KR20100128258A - Novel ruthenium-based dyes and preparation methods thereof - Google Patents
Novel ruthenium-based dyes and preparation methods thereof Download PDFInfo
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- KR20100128258A KR20100128258A KR1020100049770A KR20100049770A KR20100128258A KR 20100128258 A KR20100128258 A KR 20100128258A KR 1020100049770 A KR1020100049770 A KR 1020100049770A KR 20100049770 A KR20100049770 A KR 20100049770A KR 20100128258 A KR20100128258 A KR 20100128258A
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- dye
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- photoelectric conversion
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- 239000000975 dye Substances 0.000 title claims abstract description 69
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 110
- 239000004065 semiconductor Substances 0.000 claims description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000010419 fine particle Substances 0.000 claims description 33
- -1 cyano, hydroxy Chemical group 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 239000010409 thin film Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 239000010408 film Substances 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000006138 lithiation reaction Methods 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
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- 238000007906 compression Methods 0.000 claims description 2
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- 230000008033 biological extinction Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 23
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 238000003756 stirring Methods 0.000 description 7
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- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
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- 230000005525 hole transport Effects 0.000 description 5
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- BBKNCZFSPQICQT-UHFFFAOYSA-N 2-bromo-2',7'-ditert-butyl-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=C(Br)C=C2C21C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C12 BBKNCZFSPQICQT-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- CDKCEZNPAYWORX-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylphenyl)benzene Chemical group C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C1 CDKCEZNPAYWORX-UHFFFAOYSA-N 0.000 description 3
- OPPSYCGZHQVDPM-UHFFFAOYSA-N 2-bromo-4-tert-butyl-1-(4-tert-butylphenyl)benzene Chemical group C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C1Br OPPSYCGZHQVDPM-UHFFFAOYSA-N 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000012535 impurity Substances 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
- 239000011859 microparticle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 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
- FXSCJZNMWILAJO-UHFFFAOYSA-N 2-bromo-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3CC2=C1 FXSCJZNMWILAJO-UHFFFAOYSA-N 0.000 description 2
- MTCARZDHUIEYMB-UHFFFAOYSA-N 2-bromofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Br)=CC=C3C2=C1 MTCARZDHUIEYMB-UHFFFAOYSA-N 0.000 description 2
- WADWZNSXIVNIAC-UHFFFAOYSA-N 3-methoxy-1,3-oxazolidin-2-one Chemical compound CON1CCOC1=O WADWZNSXIVNIAC-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic 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)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 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
- 230000008021 deposition Effects 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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- 150000002366 halogen compounds Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 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 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 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
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- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Classifications
-
- 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
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
본 발명은 신규한 루테늄(Ru)계 염료 및 이의 제조방법에 관한 것으로, 보다 상세하게는 염료감응태양전지(dye-sensitized solar cell, DSSC)에 염료로 사용되어 종래의 염료보다 현저히 향상된 광전기 변환 효율을 나타내며, 이산화티탄과의 결합력을 강화시키고, Jsc(short circuit photocurrent density, 단회로 광전류 밀도)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있는 염료 및 이의 제조방법에 관한 것이다.The present invention relates to a novel ruthenium (Ru) -based dye and a method for manufacturing the same, and more particularly, it is used as a dye in a dye-sensitized solar cell (DSSC), significantly improved photoelectric conversion efficiency than conventional dyes The present invention relates to a dye and a method for manufacturing the same, which enhance the binding force with titanium dioxide, and have a high J sc (short circuit photocurrent density) and a molar extinction coefficient, thereby greatly improving the efficiency of a solar cell. .
Description
본 발명은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되는 신규한 루테늄(ruthenium)계 염료 및 이의 제조방법에 관한 것이다.
The present invention relates to a novel ruthenium-based dye used in dye-sensitized solar cells (DSSC) and a method for producing 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 있는 가능성을 가지고 있으며, 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀(hole) 쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Since the development of the dye-sensitized nanoparticle titanium oxide solar cell by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of absorbing and generating electron-hole pairs, and a transition metal oxide for transferring generated electrons.
종래 염료감응태양전지에 사용되는 염료로는 대표적인 것으로는 하기 화합물들을 들 수 있다.Typical dyes used in dye-sensitized solar cells include the following compounds.
*TBA : 테트라부틸암모늄 양이온(tetrabutylammonium cation)* TBA: tetrabutylammonium cation
그러나, 아직도 상기 염료들과 비교하여 산화물 반도체 미립자와의 결합력, 광전기 변환효율, Jsc(단회로 광전류 밀도) 및 몰 흡광계수를 높여 태양전지의 효율성 및 내구성을 더욱 높일 것이 요청되고 있으며, 새로운 염료에 대한 연구가 필요한 실정이다.
However, it is still required to increase the efficiency and durability of the solar cell by increasing the binding force with the oxide semiconductor fine particles, the photoelectric conversion efficiency, the J sc (short circuit photocurrent density) and the molar extinction coefficient compared to the above dyes. There is a need for research.
따라서, 본 발명은 종래의 루테늄계 염료보다 현저히 향상된 광전기변환효율을 나타내며, 산화물 반도체 미립자와의 결합력을 강화시키고, Jsc(단회로 광전류 밀도)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있는 염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.Therefore, the present invention exhibits significantly improved photoelectric conversion efficiency than conventional ruthenium-based dyes, enhances the bonding force with oxide semiconductor fine particles, and has excellent J sc (single-circuit photocurrent density) and molar extinction coefficient to greatly increase the efficiency of solar cells. It is an object to provide a dye which can be improved and a method for producing the same.
또한 본 발명은 상기 염료를 포함하여 현저히 향상된 광전기 변환효율을 나타내며, 산화물 반도체 미립자와의 결합력이 강화되고, Jsc(단회로 광전류 밀도)와 몰흡광계수가 우수한 염료증감 광전변환소자, 및 효율이 현저히 향상된 염료감응태양전지를 제공하는 것을 목적으로 한다.
In addition, the present invention exhibits a remarkably improved photovoltaic conversion efficiency including the dye, enhanced binding force with oxide semiconductor fine particles, dye-sensitized photoelectric conversion device excellent in J sc (short circuit photocurrent density) and molar absorption coefficient, and efficiency It is an object to provide a significantly improved dye-sensitized solar cell.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 루테늄계 염료를 제공한다:In order to achieve the above object, the present invention provides a ruthenium-based dye represented by the following formula (1):
상기 식에서, Where
a1 환은 하나 이상의 치환기를 가질 수 있으며, 치환기는 할로겐, 아미드, 시아노, 하이드록시, 니트로, C1-20 알킬, C1-20 알콕시 또는 아실일 수 있고;the a1 ring may have one or more substituents and the substituents may be halogen, amide, cyano, hydroxy, nitro, C 1-20 alkyl, C 1-20 alkoxy or acyl;
A 및 B는 각각 독립적으로 수소 또는
Ar1 및 Ar2는 각각 독립적으로 C6-30 아릴 또는 스파이로바이플루오레닐이고, Ar1 및 Ar2 둘 중 적어도 하나는 스파이로바이플루오레닐이며, 상기 Ar1 및 Ar2는 하나 이상의 하이드록시, 할로겐, 니트로, C1-12 알킬 또는 C1-12 알콕시로 치환될 수 있고;And Ar 1 and Ar 2 are each independently a C 6-30 aryl-by-fluorenyl or spy, Ar 1 and Ar 2, at least one of the two is a by-fluorenyl a spy, the Ar 1 and Ar 2 is one or more May be substituted with hydroxy, halogen, nitro, C 1-12 alkyl or C 1-12 alkoxy;
X는 하나 이상의 하이드록시, 할로겐, 니트로, C1-12 알킬 또는 C1-12 알콕시로 치환되거나 치환되지 않은 페닐렌이고;X is phenylene unsubstituted or substituted with one or more hydroxy, halogen, nitro, C 1-12 alkyl or C 1-12 alkoxy;
Y는 하나 이상의 하이드록시, 할로겐, 니트로, C1-12 알킬, C1-12 알콕시로 치환되거나 치환되지 않은 티오펜이거나, 또는 연결선이다.
Y is thiophene substituted or unsubstituted with one or more hydroxy, halogen, nitro, C 1-12 alkyl, C 1-12 alkoxy, or is a connecting line.
또한 본 발명은 (i) 하기 화학식 2의 화합물을 n-부틸리튬으로 리튬치환반응(lithiation)시킨 후 연속적으로 디메틸포름아미드와 반응시켜 하기 화학식 3의 화합물을 제조하고,In another aspect, the present invention (i) lithium compound of the following formula (2) Li-thiation reaction (lithiation) with n-butyllithium and subsequently reacted with dimethylformamide to prepare a compound of formula (3),
(ii) 화학식 3의 화합물을 하기 화학식 4 또는 화학식 4-1과 반응시켜 하기 화학식 5의 화합물을 제조하고, (ii) reacting a compound of formula 3 with formula 4 or formula 4-1 to prepare a compound of formula 5
(ⅲ) 화학식 5의 화합물을 화학식 6; 화학식 7; 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 포함하는 상기 화학식 1로 표시되는 염료의 제조방법을 제공한다:(Iii) a compound of Formula 5 is represented by Formula 6; Formula 7; And it provides a method for producing a dye represented by the formula (1) comprising sequentially reacting with a compound of formula (8):
[화학식 4-1][Formula 4-1]
상기 화학식 2-8에서 Ar1, Ar2, X 및 Y는 상기 화학식 1에서 정의한 바와 같다.
Ar 1 , Ar 2 , X and Y in Formula 2-8 are as defined in Formula 1.
또한 본 발명은 상기 화학식 1로 표시되는 화합물을 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자를 제공한다.
In another aspect, the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particle carrying a compound represented by the formula (1).
또한 본 발명은 상기 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.
In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
본 발명의 신규한 루테늄계 염료는 종래의 염료보다 현저히 향상된 광전기 변환 효율을 나타내며, 이산화티탄과의 결합력을 강화시키고, Jsc(단회로 광전류 밀도)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있다.
The novel ruthenium-based dye of the present invention exhibits significantly improved photoelectric conversion efficiency than conventional dyes, enhances the binding force with titanium dioxide, and improves the efficiency of the solar cell due to excellent J sc (short circuit photocurrent density) and molar extinction coefficient. It can greatly improve.
본 발명자들은, 화학식 1로 표시되는 화합물을 산화물 반도체 미립자에 담지시켜 염료감응태양전지를 제조할 경우 산화물 반도체 미립자에 강하게 결합하여 내구성이 뛰어나며, 광전기 변환효율, Jsc(단회로 광전류 밀도) 및 몰 흡광계수가 높아 기존에 존재하였던 염료감응태양전지보다도 우수한 효율을 나타냄을 확인하고 본 발명을 완성하게 되었다.
The present inventors, when manufacturing a dye-sensitized solar cell by supporting the compound represented by the formula (1) in the oxide semiconductor fine particles, it is strongly bonded to the oxide semiconductor fine particles and excellent in durability, photoelectric conversion efficiency, J sc (short circuit photocurrent density) and mol It was confirmed that the higher the extinction coefficient than the existing dye-sensitized solar cells exhibited higher efficiency and completed the present invention.
본 발명의 루테늄계 염료는 바람직하게는 하기 구조들 중 어느 하나로 표시될 수 있다:
Ruthenium-based dyes of the present invention may preferably be represented by any of the following structures:
또한 본 발명은 상기 화학식 1로 표시되는 염료의 제조방법을 제공하는 바, 상기 염료는 (i) 하기 화학식 2의 화합물을 n-부틸리튬으로 리튬치환반응(lithiation)시킨 후 연속적으로 디메틸포름아미드와 반응시켜 하기 화학식 3의 화합물을 제조하고,In another aspect, the present invention provides a method for producing a dye represented by the formula (1), wherein the dye is (i) Lithium-substituted with the compound of formula (2) with n-butyllithium (lithiation) and continuously with dimethylformamide Reaction to prepare a compound of formula
(ii) 화학식 3의 화합물을 하기 화학식 4 또는 화학식 4-1과 반응시켜 하기 화학식 5의 화합물을 제조하고, (ii) reacting a compound of formula 3 with formula 4 or formula 4-1 to prepare a compound of formula 5
(ⅲ) 화학식 5의 화합물을 화학식 6; 화학식 7; 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 통하여 제조할 수 있다.
(Iii) a compound of Formula 5 is represented by Formula 6; Formula 7; And it can be prepared through the reaction with the compound of formula (8) sequentially.
구체적인 일예로 하기 화학식 1a의 화합물은 화학식 1a로 표시되는 염료는 화학식 2-1의 화합물을 n-부틸리튬으로 리튬치환반응(lithiation)시킨 후 연속적으로 디메틸포름아미드와 반응시켜 화학식 3-1의 화합물을 제조하고, 화학식 3-1의 화합물을 유기용매(예: 테트라히드로퓨란(THF)) 중에서 NaH 존재 하에 화학식 4의 화합물과 혼합하고 환류시켜 화학식 5의 화합물을 제조하고, 화학식 5의 화합물을 유기용매(예: 디메틸포름아미드(DMF)) 중에서 화학식 6의 화합물과 반응시킨 후 연속하여 화학식 7 및 8의 화합물과 순차적으로 반응시킴으로써 제조될 수 있다.As a specific example, the compound represented by Chemical Formula 1a may be a dye represented by Chemical Formula 1a. The compound of Chemical Formula 3-1 may be reacted with dimethylformamide after lithium lithiation with n-butyllithium. To prepare a compound of formula 5 by mixing the compound of formula 3-1 with a compound of formula 4 in an organic solvent (e.g. tetrahydrofuran (THF)) in the presence of NaH and reflux, and the compound of formula 5 It can be prepared by reacting with a compound of formula 6 in a solvent (eg dimethylformamide (DMF)) and subsequently with the compound of formula 7 and 8 in sequence.
[화학식 1a][Formula 1a]
[화학식 2-1][Formula 2-1]
[화학식 3-1][Formula 3-1]
다른 예로서 하기 화학식 1b의 화합물은As another example, the compound of Formula 1b
(i) 하기 화학식 2-1의 화합물을 하기 화학식 9의 화합물과 스즈끼(Suzuki) 커플링 반응시켜 하기 화학식 10의 화합물을 제조하고,(i) Suzuki coupling reaction of a compound of Formula 2-1 with a compound of Formula 9 to prepare a compound of Formula 10,
(ii) 화학식 10의 화합물을 n-부틸리튬으로 리튬치환반응(lithiation)시킨 후 연속적으로 디메틸포름아미드와 반응시켜 하기 화학식 11의 화합물을 제조하고,(ii) reacting the compound of Formula 10 with n-butyllithium for lithiation and subsequently reacting with dimethylformamide to prepare a compound of Formula 11
(iii) 화학식 11의 화합물을 하기 화학식 4, 화학식 6, 화학식 7 및 화학식 8의 화합물과 결과물을 순차적으로 반응시키는 것을 통하여 제조할 수 있다.(iii) The compound of Formula 11 may be prepared by sequentially reacting the compound of Formula 4, Formula 6, Formula 7, and Formula 8 with the resultant.
[화학식 1b][Chemical Formula 1b]
[화학식 2-1][Formula 2-1]
또 다른 예로서 하기 화학식 1c의 화합물은 (i) 하기 화학식 2-1의 화합물을 n-부틸리튬으로 리튬치환반응(lithiation)시킨 후 연속적으로 디메틸포름아미드와 반응시켜 하기 화학식 3-1의 화합물을 제조하고,As another example, the compound of Formula 1c may be (i) lithium-third-reacting the compound of Formula 2-1 with n-butyllithium and subsequently reacting with dimethylformamide to react the compound of Formula 3-1. Manufacturing,
(ii) 화학식 3-1의 화합물을 하기 화학식 4-1, 화학식 6, 화학식 7 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 통하여 제조할 수 있다:(ii) Compounds of formula 3-1 may be prepared by sequentially reacting with compounds of formulas 4-1, 6, 7, and 8:
[화학식 1c][Formula 1c]
[화학식 2-1][Formula 2-1]
[화학식 3-1][Formula 3-1]
[화학식 4-1][Formula 4-1]
또 다른 예로서 하기 화학식 1d의 화합물은 (i) 하기 화학식 2의 화합물을 하기 화학식 9의 화합물과 스즈끼(Suzuki) 커플링 반응시켜 하기 화학식 10의 화합물을 제조하고,As another example, the compound of Formula 1d may be prepared by (i) coupling a compound of Formula 2 with a compound of Formula 9 to Suzuki to prepare a compound of Formula 10,
(ii) 화학식 10의 화합물을 n-부틸리튬으로 리튬치환반응(lithiation)시킨 후 연속적으로 디메틸포름아미드와 반응시켜 하기 화학식 11의 화합물을 제조하고,(ii) reacting the compound of Formula 10 with n-butyllithium for lithiation and subsequently reacting with dimethylformamide to prepare a compound of Formula 11
(iii) 화학식 11의 화합물을 하기 화학식 4-1, 화학식 6, 화학식 7 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 통하여 제조할 수 있다:(iii) a compound of formula 11 may be prepared by sequentially reacting with a compound of formulas 4-1, 6, 7, and 8:
[화학식 1d]≪ RTI ID = 0.0 &
[화학식 2-1][Formula 2-1]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
또한 본 발명은 염료증감 광전변환소자를 제공하는 바, 상기 염료증감 광전변환소자는 산화물 반도체 미립자에 상기 화학식 1로 표시되는 염료를 담지시킨 것을 특징으로 한다. 본 발명은 염료증감 광전변환소자는 상기 화학식 1로 표시되는 염료를 사용하는 것 이외에 종래 염료를 이용하여 태양전지용 염료증감 광전변환소자를 제조하는 방법들이 적용될 수 있음은 물론이며, 바람직하게는 본 발명의 염료증감 광전변환소자는 산화물 반도체 미립자를 이용해서 기판상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명의 염료를 담지시킨 것이 좋다.In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles. The present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by the formula (1) can be applied to the method of manufacturing a dye-sensitized photoelectric conversion device for solar cells using a conventional dye, of course, preferably the present invention The dye-sensitized photoelectric conversion device may be prepared by fabricating a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the dye of the present invention on the thin film.
본 발명에서 산화물 반도체의 박막을 설치하는 기판으로서는 그 표면이 도전성인 것이 바람직하며, 시중에서 판매되는 것을 사용할 수도 있다. 구체적인 일예로 글라스의 표면 또는 폴리에틸렌테레프탈레이트 혹은 폴리에테르설폰 등의 투명성이 있는 고분자 재료의 표면에 인듐, 불소, 안티몬을 도포한 산화주석 등의 도전성 금속산화물이나 강, 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 invention, it is preferable that the surface is electroconductive as a board | substrate which provides the thin film of an oxide semiconductor, and what is marketed can also be used. As a specific example, conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony on a surface of glass or a transparent polymer material such as polyethylene terephthalate or polyethersulfone, or a metal thin film such as steel, silver, or gold may be used. The formed thing can be used. In this case, the conductivity is preferably 1000 Ω or less, particularly preferably 100 Ω or less.
또한 산화물 반도체의 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, 이들 중 산화티탄, 산화아연, 산화주석이 더욱 바람직하며, 산화티탄이 가장 바람직하다. 상기 산화물 반도체는 단독으로 사용할 수도 있지만, 혼합하거나 반도체의 표면에 코팅시켜서 사용할 수도 있다. As the fine particles of the oxide semiconductor, 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. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, among these, 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.
또한 상기 산화물 반도체의 미립자의 입경은 평균 입경으로서 1 ∼ 500 nm인 것이 좋으며, 더욱 바람직하게는 1 ∼ 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 fine particles of the oxide semiconductor 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 등으로 직접 기판상에 박막으로 형성하는 방법, 기판을 전극으로 하여 전기적으로 반도체 미립자 박막을 석출시키는 방법, 반도체 미립자의 슬러리 또는 반도체 알콕사이드 등의 반도체 미립자의 전구체를 가수분해함으로써 얻을 수 있은 미립자를 함유하는 페이스트를 기판상에 도포한 후, 건조, 경화 혹은 소성하는 방법 등에 의해 제조할 수 있으며, 페이스트를 기판상에 도포하는 방법이 바람직하다. 이 방법의 경우, 슬러리는 2차 응집하고 있는 산화물 반도체 미립자를 통상의 방법에 의해 분산매 중에 평균 1차 입경이 1 ∼ 200 nm이 되도록 분산시킴으로써 얻을 수 있다.The oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on a substrate by spray spraying, a method of electrically depositing a semiconductor fine particle thin film using a substrate as an electrode, a slurry of semiconductor fine particles or semiconductor fine particles such as a semiconductor alkoxide. After applying the paste containing the fine particles obtained by hydrolyzing the precursor onto the substrate, it can be produced by a method of drying, curing or baking, and a method of applying the paste onto the substrate is preferred. In the case of this method, a slurry can be obtained by disperse | distributing the oxide semiconductor microparticles | fine-particles which are secondary aggregated so that an average primary particle diameter may be 1-200 nm in a dispersion medium by a conventional method.
슬러리를 분산시키는 분산매로서는 반도체 미립자를 분산시킬 수 있는 것이면 특별히 제한 없이 사용할 수 있으며, 물, 에탄올 등의 알코올, 아세톤, 아세틸아세톤 등의 케톤 또는 헥산 등의 탄화수소를 이용할 수 있고, 이것들은 혼합해서 사용할 수 있고, 이 중 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, 또는 아세틸아세톤, 아크릴산, 폴리에틸렌글리콜, 폴리비닐알코올 등을 들 수 있다.The dispersion medium for dispersing the slurry can be used without particular limitation so long as it can disperse the semiconductor fine particles, and alcohols 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. Among them, it is preferable to use water among them in order to reduce the viscosity change of the slurry. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles | fine-particles. Specific examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid and nitric acid, or acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.
슬러리를 도포한 기판은 소성할 수 있고, 그 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. The substrate coated with the slurry can be fired, and its firing temperature is at least 100 ° C, preferably at least 200 ° C, and the upper limit is generally below the melting point (softening point) of the substrate, and usually the upper limit is 900 ° C, preferably 600. It is below ℃. In the present invention, the firing time is not particularly limited, but is generally within 4 hours.
본 발명에서 기판상의 박막의 두께는 1 ∼ 200 ㎛인 것이 적합하며, 바람직하게는 1 ∼ 50 ㎛이다. 소성을 실시하는 경우 산화물 반도체 미립자의 박층이 일부 용착하지만, 그러한 용착은 본 발명을 위해서는 특별하게 지장은 없다.It is preferable that the thickness of the thin film on a board | substrate in this invention is 1-200 micrometers, Preferably it is 1-50 micrometers. Although some thin layers of oxide semiconductor fine particles are welded when firing, such welding is not particularly troubled for the present invention.
또한 상기 산화물 반도체 박막에 2차 처리를 실시할 수도 있다. 일 예로 반도체와 동일한 금속의 알콕사이드, 염화물, 질소화물, 황화물 등의 용액에 직접, 기판별로 박막을 침적시켜서 건조 혹은 재소성 함으로써 반도체 박막의 성능을 향상시킬 수도 있다. 금속 알콕사이드로서는 티탄 에톡사이드, 티탄 이소프로에폭사이드, 티탄 t-부톡사이드, n-디부틸-디아세틸 주석 등을 들 수 있고, 그것들의 알코올 용액을 이용할 수 있다. 염화물로서는 예를 들면 4염화 티탄, 사염화주석, 염화아연 등을 들 수 있고, 그 수용액을 이용할 수 있다. 이렇게 하여 수득된 산화물 반도체 박막은 산화물 반도체의 미립자로 이루어져 있다.In addition, the oxide semiconductor thin film may be subjected to secondary treatment. For 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 an 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, and an alcohol solution thereof can be used. As a chloride, titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.
또한 본 발명에서 박막 상으로 형성된 산화물 반도체 미립자에 염료를 담지시키는 방법은 특별히 한정되지 않으며, 구체적인 예로서 상기 화학식 1로 표시되는 염료를 용해할 수 있는 용매로 용해해서 얻은 용액, 또는 염료를 분산시켜서 얻은 분산액에 상기 산화물 반도체 박막이 설치된 기판을 침지시키는 방법을 들 수 있다. 용액 또는 분산액 중의 농도는 염료에 의해 적당하게 결정할 수 있다. 침적시간은 대체로 상온에서 용매의 비점까지이고, 또 침적시간은 1분에서 48시간 정도이다. 염료를 용해시키는데 사용할 수 있는 용매의 구체적인 예로는 메탄올, 에탄올, 아세토니트릴, 디메틸설폭사이드, 디메틸포름아미드, 아세톤, t-부탄올 등을 들 수 있다. 용액의 염료 농도는 보통 1× 10-6 M ∼ 1 M이 적합하고, 바람직하게는 1× 10-5 M ∼ 1× 10-1 M 일 수 있다. 이렇게 해서 염료로 증감된 박막 상의 산화물 반도체 미립자를 가진 본 발명의 광전변환소자를 얻을 수 있다.In addition, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, as a specific example by dispersing a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving, or dye The method of immersing the board | substrate with which the said oxide semiconductor thin film was provided in the obtained dispersion liquid is mentioned. The concentration in the solution or dispersion can be appropriately determined by the dye. The deposition time is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours. 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. The dye concentration of the solution is usually 1 x 10 -6 M to 1 M is suitable, preferably 1 x 10 -5 M to 1 x 10 -1 M. In this way, the photoelectric conversion element of this invention which has oxide semiconductor microparticles | fine-particles on the thin film sensitized with dye can be obtained.
본 발명에서 담지하는 화학식 1로 표시되는 염료는 1종류일 수도 있고, 수 종류 혼합할 수도 있다. 또한 혼합하는 경우에는 본 발명의 염료와 함께 다른 염료나 금속 착체 염료를 혼합할 수 있다. 혼합할 수 있는 금속 착체 염료의 예는 특별하게 제한되지 않지만, 루테늄 착체나 그 4급염, 프탈로시아닌, 포르피린 등이 바람직하고, 혼합 이용하는 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 dye represented by the formula (1) supported by the present invention may be one kind or may be mixed in several kinds. In addition, when mixing, another dye or a metal complex dye can be mixed with the dye of this invention. Examples of the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin, and the like are preferable, and organic dyes used for mixing include metal-free phthalocyanine, porphyrin, cyanine, merocyanine, Methine dyes such as oxonol, triphenylmethane, and acrylic acid dyes as shown in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene-based dyes (MK Nazeeruddin, A). .Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., Vol. 115, p . 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 carboxylic acids such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, methyl ester of cholate, and sodium cholate, steroidal compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and calix 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 전극표면을 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 semiconductor electrode surface 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.
또한 본 발명은 상기 염료감응 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공하는 바, 상기 화학식 1로 표시되는 염료를 담지시킨 산화물 반도체 미립자를 이용한 염료증감 광전변환소자를 사용하는 것 이외에 종래 광전변환소자를 사용하여 태양전지를 제조하는 통상의 방법들이 적용될 수 있음은 물론이며, 구체적인 예로 상기 산화물 반도체 미립자에 화학식 1로 표시되는 염료를 담지시킨 광전변환소자 전극(음극), 대전극(양극), 산화환원 전해질, 정공수송 재료 또는 p형 반도체 등으로 구성될 수 있다.In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1) In addition, conventional methods for manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and, as a specific example, a photoelectric conversion device electrode (cathode) and a counter electrode supporting the dye represented by Formula 1 on the oxide semiconductor fine particles. (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.
바람직하게는, 본 발명의 염료감응태양전지의 구체적인 제조방법의 일예로는 전도성 투명 기판 위에 산화티타늄 페이스트를 코팅하는 단계, 페이스트가 코팅된 기판을 소성하여 산화티타늄 박막을 형성하는 단계, 산화티타늄 박막이 형성된 기판을 화학식 1로 표시되는 염료가 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.Preferably, one example of a specific method of manufacturing a dye-sensitized solar cell of the present invention is the step of coating a titanium oxide paste on a conductive transparent substrate, baking the substrate coated with a paste to form a titanium oxide thin film, titanium oxide thin film Impregnating the formed substrate into a mixed solution in which the dye represented by Chemical Formula 1 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon. Forming a hole penetrating a glass substrate and a counter electrode, placing a thermoplastic polymer film between the counter electrode and the dye-adsorbed titanium oxide film electrode, and performing a heat compression process to perform the counter electrode and titanium oxide. Bonding a film electrode to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the hole; Implanting be and can be prepared through the step of sealing the thermoplastic polymer.
산화환원 전해질, 정공수송 재료, p형 반도체 등의 형태는 액체, 응고체(겔 및 겔상), 고체 등 일 수 있다. 액상의 것으로서는 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 것으로서는 산화환원 전해질, 용해염, 정공수송재료, p형 반도체 등을 사용할 수 있다. Redox electrolytes, hole transport materials, p-type semiconductors, and the like may be in the form of liquids, coagulants (gels and gels), solids, and the like. As liquids, redox electrolytes, dissolved salts, hole transport materials, p-type semiconductors, and the like are dissolved in a solvent, and at room temperature, dissolved salts, etc., in the case of coagulation bodies (gels and gels), these are polymer matrices or low molecular gelling agents. What was contained in etc. can be mentioned, respectively. As the solid, a redox electrolyte, a dissolved salt, a hole transport material, a p-type semiconductor, or the like can be used.
정공수송 재료로서는 아민 유도체나 폴리아세티틸렌, 폴리아닐린, 폴리티오펜 등의 도전성 고분자, 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.Examples of the hole transport material include an amine derivative, a conductive polymer such as polyacetylene, polyaniline, and polythiophene, and an object using a discotech liquid crystal phase such as triphenylene-based 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.
본 발명의 태양전지에 이용하는 산화환원 전해질로서는 할로겐 이온을 대이온으로 하는 할로겐 화합물 및 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.As the redox electrolyte used in the solar cell of the present invention, a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen redox-based electrolytes are 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 양전해질의 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 - 99 중량%인 것이 좋으며, 0.1 - 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 a gel positive 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 발명의 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 of the present invention, a counter electrode (anode) is disposed in a photoelectric conversion element (cathode) on which a dye is carried on an oxide semiconductor fine particle on a substrate so as to face it, and a solution containing a redox electrolyte is filled therebetween. Can be obtained.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
[실시예][Example]
염료의 합성Synthesis of Dyes
모든 반응은 아르곤 분위기에서 진행되었고, 용매는 시그마-알드리치(Sigma-Adrich)사에서 구입한 적합한 시약으로 증류되었다. 1H NMR 스펙트럼은 Varian Mercury 300 스펙트로미터로 측정하였다. 흡광 스펙트럼은 Perkin-Elmer Lambda 2S UV-visible 스펙트로미터로 측정하였다.
All reactions were run in an argon atmosphere and the solvent was distilled off with a suitable reagent purchased from Sigma-Adrich. 1 H NMR spectra were measured on a Varian Mercury 300 spectrometer. Absorbance spectra were measured with a Perkin-Elmer Lambda 2S UV-visible spectrometer.
[실시예 1] 2-브로모-9-플루오레논의 합성Example 1 Synthesis of 2-bromo-9-fluorenone
2-브로모플루오렌 (19.6 g, 80 mmol), 피리딘 (200ml), 25% 테트라메틸암모늄 하이드록사이드 (2ml)를 넣고, 실온에서 공기 버블링해 주면서 12시간 동안 교반하였다. 여기에 황산을 넣고 여과한 후, 에탄올로 재결정하여 노란색 고체 2-브로모-9-플루오레논 (17.8 g, 85.1 %)을 얻었다.
2-bromofluorene (19.6 g, 80 mmol), pyridine (200 ml), 25% tetramethylammonium hydroxide (2 ml) were added and stirred for 12 hours while bubbling air at room temperature. Sulfuric acid was added thereto, followed by filtration and recrystallization with ethanol to give a yellow solid 2-bromo-9-fluorenone (17.8 g, 85.1%).
[실시예 2] 4,4'-디-tert-부틸바이페닐의 합성Example 2 Synthesis of 4,4'-di-tert-butylbiphenyl
바이페닐(30. g, 200 mmol), 무수 염화철 (160 mg) 및 염화메틸렌 (200ml)을 혼합하고 실온에서 교반하였다. 여기에 tert-부틸 클로라이드 (46.4 ml, 432mmol)를 천천히 가한 후 12시간 동안 교반하였다. 반응 종료 후, 헥산 (200 ml)으로 3회 추출하고, 무수 황산마그네슘으로 탈수시켜 감압증류하였다. 별도의 정제 없이 4,4'-디-tert-부틸바이페닐 (42 g, 97.2 %)을 얻었다.
Biphenyl (30. g, 200 mmol), anhydrous iron chloride (160 mg) and methylene chloride (200 ml) were mixed and stirred at room temperature. Tert-butyl chloride (46.4 ml, 432 mmol) was slowly added thereto, followed by stirring for 12 hours. After the completion of the reaction, the mixture was extracted three times with hexane (200 ml), dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. 4,4'-di-tert-butylbiphenyl (42 g, 97.2%) was obtained without further purification.
[실시예 3] 2-브로모-4,4'-디-tert-부틸바이페닐의 합성Example 3 Synthesis of 2-bromo-4,4'-di-tert-butylbiphenyl
4,4'-디-tert-부틸바이페닐 (7.98 g, 30 mmol), 무수 염화철(20 mg), 클로로포름 (30ml)을 혼합하고 0℃를 유지하면서 교반하였다. 이어, 20ml의 클로로포름에 녹인 브롬 (4.8 g, 30 mmol)을 천천히 가한 후 12시간 동안 교반하였다. 반응 종료 후, 오렌지색이 사라질 때까지 탄산나트륨을 넣고 헥산 (100 ml)으로 3회 추출하고, 무수 황산마그네슘으로 탈수시켜 감압증류하였다. 불순물이 포함된 2-브로모-4,4'-디-tert-부틸바이페닐을 얻었다.
4,4'-di-tert-butylbiphenyl (7.98 g, 30 mmol), anhydrous iron chloride (20 mg) and chloroform (30 ml) were mixed and stirred while maintaining 0 ° C. Then, bromine (4.8 g, 30 mmol) dissolved in 20 ml of chloroform was slowly added, followed by stirring for 12 hours. After completion of the reaction, sodium carbonate was added until the orange color disappeared, extracted three times with hexane (100 ml), dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. 2-Bromo-4,4'-di-tert-butylbiphenyl containing impurity was obtained.
[실시예 4] 2-브로모-(2', 7'-디-tert-부틸)-9,9'-스파이로바이플루오렌의 합성Example 4 Synthesis of 2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene
불순물이 포함된 2-브로모-4,4'-디-tert-부틸바이페닐 (6.12 g, 10 mmol)을 테트라하이드로퓨란 (100 ml)에 녹인 후, -78℃를 유지하였다. 여기에 n-뷰틸리튬 (12 ml, 15 mmol)을 천천히 가한 후 1 시간 동안 교반하였다. 여기에 2-브로모플루오렌 (2.6 g, 10 mmol)을 테트라하이드로퓨란 (40 ml)에 녹여 넣은 후 실온에서 12시간 동안 교반하였다. 반응을 종료한 후 에틸아세테이트로 추출하고 무수 황산마그네슘으로 탈수시킨 후 감압증류 하였다. 그 혼합물을 아세트산 (30 ml)에 녹여 교반하고, 진한 염산 한 방울을 가한 후 한 시간 동안 환류시켰다. 실온으로 냉각시키고, 침전물을 여과하고 물로 세척하여 2-브로모-(2', 7'-디-tert-부틸)-9,9'-스파이로바이플루오렌과 4,4'-디-tert-부틸바이페닐의 혼합물을 얻었다. 상기 혼합물을 실리카겔이 충진된 컬럼에서 n-헥산을 이동상으로 하여 분리시켜 2-브로모-(2', 7'-디-tert-부틸)-9,9'-스파이로바이플루오렌 (2.74 g, 54 %)을 얻었다.
2-bromo-4,4'-di-tert-butylbiphenyl (6.12 g, 10 mmol) containing impurities was dissolved in tetrahydrofuran (100 ml) and then maintained at -78 ° C. N-butyllithium (12 ml, 15 mmol) was slowly added thereto, followed by stirring for 1 hour. 2-bromofluorene (2.6 g, 10 mmol) was dissolved in tetrahydrofuran (40 ml) and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, dehydrated with anhydrous magnesium sulfate, and distilled under reduced pressure. The mixture was dissolved in acetic acid (30 ml) and stirred, and a drop of concentrated hydrochloric acid was added and refluxed for one hour. After cooling to room temperature, the precipitate is filtered and washed with water to give 2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene and 4,4'-di-tert A mixture of -butylbiphenyl was obtained. The mixture was separated by a mobile phase of n-hexane in a silica gel packed column to give 2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene (2.74 g , 54%).
[실시예 5] 2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-2-일)-N-페닐-9,9'-스파이로바이[플루오렌]-2-아민의 합성Example 5 2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -2-yl)- Synthesis of N-phenyl-9,9'-spirobi [fluorene] -2-amine
2-브로모-(2', 7'-디-tert-부틸)-9,9'-스파이로바이플루오렌 (2.74 g, 6.93 mmol), 아닐린 (0.26 g, 2.77 mmol), t-부톡시나트륨 (0.67 g, 6.93 mmol, 2.5 eq), Pd2(ba)3 0.04 g(0.12 mmol) 및 P(t-Bu)3 (0.03 g, 0.12 mmol)에 톨루엔 50 mL를 넣고 10 시간 동안 질소 분위기 하에서 환류시켰다. 반응액을 실온으로 냉각시킨 후 증류수 30 mL를 첨가하고 교반하였다. 이어서, 톨루엔층을 추출하고, 이를 무수 황산마그네슘으로 건조시킨 후 여과하고 감압하에서 용매를 제거하였다. 반응 혼합물을 노르말 헥산으로 전개하고 컬럼 크로마토그래피로 정제하여 2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-2-일)-N-페닐-9,9'-스파이로바이[플루오렌]-2-아민 1.57 g (60 %)를 얻었다.
2-bromo- (2 ', 7'-di-tert-butyl) -9,9'-spirobifluorene (2.74 g, 6.93 mmol), aniline (0.26 g, 2.77 mmol), t-butoxy 50 mL of toluene was added to sodium (0.67 g, 6.93 mmol, 2.5 eq), Pd 2 (ba) 3 0.04 g (0.12 mmol), and P (t-Bu) 3 (0.03 g, 0.12 mmol) for 10 hours under nitrogen atmosphere. Under reflux. After cooling the reaction solution to room temperature, 30 mL of distilled water was added and stirred. The toluene layer was then extracted, dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure. The reaction mixture was developed with normal hexane and purified by column chromatography to give 2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia [ 1.57 g (60%) of fluorene] -2-yl) -N-phenyl-9,9'-spirobi [fluorene] -2-amine was obtained.
[실시예 6] N-(4-브로모페닐)-2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-2-일)-9,9'-스파이로바이[플루오렌]-2-아민의 합성Example 6 N- (4-bromophenyl) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia Synthesis of [Fluoren] -2-yl) -9,9'-spirobi [fluorene] -2-amine
DMF 50 mL에 2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-2-일)-N-페닐-9,9'-스파이로바이[플루오렌]-2-아민 (1.57 g, 1.66 mmol)을 넣고 교반하였다. 이 반응 용액에 0.3 g(1.66 mmol)의 NBS를 넣고 50 ℃에서 2 시간 교반한 후, 증류수 100 mL를 붓고 교반하였다. 형성된 고체를 여과하고, 이것을 THF에 녹인 후 무수 황산마그네슘으로 건조시키고 감압 하에서 용매 THF를 제거하여 액체의 반응 혼합물을 얻었으며, 시간이 지남에 따라 반응 혼합물에서 고체가 형성되었다. 여기에 에탄올 50 mL를 가하고 교반한 후, 불순물을 씻고 여과 및 건조하여 원하는 N-(4-브로모페닐)-2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-2-일)-9,9'-스파이로바이[플루오렌]-2-아민 0.60 g (35 %)을 얻었다.
2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -2-yl) -N in 50 mL of DMF -Phenyl-9,9'-spirobi [fluorene] -2-amine (1.57 g, 1.66 mmol) was added and stirred. 0.3 g (1.66 mmol) of NBS was added to the reaction solution, followed by stirring at 50 ° C. for 2 hours, followed by pouring 100 mL of distilled water and stirring. The solid formed was filtered, dissolved in THF, dried over anhydrous magnesium sulfate, and the solvent THF was removed under reduced pressure to obtain a reaction mixture of liquid, which formed a solid in the reaction mixture over time. 50 mL of ethanol was added thereto, stirred, and the impurities were washed, filtered and dried to obtain N- (4-bromophenyl) -2 ', 7'-di-tert-butyl-N- (2', 7'- 0.60 g (35%) of di-tert-butyl-9,9'-spirobi [fluorene] -2-yl) -9,9'-spirobi [fluorene] -2-amine was obtained.
[실시예 7] 2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-3-일)-N-(4-(3-헥실티오펜-2-일)페닐)-9,9'-스파이로바이[플루오렌]-2-아민("화학식 10의 화합물")의 합성Example 7 2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl)- Synthesis of N- (4- (3-hexylthiophen-2-yl) phenyl) -9,9'-spirobi [fluorene] -2-amine ("compound of formula 10")
N-(4-브로모페닐)-2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-2-일)-9,9'-스파이로바이[플루오렌]-2-아민 ("화학식 2의 화합물", 0.58 g, 0.56 mmol), 4-헥실티오펜-5-일 보론산 ("화학식 9의 화합물", 0.12 g, 0.56 mmol) 테트라키스-(트리페닐포스핀)팔라듐(0) (0.012 g, 0.011 mmol), 2 M 탄산칼륨 수용액을 넣고 질소 가스 상태하에서 12 시간 동안 환류시켜 교반하였다. 교반이 끝난 후 염화메틸렌과 물을 사용하여 유기층을 추출한 후 감압증류 한 뒤 컬럼 정제를 하여(용리액 - M.C : Hx = 1 : 4), 2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-3-일)-N-(4-(3-헥실티오펜-2-일)페닐)-9,9'-스파이로바이[플루오렌]-2-아민 0.54 g (75%)를 얻었다.
N- (4-bromophenyl) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia [fluorene]- 2-yl) -9,9'-spirobi [fluorene] -2-amine ("Compound of formula 2", 0.58 g, 0.56 mmol), 4-hexylthiophen-5-yl boronic acid ("Formula 9 ", 0.12 g, 0.56 mmol) tetrakis- (triphenylphosphine) palladium (0) (0.012 g, 0.011 mmol) and 2 M aqueous potassium carbonate solution were added and refluxed under nitrogen gas for 12 hours, followed by stirring. . After stirring, the organic layer was extracted with methylene chloride and water, distilled under reduced pressure, and purified by column (eluent-MC: Hx = 1: 4), 2 ', 7'-di-tert-butyl-N- ( 2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) -N- (4- (3-hexylthiophen-2-yl) phenyl) -9 0.54 g (75%) of, 9'-spirobi [fluorene] -2-amine was obtained.
[실시예 8] 5-(4-((2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-3-일)(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-7-일)아미노)페닐)-4-헥실티오펜-2-카바알데히드("화학식 11의 화합물")의 합성Example 8 5- (4-((2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) (2', 7'-di- Synthesis of tert-butyl-9,9'-spirobi [fluorene] -7-yl) amino) phenyl) -4-hexylthiophen-2-carbaaldehyde (“Compound 11”)
2',7'-디-tert-부틸-N-(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-3-일)-N-(4-(3-헥실티오펜-2-일)페닐)-9,9'-스파이로바이[플루오렌]-2-아민("화학식 10의 화합물", 0.54 g, 0.42 mmol)의 무수 에탄올 용액에, n-BuLi(0.35 ml, 헥산 중의 1.6 M 용액)를 아르곤 하에서 첨가하였다. 3시간 후에, 여기에 DMF(0.05 g, 0.7 mmol)를 아르곤 하에서 0 ℃에서 첨가하고 5% KOH로 세척하였다. 반응용액을 황산마그네슘으로 건조하고 용매를 제거한 후 얻어진 고형물을 실리카 겔 크로마토그래피(용리액 - MC : Hx = 1 : 1)하여 5-(4-((2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-3-일)(2',7'-디-tert-부틸-9,9'-스파이로바이[플루오렌]-7-일)아미노)페닐)-4-헥실티오펜-2-카바알데히드("화학식 11의 화합물") 0.41 g (75%)을 얻었다.
2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) -N- (4- In anhydrous ethanol solution of (3-hexylthiophen-2-yl) phenyl) -9,9'-spirobi [fluorene] -2-amine ("compound of formula 10", 0.54 g, 0.42 mmol), n- BuLi (0.35 ml, 1.6 M solution in hexane) was added under argon. After 3 h, DMF (0.05 g, 0.7 mmol) was added thereto at 0 ° C. under argon and washed with 5% KOH. The reaction solution was dried over magnesium sulfate, the solvent was removed, and the obtained solid was subjected to silica gel chromatography (eluent-MC: Hx = 1: 1) to give 5- (4-((2 ', 7'-di-tert-butyl-). 9,9'-spirobi [fluorene] -3-yl) (2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -7-yl) amino) phenyl 0.41 g (75%) of 4-hexylthiophene-2-carbaaldehyde ("Compound of formula 11") was obtained.
[실시예 9] 4-((2',7'-디-터트-부틸-9,9'-스파이로바이[플루오렌]-3-일)(2',7'-디-터트-부틸-9,9'-스파이로바이[플루오렌]-7-일)아미노)벤즈알데하이드("화학식 3의 화합물")의 합성Example 9 4-((2 ', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3-yl) (2', 7'-di-tert-butyl Synthesis of -9,9'-Spirobi [fluorene] -7-yl) amino) benzaldehyde ("Compound of Formula 3")
상기 [실시예 8]에서 화학식 10의 화합물 대신 화학식 2의 화합물(0.43 g, 0.42 mmol)을 사용하여 화학식 3의 화합물을 합성하였다.
In Example 8, the compound of Formula 3 was synthesized using the compound of Formula 2 (0.43 g, 0.42 mmol) instead of the compound of Formula 10.
[실시예 10] 4-브로모메틸-4'-메틸-2,2'-바이피리딘의 합성Example 10 Synthesis of 4-bromomethyl-4'-methyl-2,2'-bipyridine
이 화합물은 기존 문헌(Inorg. Chem. 1991, 30, 2942)의 합성방법을 이용하였다. 1H NMR (CDCl3): 8.65 (d, JH-H = 4.5 Hz, 1H), 8.54 (d, JH-H = 4.5 Hz, 1H), 8.43 (s, 1H), 8.24(s, 1H), 7.34 (d, JH-H = 4.5Hz, 1H), 7.17 (d, JH-H = 4.5Hz, 1H), 4.47(s, 2H), 2.45(s, 3H).
This compound utilizes the synthesis method of the existing literature ( Inorg. Chem. 1991, 30 , 2942). 1 H NMR (CDCl 3 ): 8.65 (d, JH-H = 4.5 Hz, 1H), 8.54 (d, JH-H = 4.5 Hz, 1H), 8.43 (s, 1H), 8.24 (s, 1H), 7.34 (d, JH-H = 4.5 Hz, 1H), 7.17 (d, JH-H = 4.5 Hz, 1H), 4.47 (s, 2H), 2.45 (s, 3H).
[실시예 11] 4,4'-비스브로모메틸-2,2'-바이피리딘의 합성Example 11 Synthesis of 4,4'-bisbromomethyl-2,2'-bipyridine
이 화합물은 기존 문헌(Inorg. Chem. 1991, 30, 2942)의 합성 방법을 이용하였다. 1H NMR (CDCl3): 8.67 (d, JH-H = 4.5 Hz, 2H), 8.43 (s, 2H), 7.36 (d, JH-H = 4.5 Hz, 2H), 4.48 (s, 4H).
This compound used the synthesis method of the existing literature ( Inorg. Chem. 1991, 30 , 2942). 1 H NMR (CDCl 3 ): 8.67 (d, JH-H = 4.5 Hz, 2H), 8.43 (s, 2H), 7.36 (d, JH-H = 4.5 Hz, 2H), 4.48 (s, 4H).
[실시예 12] 4-다이에틸포스포노메틸-4'-메틸-2,2'-바이피리딘("화학식 4의 화합물")의 합성Example 12 Synthesis of 4-diethylphosphonomethyl-4'-methyl-2,2'-bipyridine ("Compound of Formula 4")
실시예 10의 화합물 (2 g, 7.60 mmol)과 과량의 트라이에틸포스파이트(5 mL, 0.29 mol)의 혼합 용액을 6시간 동안 80 ℃ 조건하에서 교반시켰다. 그 이후 상온까지 온도를 내린 후 진공 조건하에서 과량의 트라이에틸포스파이트를 제거하였다. 오일성의 잔유물을 칼럼 크로마토그래피하여 옅은 노란색의 표제 화합물을 얻었다. 1H NMR (CDCl3): 8.60 (d, JH-H = 4.5 Hz, 1H), 8.52 (d, JH-H = 4.5 Hz, 1H), 8.32 (s, 1H), 8.22 (s, 1H), 7.31 (d, JH-H = 5.4 Hz, 1H), 7.12 (d, JH-H = 5.4 Hz, 1H), 4.06 (dq, 3JH-P= 7.2 Hz, 4H), 3.22 (d, 2JH-P = 21.3 Hz, 2H), 2.43 (s, 3H), 1.26 (t, 3JH-H = 7.2 Hz, 6H).
A mixed solution of the compound of Example 10 (2 g, 7.60 mmol) and excess triethylphosphite (5 mL, 0.29 mol) was stirred under 80 ° C. conditions for 6 hours. Thereafter, after cooling to room temperature, excess triethylphosphite was removed under vacuum conditions. The oily residue was column chromatographed to give the title compound as pale yellow. 1 H NMR (CDCl 3 ): 8.60 (d, JH-H = 4.5 Hz, 1H), 8.52 (d, JH-H = 4.5 Hz, 1H), 8.32 (s, 1H), 8.22 (s, 1H), 7.31 (d, JH-H = 5.4 Hz, 1H), 7.12 (d, JH-H = 5.4 Hz, 1H), 4.06 (dq, 3 JH-P = 7.2 Hz, 4H), 3.22 (d, 2 JH-P = 21.3 Hz, 2H), 2.43 (s, 3 H), 1.26 (t, 3 JH-H = 7.2 Hz, 6H).
[[
실시예Example
13] 4,4'- 13] 4,4'-
비스Vis
((
다이에틸포스포노메틸Diethylphosphonomethyl
)-2,2'-) -2,2'-
바이피리딘("화학식 4-1의 화합물)의Of bipyridine (a compound of Formula 4-1)
합성 synthesis
상기 [실시예 12]에서 실시예 10의 화합물 대신 실시예 11의 화합물화합물을 사용하여 합성하였다. 1H NMR (CDCl3): 8.60 (d, JH-H = 5.1 Hz, 2H), 8.33 (s, 2H), 7.32 (d, JH-H = 5.1 Hz, 2H), 4.07 (dq, 3JH-P = 11.4Hz,3JH-H = 7.2 Hz, 8H), 3.23 (d, 2JH-P = 22.2 Hz, 4H), 1.27 (t, 3JH-H = 7.2 Hz, 12H).In Example 12, the compound of Example 11 was used instead of the compound of Example 10. 1 H NMR (CDCl 3 ): 8.60 (d, JH-H = 5.1 Hz, 2H), 8.33 (s, 2H), 7.32 (d, JH-H = 5.1 Hz, 2H), 4.07 (dq, 3 JH-P = 11.4 Hz, 3 JH- H = 7.2 Hz, 8H), 3.23 (d, 2 JH-P = 22.2 Hz, 4H), 1.27 (t, 3 JH-H = 7.2 Hz, 12H).
[실시예 14] (E)-2',7'-디-터트-부틸-N-(2',7'-디-터트-부틸-9,9'-스파이로바이[플루오렌]-3-일)-N-(4-(2-(4'-메틸-2,2'-바이피리딘-4-일)비닐)페닐)-9,9'-스파이로바이[플루오렌]-2-아민("화학식 5의 화합물")의 합성Example 14 (E) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobia [fluorene] -3 -Yl) -N- (4- (2- (4'-methyl-2,2'-bipyridin-4-yl) vinyl) phenyl) -9,9'-spirobiby [fluorene] -2- Synthesis of Amine ("Compound of Formula 5")
화학식 3의 화합물 (1.37 g, 1.41 mmol)과 화학식 4의 화합물 (0.45 g, 1.41 mmol)이 용해된 THF 용액(30 mL)에 포타슘 t-부톡사이드 (0.16 g, 1.41 mmol)를 적가한 후 상온에서 10시간 동안 교반하였다. 그 후 물 10mL를 적가한 후 THF만 진공상태에서 건조하고 다이클로로메탄으로 추출한 후 다이클로로메탄/헥산으로 재결정하여 표제 화합물을 얻었다.
Potassium t -butoxide (0.16 g, 1.41 mmol) was added dropwise to a THF solution (30 mL) in which a compound of Formula 3 (1.37 g, 1.41 mmol) and a compound of Formula 4 (0.45 g, 1.41 mmol) were dissolved. Stirred for 10 h. Thereafter, 10 mL of water was added dropwise, only THF was dried in vacuo, extracted with dichloromethane, and recrystallized with dichloromethane / hexane to obtain the title compound.
[실시예 15] (E)-2',7'-디-터트-부틸-N-(2',7'-디-터트-부틸-9,9'-스파이로바이[플루오렌]-3-일)-N-(4-(3-헥실-5-(2-(4'-메틸-2,2'-바이피리딘-4-일)비닐)티오펜-2-일)페닐)-9,9'-스파이로바이[플루오렌]-2-아민("화학식 12의 화합물")의 합성Example 15 (E) -2 ', 7'-di-tert-butyl-N- (2', 7'-di-tert-butyl-9,9'-spirobi [fluorene] -3 -Yl) -N- (4- (3-hexyl-5- (2- (4'-methyl-2,2'-bipyridin-4-yl) vinyl) thiophen-2-yl) phenyl) -9 Synthesis of 9'-Spyrobi [fluorene] -2-amine (“Compound 12”)
상기 [실시예 14]에서 화학식 3의 화합물 대신 화학식 11의 화합물 (1.49 g, 1.41 mmol)을 사용하여 화학식 12의 화합물을 얻었다.The compound of Formula 12 was obtained by using the compound of Formula 11 (1.49 g, 1.41 mmol) instead of the compound of Formula 3 in [Example 14].
[화학식 12][Formula 12]
[실시예 16] 화학식 5-1의 화합물의 합성Example 16 Synthesis of Compound of Formula 5-1
상기 [실시예 14]에서 화학식 4의 화합물 대신 화학식 4-1의 화합물 (0.65 g, 1.41 mmol)과 포타슘 t-부톡사이드 (0.32 g, 1.41 mmol)을 사용하여 화학식 5-1의 화합물을 얻었다.In Example 14, the compound of Formula 4-1 was obtained by using the compound of Formula 4-1 (0.65 g, 1.41 mmol) and potassium t-butoxide (0.32 g, 1.41 mmol) instead of the compound of Formula 4.
[화학식 5-1][Formula 5-1]
[실시예 17] 화학식 12-1의 화합물의 합성Example 17 Synthesis of Compound of Formula 12-1
상기 [실시예 14]에서 화학식 3의 화합물 대신 화학식 11의 화합물 (1.49 g, 1.41 mmol)을, 화학식 4의 화합물 대신 화학식 4-1의 화합물 (0.65 g, 1.41 mmol)을, 그리고 포타슘 t-부톡사이드 (0.32 g, 1.41 mmol)을 사용하여 화학식 12-1의 화합물을 얻었다.In Example 14, the compound of Formula 11 (1.49 g, 1.41 mmol) instead of the compound of Formula 3, the compound of Formula 4-1 (0.65 g, 1.41 mmol) instead of the compound of Formula 4, and potassium t-butoxide Side (0.32 g, 1.41 mmol) was used to give the compound of Formula 12-1.
[화학식 12-1]
[Formula 12-1]
[실시예 18] 화학식 1a의 화합물의 합성Example 18 Synthesis of Compound of Formula 1a
화학식 5의 화합물 (0.45 g, 0.40 mmol)과 다이클로로(p-사이멘)루테늄(II) 다이머("화학식 6의 화합물", 0.12 g, 0.20 mmol)를 DMF로 녹이고 그 용액을 80 ℃에서 4시간 동안 교반하였다. 4,4'-다이카복실산-2,2'-바이피리딘("화학식 7의 화합물", 0.097 g, 0.40 mmol)을 적가한 후 160 ℃에서 4시간 동안 교반하였다. 다시 이 용액에 암모늄사이오시아네이트("화학식 9의 화합물", 0.91, 11.96 mmol)를 넣고 130 ℃에서 4시간 동안 교반 후 진공 하에서 용매를 건조하고 물(200 mL)을 넣고 화합물을 침전시켰다. 거름종이를 이용하여 침전물을 거르고 대기 중에서 건조시켰다. 이 침전물을 다시 메탄올에 녹인 테트라부틸암모늄 하이드록사이드 1.2 mmol을 적가하여 녹이고, 녹인 용액은 Sephadex LH-20을 이용하여 메탄올로 칼럼 크로마토그래피로 분리하였다. 분리한 염료 용액은 묽은 질산 용액을 첨가하여 다시 염료 침전물을 얻은 후 거름종이로 분리하여, 진한 보라색 분말의 표제 화합물을 얻었다. Dissolve the compound of formula 5 (0.45 g, 0.40 mmol) and dichloro ( p -cymene) ruthenium (II) dimer ("compound of formula 6", 0.12 g, 0.20 mmol) in DMF and the solution at 80 ° C. Stir for hours. 4,4'-dicarboxylic acid-2,2'-bipyridine ("Compound of formula 7", 0.097 g, 0.40 mmol) was added dropwise and stirred at 160 ° C. for 4 hours. In this solution, ammonium cyocyanate (“Compound 9”, 0.91, 11.96 mmol) was added thereto, stirred at 130 ° C. for 4 hours, and then dried under vacuum, water (200 mL) was added, and the compound was precipitated. The precipitate was filtered using filter paper and dried in air. This precipitate was dissolved by dropwise addition of 1.2 mmol of tetrabutylammonium hydroxide dissolved in methanol, and the dissolved solution was separated by column chromatography with methanol using Sephadex LH-20. The separated dye solution was added with a dilute nitric acid solution to obtain a dye precipitate, and then separated by a filter paper to obtain the title compound as a dark purple powder.
[화학식 1a][Formula 1a]
MS: m/z 1602[M+]. Anal. Calcd for C99H85N7O4RuS2: C, 74.22; H, 5.35 ; N, 6.12 ; O, 3.99 ; Ru, 6.31 ; S, 4.00. Found: C, 74.07; H, 5.34 ; N, 6.11 ; O, 3.98 ; Ru, 6.30 ; S, 3.99.
MS: m / z 1602 [M < + >]. Anal. Calcd for C 99 H 85 N 7 O 4 RuS 2 : C, 74.22; H, 5. 35; N, 6. 12; 0, 3.99; Ru, 6.31; S, 4.00. Found: C, 74.07; H, 5. 34; N, 6.11; 0, 3.98; Ru, 6.30; S, 3.99.
[실시예 19] 화학식 1b의 화합물의 합성Example 19 Synthesis of Compound of Formula 1b
상기 [실시예 18]에서 화학식 5의 화합물 대신 화학식 12의 화합물 (0.52 g, 0.40 mmol)을 사용하여 표제 화합물을 얻었다.In Example 18, the title compound was obtained using the compound of Formula 12 (0.52 g, 0.40 mmol) instead of the compound of Formula 5.
[화학식 1b][Chemical Formula 1b]
MS: m/z 1767[M+]. Anal. Calcd for C109H99N7O4RuS3: C, 74.04; H, 5.64 ; N, 5.54 ; O, 3.62 ; Ru, 5.72 ; S, 5.44. Found: C, 73.89; H, 5.63 ; N, 5.53 ; O, 3.61 ; Ru, 5.71 ; S, 5.43.
MS: m / z 1767 [M < + >]. Anal. Calcd for C 109 H 99 N 7 O 4 RuS 3 : C, 74.04; H, 5. 64; N, 5.54; 0, 3.62; Ru, 5.72; S, 5.44. Found: C, 73.89; H, 5.63; N, 5.53; 0, 3.61; Ru, 5.71; S, 5.43.
[실시예 20] 화학식 1c의 화합물의 합성Example 20 Synthesis of Compound of Formula 1c
상기 [실시예 18]에서 화학식 5의 화합물 대신 화학식 5-1의 화합물 (0.84 g, 0.40 mmol)을 사용하여 표제 화합물을 얻었다.In Example 18, the title compound was obtained using the compound of Formula 5-1 (0.84 g, 0.40 mmol) instead of the compound of Formula 5.
[화학식 1c][Formula 1c]
MS: m/z 2558[M+]. Anal. Calcd for C172H150N8O4RuS2: C, 80.75 ; H, 5.91 ; N, 4.38 ; O, 2.50 ; Ru, 3.95 ; S, 2.51. Found: C, 80.59; H, 5.90 ; N, 4.37 ; O, 2.49 ; Ru, 3.95 ; S, 2.50.
MS: m / z 2558 [M < + >]. Anal. Calcd for C 172 H 150 N 8 O 4 RuS 2 : C, 80.75; H, 5.91; N, 4.38; 0, 2.50; Ru, 3.95; S, 2.51. Found: C, 80.59; H, 5. 90; N, 4.37; 0, 2.49; Ru, 3.95; S, 2.50.
[실시예 21] 화학식 1d의 화합물의 합성Example 21 Synthesis of Compound of Formula 1d
상기 [실시예 18]에서 화학식 5의 화합물 대신 화학식 12-1의 화합물 (0.97 g, 0.40 mmol)을 사용하여 표제 화합물을 얻었다.In Example 18, the title compound was obtained using the compound of Formula 12-1 (0.97 g, 0.40 mmol) instead of the compound of Formula 5.
[화학식 1d]≪ RTI ID = 0.0 &
MS: m/z 2891[M+]. Anal. Calcd for C192H178N8O4RuS4: C, 79.77 ; H, 6.21 ; N, 3.88 ; O, 2.21 ; Ru, 3.50 ; S, 4.44. Found: C, 79.61; H, 6.20 ; N, 3.87 ; O, 2.20 ; Ru, 3.49 ; S, 4.43.
MS: m / z 2891 [M < + >]. Anal. Calcd for C 192 H 178 N 8 O 4 RuS 4 : C, 79.77; H, 6. 21; N, 3.88; 0, 2.21; Ru, 3.50; S, 4.44. Found: C, 79.61; H, 6. 20; N, 3.87; 0, 2.20; Ru, 3.49; S, 4.43.
실험: 염료감응태양전지의 제조 및 물성 측정Experiment: Preparation and Measurement of Dye-Sensitized Solar Cell
염료 화합물의 전류-전압 특성을 평가하기 위해 12 ㎛ TiO2 투명층을 이용하여 태양전지를 제조하였다. TiO2 페이스트(Solaronix, 13 nm 페이스트)를 스크린 프린팅하여 8 ㎛ 두께의 TiO2 투명층을 제조하였다. 이 TiO2 필름을 40 mM TiCl4 용액으로 처리하고 500 ℃에서 30분간 건조하였다. 처리된 필름을 60 ℃로 냉각한 후, 본 발명의 실시예에서 제조된 염료 화합물 1a, 1b, 1c 및 1d 각각을 디메틸포름아미드 용액에 함침시켰다. 참조(Reference)로서 N3의 에탄올 용액을 사용하였다. 염료-흡착된 TiO2 전극과 백금-대전극 사이에 스페이서로서 고온용융 필름(Surlyn 1702, 25 ㎛ 두께)을 놓고 가열하여 밀봉된 샌드위치 전지를 조합하였다. 전해질 용액으로는 아세토니트릴 중에 0.6 M 3-헥실-1,2-디메틸이미다졸리움 요오드, 0.04 M I2, 0.025 M GSCn 및 0.28 M tert-부틸피리딘을 용해시킨 것을 사용하였다.In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured using a 12 μm TiO 2 transparent layer. A TiO 2 paste (Solaronix, 13 nm paste) was screen printed to produce an 8 μm thick TiO 2 transparent layer. This TiO 2 film was treated with 40 mM TiCl 4 solution and dried at 500 ° C. for 30 minutes. After the treated film was cooled to 60 ° C., each of the dye compounds 1a, 1b, 1c and 1d prepared in the Examples of the present invention was impregnated with the dimethylformamide solution. As reference, an ethanol solution of N3 was used. A sealed sandwich cell was assembled by heating a hot melt film (Surlyn 1702, 25 μm thick) as a spacer between the dye-adsorbed TiO 2 electrode and the platinum-electrode. As the electrolyte solution, a solution of 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI 2 , 0.025 M GSCn and 0.28 M tert -butylpyridine was dissolved in acetonitrile.
참조 화합물로서 사용된 N3는 종래 염료감응태양전지에 사용되는 루테늄계 촉매로 하기와 같은 구조를 갖는다.N3 used as a reference compound is a ruthenium-based catalyst used in conventional dye-sensitized solar cells and has a structure as follows.
[염료 N3][Dye N3]
태양전지의 광전자화학특성을 측정하여 하기 표 1에 나타내었다. The photoelectrochemical properties of the solar cell were measured and shown in Table 1 below.
상기 표 1에서, Jsc는 단회로 광전류 밀도(short-circuit photocurrent density), Voc는 오픈 회로 광전압(open circuit photovoltage), FF는 충전 인자(fill factor)를 나타내며, 상기 표 1에 나타난 바와 같이 본 발명의 염료는 염료감응태양전지의 염료로서 유효하게 사용할 수 있음을 확인할 수 있으며, 성능에 있어서도 우수한 것을 확인할 수 있다.In Table 1, J sc is a short-circuit photocurrent density, V oc is an open circuit photovoltage, FF is a fill factor, as shown in Table 1 Likewise, it can be confirmed that the dye of the present invention can be effectively used as a dye of a dye-sensitized solar cell, and it can be confirmed that it is also excellent in performance.
Claims (9)
[화학식 1]
상기 식에서,
a1 환은 하나 이상의 치환기를 가질 수 있으며, 치환기는 할로겐, 아미드, 시아노, 하이드록시, 니트로, C1-20 알킬, C1-20 알콕시 또는 아실일 수 있고;
A 및 B는 각각 독립적으로 수소 또는
Ar1 및 Ar2는 각각 독립적으로 C6-30 아릴 또는 스파이로바이플루오레닐이고, Ar1 및 Ar2 둘 중 적어도 하나는 스파이로바이플루오레닐이며, 상기 Ar1 및 Ar2는 하나 이상의 하이드록시, 할로겐, 니트로, C1-12 알킬 또는 C1-12 알콕시로 치환될 수 있고;
X는 하나 이상의 하이드록시, 할로겐, 니트로, C1-12 알킬 또는 C1-12 알콕시로 치환되거나 치환되지 않은 페닐렌이고;
Y는 하나 이상의 하이드록시, 할로겐, 니트로, C1-12 알킬 또는 C1-12 알콕시로 치환되거나 치환되지 않은 티오펜이거나, 또는 연결선이다.Ruthenium-based dyes represented by Formula 1 below:
[Formula 1]
Where
the a1 ring may have one or more substituents and the substituents may be halogen, amide, cyano, hydroxy, nitro, C 1-20 alkyl, C 1-20 alkoxy or acyl;
A and B are each independently hydrogen or
And Ar 1 and Ar 2 are each independently a C 6-30 aryl-by-fluorenyl or spy, Ar 1 and Ar 2, at least one of the two is a by-fluorenyl a spy, the Ar 1 and Ar 2 is one or more May be substituted with hydroxy, halogen, nitro, C 1-12 alkyl or C 1-12 alkoxy;
X is phenylene unsubstituted or substituted with one or more hydroxy, halogen, nitro, C 1-12 alkyl or C 1-12 alkoxy;
Y is thiophene substituted or unsubstituted with one or more hydroxy, halogen, nitro, C 1-12 alkyl or C 1-12 alkoxy, or is a connecting line.
상기 염료가 하기 구조들 중 하나로 표시되는 특징으로 하는, 루테늄계 염료:
A ruthenium-based dye, wherein the dye is represented by one of the following structures:
(ii) 화학식 3의 화합물을 하기 화학식 4 또는 화학식 4-1과 반응시켜 하기 화학식 5의 화합물을 제조하고,
(ⅲ) 화학식 5의 화합물을 화학식 6; 화학식 7; 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 포함하는 상기 화학식 1로 표시되는 염료의 제조방법을 제공한다:
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 4-1]
[화학식 5]
[화학식 6]
[화학식 7]
[화학식 8]
상기 화학식 2-8에서 Ar1, Ar2, X 및 Y는 상기 청구항 제1항의 화학식 1에서 정의한 바와 같다.(i) preparing a compound represented by the following Chemical Formula 3 by lithiation of the compound represented by the following Chemical Formula 2 with n-butyllithium and subsequently reacted with dimethylformamide;
(ii) reacting a compound of formula 3 with formula 4 or formula 4-1 to prepare a compound of formula 5
(Iii) a compound of Formula 5 is represented by Formula 6; Formula 7; And it provides a method for producing a dye represented by the formula (1) comprising sequentially reacting with a compound of formula (8):
(2)
(3)
[Chemical Formula 4]
[Formula 4-1]
[Chemical Formula 5]
[Formula 6]
[Formula 7]
[Chemical Formula 8]
Ar 1 , Ar 2 , X and Y in Chemical Formula 2-8 are as defined in Chemical Formula 1 of claim 1.
포섭화합물의 존재 하에서, 상기 산화물 반도체 미립자에 루테늄계 염료를 담지시키는 것을 특징으로 하는 염료증감 광전변환소자.The method of claim 4, wherein
A dye-sensitized photoelectric conversion device characterized in that a ruthenium-based dye is supported on the oxide semiconductor fine particles in the presence of an inclusion compound.
상기 산화물 반도체 미립자가 이산화티탄을 필수성분으로 포함하는 것을 특징으로 하는 염료증감 광전변환소자.The method of claim 4, wherein
Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide as an essential component.
상기 산화물 반도체 미립자가 평균 입경이 1 ∼ 500 nm인 것을 특징으로 하는 염료증감 광전변환소자.The method of claim 4, wherein
Dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles have an average particle diameter of 1 to 500 nm.
상기 염료감응태양전지가, 전도성 투명 기판 위에 산화티타늄 페이스트를 코팅하는 단계, 페이스트가 코팅된 기판을 소성하여 산화티타늄 박막을 형성하는 단계, 산화티타늄 박막이 형성된 기판을 화학식 1로 표시되는 염료가 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 필름 전극을 접합시키는 단계, 상기 홀을 통하여 대전극과 산화티타늄 필름 전극 사이의 열가소성 고분자 필름에 전해질을 주입하는 단계, 및 상기 열가소성 고분자를 실링하는 단계를 통하여 제조되는 것을 특징으로 하는 염료감응태양전지.The method of claim 8,
Wherein the dye-sensitized solar cell, coating a titanium oxide paste on a conductive transparent substrate, baking the paste-coated substrate to form a titanium oxide thin film, the dye represented by the formula (1) is dissolved in a substrate formed with a titanium oxide thin film Impregnating the mixed solution to form a titanium oxide film electrode on which dye is adsorbed, providing a second glass substrate having a counter electrode formed thereon, a hole penetrating the second glass substrate and the counter electrode. Forming 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 to bond the counter electrode and the titanium oxide film electrode to each other; Injecting an electrolyte into the thermoplastic polymer film between the pole and the titanium oxide film electrode, and the thermoplastic polymer The dye-sensitized solar cell, characterized in that is produced through the step of sealing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101407894B1 (en) * | 2013-02-25 | 2014-06-17 | 한국에너지기술연구원 | Dye solar cell with chemically bonded co-adsorbent and method of manufacturing the same |
| WO2016031406A1 (en) * | 2014-08-27 | 2016-03-03 | 富士フイルム株式会社 | Compound, composition, film and optical device |
| EP3309804A4 (en) * | 2015-06-11 | 2018-06-27 | Fujifilm Corporation | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution and oxide semiconductor electrode |
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2010
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101407894B1 (en) * | 2013-02-25 | 2014-06-17 | 한국에너지기술연구원 | Dye solar cell with chemically bonded co-adsorbent and method of manufacturing the same |
| WO2016031406A1 (en) * | 2014-08-27 | 2016-03-03 | 富士フイルム株式会社 | Compound, composition, film and optical device |
| JPWO2016031406A1 (en) * | 2014-08-27 | 2017-06-29 | 富士フイルム株式会社 | Compound, composition, film, optical instrument |
| EP3309804A4 (en) * | 2015-06-11 | 2018-06-27 | Fujifilm Corporation | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution and oxide semiconductor electrode |
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