CN102803394A - Novel organic dye and method for producing same - Google Patents
Novel organic dye and method for producing same Download PDFInfo
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- CN102803394A CN102803394A CN2010800270689A CN201080027068A CN102803394A CN 102803394 A CN102803394 A CN 102803394A CN 2010800270689 A CN2010800270689 A CN 2010800270689A CN 201080027068 A CN201080027068 A CN 201080027068A CN 102803394 A CN102803394 A CN 102803394A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 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
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003435 aroyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 1
- 229960001091 chenodeoxycholic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 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
- RDFLLVCQYHQOBU-ZOTFFYTFSA-O cyanin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=[O+]C1=CC(O)=C2)C=3C=C(O)C(O)=CC=3)=CC1=C2O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 RDFLLVCQYHQOBU-ZOTFFYTFSA-O 0.000 description 1
- PORCMJJTZXANLJ-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) Chemical compound [Fe++].[Fe++].c1cc[cH-]c1.c1cc[cH-]c1.c1cc[cH-]c1.c1cc[cH-]c1 PORCMJJTZXANLJ-UHFFFAOYSA-N 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
- 230000008021 deposition Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WLPSNBGDESCKIL-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO WLPSNBGDESCKIL-UHFFFAOYSA-N 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
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 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
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 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
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 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
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 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
- 239000000434 metal complex dye Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- 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
- 229940067003 orabase Drugs 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 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
- 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
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl 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
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 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
- 239000012265 solid product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 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
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-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
- 125000005580 triphenylene group Chemical group 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
- 238000001291 vacuum drying Methods 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
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing 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
- 229910052727 yttrium Inorganic materials 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
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The organic dye of the present invention is used as a dye-sensitized photoelectric conversion element in a dye-sensitized solar cell (DSSC), and exhibits higher molar absorption coefficient, Jsc (short-circuit photocurrent density), and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of the solar cell.
Description
Technical field
(dye-sensitized solar cell, new dye sensitizing photo-electric conversion element DSSC) is with organic dye and method of manufacture thereof to the present invention relates to be used for dye sensitization solar battery.
Background technology
1991 Switzerland state-run Lausanne Instituto Superior Technico (EPFL) Michael's lattice Lay after just the research group of you (Michael Gratzel) has developed dye sensitization nano rice corpuscles titanium oxide solar cell, carried out much researchs about this field.Dye sensitization solar battery is that solar battery efficiency is high than existing silicon, and manufacturing cost is significantly low, and therefore, it is solar cell that expectation can replace existing uncrystalline silicon.With silicon is that solar cell is different, and dye sensitization solar battery is generating right dyestuff in electronics-hole (hole) and the photoelectrochemistry solar cell of the transition metal oxide that transmits the electronics that is generated as main composition material through absorbing visible light.
Widely used as the dyestuff of dye sensitization solar battery in the past is the ruthenium metal complex that demonstrates high-photoelectric transformation efficiency, but there is too expensive shortcoming in this ruthenium metal complex.
Recent findings; Shift (charge-transfer at extinction efficient, redox reaction stability and intramolecular charge; CT) be that the aspect of absorption shows organic dye excellent rerum natura, that do not contain metal and can replace expensive ruthenium metal complex and use as the used by dye sensitization solar battery dyestuff, carry out so the research of the organic dye that do not contain metal concentrated.
Organic dye generally has the structure of electron donor(ED) (electron donor)-electron acceptor(EA) (electron acceptor) residue that connects through π-key unit.In most organic dye, sulfonamide derivatives plays the effect of electron donor(ED), and 2-alpha-cyanoacrylate or rhodanine residue play the effect of electron acceptor(EA), and these two positions connect through π such as methyne unit or thiophene chain-key system.
In general; Through structural changes as the amine unit of electron donor(ED); The characteristic electrons such as absorption spectrum of inducing to blue side displacement (shift) are changed, regulate absorption spectrum and redox potential (redox potential) through the variation of π-key length.
But; Known most organic dye reveals low efficiency of conversion and low driving stability than ruthenium metal complex dye sheet at present; So be intended to kind or π-key length at present, and developing the effort that has the molar absorptivity of obvious raising and show the new dyestuff of high photoelectric transformation efficiency than organic dye in the past through changing such electron donor(ED) and acceptor.
Summary of the invention
Technical problem
The object of the present invention is to provide a kind ofly to demonstrate higher molar absorptivity and photoelectric transformation efficiency, thereby the dye-sensitized photoelectric conversion device that can improve the efficient of dye sensitization solar battery is greatly used organic dye than conventional metal coordination compound dyestuff.
Another object of the present invention provides the method for manufacture of above-mentioned organic dye.
Another purpose again of the present invention provides through containing photoelectric transformation efficiency, Jsc (the short-circuit photocurrent density that above-mentioned organic dye shows obvious raising; And the solar cell that efficient obviously improves through containing it short circuit photocurrent density) and the excellent dye-sensitized photoelectric conversion device of molar absorptivity.
Solve the method for problem
According to above-mentioned purpose, the present invention provides by the dye-sensitized photoelectric conversion device of following Chemical formula 1 or 2 expressions and uses organic dye:
[Chemical formula 1]
[Chemical formula 2]
In the above-mentioned formula,
A is C or N, but A is when being N, and b and c are 0,
B is O, S, CR
1R
2Or NR
3, at this moment, R
1To R
3Be hydrogen or C1-12 alkyl independently of one another,
Ar
1To Ar
5Independently of one another for replacing or non-substituted C
6-C
50Aryl, at this moment, A
1To Ar
3Can be interconnection and form ring,
A is 0 or 1,
B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,
D is 0 or 1,
E is 0 or 1,
An independently selected
Sp is independently of one another for being selected from
In more than a kind, this moment L be selected from O, S, CR independently of one another
6R
7, SiR
8R
9And NR
10In, R
4And R
5Be selected from hydrogen, replacement or non-substituted C independently of one another
1-12Alkyl, replacement or non-substituted C
6-30Aryl and replacement or non-substituted C
6-20In the heteroaryl, or can interconnect and form ring, R
6To R
10Be hydrogen or replacement or non-substituted C independently of one another
1-12Alkyl, n are 1 to 10 integer.
In addition, the present invention provides the method for manufacture of above-mentioned organic dye, comprising:
(1) make the compound of following chemical formula 3 and the compound of following chemical formula 4 carry out the step that linked reaction is come the compound of manufacturing chemistry formula 5;
(2) compound that makes said chemical formula 5 in organic solvent with BuLi or CF
3COOH reacts the step of the compound of making following chemical formula 6; And
(3) compound that makes said chemical formula 6 is at CH
3In the presence of piperidines, carry out the step of association reaction among the CN with the compound that anchoring group is provided:
[chemical formula 3]
[chemical formula 4]
Y——Sp——Z
[chemical formula 5]
[chemical formula 6]
In the above-mentioned formula,
Ring W is
independently of one another
X is Br or
Y is *---B (OH)
2Or *---CHO,
Z is H or
A, Ar
1To Ar
4, a, b, c, e be identical with above-mentioned definition with Sp.
According to above-mentioned another purpose again, the present invention provides a kind of dye-sensitized photoelectric conversion device, it is characterized in that, contains the oxide semiconductor particulate and supports the above-mentioned organic dye in said oxide semiconductor particulate.
According to above-mentioned another purpose again, the present invention provides a kind of dye sensitization solar battery, it is characterized in that, comprises above-mentioned dye-sensitized photoelectric conversion device.
The invention effect
Dye composition of the present invention is used for dye sensitization solar battery (DSSC), reveals higher molar absorptivity, Jsc (short-circuit photocurrent density) and photoelectric transformation efficiency than in the past dye sheet, thereby can improve the efficient of solar cell greatly.
Embodiment
Below, illustrate in greater detail the present invention.
In this specification sheets full text, " alkyl " is meant the saturated C of straight or branched
1To C
6The hydrocarbon free radical chain.Can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl and hexyl etc. as object lesson, but be not limited thereto.
In this specification sheets full text, " alkoxyl group " is meant-the ORa base that, Ra is the alkyl identical with above-mentioned definition here.As object lesson, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc., but be not limited thereto.
This specification sheets in full in, " aryl " is meant any substituted phenyl ring or through more than one any substituting group and close the ring system that forms.As above-mentioned any substituent example, can enumerate substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocyclic radical, aryl, have or do not have alkoxyl group, aryloxy, aralkoxy, acyl group, aroyl, 4-hetaroylpyrazol, acyloxy and the aryl acyloxy of 1 to 3 fluoro substituents.Above-mentioned ring or ring system can be carried out arbitrarily and close with having more than one substituting group or do not have substituent aromatic ring (comprising phenyl ring), carbocyclic ring or heterocycle.As the example of " aryl ", comprise phenyl, naphthyl, tetralyl, xenyl, indanyl, anthryl, phenanthryl and their substitutive derivative, but be not limited thereto.
In this specification sheets full text; " heteroaryl " is meant in ring, to have heteroatomic monocyclic 5 to 6 yuan of cyclic aromatic series rings more than such as oxygen, sulphur and nitrogen; Perhaps refer to hetero-aromatic ring, aromatic ring, heterocycle or carbocyclic ring and so on ring more than and the aromatic ring that closes (for example, two ring or three ring systems).Object lesson as heteroaryl; Can enumerate pyridyl, pyrryl,
azoles base, indyl, pseudoindoyl, purine radicals, furans, thienyl, cumarone, benzothienyl, carbazyl, imidazolyl, thiazolyl, different
azoles base, pyrazolyl, isothiazolyl, quinolyl, isoquinolyl, pyridazinyl, pyrimidyl, pyrazinyl (they can be substituted or non-replacement) etc., but be not limited thereto.
In this specification sheets full text, " replacement " or " being substituted " is meant that the substituting group that in compound or functional group, has at least one hydrogen to be selected from halogen, alkyl, alkenyl, alkynyl, aryl, alkoxyl group, hydroxyl, carboxyl, carbamyl, alkoxy carbonyl, nitro, haloalkyl, amino, alkyl-carbonyl-amino, naphthenic base, cyanic acid and the thiol group replaces.
In this specification sheets full text, " * " expression bonding position of using in the chemical structural formula.
Characteristic according to organic dye of the present invention is the structure with following Chemical formula 1 or 2; Thereby when being used for dye sensitization solar battery (DSSC), show the molar absorptivity, Jsc (short-circuit photocurrent density) and the photoelectric transformation efficiency that improve as dye-sensitized photoelectric conversion device:
[Chemical formula 1]
[Chemical formula 2]
In the above-mentioned formula,
A is C or N, but A is when being N, and b and c are 0,
B is O, S, CR
1R
2Or NR
3, at this moment, R
1To R
3Be hydrogen or C1-12 alkyl independently of one another,
Ar
1To Ar
5Independently of one another for replacing or non-substituted C
6-C
50Aryl, at this moment, A
1To Ar
3Can be interconnection and form ring,
A is 0 or 1,
B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,
D is 0 or 1,
E is 0 or 1,
An independently selected
Sp is independently of one another for being selected from
Preferably, in the above-mentioned Chemical formula 1 or 2,
A is C or N, but A is when being N, and b and c are 0,
B is S or CR
1R
2, at this moment, R
1And R
2Be hydrogen or methyl independently of one another,
Ar
1To Ar
5Be C independently of one another
6-C
50Aryl, or by alkyl or the substituted C of alkoxyl group
6-C
50Aryl, more preferably phenyl, p-methoxy-phenyl or dimethyl-fluorenyl,
A is 0 or 1,
B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,
D is 0 or 1,
E is 0 or 1,
An is
Sp selected
in.
As organic dye object lesson according to the present invention, be preferably in the following chemical formula 7 to 122.
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[Chemical formula 1 0]
[Chemical formula 1 1]
[Chemical formula 1 2]
[Chemical formula 1 3]
[Chemical formula 1 4]
[Chemical formula 1 5]
[Chemical formula 1 6]
[Chemical formula 1 7]
[Chemical formula 1 8]
[Chemical formula 1 9]
[Chemical formula 2 0]
[Chemical formula 2 1]
[Chemical formula 2 2]
[Chemical formula 2 3]
[Chemical formula 2 4]
[Chemical formula 2 5]
[Chemical formula 2 6]
[Chemical formula 2 7]
[Chemical formula 2 8]
[Chemical formula 2 9]
[chemical formula 30]
[chemical formula 31]
[chemical formula 32]
[chemical formula 33]
[chemical formula 34]
[chemical formula 35]
[chemical formula 36]
[chemical formula 37]
[chemical formula 38]
[chemical formula 39]
[chemical formula 40]
[chemical formula 41]
[chemical formula 42]
[chemical formula 43]
[chemical formula 44]
[chemical formula 45]
[chemical formula 46]
[chemical formula 47]
[chemical formula 48]
[chemical formula 49]
[chemical formula 50]
[chemical formula 51]
[chemical formula 52]
[chemical formula 53]
[chemical formula 54]
[chemical formula 55]
[chemical formula 56]
[chemical formula 57]
[chemical formula 58]
[chemical formula 59]
[chemical formula 60]
[chemical formula 61]
[chemical formula 62]
[chemical formula 63]
[chemical formula 64]
[chemical formula 65]
[chemical formula 66]
[chemical formula 67]
[chemical formula 68]
[chemical formula 69]
[chemical formula 70]
[chemical formula 71]
[chemical formula 72]
[chemical formula 73]
[chemical formula 74]
[chemical formula 75]
[chemical formula 76]
[chemical formula 77]
[chemical formula 78]
[chemical formula 79]
[chemical formula 80]
[chemical formula 81]
[chemical formula 82]
[chemical formula 83]
[chemical formula 84]
[chemical formula 85]
[chemical formula 86]
[chemical formula 87]
[chemical formula 88]
[chemical formula 89]
[chemical formula 90]
[chemical formula 91]
[chemical formula 92]
[chemical formula 93]
[chemical formula 94]
[chemical formula 95]
[chemical formula 96]
[chemical formula 97]
[chemical formula 98]
[chemical formula 99]
[Chemical formula 1 00]
[Chemical formula 1 01]
[Chemical formula 1 02]
[Chemical formula 1 03]
[Chemical formula 1 04]
[Chemical formula 1 05]
[Chemical formula 1 06]
[Chemical formula 1 07]
[Chemical formula 1 08]
[Chemical formula 1 09]
[Chemical formula 1 10]
[Chemical formula 1 11]
[Chemical formula 1 12]
[Chemical formula 1 13]
[Chemical formula 1 14]
[Chemical formula 1 15]
[Chemical formula 1 16]
[Chemical formula 1 17]
[Chemical formula 1 18]
[Chemical formula 1 19]
[Chemical formula 1 20]
[Chemical formula 1 21]
[Chemical formula 1 22]
Can make through the method for manufacture that may further comprise the steps according to organic dye of the present invention:
(1) make the compound of following chemical formula 3 and the compound of following chemical formula 4 carry out the step that linked reaction is come the compound of manufacturing chemistry formula 5;
(2) compound that makes said chemical formula 5 in organic solvent with BuLi or CF
3COOH reacts the step of the compound of making following chemical formula 6; And
(3) compound that makes said chemical formula 6 is at CH
3In the presence of piperidines, carry out the step of association reaction among the CN with the compound that anchoring group is provided:
[chemical formula 3]
[chemical formula 4]
Y——Sp——Z
[chemical formula 5]
[chemical formula 6]
In the above-mentioned formula,
X is Br or
Y is *---B (OH)
2Or *---CHO,
Z is H or
A, Ar
1To Ar
4, a, b, c, e be identical with above-mentioned definition with Sp.
More detailed, at first make the compound of above-mentioned chemical formula 3 and the compound of above-mentioned chemical formula 4 carry out the compound that linked reaction is come manufacturing chemistry formula 5.
Preferred following enforcement of above-mentioned linked reaction: when substituent X is Br in chemical formula 3, at Pd (PPh
3)
4Deng catalyzer and K
2CO
3Under the existence in alkali, in N organic solvents such as (DMF), with Y be *---B (OH)
2Chemical formula 4 compounds react and implement; Preferably in chemical formula 3, substituent X does
The time, in the presence of the catalyzer such as t-BuO-K+, in THF organic solvents such as (THF), with Y be *---chemical formula 4 compounds of CHO react to be implemented.
At this moment, chemical formula 3 that uses as starting substance and 4 compound can be bought with the usual method manufacturing or from market and use.The compound of above-mentioned chemical formula 3 preferably uses a kind of compound among the following chemical formula 3-1 to 3-6.
[chemical formula 3-1]
[chemical formula 3-2]
[chemical formula 3-3]
[chemical formula 3-4]
[chemical formula 3-5]
[chemical formula 3-6]
In addition, the compound of above-mentioned chemical formula 4 preferably uses any in the compound of following chemical formula 4-1 to 4-3.
[chemical formula 4-1]
[chemical formula 4-2]
[chemical formula 4-3]
Then, with the compound of the chemical formula of making 5 in organic solvents such as DMF with BuLi or CF
3COOH reacts and the compound of manufacturing chemistry formula 6.
At this moment; In above-mentioned chemical formula 5; When Z is H; In organic solvent, react, when Z is
, preferably react with CF3COOH with BuLi.
With the compound of the chemical formula 6 that as a result of obtains at CH
3Provide the compound of anchoring group to carry out association reaction with cyanoacetic acid etc. among the CN, in the presence of piperidines, thereby can make according to organic dye of the present invention.
Particularly, can utilize the method for record in the reactions formula 1 to 10 to make according to organic dye of the present invention, but this is an example, the invention is not restricted to this.
[reaction formula 1]
[reaction formula 2]
[reaction formula 3]
[reaction formula 4]
[reaction formula 5]
[reaction formula 6]
[reaction formula 7]
[reaction formula 8]
[reaction formula 9]
[reaction formula 10]
Organic dye according to the present invention through above-mentioned method of manufacture manufacturing is used for dye sensitization solar battery (DSSC) as dye-sensitized photoelectric conversion device; Demonstrate higher molar absorptivity, Jsc (short-circuit photocurrent density) and the photoelectric transformation efficiency of dyestuff than in the past, thereby can improve the efficient of solar cell greatly.
Therefore, the present invention provides the dye-sensitized photoelectric conversion device that contains above-mentioned organic dye.
Particularly, the characteristic according to dye-sensitized photoelectric conversion device of the present invention is to comprise the oxide semiconductor particulate and support the above-mentioned organic dye in above-mentioned oxide semiconductor particulate.
Dye-sensitized photoelectric conversion device according to the present invention is except using above-mentioned organic dye; Certainly be suitable for the method for utilizing common dyestuff to make the used for solar batteries dye-sensitized photoelectric conversion device; Preferably; Dye-sensitized photoelectric conversion device of the present invention can utilize the oxide semiconductor particulate on substrate, to make the film of oxide semiconductor, then on above-mentioned film, supports organic dye according to the present invention and makes.
At this moment, as the substrate of the film that forms oxide semiconductor, preferably its surface has the substrate of electroconductibility, also can use the substrate that can buy on the market.As concrete example; The surface that can be utilized in glass or transparent macromolecular material such as polyethylene terephthalate, polyethersulfone forms the film of the conductive metal oxides such as White tin oxide that are coated with indium, fluorine, antimony, the perhaps substrate of mfs such as copper, silver, gold.At this moment, electroconductibility generally is preferably below 1000 Ω, is preferably below 100 Ω especially.
As above-mentioned oxide semiconductor particulate, be preferably MOX.As concrete example, can use the oxide compound of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium etc.The oxide compound of wherein preferred titanium, tin, zinc, niobium, indium etc., more preferably titanium oxide, zinc oxide, White tin oxide most preferably are titanium oxide.Above-mentioned oxide semiconductor can use separately, also can mix or coat semi-conductive surface and use.
The particle diameter of above-mentioned oxide semiconductor particulate is preferably 1 to 500nm, more preferably 1 to 100nm in median size.In addition, the particulate of this oxide semiconductor can mix the particulate of the particulate of big particle diameter and small particle size or utilize with the multiwalled mode.
Above-mentioned oxide semiconductor thin-film can be made through following method: make directly film forming method on substrate of oxide semiconductor particulate through atomizer spray etc.; With substrate as electrode and the method that the semiconductive particles film is separated out in electricity consumption; With the silt oar of semiconductive particles or contain that precursor with semiconductive particles such as semi-conductor alkoxide is hydrolyzed and after the paste of the particulate made coats on the substrate; The method of carrying out drying, solidify or burning till etc.; Wherein, preferably paste is coated the method on the substrate.
Employing utilizes under the situation of method of silt oar of above-mentioned semiconductive particles, and above-mentioned silt oar can utilize usual method to be dispersed in the dispersion medium through the oxide semiconductor particulate with secondary aggregation, and making its average primary particle diameter is 1 to 200nm to obtain.
As the dispersion medium that disperses the silt oar, so long as can make semiconductive particles dispersive dispersion medium, just can limit ground not especially and use, can utilize hydrocarbon such as ketone such as alcohol such as water, ethanol, acetone, methyl ethyl diketone, or hexane, can they be mixed and use.Wherein, consider,, preferably make water as dispersion medium from reducing silt oar viscosity variation aspect.In addition, be purpose with the dispersion state of steady oxide semiconductive particles, can use dispersion stabilizer.As the object lesson of operable dispersion stabilizer, can enumerate acid such as acetic acid, hydrochloric acid, nitric acid, methyl ethyl diketone, vinylformic acid, polyoxyethylene glycol, Z 150PH etc.
In addition, the firing temperature when burning till the substrate that is coated with the silt oar is more than 100 ℃, is preferably more than 200 ℃, and the upper limit is roughly below the fusing point (softening temperature) of base material in addition, is limited to 900 ℃ on usually, is preferably below 600 ℃.In the present invention, firing time is not special to be limited, but preferably is roughly in 4 hours.
In the present invention, the film thickness of the oxide semiconductor particulate that on substrate, forms is preferably 1 to 200 μ m, more preferably 1 to 50 μ m.In addition, when burning till, the welding of the part of the film of oxide semiconductor particulate possibility, such welding does not cause special influence to the present invention.
Can also implement secondary treatment to above-mentioned oxide semiconductor thin-film.As an example, in the solution of the alkoxide of the metal identical, muriate, nitride, sulfide etc.,, carry out drying or burn till again, thereby can improve the performance of semiconductor film directly according to the different substrate deposit film with semi-conductor.As above-mentioned metal alkoxide, can enumerate ethanol titanium salt, Virahol titanium salt, trimethyl carbinol titanium salt, positive dibutyl diacetyl tin etc., at this moment,, can utilize alcohol to use alcoholic solution as solvent.As above-mentioned muriate, for example can enumerate titanium tetrachloride, tin tetrachloride, zinc chloride etc., at this moment,, can utilize water to use the aqueous solution as solvent.The oxide semiconductor thin-film that obtains like this is made up of the particulate of oxide semiconductor.
In the present invention; On the oxide semiconductor particulate that forms with film like, support the method for dyestuff; There is not special qualification; As object lesson, can enumerate with above-mentioned chemical formula (I) and (II) organic dye of expression with can its dissolved solvent being dissolved and the solution made or above-mentioned organic dye disperseed and the above-mentioned method that is provided with the substrate of oxide semiconductor thin-film of dipping in the dispersion liquid made.
The concentration of the organic dye in above-mentioned solution or the dispersion liquid can come suitably to determine according to dyestuff.Dye strength is preferably 1 * 10-6M to 1M, 1 * 10-5M to 1 * 10-1M more preferably.
Temperature during deposition is roughly the boiling point of normal temperature to solvent, and in addition, depositing time is about 1 minute to 48 hours.
The object lesson of operable solvent during as dissolving dye can be enumerated methyl alcohol, ethanol, acetonitrile, DMSO 99.8MIN., N, acetone, the trimethyl carbinol etc.
In addition, the organic dye that supports can be a kind, also can mix multiple.Carrying out under the blended situation, can other organic dye or metal complex dyestuff mixed with organic dye according to the present invention.Example that can blended metal complex dyestuff does not have special qualification, but preferred ruthenium complex or its quaternary salt, phthalocyanine, porphyrin etc. as other organic dye, can be enumerated phthalocyanine, the porphyrin of no metal; Perhaps cyanin, merocyanine, oxonols, tritane system; WO2002/011213 number methyne based dye such as disclosed acrylic acid series dyestuff, perhaps dyestuff (reference literature [M.K.Nazeeruddin, the A.Kay of xanthene system, azo system, anthraquinone system, perylene system etc.; I.Rodicio, R.Humphry-Baker, E.Muller; P.Liska, N.Vlachopoulos, M.Gratzel; J.Am.Chem.Soc., the 115th volume, 6382 pages (1993)).Utilize under the situation of dyestuff more than 2 kinds, can dyestuff be adsorbed in semiconductor film successively, also can mixed dissolution and adsorb.
In addition, in the present invention, when the film of oxide semiconductor particulate supports dyestuff,, preferably in the presence of inclusion compound, support dyestuff in order to prevent the combination between the dyestuff.As above-mentioned inclusion compound, can use cholic acid classes such as Septochol, dehydrodeoxycholic acid, gallodesoxycholic acid, Methyl cholate, Sodium cholic acid, steroid based compounds such as polyethylene oxide, cholic acid, crown ether, Schardinger dextrins, calixarene, polyethylene oxide etc.
In addition, support dyestuff after, can wait with the compound that amine compound such as 4-tert .-butylpyridine or acetic acid, propionic acid etc. have an acidic-group and handle the substrate that is provided with the semiconductive particles film.Treatment process for example can use in the ethanolic soln of amine dipping to be provided with the method etc. of the substrate of the semiconductive particles film that has supported dyestuff.
Like this, can obtain to have photo-electric conversion element with oxide semiconductor particulate with the film like of dye sensitization.
The present invention provides to comprise that above-mentioned dye sensitization photo-electric conversion element is the dye sensitization solar battery of characteristic.
Above-mentioned dye sensitization solar battery can be included in photo-electric conversion element electrode (negative electrode), counter electrode (anode), redox electrolytes matter, hole transporting material or the p N-type semiconductorN etc. that support organic dye on the oxide semiconductor particulate and constitute.
The dye-sensitized photoelectric conversion device of the oxide semiconductor particulate that above-mentioned dye sensitization solar battery has supported above-mentioned organic dye except use has utilized, can be suitable for the usual method that in the past used photo-electric conversion element to make solar cell.As concrete example, can pass through the following steps manufacturing: the step of coating titanium oxide paste on the conductive clear substrate according to dye sensitization solar battery of the present invention; Burn till the substrate that is coated with paste and the step that forms thin film of titanium oxide; The substrate that will be formed with thin film of titanium oxide is immersed in the mixing solutions that is dissolved with organic dye, forms the step of the oxidation titanium film electrode that is adsorbed with dyestuff; The step of second glass substrate that is formed with counter electrode is set at an upper portion thereof; Form the step in the hole (hole) that connects second glass substrate and counter electrode; Be adsorbed with at above-mentioned counter electrode and above-mentioned between the oxidation titanium film electrode of dyestuff the thermal plastic high polymer film is set, and implement hot pressing process, thereby make the step of above-mentioned counter electrode and oxidation titanium film electrode engagement; Inject electrolytical step through the thermal plastic high polymer film of above-mentioned hole between above-mentioned counter electrode and oxidation titanium film electrode; And the step that seals with above-mentioned thermal plastic high polymer.
Above-mentioned redox electrolytes matter, hole transporting material, p N-type semiconductorN etc. can utilize with forms such as liquid state, congealed solid (gel and gel), solids.Under the situation about utilizing with liquid state, can enumerate respectively with redox electrolytes matter, melting salt, hole transporting material, p N-type semiconductorN etc. be dissolved in respectively in the solvent or normal temperature melting salt etc.; Under the situation of congealed solid (gel and gel), can enumerate respectively make they be contained in polymeric matrix or the low molecule jelling agent etc. etc.Under the situation with the utilization of solid form, can use solid-state redox electrolytes matter, melting salt, hole transporting material, p N-type semiconductorN etc.
As hole transporting material, can use known hole transporting material, as object lesson, can use and utilize electroconductive polymers such as sulfonamide derivatives or polyacetylene, polyaniline, Polythiophene, the material of the discotic mesogenic phase of triphenylene based compound etc.In addition, can use CuI, CuSCN etc. as the p N-type semiconductorN.Preferably use the counter electrode that has electroconductibility, the reduction reaction of redox electrolytes matter is played katalysis as counter electrode.For example, the counter electrode of platinum, carbon, rhodium, ruthenium etc. that can use on glass or polymeric membrane vapor deposition perhaps is coated with the counter electrode of electrically conductive microparticle.
As above-mentioned redox electrolytes matter; Can use the halogen reducto oxydative system ionogen that halide-ions is formed as the halogen compounds-halogenic molecule of counter ion; The burning reduction of metal complexes such as Prussian blue-Prussian blue or ferrocene-ferrocene
ion, cobalt coordination compound etc. is that organic oxidation reduction such as ionogen, alkyl sulfhydryl-alkyl disulfide, viologen dyestuff, quinhydrones-quinone are ionogen etc., preferred halogen reducto oxydative system ionogen.As the halogenic molecule in the halogen reducto oxydative system ionogen of forming by halogen compounds-halogenic molecule, preferred iodine molecule.In addition, as halide-ions can be used LiI, NaI, KI, CaI as the halogen compounds of counter ion
2, MgI
2, metal halide salt such as CuI, perhaps tetraalkyl ammonium iodide, imidazoles
Iodine, compare pyridine
The organic ammonium salt of halogens such as iodine, perhaps I
2
In addition, when redox electrolytes matter was existed by the form of the solution that comprises it, this solvent can use had the inert solvent on the electrochemistry.Can enumerate acetonitrile, Texacar PC, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, terepthaloyl moietie, Ucar 35, glycol ether, Tri Ethyleneglycol, GBL, glycol dimethyl ether, methylcarbonate, 1 as object lesson; 3-dioxolane, methyl-formiate, 2-methyltetrahydrofuran, 3-methoxyl group-
azoles alkane-2-ketone, tetramethylene sulfone, THF, water etc., preferred especially acetonitrile, Texacar PC, ethylene carbonate, 3-methoxypropionitrile, terepthaloyl moietie, 3-methoxyl group-
azoles alkane-2-ketone, GBL etc.Above-mentioned solvent can use a kind or mixing use.Under the situation of gel-like electrolyte, can use the material that in matrix such as oligopolymer and polymkeric substance, contains ionogen or electrolyte solution, perhaps in low molecule jelling agent etc., contain the material of ionogen or electrolyte solution equally.The concentration of redox electrolytes matter is preferably 0.01 to 99 weight %, more preferably 0.1 to 30 weight %.
Can dispose counter electrode (anode) with mode opposed through the photo-electric conversion element (negative electrode) that the oxide semiconductor particulate on substrate supports dyestuff according to solar cell of the present invention, and in the middle of their, fill and contain the solution of redox electrolytes matter and obtain with it.
Below, according to embodiment the present invention is described more specifically.But these embodiment are used for illustration the present invention, the present invention not limit by these.
Embodiment 1: chemical formula 8 synthetic
1) midbody (8a) is synthetic
With 2,7-two bromo-9-phenylacridines (2,7-dibromo-9-phenylacridine), 3 ', 4-dihexyl-2,2 '-two thiophene-5-ylboronic acid (3 ', 4-dihexyl-2,2 '-bithiophen-5-ylboronic acid), Pd (PPh
3)
4K with 2M
2CO
3The aqueous solution refluxed 12 hours after in N (DMF), mixing.With the reaction soln cooling that as a result of obtains, add water (30ml) and salt solution after, separate organic layer and make with extra care, obtained having the midbody (10a) of following chemical structural formula.
[midbody 8a]
2) midbody (8b) is synthetic
In ethanol solution, add the midbody (8a) of above-mentioned manufacturing, under argon gas, further add n-BuLi.After 3 hours, to as a result of in the reactant that obtains, under argon gas, adding DMF at 0 ℃, the KOH with 5% cleans.The reaction soln that as a result of obtains use dried over mgso,, make with extra care and obtained midbody (8b) except that after desolvating.
[midbody 8b]
3) chemical combination formula 8 is synthetic
Behind the midbody (8b) and cyanoacetic acid mixing with above-mentioned manufacturing, carry out vacuum-drying.After adding to the dry thing that as a result of obtains in MeCN and the piperidines, refluxed 6 hours.After the cooling of result's reaction soln, under vacuum, remove organic layer, with as a result of and the solid product that obtains is made with extra care with silica gel chromatography, obtained having the compound 8 of following chemical structural formula.
Ultimate analysis (Elemental Analysis): C, 72.46; H, 6.44; N, 3.78; O, 5.76; S, 11.55)
[chemical formula 8]
Embodiment 2: chemical combination formula 10 synthetic
1) midbody (10a) is synthetic
Replace 3 '; 4-dihexyl-2; 2 '-two thiophene-5-ylboronic acid uses 7-, and (5-(5; 5-dimethyl--1,3-two
alkane-2-yl) thieno-[3,2-b] thiophene-2-yl)-2; 3-dihydro-thiophene [3; 4-b] [1,4] two
English-5-ylboronic acid, in addition; According to implementing, obtained the midbody (10a) of following chemical structural formula with the foregoing description 1 identical method.
[midbody 10a]
2) midbody (10b) is synthetic
The foregoing description 1 2) in, the midbody (10a) of above-mentioned manufacturing is dissolved in the THF (THF), in the solution that obtains, drip trifluoroacetic acid and water, stirring is 4 hours under nitrogen atmosphere.
After stir finishing, to the reaction soln that as a result of obtains, utilize methylene dichloride and water to extract organic layer after, evaporate, make with extra care and obtained the midbody (10b) of following chemical structural formula with column chromatography.
[midbody 10b]
3) chemical combination formula 10 is synthetic
The foregoing description 1 3) in, replace midbody (8b) to use midbody (10b), in addition,, obtained the compound of following chemical structural formula 10 according to implementing with the foregoing description 1 identical method.
Ultimate analysis: C, 61.12; H, 2.72; N, 4.19; O, 12.77; S, 19.20
[Chemical formula 1 0]
Embodiment 3: Chemical formula 18 synthetic
1) midbody (18a) is synthetic
Make tetraethyl-(9-phenylacridine-2; 7-two bases) (5-(5 for two (methylene radical) diphosphates and 7-; 5-dimethyl--1; 3-two
alkane-2-yl) thieno-[3; 2-b] thiophene-2-yl)-2; 3-dihydro-thiophene also [3; 4-b] [1,4] two
English-5-formaldehyde carries out Wittig (Wittig) reaction in the presence of potassium tert.-butoxide, in the THF solvent, obtained the midbody (18a) of following chemical structural formula.
[midbody 18a]
2) midbody (18b) is synthetic
The midbody (18a) that replaces the above-mentioned manufacturing of midbody (8a) use of the foregoing description 1 in addition, according to implementing with embodiment 1 identical method, has obtained the midbody (18b) of following chemical structural formula.
[midbody 18b]
3) chemical combination formula 18 is synthetic
In the foregoing description 1, replace midbody (8b) to use the midbody (18b) of above-mentioned manufacturing, in addition,, obtained the compound of following chemical structural formula 18 according to implementing with embodiment 1 identical method.
Ultimate analysis: C, 62.54; H, 3.15; N, 3.98; O, 12.12; S, 18.21
[Chemical formula 1 8]
Embodiment 4: chemical formula 40 synthetic
In the foregoing description 1, replace 2,7-two bromo-9-phenylacridines use 3; 6-two bromo-N, two (9,9-dimethyl--9H-fluorenes-2-yl)-10-phenylanthracene-9-amine of N-; In addition, according to implementing successively, obtained the compound of following chemical structural formula 40 with embodiment 1 identical method.
Ultimate analysis: C, 78.00; H, 6.48; N, 2.78; O, 4.24; S, 8.50
[chemical formula 40]
Embodiment 5: chemical combination formula 115 synthetic
Replace 3,6-two bromo-N, N-two (9; 9-dimethyl--9H-fluorenes-2-yl)-10-phenylanthracene-9-amine use N-(4-(3,6-two bromo-10-phenylanthracene-9-yls) phenyl)-N-(9,9-dimethyl--9H-fluorenes-2-yl)-9; 9-dimethyl--9H-fluorenes-2-amine; In addition, according to implementing, obtained the compound of following chemical structural formula 115 with the foregoing description 4 identical methods.
Ultimate analysis: C, 75.77; H, 4.66; Br, 18.00; N, 1.58
[Chemical formula 1 15]
Embodiment 6: chemical combination formula 42 synthetic
Replace 2,7-two bromo-9-phenylacridines use 3,6-two bromo-N, and two (9,9-dimethyl--9H-fluorenes-2-yl)-10-phenylanthracene-9-amine of N-in addition, are implemented with method identical among the embodiment 1 successively, have obtained the compound of following chemical structural formula 42.
Ultimate analysis: C, 70.31; H, 3.81; N, 3.00; O, 9.14; S, 13.74
[chemical formula 42]
Embodiment 7: chemical combination formula 50 synthetic
Replace tetraethyl-(9-phenylacridine-2; 7-two bases) (10-(two (9 for two (methylene radical) diphosphate use tetraethyl-; 9-dimethyl--9H-fluorenes-2-yl) amino)-and 9-phenylanthracene-2,7-two bases) two (methylene radical) diphosphate, in addition; According to implementing successively, obtained the compound of following chemical structural formula 50 with embodiment 3 identical methods.
Ultimate analysis: C, 71.00; H, 4.09; N, 2.89; O, 8.80; S, 13.22
[chemical formula 50]
Embodiment 8: chemical combination formula 116 synthetic
(4-(3 to replace tetraethyl-(10-(two (9,9-dimethyl--9H-fluorenes-2-yl) amino)-9-phenylanthracene-2,7-two bases) two (methylene radical) diphosphate to use N-; 6-two bromo-10-phenylanthracene-9-yls) phenyl)-N-(9; 9-dimethyl--9H-fluorenes-2-yl)-9,9-dimethyl--9H-fluorenes-2-amine, in addition; According to implementing, obtained the compound of following chemical structural formula 116 with the foregoing description 7 identical methods.
Ultimate analysis: C, 72.18; H, 4.15; N, 2.74; O, 8.36; S, 12.57
[Chemical formula 1 16]
Embodiment 9: Chemical formula 1 17 synthetic
Replace 3,6-two bromo-N, N-two (9; 9-dimethyl--9H-fluorenes-2-yl)-and 10-phenylanthracene-9-amine use 2,7-two bromo-9,9-dimethyl--10-(4-p-methoxy-phenyl)-9; The 10-acridan; In addition, according to implementing, obtained the compound of following chemical structural formula 117 with the foregoing description 6 identical methods.
Ultimate analysis: C, 61.06; H, 3.32; N, 3.96; O, 13.56; S, 18.11
[Chemical formula 1 17]
Embodiment 10: chemical combination formula 118 synthetic
Replace 3,6-two bromo-N, N-two (9; 9-dimethyl--9H-fluorenes-2-yl)-and 10-phenylanthracene-9-amine use 3,7-two bromo-10-(4-p-methoxy-phenyl)-10H-thiodiphenylamine, in addition; According to implementing, obtained the compound of following chemical structural formula 118 with the foregoing description 6 identical methods.
Ultimate analysis: C, 58.21; H, 2.78; N, 3.99; O, 13.68; S, 21.33
[Chemical formula 1 18]
Embodiment 11: chemical combination formula 119 synthetic
Replace 3,6-two bromo-N, N-two (9; 9-dimethyl--9H-fluorenes-2-yl)-and 10-phenylanthracene-9-amine use 3,6-two bromo-9-(4-p-methoxy-phenyl)-9H-carbazole, in addition; According to implementing, obtained the compound of following chemical structural formula 119 with the foregoing description 6 identical methods.
Ultimate analysis: C, 60.04; H, 2.87; N, 4.12; O, 14.11; S, 18.86
[Chemical formula 1 19]
Embodiment 12: Chemical formula 1 20 synthetic
(10-(two (9 to replace tetraethyl-; 9-dimethyl--9H-fluorenes-2-yl) amino)-and 9-phenylanthracene-2,7-two bases) two (methylene radical) diphosphate use tetraethyl-(9,9-dimethyl--10-(4-p-methoxy-phenyl)-9; 10-acridan-2; 7-two bases) two (methylene radical) diphosphate in addition, has obtained the compound of following chemical structural formula 120 according to implementing with embodiment 7 identical methods.
Ultimate analysis: C, 62.40; H, 3.70; N, 3.76; O, 12.90; S, 17.23
[Chemical formula 1 20]
Embodiment 13: Chemical formula 1 21 synthetic
(10-(two (9 in embodiment 6, to replace tetraethyl-; 9-dimethyl--9H-fluorenes-2-yl) amino)-9-phenylanthracene-2; 7-two bases) two (methylene radical) diphosphates and use tetraethyl-(10-(4-p-methoxy-phenyl)-10H-thiodiphenylamine-3; 7-two bases) two (methylene radical) diphosphate in addition, has obtained the compound of following chemical structural formula 121 according to implementing with the foregoing description 6 identical methods.
Ultimate analysis: C, 59.71; H, 3.19; N, 3.80; O, 13.02; S, 20.29
[Chemical formula 1 21]
Embodiment 14: Chemical formula 1 22 synthetic
(10-(two (9 to replace tetraethyl-; 9-dimethyl--9H-fluorenes-2-yl) amino)-9-phenylanthracene-2; 7-two bases) two (methylene radical) diphosphate uses tetraethyl-(9-(4-p-methoxy-phenyl)-9H-carbazole-3; 6-two bases) two (methylene radical) diphosphate in addition, has obtained the compound of following chemical structural formula 122 according to implementing with the foregoing description 7 identical methods.
Ultimate analysis: C, 61.49; H, 3.28; N, 3.91; O, 13.40; S, 17.91
[Chemical formula 1 22]
The manufacturing of dye sensitization solar battery
In order to estimate I-E characteristic, utilize the TiO2 transparent layer of 13+10 μ m to make dye sensitization solar battery according to dyestuff of the present invention.
In detail, FTO (Pilkington, the 8 Ω sq-1) glass substrate with washing impregnated in the TiCl4 aqueous solution of 40mM.TiO2 paste (Solaronix, 13nm anatase octahedrite) is carried out the TiO2 layer that 13 μ m thickness are made in silk screen printing, and for scattering of light, (CCIC HWP-400) has made the 2nd TiO2 scattering layer of 10 μ m thickness with other pastes.After the TiO2 electrode of making impregnated in solution according to dyestuff of the present invention (containing the 3a of 10mM, in the ethanol of 7a-dihydroxyl-5b-cholic acid the compound to make among 0.3mM dissolving the foregoing description 1-14) respectively, at room temperature placed 18 hours.On the FTO substrate, be coated with H2PtCl6 solution (containing Pt 2mg among the ethanol 1mL) and make counter electrode.Then, will in acetonitrile, dissolve the 3-hexyl-1 of 0.6M, 2-dimethyl-iodate imidazoles
0.04M I
2, 0.025M the ionogen that forms of the tert .-butylpyridine of guanidine thiocyanate and 0.28M of LiI, 0.05M be injected into and make dye sensitization solar battery in the battery.The sensitive cell performance of dye sensitization solar battery is to utilize the 1000W xenon light source to measure, and its result is shown in below table 1.
Table 1
| Distinguish | Efficient (η) (%) | Distinguish | Efficient (η) (%) |
| Embodiment 1 | 4.2 | Embodiment 8 | 4.8 |
| Embodiment 2 | 4.4 | Embodiment 9 | 4.3 |
| Embodiment 3 | 4.6 | Embodiment 10 | 5.2 |
| Embodiment 4 | 5.0 | Embodiment 11 | 4.4 |
| Embodiment 5 | 4.8 | Embodiment 12 | 4.4 |
| Embodiment 6 | 5.4 | Embodiment 13 | 5.6 |
| Embodiment 7 | 5.5 | Embodiment 14 | 4.5 |
Shown in last table 1, dyestuff of the present invention shows excellent efficient.
Though utilize above-mentioned concrete embodiment to understand the present invention, in the scope that the present invention requires to protect, those skilled in the art can carry out various deformation and change with the present invention.
Utilize possibility on the industry
Dye composition of the present invention is used for dye sensitization solar battery (DSSC) and demonstrates molar absorptivity, Jsc (short-circuit photocurrent density) and the photoelectric transformation efficiency that improves than in the past dyestuff, thereby can improve the efficient of solar cell greatly.
Claims (9)
1. the dye-sensitized photoelectric conversion device by following Chemical formula 1 or 2 expressions is used organic dye:
Chemical formula 1
Chemical formula 2
In the said formula,
A is C or N, but A is when being N, and b and c are 0,
B is O, S, CR
1R
2Or NR
3, at this moment, R
1To R
3Be hydrogen or C1-12 alkyl independently of one another,
Ar
1To Ar
5Independently of one another for replacing or non-substituted C
6-C
50Aryl,
At this moment, A
1To Ar
3Can be interconnection and form ring,
A is 0 or 1,
B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,
D is 0 or 1,
E is 0 or 1,
Be selected from the group of forming by
Sp independently of one another for be selected from by
In the group of forming more than a kind, this moment, L was selected from by O, S, CR independently of one another
6R
7, SiR
8R
9And NR
10In the group of forming, R4 and R5 are selected from by hydrogen, replacement or non-substituted C independently of one another
1-12Alkyl, replacement or non-substituted C
6-30Aryl and replacement or non-substituted C
6-20In the group that heteroaryl is formed, or can interconnect and form ring, R
6To R
10Be hydrogen or replacement or non-substituted C independently of one another
1-12Alkyl, n are 1 to 10 integer.
2. organic dye according to claim 1 is characterized in that,
A is C or N, but when A was N, b and c were 0,
B is S or CR
1R
2, this moment R
1And R
2Be hydrogen or methyl independently of one another,
Ar
1To Ar
5Be C independently of one another
6-C
50Aryl or by alkyl or the substituted C of alkoxyl group
6-C
50Aryl,
A is 0 or 1,
B and c are 0 or 1 independently of one another, but c is 1 o'clock, and b must be 1,
D is 0 or 1,
E is 0 or 1,
An is
Sp selected
the group consisting of.
3. organic dye according to claim 1 is characterized in that, said organic dye is selected from the compound of following chemical formula 7 to 122 expressions:
Chemical formula 7
Chemical formula 8
Chemical formula 9
Chemical formula 10
Chemical formula 11
Chemical formula 12
Chemical formula 13
Chemical formula 14
Chemical formula 15
Chemical formula 16
Chemical formula 17
Chemical formula 18
Chemical formula 19
Chemical formula 20
Chemical formula 21
Chemical formula 22
Chemical formula 23
Chemical formula 24
Chemical formula 25
Chemical formula 26
Chemical formula 27
Chemical formula 28
Chemical formula 29
Chemical formula 30
Chemical formula 31
Chemical formula 32
Chemical formula 33
Chemical formula 34
Chemical formula 35
Chemical formula 36
Chemical formula 37
Chemical formula 38
Chemical formula 39
Chemical formula 40
Chemical formula 41
Chemical formula 42
Chemical formula 43
Chemical formula 44
Chemical formula 45
Chemical formula 46
Chemical formula 47
Chemical formula 48
Chemical formula 49
Chemical formula 50
Chemical formula 51
Chemical formula 52
Chemical formula 53
Chemical formula 54
Chemical formula 55
Chemical formula 56
Chemical formula 57
Chemical formula 58
Chemical formula 59
Chemical formula 60
Chemical formula 61
Chemical formula 62
Chemical formula 63
Chemical formula 64
Chemical formula 65
Chemical formula 66
Chemical formula 67
Chemical formula 68
Chemical formula 69
Chemical formula 70
Chemical formula 71
Chemical formula 72
Chemical formula 73
Chemical formula 74
Chemical formula 75
Chemical formula 76
Chemical formula 77
Chemical formula 78
Chemical formula 79
Chemical formula 80
Chemical formula 81
Chemical formula 82
Chemical formula 83
Chemical formula 84
Chemical formula 85
Chemical formula 86
Chemical formula 87
Chemical formula 88
Chemical formula 89
Chemical formula 90
Chemical formula 91
Chemical formula 92
Chemical formula 93
Chemical formula 94
Chemical formula 95
Chemical formula 96
Chemical formula 97
Chemical formula 98
Chemical formula 99
Chemical formula 1 00
Chemical formula 1 01
Chemical formula 1 02
Chemical formula 1 03
Chemical formula 1 04
Chemical formula 1 05
Chemical formula 1 06
Chemical formula 1 07
Chemical formula 1 08
Chemical formula 1 09
Chemical formula 1 10
Chemical formula 1 11
Chemical formula 1 12
Chemical formula 1 13
Chemical formula 1 14
Chemical formula 1 15
Chemical formula 1 16
Chemical formula 1 17
Chemical formula 1 18
Chemical formula 1 19
Chemical formula 1 20
Chemical formula 1 21
Chemical formula 1 22
4. the described dye-sensitized photoelectric conversion device of claim 1 comprises with the method for manufacture of organic dye:
(1) make the compound of following chemical formula 3 and the compound of following chemical formula 4 carry out the step that linked reaction is come the compound of manufacturing chemistry formula 5;
(2) compound that makes said chemical formula 5 in organic solvent with BuLi or CF
3COOH reacts the step of the compound of making following chemical formula 6; And
(3) compound that makes said chemical formula 6 is at CH
3In the presence of piperidines, carry out the step of association reaction among the CN with the compound that anchoring group is provided,
Chemical formula 3
Chemical formula 4
Y——Sp——Z
Chemical formula 5
Chemical formula 6
In the said formula,
X is Br or
Y is *---B (OH)
2Or *---CHO,
Z is H or
A, Af1 to Ar4, a, b, c, e and Sp are identical with the definition in the claim 1.
5. a dye-sensitized photoelectric conversion device contains the oxide semiconductor particulate and supports in the described organic dye of the claim 1 of said oxide semiconductor particulate.
6. dye-sensitized photoelectric conversion device according to claim 1 is characterized in that, said organic dye is in the presence of inclusion compound, to support in the oxide semiconductor particulate.
7. dye-sensitized photoelectric conversion device according to claim 1 is characterized in that, said oxide semiconductor particulate contains titanium oxide.
8. dye-sensitized photoelectric conversion device according to claim 1 is characterized in that, said oxide semiconductor particulate has 1 to 500nm median size.
9. a dye sensitization solar battery is characterized in that, comprises that the described dye-sensitized photoelectric conversion device of claim 5 is as electrode.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2009-0055229 | 2009-06-19 | ||
| KR20090055223 | 2009-06-19 | ||
| KR20090055227 | 2009-06-19 | ||
| KR20090055229 | 2009-06-19 | ||
| KR10-2009-0055223 | 2009-06-19 | ||
| KR10-2009-0055227 | 2009-06-19 | ||
| KR10-2010-0057781 | 2010-06-17 | ||
| KR1020100057781A KR20100136929A (en) | 2009-06-19 | 2010-06-17 | Novel organic dye and preparation thereof |
| PCT/KR2010/003947 WO2010147425A2 (en) | 2009-06-19 | 2010-06-18 | Novel organic dye and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102803394A true CN102803394A (en) | 2012-11-28 |
Family
ID=43356941
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|---|---|---|---|
| CN2010800270689A Pending CN102803394A (en) | 2009-06-19 | 2010-06-18 | Novel organic dye and method for producing same |
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|---|---|
| JP (1) | JP2012530796A (en) |
| KR (1) | KR20100136929A (en) |
| CN (1) | CN102803394A (en) |
| TW (1) | TW201112469A (en) |
| WO (1) | WO2010147425A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408963A (en) * | 2013-08-08 | 2013-11-27 | 陕西师范大学 | Double bridged chain organic dyestuff adopting urea as donor and application of dyestuff |
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| CN110337466A (en) * | 2017-03-29 | 2019-10-15 | 保土谷化学工业株式会社 | Sensitizing dye, photoelectric conversion sensitizing dye composition, photo-electric conversion element and dye-sensitized solar cell using it |
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| JP5875988B2 (en) * | 2009-12-30 | 2016-03-02 | ドンジン セミケム カンパニー リミテッド | Novel organic dye and method for producing the same |
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| WO2012147330A1 (en) * | 2011-04-27 | 2012-11-01 | 保土谷化学工業株式会社 | Compound with acridan ring structure, and organic electroluminescent element |
| TW201245119A (en) * | 2011-05-09 | 2012-11-16 | Everlight Chem Ind Corp | Dye compound and dye-sensitized solar cell using the same, and dye solution |
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| KR102283122B1 (en) * | 2017-11-15 | 2021-07-29 | 주식회사 엘지화학 | Heterocyclic compound and organic photovoltaic device comprising the same |
| WO2023219033A1 (en) * | 2022-05-11 | 2023-11-16 | 富士フイルム株式会社 | Photoelectric conversion element, imaging element, light sensor, and compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004082061A1 (en) * | 2003-03-14 | 2004-09-23 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| WO2007100033A1 (en) * | 2006-03-02 | 2007-09-07 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2008130306A (en) * | 2006-11-20 | 2008-06-05 | Konica Minolta Business Technologies Inc | Photoelectric conversion element, and solar cell |
| JP2009048925A (en) * | 2007-08-22 | 2009-03-05 | Nippon Kayaku Co Ltd | Dye-sensitized photoelectric conversion element |
-
2010
- 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
- 2010-06-18 TW TW099119905A patent/TW201112469A/en unknown
- 2010-06-18 WO PCT/KR2010/003947 patent/WO2010147425A2/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004082061A1 (en) * | 2003-03-14 | 2004-09-23 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| WO2007100033A1 (en) * | 2006-03-02 | 2007-09-07 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2008130306A (en) * | 2006-11-20 | 2008-06-05 | Konica Minolta Business Technologies Inc | Photoelectric conversion element, and solar cell |
| JP2009048925A (en) * | 2007-08-22 | 2009-03-05 | Nippon Kayaku Co Ltd | Dye-sensitized photoelectric conversion element |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408963B (en) * | 2013-08-08 | 2014-08-27 | 陕西师范大学 | Double bridged chain organic dyestuff adopting urea as donor and application of dyestuff |
| CN103408963A (en) * | 2013-08-08 | 2013-11-27 | 陕西师范大学 | Double bridged chain organic dyestuff adopting urea as donor and application of dyestuff |
| CN105294735B (en) * | 2015-11-25 | 2018-03-20 | 武汉工程大学 | A kind of phenothiazines organic molecule donor and preparation method thereof |
| CN105294735A (en) * | 2015-11-25 | 2016-02-03 | 武汉工程大学 | Phenothiazine organic small molecule donor and preparation method thereof |
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| WO2018032945A1 (en) * | 2016-08-17 | 2018-02-22 | 国家纳米科学中心 | Benzothiophene (benzoselenophene) modification-containing photoelectric compound, preparation method therefor, and use thereof |
| CN106800515A (en) * | 2016-12-08 | 2017-06-06 | 烟台九目化学制品有限公司 | A kind of electroluminescent organic material and its application with fluorenamine structure |
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| CN114752227A (en) * | 2017-03-29 | 2022-07-15 | 保土谷化学工业株式会社 | Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion element using same, and dye-sensitized solar cell |
| CN114752227B (en) * | 2017-03-29 | 2023-09-01 | 保土谷化学工业株式会社 | Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion element using same, and dye sensitized solar cell |
| CN110372719A (en) * | 2019-08-09 | 2019-10-25 | 浙江工业大学 | N- fluorenyl benzo carbazole class compound, preparation method and applications |
| CN110372719B (en) * | 2019-08-09 | 2020-08-11 | 浙江工业大学 | N-fluorenyl benzocarbazole compound, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100136929A (en) | 2010-12-29 |
| TW201112469A (en) | 2011-04-01 |
| JP2012530796A (en) | 2012-12-06 |
| WO2010147425A2 (en) | 2010-12-23 |
| WO2010147425A3 (en) | 2011-04-28 |
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