KR20100136929A - Novel organic dye and preparation thereof - Google Patents
Novel organic dye and preparation thereof Download PDFInfo
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- KR20100136929A KR20100136929A KR1020100057781A KR20100057781A KR20100136929A KR 20100136929 A KR20100136929 A KR 20100136929A KR 1020100057781 A KR1020100057781 A KR 1020100057781A KR 20100057781 A KR20100057781 A KR 20100057781A KR 20100136929 A KR20100136929 A KR 20100136929A
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- South Korea
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- formula
- dye
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- independently
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims description 71
- 150000001875 compounds Chemical class 0.000 claims description 63
- 239000004065 semiconductor Substances 0.000 claims description 49
- 239000010419 fine particle Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 5
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- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 238000004873 anchoring Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- 230000008033 biological extinction Effects 0.000 abstract 1
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- 230000015572 biosynthetic process Effects 0.000 description 19
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000008859 change Effects 0.000 description 4
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- XLZVAPMTMLRCIG-UHFFFAOYSA-N 2,7-dibromo-9-phenylacridine Chemical compound BrC1=CC2=C(C3=CC(=CC=C3N=C2C=C1)Br)C1=CC=CC=C1 XLZVAPMTMLRCIG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
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- 239000002612 dispersion medium Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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 1
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical class C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
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- IOKFBTWWWGKNHE-UHFFFAOYSA-N 1-(4-methoxyphenyl)-10H-phenothiazine Chemical compound COC1=CC=C(C=C1)C1=CC=CC=2SC3=CC=CC=C3NC1=2 IOKFBTWWWGKNHE-UHFFFAOYSA-N 0.000 description 1
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- BUMYRCXCJAWWFV-UHFFFAOYSA-N N-[4-(3,6-dibromo-10-phenylanthracen-9-yl)phenyl]-N-(9,9-dimethylfluoren-2-yl)-9,9-dimethylfluoren-2-amine Chemical compound CC1(C2=CC=CC=C2C3=C1C=C(C=C3)N(C4=CC=C(C=C4)C5=C6C=CC(=CC6=C(C7=C5C=CC(=C7)Br)C8=CC=CC=C8)Br)C9=CC1=C(C=C9)C2=CC=CC=C2C1(C)C)C BUMYRCXCJAWWFV-UHFFFAOYSA-N 0.000 description 1
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical class O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
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- RODWDXFRRQSGRP-UHFFFAOYSA-N [I+].C(CCCCC)N1C(=[N+](C=C1)C)C Chemical compound [I+].C(CCCCC)N1C(=[N+](C=C1)C)C RODWDXFRRQSGRP-UHFFFAOYSA-N 0.000 description 1
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- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
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- 125000003806 alkyl carbonyl amino group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 125000003435 aroyl group Chemical group 0.000 description 1
- 125000005333 aroyloxy group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229940097362 cyclodextrins Drugs 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
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 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 1
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- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 125000001041 indolyl group Chemical group 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([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
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- 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
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
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- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 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
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B15/00—Acridine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B21/00—Thiazine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
-
- C—CHEMISTRY; METALLURGY
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Abstract
Description
본 발명은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되는 신규한 염료증감 광전변환소자용 유기염료 및 이의 제조방법에 관한 것이다.The present invention relates to a novel organic dye for dye-sensitized photovoltaic devices used in dye-sensitized solar cells (DSSC) and a method of manufacturing the same.
1991년도 스위스 국립 로잔 고등기술원 (EPFL)의 마이클 그라첼(Michael Gratzel) 연구팀에 의해 염료감응 나노입자 산화티타늄 태양전지가 개발된 이후 이 분야에 관한 많은 연구가 진행되고 있다. 염료감응태양전지는 기존의 실리콘계 태양전지에 비해 효율이 높고 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있을 것으로 기대된다. 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀(hole) 쌍을 생성할 수 있는 염료와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Since the development of dye-sensitized nanoparticle titanium oxide solar cells in 1991 by Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL), much work has been done in this area. Dye-sensitized solar cells are expected to be able to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. Unlike silicon solar cells, dye-sensitized solar cells are photoelectrochemical solar cells that consist mainly of dyes that absorb visible light to form electron-hole pairs, and transition metal oxides that transfer the generated electrons. .
종래 염료감응태양전지의 염료로서 높은 광전기 전환효율을 나타내는 루테늄 금속 착체가 널리 사용되어 왔다. 그러나, 이 루테늄 금속 착체는 가격이 너무 비싸다는 단점이 있었다.Conventionally, ruthenium metal complexes exhibiting high photoelectric conversion efficiency have been widely used as dyes in dye-sensitized solar cells. However, this ruthenium metal complex has the disadvantage that the price is too expensive.
최근, 흡광효율, 산화환원 반응 안정성 및 분자내 전하-전달(charge-transfer, CT)계 흡수의 측면에서 우수한 물성을 나타내는 금속을 함유하지 않은 유기염료가, 고가의 루테늄 금속 착체를 대체하여 염료감응태양전지용 염료로서 사용될 수 있음이 발견되어, 금속을 함유하지 않는 유기염료에 대한 연구가 중점적으로 이루어지고 있다.In recent years, organic dyes containing no metals exhibiting excellent physical properties in terms of light absorption efficiency, redox reaction stability, and intermolecular charge-transfer (CT) absorption have replaced dyes by replacing expensive ruthenium metal complexes. It has been found that it can be used as a dye for solar cells, and research on organic dyes containing no metals has been focused on.
유기염료는 일반적으로 π-결합 유닛에 의해 연결되는 전자 공여체(electron donor)-전자 수용체(electron acceptor) 잔기의 구조를 갖는다. 대부분의 유기염료에서, 아민 유도체가 전자 공여체의 역할을 하고, 2-시아노아크릴산 또는 로다닌 잔기가 전자 수용체의 역할을 하며, 이 두 부위는 메타인 유닛 또는 티오펜 체인과 같은 π-결합 시스템에 의해 연결된다.Organic dyes generally have a structure of electron donor-electron acceptor residues linked by π-binding units. In most organic dyes, amine derivatives act as electron donors, 2-cyanoacrylic acid or rhodanine residues act as electron acceptors, and these two sites are π-binding systems such as metaine units or thiophene chains. Is connected by.
일반적으로, 전자 공여체인 아민 유닛의 구조적 변화를 통해 청색 쪽으로 쉬프트(shift)된 흡광 스펙트럼을 유도하는 등의 전자 특성을 변화시키고, π-결합 길이의 변화를 통해 흡광 스펙트럼과 산화환원 전위(redox potential)를 조절할 수 있다.In general, the structural properties of the amine unit, an electron donor, change the electronic properties such as inducing an absorbance spectrum shifted toward the blue side, and the change in the π-bond length results in the absorption spectrum and redox potential. ) Can be adjusted.
그러나, 이제까지 알려진 대부분의 유기염료는 루테늄 금속 착체 염료에 비해 낮은 변환효율과 낮은 구동 안정성을 나타내기 때문에, 이러한 전자 공여체와 수용체의 종류 또는 π-결합 길이를 변화시킴으로써, 종래 유기염료들에 비해 현저히 향상된 몰흡광계수를 가지며 높은 광전기 변환효율을 나타내는 새로운 염료를 개발하려는 노력이 지속되고 있는 실정이다.However, since most of the organic dyes known so far exhibit low conversion efficiency and low driving stability compared to ruthenium metal complex dyes, by changing the type or π-bond length of these electron donors and acceptors, it is remarkably compared with conventional organic dyes. Efforts have been made to develop new dyes having an improved molar absorption coefficient and showing high photoelectric conversion efficiency.
본 발명의 목적은 종래의 금속 착체 염료보다 향상된 몰흡광계수 및 광전기 변환효율을 나타내어 염료감응태양전지의 효율을 크게 향상시킬 수 있는 염료증감 광전변환소자용 유기염료를 제공하는 것이다. An object of the present invention is to provide an organic dye for a dye-sensitized photoelectric conversion device that can improve the efficiency of the dye-sensitized solar cell by showing an improved molar absorption coefficient and photoelectric conversion efficiency than the conventional metal complex dye.
본 발명의 다른 목적은 상기 유기염료의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing the organic dye.
본 발명의 또 다른 목적은 상기 유기염료를 포함하여 현저히 향상된 광전기 변환효율을 나타내며, Jsc(단회로 광전류 밀도, short circuit photocurrent density)와 몰흡광계수가 우수한 염료증감 광전변환소자, 및 이를 포함하여 효율이 현저히 향상된 태양전지를 제공하는 것이다.Still another object of the present invention is a dye-sensitized photoelectric conversion device including the organic dye exhibiting a markedly improved photoelectric conversion efficiency, excellent Jsc (short circuit photocurrent density) and a molar absorption coefficient, and efficiency including the same It is to provide this remarkably improved solar cell.
상기 목적에 따라, 본 발명은 하기 화학식 1 또는 2로 표시되는 염료증감 광전변환소자용 유기염료를 제공한다:In accordance with the above object, the present invention provides an organic dye for dye-sensitized photoelectric conversion device represented by the following formula (1) or (2):
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 식에서, Where
A는 C 또는 N이고, 단 A가 N이면 b 및 c는 0이며,A is C or N, provided that if A is N then b and c are 0,
B는 O, S, CR1R2 또는 NR3이고, 이때 R1 내지 R3은 각각 독립적으로 수소 또는 C1-12 알킬이며, B is O, S, CR 1 R 2 Or NR 3, wherein R 1 To R 3 are each independently hydrogen or C 1-12 alkyl,
Ar1 내지 Ar5는 각각 독립적으로 치환 또는 비치환된 C6-C50의 아릴기이고, 이때 A1 내지 Ar3은 서로 연결되어 환을 형성할 수도 있으며, Ar 1 to Ar 5 are each independently a substituted or unsubstituted C 6 -C 50 aryl group, wherein A 1 to Ar 3 may be connected to each other to form a ring,
a는 0 또는 1이고,a is 0 or 1,
b 및 c는 각각 독립적으로 0 또는 1이고, 단 c가 1이면 b는 반드시 1이며,b and c are each independently 0 or 1, provided that c is 1, b is necessarily 1,
d는 0 또는 1이고,d is 0 or 1,
e는 0 또는 1이며, e is 0 or 1,
An은 각각 독립적으로 
Sp는 각각 독립적으로 
Sp each independently
또한 본 발명은 Also,
(1) 하기 화학식 3의 화합물을 하기 화학식 4의 화합물과 커플링 반응시켜 화학식 5의 화합물을 제조하는 단계;(1) coupling a compound of Formula 3 with a compound of Formula 4 to prepare a compound of Formula 5;
(2) 상기 화학식 5의 화합물을 유기용매 중에서 BuLi 또는 CF3COOH와 반응시켜 하기 화학식 6의 화합물을 제조하는 단계; 및(2) preparing a compound of formula 6 by reacting the compound of formula 5 with BuLi or CF 3 COOH in an organic solvent; And
(3) 상기 화학식 6의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 앵커링기 제공 화합물과 결합반응시키는 단계를 포함하는 상기 유기염료의 제조방법을 제공한다:(3) providing a method of preparing the organic dye, including the step of coupling the compound of Formula 6 with an anchoring group-providing compound in the presence of piperidine in CH 3 CN:
[화학식 3](3)
[화학식 4][Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Formula 6]
상기 식에서, Where
고리 W는 각각 독립적으로 
X는 Br 또는 
Y는 
Z는 H 또는 
A, Ar1 내지 Ar4, a, b, c, e 및 Sp는 앞서 정의한 바와 같다.
A, Ar 1 to Ar 4 , a, b, c, e and Sp are as defined above.
상기 또 다른 목적에 따라, 본 발명은 산화물 반도체 미립자; 및 상기 산화물 반도체 미립자에 담지된 상기 유기염료를 포함하는 것을 특징으로 하는 염료증감 광전변환소자를 제공한다.According to still another object, the present invention provides an oxide semiconductor fine particle; And it provides a dye-sensitized photoelectric conversion device comprising the organic dye supported on the oxide semiconductor fine particles.
상기 또 다른 목적에 따라, 본 발명은 상기 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.In accordance with still another object, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
본 발명의 염료 화합물은 염료감응태양전지(DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있다.The dye compound of the present invention can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar absorption coefficient, Jsc (single-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of the solar cell.
이하 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 명세서 전반에 걸쳐서 “알킬”이란 선형 또는 분지형의 포화된 C1 내지 C6의 탄화수소 라디칼 사슬을 의미한다. 구체적인 예로는 메틸, 에틸, n-프로필, 아이소프로필, n-부틸, 아이소부틸, t-부틸, n-펜틸, 이소펜틸 및 헥실 등을 들 수 있으나, 이에 한정되지는 않는다. Throughout this specification, “alkyl” refers to a linear or branched saturated C 1 To C 6 hydrocarbon radical chain. Specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl and hexyl.
본 명세서 전반에 걸쳐서 “알콕시”란 -ORa 기를 의미하는 것으로, 여기서 Ra는 앞서 정의한 바와 같은 알킬이다. 구체적인 예로는 메톡시, 에톡시, n-프로폭시, 아이소프로폭시, n-부톡시, t-부톡시 등을 들 수 있으나, 이에 한정되지는 않는다. Throughout this specification, "alkoxy" refers to the group -ORa, where Ra is alkyl as defined above. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, and the like.
본 명세서 전반에 걸쳐서 “아릴”이란 임의로 치환된 벤젠 고리 또는 하나 이상의 임의 치환기들의 융합에 의해 형성될 수 있는 고리계를 의미한다. 상기 임의 치환기의 예로는 치환된 C1 -3 알킬, 치환된 C2 -3 알케닐, 치환된 C2 -3 알키닐, 헤테로아릴, 헤테로사이클, 아릴, 1 내지 3개의 플루오르 치환기를 갖거나 갖지 않는 알콕시, 아릴옥시, 아르알콕시, 아실, 아로일, 헤테로아로일, 아실옥시 및 아로일옥시를 들 수 있다. 상기 고리 또는 고리계는 하나 이상의 치환기를 갖거나 갖지 않는 아릴 고리(벤젠 고리 포함), 카보사이클 고리 또는 헤테로사이클 고리에 임의로 융합될 수 있다. “아릴”의 예로는 페닐, 나프틸, 테트라하이드로나프틸, 바이페닐, 인다닐, 안트라실, 페난트릴 및 이들의 치환된 유도체가 포함되나, 이에 국한되지는 않는다.Throughout this specification “aryl” refers to a ring system that can be formed by the optionally substituted benzene ring or the fusion of one or more optional substituents. Examples of the optional substituents is or without a substituted C 1 -3 alkyl, substituted C 2 -3 alkenyl, substituted C 2 -3 alkynyl, heteroaryl, heterocycle, aryl, one to three fluorine substituents Alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy and aroyloxy. The ring or ring system may be optionally fused to an aryl ring (including benzene ring), carbocycle ring or heterocycle ring with or without one or more substituents. Examples of “aryl” include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, phenanthryl and substituted derivatives thereof.
본 명세서 전반에 걸쳐서 “헤테로아릴”이란 고리 내에 산소, 황 및 질소 등의 하나 이상의 헤테로원자를 갖는 단환의 5 내지 6원 방향족 고리를 의미하거나, 헤테로아릴 고리, 아릴 고리, 헤테로사이클 고리 또는 카보사이클 고리와 같은 하나 이상의 고리에 융합된 방향족 고리(예를 들어, 이환 또는 삼환 고리계)를 의미한다. 헤테로아릴의 구체적인 예로는 피리디닐, 피롤릴, 옥사졸릴, 인돌릴, 이소인돌릴, 퓨리닐, 퓨라닐, 티에닐, 벤조퓨라닐, 벤조티오페닐, 카바졸릴, 이미다졸릴, 티아졸릴, 이속사졸릴, 피라졸릴, 이소티아졸릴, 퀴놀릴, 이소퀴놀릴, 피리다질, 피리미딜, 피라질(이들은 치환되거나 비치환될 수 있음) 등을 들 수 있으나 이에 한정되지는 않는다.Throughout this specification, "heteroaryl" means a monocyclic 5-6 membered aromatic ring having one or more heteroatoms such as oxygen, sulfur and nitrogen in the ring, or a heteroaryl ring, aryl ring, heterocycle ring or carbocycle Aromatic rings (eg, bicyclic or tricyclic ring systems) fused to one or more rings, such as rings. Specific examples of heteroaryl include pyridinyl, pyrrolyl, oxazolyl, indolyl, isoindolyl, purinyl, furanyl, thienyl, benzofuranyl, benzothiophenyl, carbazolyl, imidazolyl, thiazolyl, isox Sazolyl, pyrazolyl, isothiazolyl, quinolyl, isoquinolyl, pyridazyl, pyrimidyl, pyrazil, which may be substituted or unsubstituted, and the like.
본 명세서 전반에 걸쳐서 “치환” 또는 “치환된”이란, 화합물 또는 작용기에 있어서 적어도 하나의 수소가 할로겐, 알킬, 알케닐, 알키닐, 아릴, 알콕시, 히드록시, 카르복시, 카바모일, 알콕시카르보닐, 니트로, 할로알킬, 아미노, 알킬카보닐아미노, 사이클로알킬기, 시아노 및 티올로 이루어진 군에서 선택되는 치환기로 치환된 것을 의미한다.Throughout this specification, "substituted" or "substituted" means that at least one hydrogen in the compound or functional group is halogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, hydroxy, carboxy, carbamoyl, alkoxycarbonyl It means substituted with a substituent selected from the group consisting of, nitro, haloalkyl, amino, alkylcarbonylamino, cycloalkyl group, cyano and thiol.
본 명세서 전반에 걸쳐서 화학구조식 중에 사용된 “*”는 결합부위를 의미한다.
Throughout this specification, "*" as used in the chemical formula means a bonding site.
본 발명에 따른 유기염료는 하기 화학식 1 또는 2의 구조를 가져 염료증감 광전변환소자로서 염료감응태양전지(DSSC)에 사용시 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내는 것을 특징으로 한다:The organic dye according to the present invention has a structure represented by the following formula (1) or (2) to show an improved molar absorption coefficient, Jsc (single circuit photocurrent density) and photoelectric conversion efficiency when used in a dye-sensitized solar cell (DSSC) as a dye-sensitized photoelectric conversion device. Features:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 식에서, Where
A는 C 또는 N이고, 단 A가 N이면 b 및 c는 0이며,A is C or N, provided that if A is N then b and c are 0,
B는 O, S, CR1R2 또는 NR3이고, 이때 R1 내지 R3은 각각 독립적으로 수소 또는 C1-12 알킬이며, B is O, S, CR 1 R 2 Or NR 3, wherein R 1 To R 3 are each independently hydrogen or C 1-12 alkyl,
Ar1 내지 Ar5는 각각 독립적으로 치환 또는 비치환된 C6-C50의 아릴기이고, 이때 A1 내지 Ar3은 서로 연결되어 환을 형성할 수도 있으며, Ar 1 Ar 5 to each independently represent a substituted or unsubstituted C 6 -C 50 aryl group, wherein A 1 to Ar 3 may be connected to each other to form a ring,
a는 0 또는 1이고,a is 0 or 1,
b 및 c는 각각 독립적으로 0 또는 1이고, 단 c가 1이면 b는 반드시 1이며,b and c are each independently 0 or 1, provided that c is 1, b is necessarily 1,
d는 0 또는 1이고,d is 0 or 1,
e는 0 또는 1이며, e is 0 or 1,
An은 각각 독립적으로 
Sp는 각각 독립적으로 
바람직하게는, 상기 화학식 1 또는 2에 있어서,Preferably, in Chemical Formula 1 or 2,
A는 C 또는 N이고, 단, A가 N이면 b 및 c는 0이며,A is C or N, provided that when A is N, b and c are 0,
B는 S 또는 CR1R2이고, 이때 R1 및 R2는 각각 독립적으로 수소 또는 메틸기이며, B is S or CR 1 R 2, wherein R 1 and R 2 are each independently hydrogen or a methyl group,
Ar1 내지 Ar5는 각각 독립적으로 C6-C50의 아릴기, 또는 알킬 또는 알콕시기로 치환된 C6-C50의 아릴기이고, 보다 바람직하게는 페닐기, 메톡시페닐기 또는 디메틸플루오렌일기이며,Ar 1 to Ar 5 are each independently a C 6 -C 50 aryl group or a C 6 -C 50 aryl group substituted with an alkyl or alkoxy group, more preferably a phenyl group, methoxyphenyl group or dimethylfluorenyl group ,
a는 0 또는 1이고, a is 0 or 1,
b 및 c는 각각 독립적으로 0 또는 1이고, 단 c가 1이면 b는 반드시 1이며,b and c are each independently 0 or 1, provided that c is 1, b is necessarily 1,
d는 0 또는 1이고,d is 0 or 1,
e는 0 또는 1이며,e is 0 or 1,
An은 
Sp는 
Sp is
본 발명에 따른 유기염료의 구체적인 예로는 하기 화학식 7 내지 122 중 하나인 것이 바람직하다.Specific examples of the organic dyes according to the present invention are preferably one of the following Chemical Formulas 7 to 122.
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11]
(11)
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Formula 16]
[화학식 17][Formula 17]
[화학식 18][Formula 18]
[화학식 19][Formula 19]
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
[화학식 23](23)
[화학식 24][Formula 24]
[화학식 25][Formula 25]
[화학식 26][Formula 26]
[화학식 27][Formula 27]
[화학식 28][Formula 28]
[화학식 29][Formula 29]
[화학식 30][Formula 30]
[화학식 31][Formula 31]
[화학식 32][Formula 32]
[화학식 33][Formula 33]
[화학식 34][Formula 34]
[화학식 35][Formula 35]
[화학식 36][Formula 36]
[화학식 37][Formula 37]
[화학식 38][Formula 38]
[화학식 39][Formula 39]
[화학식 40][Formula 40]
[화학식 41][Formula 41]
[화학식 42][Formula 42]
[화학식 43][Formula 43]
[화학식 44][Formula 44]
[화학식 45][Formula 45]
[화학식 46][Formula 46]
[화학식 47][Formula 47]
[화학식 48][Formula 48]
[화학식 49][Formula 49]
[화학식 50][Formula 50]
[화학식 51][Formula 51]
[화학식 52][Formula 52]
[화학식 53][Formula 53]
[화학식 54][Formula 54]
[화학식 55](55)
[화학식 56](56)
[화학식 57](57)
[화학식 58](58)
[화학식 59][Chemical Formula 59]
[화학식 60](60)
[화학식 61](61)
[화학식 62][Formula 62]
[화학식 63](63)
[화학식 64]≪ EMI ID =
[화학식 65](65)
[화학식 66][Formula 66]
[화학식 67](67)
[화학식 68](68)
[화학식 69][Formula 69]
[화학식 70](70)
[화학식 71](71)
[화학식 72](72)
[화학식 73](73)
[화학식 74]≪ EMI ID =
[화학식 75](75)
[화학식 76][Formula 76]
[화학식 77][Formula 77]
[화학식 78] (78)
[화학식 79][Formula 79]
[화학식 80](80)
[화학식 81][Formula 81]
[화학식 82](82)
[화학식 83](83)
[화학식 84][Formula 84]
[화학식 85](85)
[화학식 86]≪ EMI ID =
[화학식 87][Chemical Formula 87]
[화학식 88][Formula 88]
[화학식 89](89)
[화학식 90](90)
[화학식 91][Formula 91]
[화학식 92]≪ EMI ID =
[화학식 93][Formula 93]
[화학식 94][Formula 94]
[화학식 95][Formula 95]
[화학식 96][Formula 96]
[화학식 97][Formula 97]
[화학식 98][Formula 98]
[화학식 99][Formula 99]
[화학식 100][Formula 100]
[화학식 101][Formula 101]
[화학식 102][Formula 102]
[화학식 103][Formula 103]
[화학식 104][Formula 104]
[화학식 105][Formula 105]
[화학식 106][Formula 106]
[화학식 107][Formula 107]
[화학식 108][Formula 108]
[화학식 109][Formula 109]
[화학식 110][Formula 110]
[화학식 111][Formula 111]
[화학식 112][Formula 112]
[화학식 113][Formula 113]
[화학식 114][Formula 114]
[화학식 115][Formula 115]
[화학식 116][Formula 116]
[화학식 117]Formula 117
[화학식 118][Formula 118]
[화학식 119]Formula 119
[화학식 120][Formula 120]
[화학식 121][Formula 121]
[화학식 122][Formula 122]
본 발명에 따른 유기염료는 Organic dyes according to the present invention
(1) 하기 화학식 3의 화합물을 하기 화학식 4의 화합물과 커플링 반응시켜 화학식 5의 화합물을 제조하는 단계;(1) coupling a compound of Formula 3 with a compound of Formula 4 to prepare a compound of Formula 5;
(2) 상기 화학식 5의 화합물을 유기용매중에서 BuLi 또는 CF3COOH와 반응시켜 하기 화학식 6의 화합물을 제조하는 단계; 및(2) preparing a compound of formula 6 by reacting the compound of formula 5 with BuLi or CF 3 COOH in an organic solvent; And
(3) 상기 화학식 6의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 앵커링기 제공 화합물과 결합반응시키는 단계를 포함하는 제조방법에 의해 제조될 수 있다:(3) the compound of formula 6 may be prepared by a process comprising the step of coupling with an anchoring group providing compound in the presence of piperidine in CH 3 CN:
[화학식 3](3)
[화학식 4][Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Formula 6]
상기 식에서, Where
고리 W는 각각 독립적으로 
X는 Br 또는 
Y는 
Z는 H 또는 
A, Ar1 내지 Ar4, a, b, c, e 및 Sp는 앞서 정의한 바와 같다.A, Ar1 to Ar4, a, b, c, e and Sp are as defined above.
상세하게는, 먼저 상기 화학식 3의 화합물을 상기 화학식 4의 화합물과 커플링 반응시켜 화학식 5의 화합물을 제조한다.In detail, first, the compound of Chemical Formula 3 is reacted with the compound of Chemical Formula 4 to prepare a compound of Chemical Formula 5.
상기 커플링 반응은, 화학식 3에 있어서 치환기 X가 Br인 경우 Pd(PPh3)4 등의 촉매, 및 K2CO3 등의 염기의 존재 하에서 디메틸폼아미드(DMF) 등과 같은 유기용매 중에서 Y가 
이때, 출발물질로서 사용되는 화학식 3 및 4의 화합물은 통상적인 방법으At this time, the compounds of the formulas (3) and (4) used as starting materials are conventional
로 제조하거나 상업적으로 입수하여 사용할 수 있다. 바람직하기로는 상기 화학식 3의 화합물로는 하기 화학식 3-1 내지 3-6 중 어느 하나를 사용하는 것이 좋다.Can be prepared or commercially available. Preferably, as the compound of Formula 3, any one of the following Formulas 3-1 to 3-6 may be used.
[화학식 3-1][Formula 3-1]
[화학식 3-2][Formula 3-2]
[화학식 3-3][Formula 3-3]
[화학식 3-4][Formula 3-4]
[화학식 3-5][Formula 3-5]
[화학식 3-6][Formula 3-6]
또한 상기 화학식 4의 화합물로는 하기 화학식 4-1 내지 4-3의 화합물 중 어느 하나를 사용하는 것이 좋다.In addition, it is preferable to use any one of the compounds of the following formula 4-1 to 4-3 as the compound of formula (4).
[화학식 4-1][Formula 4-1]
[화학식 4-2][Formula 4-2]
[화학식 4-3][Formula 4-3]
이어서 제조된 화학식 5의 화합물을 DMF 등의 유기용매 중에서 BuLi 또는 CF3COOH와 반응시켜 화학식 6의 화합물을 제조한다. Subsequently, the compound of Formula 5 is reacted with BuLi or CF 3 COOH in an organic solvent such as DMF to prepare a compound of Formula 6.
이때, 상기 화학식 5에 있어서, Z가 H이면 유기용매 중에서 BuLi와 반응시키고, Z가 
결과로 수득된 화학식 6의 화합물을 CH3CN 중에서 피페리딘의 존재 하에서 시아노아세트산 등의 앵커링기 제공 화합물과 결합반응시킴으로써 본 발명에 따른 유기염료를 제조할 수 있다.The organic dye according to the present invention can be prepared by combining the resulting compound of formula 6 with an anchoring group-providing compound such as cyanoacetic acid in the presence of piperidine in CH 3 CN.
구체적으로, 본 발명에 따른 유기염료는 하기 반응식 1 내지 10에 기재된 방법들에 의해 제조될 수 있으나, 이는 일례일 뿐 본 발명이 이에 한정되는 것은 아니다.Specifically, the organic dye according to the present invention may be prepared by the methods described in the following Schemes 1 to 10, but this is only an example and the present invention is not limited thereto.
[반응식 1]Scheme 1
[반응식 2] 
[반응식 3]Scheme 3
[반응식 4]Scheme 4
[반응식 5] 
[반응식 6]Scheme 6
[반응식 7]Scheme 7
[반응식 8]Scheme 8
[반응식 9]Scheme 9
[반응식 10]Scheme 10
상기와 같은 제조방법에 의해 제조된 본 발명에 따른 유기염료는, 염료증감 광전변환소자로서 염료감응태양전지(DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있다.
The organic dye according to the present invention prepared by the above manufacturing method is used in dye-sensitized solar cells (DSSC) as a dye-sensitized photoelectric conversion element, improved molar absorption coefficient, Jsc (short circuit photocurrent density) and The photoelectric conversion efficiency can be shown to greatly improve the efficiency of the solar cell.
이에 따라, 본 발명은 상기 유기염료를 포함하는 염료증감 광전변환소자를 제공한다.Accordingly, the present invention provides a dye-sensitized photoelectric conversion device comprising the organic dye.
구체적으로, 본 발명에 따른 염료증감 광전변환소자는 산화물 반도체 미립자, 및 상기 산화물 반도체 미립자에 담지된 상기 유기염료를 포함하는 것을 특징으로 한다. Specifically, the dye-sensitized photoelectric conversion device according to the present invention is characterized in that it comprises an oxide semiconductor microparticles, and the organic dye supported on the oxide semiconductor microparticles.
본 발명에 따른 염료증감 광전변환소자는 상기 유기염료를 사용하는 것 이외에 통상의 염료를 이용하여 태양전지용 염료증감 광전변환소자를 제조하는 방법들이 적용될 수 있음은 물론이며, 바람직하게는 본 발명의 염료증감 광전변환소자는 산화물 반도체 미립자를 이용해서 기판 상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명에 따른 유기염료를 담지시켜 제조할 수 있다. As a dye-sensitized photoelectric conversion device according to the present invention, in addition to using the organic dye, methods for manufacturing dye-sensitized photoelectric conversion devices for solar cells using conventional dyes may be applied, and preferably, the dyes of the present invention. The sensitized photoelectric conversion device can be manufactured by producing a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the organic dye according to the present invention on the thin film.
이때 산화물 반도체의 박막이 형성되는 기판으로서는 그 표면이 도전성인 것이 바람직하며, 상업적으로 입수가능한 것을 사용할 수도 있다. 구체적인 일예로 유리, 또는 폴리에틸렌테레프탈레이트, 폴리에테르설폰 등의 투명성 고분자 재료의 표면에, 인듐, 불소, 안티몬을 도포한 산화주석 등의 도전성 금속산화물의 박막이나, 구리, 은, 금 등의 금속 박막을 형성한 것을 이용할 수 있다. 이때 도전성은 보통 1000 Ω 이하가 바람직하며, 특히 100 Ω 이하의 것이 바람직하다.In this case, the substrate on which the thin film of the oxide semiconductor is formed is preferably conductive, and a commercially available one may be used. As a specific example, a thin film of a conductive metal oxide such as tin oxide coated with indium, fluorine, or antimony on a surface of a transparent polymer material such as glass or polyethylene terephthalate or polyether sulfone, or a metal thin film such as copper, silver, or gold What formed this can be used. In this case, the conductivity is preferably 1000 Ω or less, particularly preferably 100 Ω or less.
상기 산화물 반도체 미립자로서는 금속산화물이 바람직하다. 구체적인 예로서는 티탄, 주석, 아연, 텅스텐, 지르코늄, 갈륨, 인듐, 이트륨, 니오브, 탄탈, 바나듐 등의 산화물을 사용할 수 있다. 이들 중 티탄, 주석, 아연, 니오브, 인듐 등의 산화물이 바람직하고, 산화티탄, 산화아연, 산화주석이 더욱 바람직하며, 산화티탄이 가장 바람직하다. 상기 산화물 반도체는 단독으로 사용할 수도 있지만, 혼합하거나 반도체의 표면에 코팅시켜서 사용할 수도 있다. As the oxide semiconductor fine particles, a metal oxide is preferable. As specific examples, oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used. Among these, oxides such as titanium, tin, zinc, niobium and indium are preferable, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferred. The oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.
상기 산화물 반도체 미립자의 입경은 평균 입경으로서 1 내지 500 nm인 것이 좋으며, 더욱 바람직하게는 1 내지 100 nm인 것이 좋다. 또한 이 산화물 반도체의 미립자는 큰 입경의 것과 작은 입경의 것을 혼합하거나, 다층으로 하여 이용할 수도 있다.The particle diameter of the oxide semiconductor fine particles is preferably 1 to 500 nm, more preferably 1 to 100 nm as the average particle diameter. In addition, the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.
상기 산화물 반도체 박막은 산화물 반도체 미립자를 스프레이 분무 등을 통해 직접 기판상에 박막으로 형성하는 방법, 기판을 전극으로 하여 전기적으로 반도체 미립자 박막을 석출시키는 방법, 반도체 미립자의 슬러리, 또는 반도체 알콕사이드 등의 반도체 미립자의 전구체를 가수분해하여 제조한 미립자를 함유하는 페이스트를 기판상에 도포한 후, 건조, 경화 혹은 소성하는 방법 등에 의해 제조할 수 있으며, 이 중에서도 페이스트를 기판상에 도포하는 방법이 바람직하다. The oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on the substrate through spray spraying, a method of electrically depositing a semiconductor fine particle thin film using the substrate as an electrode, a slurry of semiconductor fine particles, or a semiconductor such as a semiconductor alkoxide. The paste containing the fine particles prepared by hydrolyzing the precursor of the fine particles can be applied onto a substrate, and then produced by drying, curing or baking. Among these, a method of applying the paste onto the substrate is preferable.
상기 반도체 미립자의 슬러리를 이용하는 방법의 경우, 상기 슬러리는 2차 응집하고 있는 산화물 반도체 미립자를 통상의 방법에 의해 분산매 중에 평균 1차 입경이 1 내지 200 nm이 되도록 분산시킴으로써 얻을 수 있다. In the case of the method using the slurry of the said semiconductor fine particle, the said slurry can be obtained by disperse | distributing the oxide semiconductor microparticles | fine-particles which are secondary aggregated in a dispersion medium by a conventional method so that an average primary particle diameter may be 1-200 nm.
슬러리를 분산시키는 분산매로서는 반도체 미립자를 분산시킬 수 있는 것이면 특별한 제한 없이 사용할 수 있으며, 물, 에탄올 등의 알코올; 아세톤, 아세틸아세톤 등의 케톤; 또는 헥산 등의 탄화수소를 이용할 수 있으며, 이들을 혼합해서 사용할 수 있다. 이중에서도 분산매로서 물을 이용하는 것이 슬러리의 점도변화를 적게 한다는 점에서 바람직하다. 또한 산화물 반도체 미립자의 분산 상태를 안정화시킬 목적으로 분산 안정제를 사용할 수 있다. 사용할 수 있는 분산 안정제의 구체적인 예로는 초산, 염산, 질산 등의 산; 아세틸아세톤; 아크릴산; 폴리에틸렌글리콜; 폴리비닐알코올 등을 들 수 있다.As a dispersion medium which disperses a slurry, as long as it can disperse semiconductor fine particles, it can use without a restriction | limiting, Alcohol, such as water and ethanol; Ketones such as acetone and acetylacetone; Or hydrocarbons, such as hexane, can be used and these can be mixed and used. Of these, it is preferable to use water as the dispersion medium in that the viscosity change of the slurry is small. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles | fine-particles. Specific examples of dispersion stabilizers that can be used include acids such as acetic acid, hydrochloric acid and nitric acid; Acetylacetone; Acrylic acid; Polyethylene glycol; Polyvinyl alcohol, and the like.
이어서 슬러리를 도포한 기판의 소성시 소성온도는 100 ℃ 이상, 바람직하게는 200 ℃ 이상이고, 또 상한은 대체로 기재의 융점(연화점) 이하로서 통상 상한은 900 ℃이며, 바람직하게는 600 ℃ 이하이다. 본 발명에서 소성시간은 특별하게 한정되지 않지만, 대체로 4시간 이내가 바람직하다. Subsequently, the baking temperature at the time of baking of the board | substrate which apply | coated the slurry is 100 degreeC or more, Preferably it is 200 degreeC or more, and the upper limit is generally below melting | fusing point (softening point) of a base material, and an upper limit is 900 degreeC normally, Preferably it is 600 degrees C or less. . In the present invention, the firing time is not particularly limited, but is generally within 4 hours.
본 발명에서 기판상에 형성되는 산화물 반도체 미립자의 박막 두께는 1 내지 200 ㎛인 것이 바람직하며, 보다 바람직하게는 1 내지 50 ㎛이다. 또한 소성시 산화물 반도체 미립자의 박막 일부가 용착될 수도 있는데, 그러한 용착은 본 발명에 특별한 영향을 미치지는 않는다.In the present invention, the thickness of the oxide semiconductor fine particles formed on the substrate is preferably 1 to 200 m, more preferably 1 to 50 m. In addition, a part of the thin film of the oxide semiconductor fine particles may be deposited during firing, but such deposition does not particularly affect the present invention.
상기 산화물 반도체 박막에 대해 2차 처리를 실시할 수도 있다. 일 예로 반도체와 동일한 금속의 알콕사이드, 염화물, 질소화물, 황화물 등의 용액에 직접, 기판별로 박막을 침적시켜서 건조 혹은 재소성함으로써 반도체 박막의 성능을 향상시킬 수도 있다. 상기 금속 알콕사이드로서는 티탄에톡사이드, 티타늄이소프로폭사이드, 티탄 t-부톡사이드, n-디부틸-디아세틸 주석 등을 들 수 있고, 이때 용매로는 알코올을 이용하여 알코올 용액으로 사용할 수 있다. 상기 염화물로서는 예를 들면 4염화 티탄, 사염화주석, 염화아연 등을 들 수 있고, 이때 용매로는 물을 이용하여 수용액으로 사용할 수 있다. 이렇게 하여 수득된 산화물 반도체 박막은 산화물 반도체의 미립자로 이루어져 있다.Secondary processing may be performed on the oxide semiconductor thin film. As an example, the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin, and the like. The solvent may be used as an alcohol solution using alcohol. Examples of the chloride include titanium tetrachloride, tin tetrachloride, and zinc chloride, and the like can be used as an aqueous solution using water as a solvent. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.
본 발명에서 박막 상으로 형성된 산화물 반도체 미립자에 염료를 담지시키는 방법은 특별히 한정되지 않으며, 구체적인 예로서 상기 화학식 (I) 및 (II)로 표시되는 유기염료를 용해할 수 있는 용매로 용해해서 제조한 용액, 또는 상기 유기염료를 분산시켜 제조한 분산액에 상기 산화물 반도체 박막이 설치된 기판을 침지시키는 방법을 들 수 있다. In the present invention, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase is not particularly limited, and as a specific example prepared by dissolving the organic dye represented by the formula (I) and (II) in a solvent capable of dissolving The method of immersing the board | substrate with which the said oxide semiconductor thin film was installed in the solution or the dispersion liquid which disperse | distributed the said organic dye is mentioned.
상기 용액 또는 분산액 중의 유기염료의 농도는 염료에 따라 적절히 결정할 수 있다. 염료 농도는 1× 10-6 M 내지 1 M이 바람직하고, 보다 바람직하게는 1× 10-5 M 내지 1× 10-1 M 일 수 있다. The concentration of the organic dye in the solution or dispersion can be appropriately determined depending on the dye. The dye concentration is preferably 1 × 10 −6 M to 1 M, more preferably 1 × 10 −5 M to 1 × 10 −1 M.
침적시 온도는 대체로 상온에서 용매의 비점까지이고, 또 침적시간은 1분에서 48시간 정도이다. The temperature during deposition is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours.
염료를 용해시키는데 사용할 수 있는 용매의 구체적인 예로는 메탄올, 에탄올, 아세토니트릴, 디메틸설폭사이드, 디메틸포름아미드, 아세톤, t-부탄올 등을 들 수 있다. Specific examples of the solvent that can be used to dissolve the dye include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, t-butanol and the like.
또한 담지하는 유기염료는 1종류일 수도 있고, 수 종류 혼합할 수도 있다. 혼합하는 경우에는 본 발명에 따른 유기염료와 함께 다른 유기염료나 금속 착체 염료를 혼합할 수 있다. 혼합할 수 있는 금속 착체 염료의 예는 특별하게 제한되지 않지만, 루테늄 착체나 그 4급염, 프탈로시아닌, 포르피린 등이 바람직하고, 다른 유기염료로는 무금속의 프탈로시아닌, 포르피린이나 시아닌, 메로시아닌, 옥소놀, 트리페닐메탄계, WO2002/011213호에 제시되는 아크릴산계 염료 등의 메틴계 염료나, 크산텐계, 아조계, 안트라퀴논계, 페릴렌계 등의 염료를 들 수 있다(문헌 [M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., 제115권, 6382쪽(1993년)] 참조). 염료를 2종 이상 이용하는 경우에는 염료를 반도체 박막에 차례로 흡착시킬 수도, 혼합 용해해서 흡착시킬 수도 있다.The organic dye to be supported may be one kind or may be mixed in several kinds. In the case of mixing, other organic dyes or metal complex dyes may be mixed with the organic dyes according to the present invention. Examples of the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes and quaternary salts thereof, phthalocyanine, porphyrin and the like are preferable, and other organic dyes include metal-free phthalocyanine, porphyrin or cyanine, merocyanine, oxo. Methine dyes such as knol, triphenylmethane, and acrylic acid dyes described in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene-based dyes. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzel, J. Am. Chem. Soc., Vol. 115, pp . 6382 (1993). . In the case of using two or more kinds of dyes, the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved and adsorbed.
또한 본 발명에서 산화물 반도체 미립자의 박막에 염료를 담지할 때, 염료끼리의 결합을 방지하기 위해서 포섭 화합물의 존재하에서 염료를 담지하는 것이 좋다. 상기 포섭화합물로서는 데옥시콜산, 데히드로데옥시콜산, 케노데옥시콜산, 콜산메틸에스테르, 콜산나트륨 등의 콜산류; 폴리에틸렌옥사이드, 콜산 등의 스테로이드계 화합물; 크라운에테르; 사이클로덱스트린; 캘릭스아렌; 폴리에틸렌옥사이드 등을 사용할 수 있다. In the present invention, when the dye is supported on the thin film of the oxide semiconductor fine particles, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the dyes from bonding. Examples of the inclusion compound include cholic acids such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, cholate methyl ester and sodium cholate; Steroid compounds such as polyethylene oxide and cholic acid; Crown ethers; Cyclodextrins; Callix arene; Polyethylene oxide and the like can be used.
또한, 염료를 담지시킨 후, 4-t-부틸 피리딘 등의 아민 화합물이나 초산, 프로피온산 등의 산성기를 가지는 화합물 등으로 반도체 미립자 박막이 설치된 기판을 처리할 수 있다. 처리방법은 예를 들면 아민의 에탄올 용액에 염료를 담지한 반도체 미립자 박막이 설치된 기판을 담그는 방법 등이 사용될 수 있다. After the dye is supported, the substrate on which the semiconductor fine particle thin film is installed can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid. As a treatment method, for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.
이렇게 해서 염료로 증감된 박막 상의 산화물 반도체 미립자를 가진 광전변환소자를 얻을 수 있다.
In this way, a photoelectric conversion element having oxide semiconductor fine particles on a thin film sensitized with a dye can be obtained.
본 발명은 상기 염료감응 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.The present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element.
상기 염료감응태양전지는 산화물 반도체 미립자에 유기염료를 담지시킨 광전변환소자 전극(음극), 대전극(양극), 산화환원 전해질, 정공수송 재료 또는 p형 반도체 등으로 구성될 수 있다.The dye-sensitized solar cell may be composed of a photoelectric conversion element electrode (cathode), a counter electrode (anode), a redox electrolyte, a hole transport material, or a p-type semiconductor, in which an organic dye is supported on oxide semiconductor fine particles.
상기 염료감응태양전지는 상기 유기염료를 담지시킨 산화물 반도체 미립자를 이용한 염료증감 광전변환소자를 사용하는 것 이외에 종래 광전변환소자를 사용하여 태양전지를 제조하는 통상의 방법들이 적용될 수 있다. 구체적인 예로 본 발명에 따른 염료감응태양전지는 전도성 투명 기판 위에 산화티타늄 페이스트를 코팅하는 단계; 페이스트가 코팅된 기판을 소성하여 산화티타늄 박막을 형성하는 단계; 산화티타늄 박막이 형성된 기판을 유기염료가 용해된 혼합용액에 함침시켜 염료가 흡착된 산화티타늄 필름 전극을 형성하는 단계; 그 상부에 대전극이 형성된 제2의 유리기판을 구비하는 단계; 제2 유리기판 및 대전극을 관통하는 홀(hole)을 형성하는 단계; 상기 대전극 및 상기 염료가 흡착된 산화티타늄 필름 전극 사이에 열가소성 고분자 필름을 두고, 가열 압착 공정을 실시하여 상기 대전극 및 산화티타늄 필름전극을 접합시키는 단계; 상기 홀을 통하여 대전극과 산화티타늄 필름 전극 사이의 열가소성 고분자 필름에 전해질을 주입하는 단계; 및 상기 열가소성 고분자를 실링하는 단계를 통하여 제조될 수 있다.The dye-sensitized solar cell may be applied to conventional methods of manufacturing a solar cell using a conventional photoelectric conversion element, in addition to using a dye-sensitized photoelectric conversion element using the oxide semiconductor fine particles carrying the organic dye. As a specific example, the dye-sensitized solar cell according to the present invention comprises the steps of coating a titanium oxide paste on a conductive transparent substrate; Baking the paste-coated substrate to form a titanium oxide thin film; Impregnating the substrate on which the titanium oxide thin film is formed into a mixed solution in which an organic dye is dissolved to form a titanium oxide film electrode to which dye is adsorbed; Providing a second glass substrate having a counter electrode formed thereon; Forming a hole penetrating the second glass substrate and the counter electrode; Bonding the counter electrode to the titanium oxide film electrode by placing a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode to which the dye is adsorbed, and performing a heat compression process; Injecting an electrolyte into the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole; And it may be prepared through the step of sealing the thermoplastic polymer.
상기 산화환원 전해질, 정공수송 재료 및 p형 반도체 등은 액상, 응고체(겔 및 겔상), 고체 등의 형태로 이용될 수 있다. 액상으로 이용되는 경우 산화환원 전해질, 용해염, 정공수송재료, p형 반도체 등을 각각 용매에 용해시킨 것이나 상온 용해염 등이, 응고체(겔 및 겔상)의 경우에는 이것들을 폴리머 매트릭스나 저분자 겔화제 등에 함유시킨 것 등을 각각 들 수 있다. 고체의 형태로 이용되는 경우에는 고상의 산화환원 전해질, 용해염, 정공수송재료, p형 반도체 등을 사용할 수 있다. The redox electrolyte, hole transport material, p-type semiconductor, and the like may be used in the form of a liquid, a solid (gel and gel), a solid, and the like. When used in a liquid phase, a redox electrolyte, a dissolving salt, a hole transport material, a p-type semiconductor, or the like is dissolved in a solvent, or a room temperature dissolving salt is a polymer matrix or a low molecular gel in the case of a coagulated body (gel and gel). The thing etc. which were contained in the topic etc. are mentioned, respectively. When used in the form of a solid, a solid phase redox electrolyte, a dissolved salt, a hole transport material, a p-type semiconductor, or the like can be used.
정공수송 재료로서는 공지의 정공수송 재료가 사용될 수 있으며, 구체적인 예로 아민 유도체나 폴리아세틸렌, 폴리아닐린, 폴리티오펜 등의 도전성 고분자; 또는 트리페닐렌계 화합물 등의 디스코테크 액정상을 이용하는 물건 등을 사용할 수 있다. 또한 p형 반도체로서는 CuI, CuSCN 등을 사용할 수 있다. 대전극으로는 도전성을 가지고 있으며, 산화환원 전해질의 환원 반응을 촉매적으로 작용하는 것이 바람직하다. 예를 들면, 글라스 또는 고분자 필름에 백금, 카본, 로듐, 루테늄 등을 증착하거나, 도전성 미립자를 도포한 것을 사용할 수 있다.Known hole transport materials may be used as the hole transport material, and specific examples include conductive polymers such as amine derivatives, polyacetylene, polyaniline, and polythiophene; Or an object using a discotech liquid crystal phase such as a triphenylene compound. Moreover, CuI, CuSCN, etc. can be used as a p-type semiconductor. It is preferable that the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.
상기 산화환원 전해질로서는 할로겐 이온을 대이온으로 하는 할로겐 화합물-할로겐 분자로 구성되는 할로겐 산화환원계 전해질; 페로시안산염-페로시안산염이나 페로센-페리시늄 이온, 코발트 착체 등의 금속착체 등의 금속 산화환원계 전해질; 알킬티올-알킬디설피드, 비올로겐 염료, 하이드로퀴논-퀴논 등의 유기산화 환원계 전해질 등을 사용할 수 있으며, 할로겐 산화환원계 전해질이 바람직하다. 할로겐 화합물-할로겐 분자로 구성되는 할로겐 산화환원계 전해질에 있어서의 할로겐 분자로서는 요오드 분자가 바람직하다. 또한 할로겐 이온을 대이온으로 하는 할로겐 화합물로서는 LiI, NaI, KI, CaI2, MgI2, CuI 등의 할로겐화 금속염, 또는 테트라알킬암모늄요오드, 이미다졸리움요오드, 피리디움요오드 등의 할로겐의 유기 암모늄염, 또는 I2를 사용할 수 있다.Examples of the redox electrolyte include a halogen redox electrolyte composed of a halogen compound-halogen molecule having halogen ions as a counter ion; Metal redox-based electrolytes such as metal complexes such as ferrocyanate-ferrocyanate, ferrocene-ferricinium ions and cobalt complexes; Organic redox-based electrolytes such as alkylthiol-alkyldisulfide, viologen dye, hydroquinone-quinone, and the like can be used, and a halogen redox-based electrolyte is preferable. As a halogen molecule in the halogen redox electrolyte composed of halogen compound-halogen molecules, an iodine molecule is preferable. As a halogen compound having a halogen ion as a large ion, halogenated metal salts such as LiI, NaI, KI, CaI 2 , MgI 2 and CuI, or organic ammonium salts of halogens such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine, Or I 2 can be used.
또한 산화환원 전해질은 이를 포함하는 용액의 형태로 구성되어 있는 경우, 그 용매로는 전기 화학적으로 불활성인 것을 사용할 수 있다. 구체적인 예로서 아세토니트릴, 프로필렌카보네이트, 에틸렌카보네이트, 3-메톡시프로피오니트릴, 메톡시아세토니트릴, 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 부틸로락톤, 디메톡시에탄, 디메틸카보네이트, 1,3-디옥소란, 메틸포르메이트, 2-메틸테트라하이드로퓨란, 3-메톡시-옥사졸리딘-2-온, 설포란, 테트라하이드로퓨란, 물 등을 들 수 있으며, 특히 아세토니트릴, 프로필렌카보네이트, 에틸렌카보네이트, 3-메톡시프로피오니트릴, 에틸렌글리콜, 3-메톡시-옥사졸리딘-2-온, 부틸로락톤 등이 바람직하다. 상기 용매들은 1종 또는 혼합해서 사용할 수 있다. 겔상 전해질의 경우에는 올리고머 및 폴리머 등의 매트릭스에 전해질 또는 전해질 용액을 함유시킨 것이나, 전분자 겔화제 등에 동일하게 전해질 또는 전해질 용액을 함유시킨 것을 사용할 수 있다. 산화환원 전해질의 농도는 0.01 내지 99 중량%인 것이 좋으며, 0.1 내지 30 중량%인 것이 더욱 바람직하다.In addition, when the redox electrolyte is configured in the form of a solution containing the same, an electrochemically inert one may be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable. The solvents may be used alone or in combination. In the case of the gel electrolyte, one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight.
본 발명에 따른 태양전지는 기판상의 산화물 반도체 미립자에 염료를 담지한 광전변환소자(음극)에 그것과 대치하도록 대전극(양극)을 배치하고 그 사이에 산화환원 전해질을 함유하는 용액을 충전하는 것에 의하여 얻어질 수 있다.
In the solar cell according to the present invention, a counter electrode (anode) is disposed in a photoelectric conversion element (cathode) on which a dye is supported on oxide semiconductor fine particles on a substrate so as to face the same, and a solution containing a redox electrolyte is filled therebetween. Can be obtained by
이하에서 본 발명을 실시예에 의거하여 보다 구체적으로 설명한다. 단, 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are only for illustrating the present invention, the present invention is not limited to these.
실시예Example 1 : 화학식 8의 합성 1: Synthesis of Chemical Formula 8
1) 중간체(8a)의 합성1) Synthesis of Intermediate (8a)
2,7-디브로모-9-페닐아크리딘(2,7-dibromo-9-phenylacridine)과 3',4-디헥실-2,2'-비티오펜-5-일 보론산(3',4-dihexyl-2,2'-bithiophen-5-ylboronic acid), Pd(PPh3)4 및 2M K2CO3 수용액을 디메틸포름아미드(DMF) 중에서 혼합한 후 12시간 동안 환류하였다. 결과로 수득된 반응 용액을 냉각시키고, 물(30ml)과 염수를 첨가한 후, 유기층을 분리 및 정제하여 하기 화학 구조식을 갖는 중간체를 얻었다.2,7-dibromo-9-phenylacridine and 3 ', 4-dihexyl-2,2'-bithiophen-5-yl boronic acid (3' , 4-dihexyl-2,2'-bithiophen-5-ylboronic acid), Pd (PPh3)4 And 2M K2CO3 The aqueous solution was mixed in dimethylformamide (DMF) and then refluxed for 12 hours. The resulting reaction solution was cooled, water (30 ml) and brine were added, and the organic layer was separated and purified to obtain an intermediate having the following chemical structure.
[중간체 8a][Intermediate 8a]
2) 중간체 (8b)의 합성2) Synthesis of Intermediate (8b)
상기에서 제조한 중간체 (8a)를 무수 에탄올 용액에 첨가하고, n-BuLi를 아르곤 하에서 추가 첨가하였다. 3시간 후, 결과로 수득된 반응물에 DMF를 아르곤 하에서 0 ℃에서 첨가하고, 5% KOH로 세척하였다. 결과로 수득된 반응용액을 황산마그네슘으로 건조하고 용매를 제거한 후 정제하여 중간체(8b)를 얻었다.The intermediate (8a) prepared above was added to anhydrous ethanol solution, and n- BuLi was further added under argon. After 3 h, DMF was added to the resulting reaction at 0 ° C. under argon and washed with 5% KOH. The resulting reaction solution was dried over magnesium sulfate, and the solvent was removed and purified to obtain an intermediate (8b).
[중간체 8b][Intermediate 8b]
3) 3) 화합식Compound 8의 합성 8, Synthesis
상기에서 제조된 중간체 (8b)와 시아노아세트산을 혼합한 후 진공건조하였다. 결과로 수득된 건조물을 MeCN 및 피페리딘에 첨가한 후 6시간 동안 환류하였다. 결과의 반응용액을 냉각시킨 후 유기층을 진공 하에서 제거하고, 결과로 수득된 고형물을 실리카 겔 크로마토그래피하여 하기 화학 구조식을 갖는 화합물 8을 얻었다.The intermediate (8b) prepared above and cyanoacetic acid were mixed and then dried in vacuo. The resulting dried product was added to MeCN and piperidine and refluxed for 6 hours. After cooling the resulting reaction solution, the organic layer was removed under vacuum, and the resulting solid was subjected to silica gel chromatography to obtain Compound 8 having the following chemical structure.
원소 분석(Elemental Analysis): C, 72.46; H, 6.44; N, 3.78; O, 5.76; S, 11.55)Elemental Analysis: C, 72.46; H, 6. 44; N, 3.78; 0, 5.76; S, 11.55)
[화학식 8]
[Chemical Formula 8]
실시예Example 2 : 2 : 화합식Compound 10의 합성 10 composite
1) 중간체(10a)의 합성1) Synthesis of Intermediate 10a
3',4-디헥실-2,2'-비티오펜-5-일 보론산 대신에 7-(5-(5,5-디메틸-1,3-디옥산-2-일)티에노[3,2-b]티오펜-2-일)-2,3-디히드로티에노[3,4-b][1,4]디옥신-5-일 보론산을 사용하는 것을 제외하고는 상기 실시예 1에서와 동일한 방법으로 실시하여 하기 화학 구조식의 중간체 (10a)를 얻었다.7- (5- (5,5-dimethyl-1,3-dioxan-2-yl) thieno [3 instead of 3 ', 4-dihexyl-2,2'-bithiophen-5-yl boronic acid The above procedure was carried out except for using, 2-b] thiophen-2-yl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl boronic acid It carried out by the same method as Example 1, and obtained the intermediate (10a) of the following chemical structural formula.
[중간체 10a][Intermediate 10a]
2) 중간체(10b)의 합성2) Synthesis of Intermediate 10b
상기 실시예 1의 2)에서 상기 제조된 중간체 (10a)를 테트라히드로퓨란(THF)에 녹인 용액에, 트리플루오로아세트산 및 물을 적가하고, 질소분위기 하에서 4시간동안 교반하였다.Trifluoroacetic acid and water were added dropwise to the solution of the intermediate (10a) prepared in Example 1 2) in tetrahydrofuran (THF) and stirred for 4 hours under a nitrogen atmosphere.
교반이 끝난 후 결과로 수득된 반응용액에 대해 메틸렌클로라이드와 물을 사용하여 유기층을 추출한 후 증발시키고, 컬럼크로마토그래피로 정제하여 하기 화학 구조식의 중간체(10b)를 얻었다.After stirring, the resulting reaction solution was extracted with methylene chloride and water, and the organic layer was extracted, and then evaporated and purified by column chromatography to obtain an intermediate (10b) having the following chemical structure.
[중간체 10b][Intermediate 10b]
3) 3) 화합식Compound 10의 합성 10 composite
상기 실시예 1의 3)에서 중간체 (8b) 대신에 중간체 (10b)를 사용하는 것을 제외하고는 상기 실시예 1에서와 동일한 방법으로 실시하여 하기 화학 구조식10의 화합물을 얻었다. Except for using the intermediate (10b) instead of the intermediate (8b) in Example 1 3) was carried out in the same manner as in Example 1 to obtain a compound of the formula 10.
원소분석: C, 61.12; H, 2.72; N, 4.19; O, 12.77; S, 19.20Elemental Analysis: C, 61.12; H, 2.72; N, 4.19; 0, 12.77; S, 19.20
[화학식 10][Formula 10]
실시예Example 3 : 화학식 18의 합성 3: Synthesis of Chemical Formula 18
1) 중간체 (18a)의 합성1) Synthesis of Intermediate (18a)
테트라에틸(9-페닐아크리딘-2,7-디일)비스(메틸렌)디포스포네이트와 7-(5-(5,5-디메틸-1,3-디옥산-2-일)티에노[3,2-b]티오펜-2-일)-2,3-디히드로티에노[3,4-b][1,4]디옥신-5-카브알데히드를 칼륨tert-부톡사이드의 존재하에서 THF용매 중에서 비티히(Wittig) 반응시켜 하기 화학구조식의 중간체 (18a)를 얻었다.Tetraethyl (9-phenylacridin-2,7-diyl) bis (methylene) diphosphonate and 7- (5- (5,5-dimethyl-1,3-dioxan-2-yl) thieno [ 3,2-b] thiophen-2-yl) -2,3-dihydrothieno [3,4-b] [1,4] dioxine-5-carbaldehyde in the presence of potassium tert-butoxide A Wittig reaction was performed in a THF solvent to obtain an intermediate (18a) having the following chemical formula.
[중간체 18a][Intermediate 18a]
2) 중간체 (18b)의 합성2) Synthesis of Intermediate (18b)
상기 실시예 1의 중간체 (8a) 대신에 상기에서 제조된 중간체(18a)를 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 하기 화학구조식의 중간체 (18b)를 얻었다.Except for using the intermediate (18a) prepared in place of the intermediate (8a) of Example 1 in the same manner as in Example 1 to obtain an intermediate (18b) of the following chemical formula.
[중간체 18b][Intermediate 18b]
3) 3) 화합식Compound 18의 합성 18 composites
상기 실시예 1에서 중간체 (8b) 대신에 상기에서 제조된 중간체 (18b)를 사용하는 것을 제외하고는 실시예 1에서와 동일한 방법으로 실시하여 하기 화학구조식 18의 화합물을 얻었다.The compound of Chemical Formula 18 was obtained in the same manner as in Example 1, except that Intermediate 18b prepared above was used instead of Intermediate 8b in Example 1.
원소분석: C, 62.54; H, 3.15; N, 3.98; O, 12.12; S, 18.21Elemental Analysis: C, 62.54; H, 3. 15; N, 3.98; 0, 12.12; S, 18.21
[화학식 18][Formula 18]
실시예Example 4 : 화학식 40의 합성 4: synthesis of formula 40
상기 실시예 1에서 2,7-디브로모-9-페닐아크리딘 대신에 3,6-디브로모-N,N-비스(9,9-디메틸-9H-플루오렌-2-일)-10-페닐안트라센-9-아민을 사용한 것을 제외하고는 실시예 1에서와 동일한 방법을 순차적으로 실시하여 하기 화학 구조식40의 화합물을 얻었다.3,6-dibromo-N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) instead of 2,7-dibromo-9-phenylacridin in Example 1 above Except for using -10-phenylanthracene-9-amine, the same method as in Example 1 was carried out sequentially to obtain a compound of formula (40).
원소분석: C, 78.00; H, 6.48; N, 2.78; O, 4.24; S, 8.50Elemental Analysis: C, 78.00; H, 6. 48; N, 2.78; 0, 4.24; S, 8.50
[화학식 40][Formula 40]
실시예Example 5 : 5: 화합식Compound 115의 합성 Synthesis of 115
3,6-디브로모-N,N-비스(9,9-디메틸-9H-플루오렌-2-일)-10-페닐안트라센-9-아민 대신에 N-(4-(3,6-디브로모-10-페닐안트라센-9-일)페닐)-N-(9,9-디메틸-9H-플루오렌-2-일)-9,9-디메틸-9H-플루오렌-2-아민을 사용하는 것을 제외하고는 상기 실시예 4에서와 동일한 방법으로 실시하여 하기 화학구조식 115의 화합물을 얻었다.3,6-dibromo-N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) -10-phenylanthracene-9-amine instead of N- (4- (3,6- Dibromo-10-phenylanthracene-9-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine Except for using the compound in the same manner as in Example 4 to obtain a compound of formula 115.
원소분석: C, 75.77; H, 4.66; Br, 18.00; N, 1.58Elemental Analysis: C, 75.77; H, 4. 66; Br, 18.00; N, 1.58
[화학식 115] [Formula 115]
실시예Example 6 : 6: 화합식Compound 42의 합성 Synthesis of 42
2,7-디브로모-9-페닐아크리딘 대신에 3,6-디브로모-N,N-비스(9,9-디메틸-9H-플루오렌-2-일)-10-페닐안트라센-9-아민을 사용한 것을 제외하고는 실시예 1에서와 동일한 방법을 순차적으로 실시하여 하기 화학구조식 42의 화합물을 얻었다.3,6-dibromo-N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) -10-phenylanthracene instead of 2,7-dibromo-9-phenylacridin Except for using the -9-amine was carried out in the same manner as in Example 1 in order to obtain a compound of the formula 42.
원소분석: C, 70.31; H, 3.81; N, 3.00; O, 9.14; S, 13.74Elemental Analysis: C, 70.31; H, 3.81; N, 3.00; 0, 9.14; S, 13.74
[화학식 42][Formula 42]
실시예Example 7 : 7: 화합식Compound 50의 합성 50 composites
테트라에틸(9-페닐아크리딘-2,7-디일)비스(메틸렌)디포스포네이트 대신에 테트라에틸(10-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)-9-페닐안트라센-2,7-디일)비스(메틸렌)디포스포네이트를 사용하는 것을 제외하고는 실시예 3에서와 동일한 방법을 순차적으로 실시하여 하기 화학구조식 50의 화합물을 얻었다.Tetraethyl (10- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) instead of tetraethyl (9-phenylacridin-2,7-diyl) bis (methylene) diphosphonate Except for using -9-phenylanthracene-2,7-diyl) bis (methylene) diphosphonate, the same method as in Example 3 was carried out sequentially to obtain a compound of formula
원소분석: C, 71.00; H, 4.09; N, 2.89; O, 8.80; S, 13.22Elemental Analysis: C, 71.00; H, 4.09; N, 2.89; 0, 8.80; S, 13.22
[화학식 50][Formula 50]
실시예Example 8 : 8 : 화합식Compound 116의 합성 Synthesis of 116
테트라에틸(10-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)-9-페닐안트라센-2,7-디일)비스(메틸렌)디포스포네이트 대신에 N-(4-(3,6-디브로모-10-페닐안트라센-9-일)페닐)-N-(9,9-디메틸-9H-플루오렌-2-일)-9,9-디메틸-9H-플루오렌-2-아민을 사용한 것을 제외하고는 상기 실시예 7에서와 동일한 방법으로 실시하여 하기 화학구조식 116의 화합물을 얻었다.N- (4 instead of tetraethyl (10- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) -9-phenylanthracene-2,7-diyl) bis (methylene) diphosphonate -(3,6-dibromo-10-phenylanthracene-9-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-flu Except for using oren-2-amine was carried out in the same manner as in Example 7 to obtain a compound of formula 116.
원소분석: C, 72.18; H, 4.15; N, 2.74; O, 8.36; S, 12.57Elemental Analysis: C, 72.18; H, 4. 15; N, 2.74; 0, 8.36; S, 12.57
[화학식 116][Formula 116]
실시예Example 9 : 화학식 117의 합성 9: Synthesis of Chemical Formula 117
3,6-디브로모-N,N-비스(9,9-디메틸-9H-플루오렌-2-일)-10-페닐안트라센-9-아민 대신에 2,7-디브로모-9,9-디메틸-10-(4-메톡시페닐)-9,10-디히드로아크리딘을 사용하는 것을 제외하고는 상기 실시예 6에서와 동일한 방법으로 실시하여 하기 화학구조식 117의 화합물을 얻었다. 2,7-dibromo-9, instead of 3,6-dibromo-N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) -10-phenylanthracene-9-amine, Except for using 9-dimethyl-10- (4-methoxyphenyl) -9,10-dihydroacridine in the same manner as in Example 6 to obtain a compound of formula 117.
원소분석: C, 61.06; H, 3.32; N, 3.96; O, 13.56; S, 18.11Elemental Analysis: C, 61.06; H, 3. 32; N, 3.96; 0, 13.56; S, 18.11
[화학식 117]Formula 117
실시예Example 10 : 10: 화합식Compound 118의 합성 Synthesis of 118
3,6-디브로모-N,N-비스(9,9-디메틸-9H-플루오렌-2-일)-10-페닐안트라센-9-아민 대신에 3,7-디브로모-10-(4-메톡시페닐)-10H-페노티아진을 사용하는 것을 제외하고는 상기 실시예 6에서와 동일한 방법으로 실시하여 하기 화학구조식 118의 화합물을 얻었다. 3,7-dibromo-10- instead of 3,6-dibromo-N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) -10-phenylanthracene-9-amine Except for using (4-methoxyphenyl) -10H-phenothiazine in the same manner as in Example 6 to obtain a compound of formula 118.
원소분석: C, 58.21; H, 2.78; N, 3.99; O, 13.68; S, 21.33Elemental Analysis: C, 58.21; H, 2.78; N, 3.99; 0, 13.68; S, 21.33
[화학식 118][Formula 118]
실시예Example 11 : 11: 화합식Compound 119의 합성 Synthesis of 119
3,6-디브로모-N,N-비스(9,9-디메틸-9H-플루오렌-2-일)-10-페닐안트라센-9-아민 대신에 3,6-디브로모-9-(4-메톡시페닐)-9H-카바졸을 사용한 것을 제외하고는 상기 실시예 6에서와 동일한 방법으로 실시하여 하기 화학구조식 119의 화합물을 얻었다. 3,6-dibromo-9- instead of 3,6-dibromo-N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) -10-phenylanthracene-9-amine Except for using (4-methoxyphenyl) -9H-carbazole was carried out in the same manner as in Example 6 to obtain a compound of formula 119.
원소분석: C, 60.04; H, 2.87; N, 4.12; O, 14.11; S, 18.86Elemental Analysis: C, 60.04; H, 2.87; N, 4.12; 0, 14.11; S, 18.86
[화학식 119]Formula 119
실시예 12 : 화학식 120의 합성Example 12 Synthesis of Chemical Formula 120
테트라에틸(10-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)-9-페닐안트라센-2,7-디일)비스(메틸렌)디포스포네이트 대신에 테트라에틸(9,9-디메틸-10-(4-메톡시페닐)-9,10-디히드로아크리딘-2,7-디일)비스(메틸렌)디포스포네이트를 사용하는 것을 제외하고는 실시예 7에서와 동일한 방법으로 실시하여 하기 화학구조식 120의 화합물을 얻었다.Tetraethyl (9) instead of 10- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) -9-phenylanthracene-2,7-diyl) bis (methylene) diphosphonate Same as in Example 7, except using, 9-dimethyl-10- (4-methoxyphenyl) -9,10-dihydroacridin-2,7-diyl) bis (methylene) diphosphonate The compound of formula 120 was obtained by the method.
원소분석: C, 62.40; H, 3.70; N, 3.76; O, 12.90; S, 17.23Elemental Analysis: C, 62.40; H, 3. 70; N, 3.76; 0, 12.90; S, 17.23
[화학식 120]
[Formula 120]
실시예Example 13 : 화학식 121의 합성 13: Synthesis of Chemical Formula 121
실시예 6에서 테트라에틸(10-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)-9-페닐안트라센-2,7-디일)비스(메틸렌)디포스포네이트 대신에 테트라에틸(10-(4-메톡시페닐)-10H-페노티아진-3,7-디일)비스(메틸렌)디포스포네이트를 사용하는 것을 제외하고는 상기 실시예 6에서와 동일한 방법으로 실시하여 하기 화학구조식 121의 화합물을 얻었다.Instead of tetraethyl (10- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) -9-phenylanthracene-2,7-diyl) bis (methylene) diphosphonate in Example 6 The same procedure as in Example 6 was carried out except that tetraethyl (10- (4-methoxyphenyl) -10H-phenothiazine-3,7-diyl) bis (methylene) diphosphonate was used. The compound of formula 121 was obtained.
원소분석: C, 59.71; H, 3.19; N, 3.80; O, 13.02; S, 20.29Elemental Analysis: C, 59.71; H, 3. 19; N, 3.80; 0, 13.02; S, 20.29
[화학식 121][Formula 121]
실시예 14 : 화학식 122의 합성Example 14 Synthesis of Chemical Formula 122
테트라에틸(10-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)-9-페닐안트라센-2,7-디일)비스(메틸렌)디포스포네이트 대신에 테트라에틸(9-(4-메톡시페닐)-9H-카바졸-3,6-디일)비스(메틸렌)디포스포네이트를 사용한 것을 제외하고는 상기 실시예 7에서와 동일한 방법으로 실시하여 하기 화학구조식 122의 화합물을 얻었다.Tetraethyl (9) instead of 10- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) -9-phenylanthracene-2,7-diyl) bis (methylene) diphosphonate The compound of formula 122 was carried out in the same manner as in Example 7, except that-(4-methoxyphenyl) -9H-carbazole-3,6-diyl) bis (methylene) diphosphonate was used. Got.
원소분석: C, 61.49; H, 3.28; N, 3.91; O, 13.40; S, 17.91Elemental Analysis: C, 61.49; H, 3. 28; N, 3.91; 0, 13.40; S, 17.91
[화학식 122][Formula 122]
염료감응태양전지의 제조Fabrication of Dye-Sensitized Solar Cell
본 발명에 따른 염료의 전류-전압 특성을 평가하기 위해, 13+10 ㎛ TiO2 투명층을 이용하여 염료감응태양전지를 제조하였다. In order to evaluate the current-voltage characteristics of the dye according to the present invention, a dye-sensitized solar cell was prepared using a 13 + 10 μm TiO 2 transparent layer.
상세하게는 세척된 FTO(Pilkington, 8 Ωsq-1) 유리기판을 40mM TiCl4 수용액 중에 함침시켰다. TiO2 페이스트(Solaronix, 13 nm 아나타제)를 스크린 프린팅하여 13㎛ 두께의 제1 TiO2 층을 제조하고, 광산란을 위해 다른 페이스트(CCIC, HWP-400)로 10㎛ 두께의 제2 TiO2 산란층을 제조하였다. 제조된 TiO2 전극을 본 발명에 따른 염료의 용액 (10mM의 3a,7a-디하이드록시-5b-콜산 함유 에탄올 중에 상기 실시예 1-14에서 제조된 화합물을 각각 0.3 mM로 용해시켜 제조함)에 함침시킨 후, 실온에서 18시간 동안 방치하였다. FTO 기판 상에 H2PtCl6 용액(에탄올 1 mL 중에 Pt 2 mg 함유)을 코팅하여 대전극을 제조하였다. 이어, 아세토니트릴 중에 0.6 M 3-헥실-1,2-디메틸이미다졸리움 요오드, 0.04 M I2, 0.025 M LiI, 0.05 M 구아니디움 티오시아네이트 및 0.28 M tert-부틸피리딘을 용해시킨 전해질을 전지에 주입하여 염료감응태양전지를 제조하였다. 염료감응태양전지의 광전지 성능은 1000W 크세논 광원을 사용하여 측정하였으며, 그 결과를 하기 표 1에 나타내었다.Specifically, the washed FTO (Pilkington, 8 μsq-1) glass substrate was impregnated in a 40 mM TiCl 4 aqueous solution. A TiO2 paste (Solaronix, 13 nm anatase) was screen printed to produce a 13 μm thick first TiO2 layer, and another paste (CCIC, HWP-400) was used to prepare a 10 μm thick second TiO2 scattering layer. . Prepared TiO2 electrode in a solution of the dye according to the present invention (prepared by dissolving 0.3 mM each of the compounds prepared in Examples 1-14 in 10 mM 3a, 7a-dihydroxy-5b-cholic acid containing ethanol) After impregnation, it was left at room temperature for 18 hours. The counter electrode was prepared by coating a solution of H 2 PtCl 6 (containing 2 mg of Pt in 1 mL of ethanol) on an FTO substrate. Then, an electrolyte in which 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI 2 , 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert -butylpyridine was dissolved in acetonitrile was obtained. Was injected into a dye-sensitized solar cell. The photovoltaic performance of the dye-sensitized solar cell was measured using a 1000W xenon light source, and the results are shown in Table 1 below.
상기 표 1에 나타나는 바와 같이 본 발명의 염료들은 우수한 효율을 나타냄을 알 수 있다.
As shown in Table 1, it can be seen that the dyes of the present invention exhibit excellent efficiency.
본 발명을 상기의 구체적인 실시예와 관련하여 기술하였지만, 첨부된 특허청구범위에 의해 정의된 본 발명의 범위 내에서 당 분야의 숙련자는 본 발명을 다양하게 변형 및 변화시킬 수 있다.Although the present invention has been described in connection with the specific embodiments described above, those skilled in the art can variously modify and change the present invention within the scope of the present invention as defined by the appended claims.
Claims (9)
[화학식 1]
[화학식 2]
상기 식에서,
A는 C 또는 N이고, 단 A가 N이면 b 및 c는 0이며,
B는 O, S, CR1R2 또는 NR3이고, 이때 R1 내지 R3은 각각 독립적으로 수소 또는 C1-12 알킬이며,
Ar1 내지 Ar5는 각각 독립적으로 치환 또는 비치환된 C6-C50의 아릴기이고,
이때 A1 내지 Ar3은 서로 연결되어 환을 형성할 수도 있으며,
a는 0 또는 1이고,
b 및 c는 각각 독립적으로 0 또는 1이고, 단 c가 1이면 b는 반드시 1이며,
d는 0 또는 1이고,
e는 0 또는 1이며,
An은 각각 독립적으로
Sp는 각각 독립적으로
[Formula 1]
(2)
Where
A is C or N, provided that if A is N then b and c are 0,
B is O, S, CR 1 R 2 or NR 3, where R 1 To R 3 are each independently hydrogen or C 1-12 alkyl,
Ar 1 to Ar 5 are each independently a substituted or unsubstituted C 6 -C 50 aryl group,
At this time, A 1 to Ar 3 may be connected to each other to form a ring,
a is 0 or 1,
b and c are each independently 0 or 1, provided that c is 1, b is necessarily 1,
d is 0 or 1,
e is 0 or 1,
An each independently
Sp each independently
A가 C 또는 N이고, 단, A가 N이면 b 및 c는 0이며,
B가 S 또는 CR1R2이고, 이때 R1 및 R2는 각각 독립적으로 수소 또는 메틸기이며,
Ar1 내지 Ar5가 각각 독립적으로 C6-C50의 아릴기, 또는 알킬 또는 알콕시기로 치환된 C6-C50의 아릴기이고,
a가 0 또는 1이고,
b 및 c가 각각 독립적으로 0 또는 1이고, 단 c가 1이면 b는 반드시 1이며,
d가 0 또는 1이고,
e가 0 또는 1이며,
An이
Sp가
하는 유기염료.The method of claim 1,
A is C or N, provided that when A is N, b and c are 0,
B is S or CR 1 R 2, wherein R 1 and R 2 are each independently hydrogen or a methyl group,
Ar 1 to Ar 5 are each independently a C 6 -C 50 aryl group or a C 6 -C 50 aryl group substituted with an alkyl or alkoxy group,
a is 0 or 1,
b and c are each independently 0 or 1, provided that c is 1, then b is necessarily 1,
d is 0 or 1,
e is 0 or 1,
An is
Sp
Organic dyes.
상기 유기염료가 하기 화학식 7 내지 122로 표시되는 화합물들로 이루어진 군에서 선택되는 것을 특징으로 하는 유기염료:
[화학식 7]
[화학식 8]
[화학식 9]
[화학식 10]
[화학식 11]
[화학식 12]
[화학식 13]
[화학식 14]
[화학식 15]
[화학식 16]
[화학식 17]
[화학식 18]
[화학식 19]
[화학식 20]
[화학식 21]
[화학식 22]
[화학식 23]
[화학식 24]
[화학식 25]
[화학식 26]
[화학식 27]
[화학식 28]
[화학식 29]
[화학식 30]
[화학식 31]
[화학식 32]
[화학식 33]
[화학식 34]
[화학식 35]
[화학식 36]
[화학식 37]
[화학식 38]
[화학식 39]
[화학식 40]
[화학식 41]
[화학식 42]
[화학식 43]
[화학식 44]
[화학식 45]
[화학식 46]
[화학식 47]
[화학식 48]
[화학식 49]
[화학식 50]
[화학식 51]
[화학식 52]
[화학식 53]
[화학식 54]
[화학식 55]
[화학식 56]
[화학식 57]
[화학식 58]
[화학식 59]
[화학식 60]
[화학식 61]
[화학식 62]
[화학식 63]
[화학식 64]
[화학식 65]
[화학식 66]
[화학식 67]
[화학식 68]
[화학식 69]
[화학식 70]
[화학식 71]
[화학식 72]
[화학식 73]
[화학식 74]
[화학식 75]
[화학식 76]
[화학식 77]
[화학식 78]
[화학식 79]
[화학식 80]
[화학식 81]
[화학식 82]
[화학식 83]
[화학식 84]
[화학식 85]
[화학식 86]
[화학식 87]
[화학식 88]
[화학식 89]
[화학식 90]
[화학식 91]
[화학식 92]
[화학식 93]
[화학식 94]
[화학식 95]
[화학식 96]
[화학식 97]
[화학식 98]
[화학식 99]
[화학식 100]
[화학식 101]
[화학식 102]
[화학식 103]
[화학식 104]
[화학식 105]
[화학식 106]
[화학식 107]
[화학식 108]
[화학식 109]
[화학식 110]
[화학식 111]
[화학식 112]
[화학식 113]
[화학식 114]
[화학식 115]
[화학식 116]
[화학식 117]
[화학식 118]
[화학식 119]
[화학식 120]
[화학식 121]
[화학식 122]
The organic dye is characterized in that the organic dye is selected from the group consisting of compounds represented by the following formulas (7) to (122):
[Formula 7]
[Chemical Formula 8]
[Formula 9]
[Formula 10]
(11)
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
[Formula 16]
[Formula 17]
[Formula 18]
[Formula 19]
[Formula 20]
[Formula 21]
[Formula 22]
[Formula 23]
[Formula 24]
[Formula 25]
[Formula 26]
[Formula 27]
[Formula 28]
[Formula 29]
[Formula 30]
[Formula 31]
[Formula 32]
[Formula 33]
[Formula 34]
[Formula 35]
[Formula 36]
[Formula 37]
[Formula 38]
[Formula 39]
[Formula 40]
[Formula 41]
[Formula 42]
[Formula 43]
[Formula 44]
[Formula 45]
[Formula 46]
[Formula 47]
[Formula 48]
[Formula 49]
[Formula 50]
[Formula 51]
[Formula 52]
[Formula 53]
[Formula 54]
[Formula 55]
[Formula 56]
[Formula 57]
[Formula 58]
[Formula 59]
[Formula 60]
[Formula 61]
[Formula 62]
[Formula 63]
[Formula 64]
[Formula 65]
[Formula 66]
[Formula 67]
[Formula 68]
[Formula 69]
[Formula 70]
[Formula 71]
[Formula 72]
[Formula 73]
[Formula 74]
[Formula 75]
[Formula 76]
[Formula 77]
[Formula 78]
[Formula 79]
[Formula 80]
[Formula 81]
[Formula 82]
[Formula 83]
[Formula 84]
[Formula 85]
[Formula 86]
[Formula 87]
[Formula 88]
[Formula 89]
[Formula 90]
[Formula 91]
[Formula 92]
[Formula 93]
[Formula 94]
[Formula 95]
[Formula 96]
[Formula 97]
[Formula 98]
[Formula 99]
[Formula 100]
[Formula 101]
[Formula 102]
[Formula 103]
[Formula 104]
[Formula 105]
[Formula 106]
[Formula 107]
[Formula 108]
[Formula 109]
[Formula 110]
[Formula 111]
[Formula 112]
[Formula 113]
[Formula 114]
[Formula 115]
[Formula 116]
Formula 117
[Formula 118]
Formula 119
[Formula 120]
[Formula 121]
[Formula 122]
(2) 상기 화학식 5의 화합물을 유기용매중에서 BuLi 또는 CF3COOH와 반응시켜 하기 화학식 6의 화합물을 제조하는 단계; 및
(3) 상기 화학식 6의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 앵커링기 제공 화합물과 결합반응시키는 단계
를 포함하는 제1항 기재의 염료증감 광전변환소자용 유기염료의 제조방법:
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
상기 식에서,
고리 W는
X는 Br 또는
Y는
Z는 H 또는
A, Ar1 내지 Ar4, a, b, c, e 및 Sp는 제1항에서 정의한 바와 같다.(1) coupling a compound of Formula 3 with a compound of Formula 4 to prepare a compound of Formula 5;
(2) preparing a compound of formula 6 by reacting the compound of formula 5 with BuLi or CF 3 COOH in an organic solvent; And
(3) combining the compound of Formula 6 with an anchoring group providing compound in the presence of piperidine in CH 3 CN
Method for producing an organic dye for dye-sensitized photoelectric conversion device according to claim 1 comprising:
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Formula 6]
Where
Ring W is
X is Br or
Y is
Z is H or
A, Ar 1 To Ar 4 , a, b, c, e and Sp are as defined in claim 1.
상기 산화물 반도체 미립자에 담지된 제1항 기재의 유기염료
를 포함하는 염료증감 광전변환소자.Oxide semiconductor fine particles; And
The organic dye according to claim 1 supported on the oxide semiconductor fine particles
Dye-sensitized photoelectric conversion device comprising a.
상기 유기염료가 포섭화합물의 존재 하에서 산화물 반도체 미립자에 담지된 것을 특징으로 하는 염료증감 광전변환소자. The method of claim 1,
The dye-sensitized photoelectric conversion device, characterized in that the organic dye is supported on the oxide semiconductor fine particles in the presence of the inclusion compound.
상기 산화물 반도체 미립자가 이산화티탄을 포함하는 것을 특징으로 하는 염료증감 광전변환소자.The method of claim 1,
Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide.
상기 산화물 반도체 미립자가 1 내지 500 nm의 평균 입경을 갖는 것을 특징으로 하는 염료증감 광전변환소자.The method of claim 1,
The dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles have an average particle diameter of 1 to 500 nm.
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| KR1020100057781A KR20100136929A (en) | 2009-06-19 | 2010-06-17 | Novel organic dye and preparation thereof |
| TW099119905A TW201112469A (en) | 2009-06-19 | 2010-06-18 | Novel organic dye and preparation thereof |
| JP2012515989A JP2012530796A (en) | 2009-06-19 | 2010-06-18 | NOVEL ORGANIC DYE AND METHOD FOR PRODUCING THE SAME |
| CN2010800270689A CN102803394A (en) | 2009-06-19 | 2010-06-18 | Novel organic dye and method for producing same |
| PCT/KR2010/003947 WO2010147425A2 (en) | 2009-06-19 | 2010-06-18 | Novel organic dye and preparation method thereof |
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| KR20090055229 | 2009-06-19 | ||
| KR1020090055223 | 2009-06-19 | ||
| KR1020100057781A KR20100136929A (en) | 2009-06-19 | 2010-06-17 | Novel organic dye and preparation thereof |
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| KR101331020B1 (en) * | 2011-05-09 | 2013-11-19 | 에버라이트 유에스에이, 인코퍼레이티드 | Dye compound, dye-sensitized solar cell using the same and dye solution |
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- 2010-06-17 KR KR1020100057781A patent/KR20100136929A/en not_active Application Discontinuation
- 2010-06-18 CN CN2010800270689A patent/CN102803394A/en active Pending
- 2010-06-18 JP JP2012515989A patent/JP2012530796A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201112469A (en) | 2011-04-01 |
| CN102803394A (en) | 2012-11-28 |
| JP2012530796A (en) | 2012-12-06 |
| WO2010147425A2 (en) | 2010-12-23 |
| WO2010147425A3 (en) | 2011-04-28 |
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