid-titanium fine particles 11. Ig was obtained in the same manner as in Example 2.
- Titanium isopropoxide and tetraethyl orthokeate were used in the atomic ratios shown in Table 2, and 150 ml of a suspension containing modified acid-titanium fine particles 11. Ig was obtained in the same manner as in Example 2.
- Titanium isopropoxide, ketyl orthokete and zirco-isopropoxide were used at the atomic ratios shown in Table 2, and in the same manner as in Example 2, suspended suspension containing 4.2 g of modified titanium oxide fine particles. 150 ml of turbid liquid was obtained.
- Titanium isopropoxide and zirconia isopropoxide were used at the atomic ratios shown in Table 2, and 150 ml of a suspension containing 8.5 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8.
- Titanium isopropoxide and zirconia isopropoxide are used in the atomic ratio as shown in Table 2, the mixture is suspended in 130 ml of toluene as a solvent, and other conditions are the same as in Example 8. As a result, 150 ml of a suspension containing 13. lg of modified acid titanium fine particles was obtained.
- Titanium isopropoxide and tetraethyl orthokeate were used in the atomic ratio as shown in Table 2, and in the same manner as in Example 8, 150 ml of a suspension containing 10.3 g of modified acid titanium fine particles was obtained.
- Example 14 Titanium isopropoxide and tetraethyl orthokeate were used in the atomic ratio as shown in Table 2, and in the same manner as in Example 8, 150 ml of a suspension containing 17. lg of modified acid titanium fine particles was obtained.
- Titanium isopropoxide and aluminum tetraisopropoxide were used in the atomic ratio as shown in Table 2, and the mixture was suspended in 130 ml of hexane as a solvent. Other conditions were as in Example 8. Similarly, a suspension of 15 Oml containing 8.2 g of modified titanium oxide fine particles was obtained.
- Titanium isopropoxide, tetraethyl orthokeate and zirco-isopropoxide are used in the atomic ratios as shown in Table 2, and the mixture is suspended in 130 ml of n-otatanol as a solvent and the other The conditions were the same as in Example 8 to obtain 150 ml of a suspension containing 14.2 g of modified titanium oxide fine particles.
- Titanium isopropoxide, tetraethyl orthokeate and zirco-isopropoxide were used at the atomic ratios shown in Table 2, and as in Example 8, suspended containing 16.5 g of modified acid titanium fine particles. 150 ml of turbid liquid was obtained.
- Titanium isopropoxide and niobium butoxide were used in an atomic ratio as shown in Table 2, and 150 ml of a suspension containing 7.6 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8. [0061]
- Example 21 Titanium isopropoxide and niobium butoxide were used in an atomic ratio as shown in Table 2, and 150 ml of a suspension containing 7.6 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8. [0061]
- Titanium isopropoxide and niobium butoxide were used in the atomic ratio as shown in Table 2, and in the same manner as in Example 8, 150 ml of a suspension containing 14.6 g of modified acid titanium fine particles was obtained.
- Titanium isopropoxide and magnesium acetate tetrahydrate were used in the atomic ratio as shown in Table 2, and the mixture was suspended in 130 ml of n-octanol as a solvent. In the same manner as in 8, a suspension of 15 Oml containing 7.7 g of modified titanium oxide fine particles was obtained.
- Titanium isopropoxide and magnesium acetate tetrahydrate were used in the atomic ratio as shown in Table 2, and 150 ml of a suspension containing 9.3 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8.
- Titanium isopropoxide and strontium isopropoxide were used at an atomic ratio as shown in Table 2, and 150 ml of a suspension containing 9.6 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8.
- Titanium isopropoxide and indium isopropoxide were used in an atomic ratio as shown in Table 2, and 150 ml of a suspension containing 9.8 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8.
- Example 28 150 ml of a suspension containing 9.5 g of modified titanium oxide fine particles was obtained in the same manner as in Example 8 using titanium isopropoxide and tungsten isopropoxide in the atomic ratio as shown in Table 2.
- Titanium isopropoxide was used in the same manner as in Example 8 to obtain 150 ml of a suspension containing titanium oxide fine particles 7. Og.
- conductive support of dye-sensitized solar cell as shown in the example of photoelectric conversion element (Fig. 1)
- Fig. 1 After coating each modified titanium oxide fine particle obtained in Examples 1 to 7 in a paste form with turbineol and baking at 450 ° C for 30 minutes, the following dye (1), dye (2), dye (3) created one of or two 3 dye were mixed in X 10- 4 Micromax ethanol solution was immersed 24 hours in sensitized with dye semiconductor electrodes (2) of the.
- a counter electrode (3) was prepared by depositing 200 A of Pt on the conductive material FTO of the same conductive glass support. These are bonded together with a sealant (5), and the charge transfer layer (4) between the two electrodes (not shown) is filled with an iodine-based charge transfer layer 4a (iodine Z lithium iodide Z methyl heximidazo Ryumu-iodide (manufactured by Shikoku Kasei Kogyo Co., Ltd.) / ⁇ butyl pyridine is filled in the cell to adjust to 0.1M / 0.1M / 0.6MZ1M in 3-methoxypropyl-tolyl) Then, it was cured with an injection roller and an ultraviolet curable sealant, and cured by irradiating with ultraviolet rays to obtain the photoelectric conversion elements of the present invention.
- iodine-based charge transfer layer 4a iodine Z lithium iodide Z methyl heximidazo
- Table 3 below shows the modified oxide titanium fine particles, the dye, the film thickness after firing of the modified titanium oxide fine particle layer used in each example, and the charge transfer layer used.
- the charge transfer layer 4b was prepared from ethylene Z-acetonitrile (6Z4) with iodine Z-iodide tetra-n-propyl ammonium at 0.05M / 0.5M.
- the dye-sensitized solar cell using the photoelectric conversion element of the present invention generates a high voltage with an open circuit voltage of 0.71 or more.
- those using modified titanium oxide fine particles modified with zirconium or aluminum generate a higher voltage with an open circuit voltage of 1 or more.
- a voltage higher than a certain level such as a calculator or a mobile phone, is the highest.
- FIG. 1 is a schematic cross-sectional view of the relevant part of one example of the dye-sensitized photoelectric conversion device of the present invention.
- [0081] 1 is a conductive material
- 2 is a semiconductor metal layer
- 3 is a counter electrode
- 4 is a charge transfer layer
- 5 is a sealing agent
- 6 is a substrate (glass support).
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JP2007500563A JP4909256B2 (ja) | 2005-01-27 | 2006-01-26 | 修飾酸化チタン微粒子及びそれを用いた光電変換素子 |
KR1020077016916A KR101290894B1 (ko) | 2005-01-27 | 2006-01-26 | 수식 산화 티탄 미립자 및 그것을 사용한 광전 변환 소자 |
CA002594857A CA2594857A1 (en) | 2005-01-27 | 2006-01-26 | Modified titanium oxide microparticle and photoelectric transducer making use of the same |
EP06712381A EP1858108A4 (en) | 2005-01-27 | 2006-01-26 | MODIFIED TITANIUM OXIDE PARTICLE AND THIS USING PHOTOELECTRIC CONVERTER |
AU2006209496A AU2006209496B2 (en) | 2005-01-27 | 2006-01-26 | Modified titanium oxide microparticle and photoelectric transducer making use of the same |
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EP (1) | EP1858108A4 (ja) |
JP (2) | JP4909256B2 (ja) |
KR (1) | KR101290894B1 (ja) |
CN (1) | CN100521249C (ja) |
AU (1) | AU2006209496B2 (ja) |
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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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JP2009148706A (ja) * | 2007-12-20 | 2009-07-09 | Showa Denko Kk | 電極触媒およびその用途、ならびに電極触媒の製造方法 |
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- 2006-01-26 AU AU2006209496A patent/AU2006209496B2/en not_active Ceased
- 2006-01-26 CA CA002594857A patent/CA2594857A1/en not_active Abandoned
- 2006-01-26 KR KR1020077016916A patent/KR101290894B1/ko not_active IP Right Cessation
- 2006-01-26 EP EP06712381A patent/EP1858108A4/en not_active Withdrawn
- 2006-01-26 WO PCT/JP2006/301199 patent/WO2006080384A1/ja active Application Filing
- 2006-01-26 CN CNB200680003411XA patent/CN100521249C/zh not_active Expired - Fee Related
- 2006-01-27 TW TW095103325A patent/TWI386372B/zh not_active IP Right Cessation
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006278023A (ja) * | 2005-03-28 | 2006-10-12 | Matsushita Electric Works Ltd | 半導体微粒子ペースト及びその製造方法、並びに光電変換素子 |
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 |
EP2037528A1 (en) * | 2006-07-05 | 2009-03-18 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized solar cell |
EP2037528A4 (en) * | 2006-07-05 | 2009-08-19 | Nippon Kayaku Kk | SOLAR CELL SENSITIVE TO COLORING |
JP2009148706A (ja) * | 2007-12-20 | 2009-07-09 | Showa Denko Kk | 電極触媒およびその用途、ならびに電極触媒の製造方法 |
JP2012521622A (ja) * | 2009-03-26 | 2012-09-13 | バンガー ユニバーシティ | 色素増感太陽電池の低温焼結 |
WO2011145551A1 (ja) | 2010-05-17 | 2011-11-24 | 日本化薬株式会社 | 熱硬化型光電変換素子用シール剤を用いた光電変換素子 |
JP2013046913A (ja) * | 2012-11-22 | 2013-03-07 | Showa Denko Kk | 電極触媒およびその用途、ならびに電極触媒の製造方法 |
WO2014084296A1 (ja) | 2012-11-30 | 2014-06-05 | 日本化薬株式会社 | 色素増感太陽電池 |
JP2015201510A (ja) * | 2014-04-07 | 2015-11-12 | 積水化学工業株式会社 | 酸化物ナノ粒子分散液及び薄膜太陽電池の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2594857A1 (en) | 2006-08-03 |
JP2012067009A (ja) | 2012-04-05 |
TWI386372B (zh) | 2013-02-21 |
KR20070091359A (ko) | 2007-09-10 |
CN100521249C (zh) | 2009-07-29 |
JP4909256B2 (ja) | 2012-04-04 |
KR101290894B1 (ko) | 2013-07-29 |
AU2006209496B2 (en) | 2010-08-19 |
CN101111969A (zh) | 2008-01-23 |
JPWO2006080384A1 (ja) | 2008-06-19 |
EP1858108A1 (en) | 2007-11-21 |
AU2006209496A1 (en) | 2006-08-03 |
TW200642960A (en) | 2006-12-16 |
US20080110497A1 (en) | 2008-05-15 |
EP1858108A4 (en) | 2012-08-29 |
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