WO2008146971A1 - Novel julolidine-based dye and preparation thereof - Google Patents
Novel julolidine-based dye and preparation thereof Download PDFInfo
- Publication number
- WO2008146971A1 WO2008146971A1 PCT/KR2007/003038 KR2007003038W WO2008146971A1 WO 2008146971 A1 WO2008146971 A1 WO 2008146971A1 KR 2007003038 W KR2007003038 W KR 2007003038W WO 2008146971 A1 WO2008146971 A1 WO 2008146971A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dye
- formula
- compound
- julolidine
- photoelectric conversion
- Prior art date
Links
- DZFWNZJKBJOGFQ-UHFFFAOYSA-N julolidine Chemical compound C1CCC2=CC=CC3=C2N1CCC3 DZFWNZJKBJOGFQ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- 239000010409 thin film Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000010408 film Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 87
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000000862 absorption spectrum Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- -1 itrium Chemical compound 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical group 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000012327 Ruthenium complex Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 4
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229940125890 compound Ia Drugs 0.000 description 4
- 239000000434 metal complex dye Substances 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- YFTHTJAPODJVSL-UHFFFAOYSA-N 2-(1-benzothiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(SC=C2)C2=C1 YFTHTJAPODJVSL-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000001815 facial effect Effects 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
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WADWZNSXIVNIAC-UHFFFAOYSA-N 3-methoxy-1,3-oxazolidin-2-one Chemical compound CON1CCOC1=O WADWZNSXIVNIAC-UHFFFAOYSA-N 0.000 description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229940125907 SJ995973 Drugs 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
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- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- XZMHJYWMCRQSSI-UHFFFAOYSA-N n-[5-[2-(3-acetylanilino)-1,3-thiazol-4-yl]-4-methyl-1,3-thiazol-2-yl]benzamide Chemical compound CC(=O)C1=CC=CC(NC=2SC=C(N=2)C2=C(N=C(NC(=O)C=3C=CC=CC=3)S2)C)=C1 XZMHJYWMCRQSSI-UHFFFAOYSA-N 0.000 description 2
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 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
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- 239000003381 stabilizer Substances 0.000 description 2
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- 239000011135 tin Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
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- DLYVTEULDNMQAR-UHFFFAOYSA-N Methylallocholat Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(=O)OC)C1(C)C(O)C2 DLYVTEULDNMQAR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910010165 TiCu Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 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 1
- 229960002471 cholic acid Drugs 0.000 description 1
- 235000019416 cholic acid Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000004696 coordination complex Chemical class 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
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002190 incident photon conversion efficiency spectrum Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method 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
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material 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
- 230000036962 time dependent Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 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
-
- 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
-
- 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
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
-
- 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
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
- C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
-
- 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
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- each Ri and R2 is independently hydrogen, Ci-12 alkyl or
- the present invention provides a dye-sensitized solar cell comprising said dye-sensitized photoelectric conversion element.
- a dye-sensitized solar cell prepared by supporting, on oxide semiconductor particles, a compounds of the Formula 1, which has a novel organic dye structure of using julolidine as an electron donor, introducing bithiophene unit in the middle linking part for increasing molar absorptivity and stability of the element, and using cyanoacrylic acid which is closely connected with Ti ⁇ 2 reforming and has the best electron transport capacity as an electron acceptor, has high photoelectric conversion efficiency, Jsc(short circuit photocurrent density) and molar absorptivity, and thus has superior efficiency to the existing dye-sensitized solar cells, and completed the present invention.
- the method for supporting dye on the oxide semiconductor thin film is not specifically limited in the present invention.
- a substrate on which the oxide semiconductor thin film is formed can be immersed in a solution obtained by dissolving the dye of the Formula 1 in a solvent capable of dissolving it, or in a dispersion obtained by dispersing the dye.
- concentration of the dye in the solution or dispersion can be appropriately determined according to the dye.
- the immersion temperature is generally from a room temperature to a boiling point of the solvent, and the immersion time is from about 1 minute to 48 hours.
- the solvent for dissolving the dye includes methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, acetone, t-butanol, etc.
- the electrode surface of the semiconductor can be treated with amine compound such as pyridine, etc., or compounds having acid group such as acetic acid, propionic acid, etc.
- amine compound such as pyridine, etc.
- compounds having acid group such as acetic acid, propionic acid, etc.
- a substrate on which a dye-supported semiconductor thin film is formed can be immersed in an ethanol solution of amine.
- the present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention.
- the dye-sensitized solar cell may consist of a photoelectric conversion element electrode(anode), a counter electrode(cathode), redox electrolyte, hole transport material or p-type semiconductor, etc.
- the hole transport material those using discotic liquid crystal phase such as amine derivatives, conductive polymer such as polyacetylene, polyaniline, polythiophene, etc., or triphenylene- based compounds can be used.
- conductive polymer such as polyacetylene, polyaniline, polythiophene, etc.
- triphenylene- based compounds can be used.
- the p-type semiconductor CuI, CuSCN, etc. can be used.
- the counter electrode preferably has conductivity, and functions as a catalyst for the reduction of oxidation-reduction electrolyte.
- those prepared by depositing platinum, carbon, rhodium, ruthenium, etc. on a glass or polymer film, or by coating conductive particles on a glass or polymer film can be used.
- halogen molecule for the halogen redox electrolyte iodine molecule is preferably used.
- halogen compound halogenated metal salt such as LiI, NaI, KI, Cal2, Mgl 2 , CuI, etc., or organic ammonium salt of halogen such as tetraalkyl ammonium iodide, imidazolium iodide, pyridium iodide, etc., or I2 can be used.
- the treated film was cooled to 60 " C, and then impregnated with each solution of the dye compounds Ia to Ic of the present invention which were prepared in the above steps VIII) to X) (0.3 mM dye in ethanol containing 10 mM kenodioxycholic acid).
- a high temperature melting film (Surlyn 1702, 25 ⁇ m thickness) was placed as a spacer between the dye-absorbed Ti ⁇ 2 electrode and a platinum- counter electrode, and heated to prepare a sealed sandwich cell.
- the graphs as shown in Fig. 1 indicate that the absorption spectrum of the compound Ib was blue shifted, and the absorption spectrum of the compound Ic was red shifted, compared to the absorption spectrum of the compound Ia.
Abstract
The present invention relates to novel julolidine-based dye and preparation thereof. The dye compound of the present invention which comprises julolidine as an electron donor, a bithiophene unit as a middle linking part, and cyanoacrylic acid as an electron acceptor can be used for a dye-sensitized solar cell (DSSC). The dye of the present invention shows improved molar absorptivity, Jsc(short circuit photocurrent density) and photoelectric conversion efficiency, compared to dyes of the prior art, and thus it can greatly improve solar cell efficiency. And, it can dramatically decrease dye synthesis cost because the dye of the present invention can be purified without using expensive columns.
Description
NOVEL JULOLIDINE-BASED DYE AND PREPARATION THEREOF
[Technical Field]
The present invention relates to novel julolidine-based dye comprising a bithiophene derivative, used for a dye-sensitized solar cell (DSSC), and a process for preparing the same. [Background Art]
Many studies regarding a dye-sensitized nanoparticle titanium oxide solar cell have been progressed since it was developed by Swiss Federal Institute of Technology Lausanne (EPFL), Michael Gratzel et al . on the year 1991. Because a dye-sensitized solar cell has higher efficiency and lower manufacture cost than the existing silicone- based solar cell, it can replace the existing amorphous silicone- based solar cell. And, differently from the si Iicone-based solar cell, the dye-sensitized solar cell is a photoelectrochemical solar cell essentially consisting of a dye molecule capable of absorbing a visible ray and generating electron-hole pair and a transition metal oxide for transmitting the generated electrons.
As the dye for a dye-sensitized solar cell, ruthenium complex having high photoelectric conversion efficiency has been widely used. However, the ruthenium complex had a defect of high cost.
Recently, it has been discovered that metal-free organic dye, which has excellent properties in terms of an absorption efficiency, oxidation-reduction stability and charge-transfer(CT) absorption in a molecule, can be used as the dye for a solar cell instead of the expensive ruthenium complex. Thus, studies focus on the metal-free organic dye. In general, the organic dye has a structure consisting of an electron donor - electron acceptor moieties which are linked by π- bond. For most organic dyes, an amine derivative functions as an electron donor, 2-cyanoacrylic acid or rhodanine moiety functions as an electron acceptor, and the two parts are linked by a π-bond system such as methaine unit or thiophene chain.
In general, the structural change of electron donor amine causes a change in electron' s properties, for example, a blue-shifted absorption spectrum, and causes a change in the π-bond length thus controlling absorption spectrum and redox potential.
However, most organic dyes so far known show lower conversion efficiencies and lower operation stability, compared to ruthenium complex dyes. Thus, there are continued efforts for developing novel dyes showing improved molar absorptivity and high photoelectric conversion efficiency compared to the existing organic dye compounds by changing the kinds of electron donor and acceptor or π-bond length. [Disclosure] [Technical Problem] Accordingly, it is an object of the present invention to provide organic dyes showing improved molar absorptivity and photoelectric conversion efficiency compared to metal complex dyes of the prior art, thus capable of largely improving the efficiency of solar cells, and a process for preparing the same. It is another object of the present invention to provide a dye- sensitized photoelectric conversion element comprising the dye of the present invention thus showing remarkably improved photoelectric conversion efficiency and having excellent Jsc(short circuit
photocurrent density) and molar absorptivity, and a solar cell having remarkably improved efficiency. [Technical Solution]
In order to achieve said objects, the present invention provides julolidine-based dye of the following Formula !'■ [Formula 1]
Ci-12 alkoxy, and when Ri or R2 is Ci-12 alkoxy, they may be bonded to each other to form an oxygen-containing heterocycle; n is an integer of 2 to 5, and two or more thiophene units can be optionally linked by a vinyl group.
Also, the present invention provides a process for preparing the julolidine-based dye having the Formula 1, comprising the steps of:
(1) subjecting bromojulolidine to a Suzuki coupling reaction with a compound of the following Formula 2 to form a compound of the following Formula 3;
(2) lithiating the compound of the Formula 3 with n-butyl lithium, and then continuously cooling it with dimethylformamide to form a compound of the following Formula 4:
(3) reacting the compound of the Formula 4 with cyanoacetic acid in CH3CN in the presence of piperidine:
[Formula 2]
[Formula 3]
Also, the present invention provides a dye-sensitized photoelectric conversion element comprising oxide semiconductor particles where the julolidine-based dye of the above Formula 1 is supported.
Also, the present invention provides a dye-sensitized solar cell comprising said dye-sensitized photoelectric conversion element. [Advantageous Effects]
The novel julolidine-based dye of the present invention shows improved molar absorptivity, Jsc(short circuit photocurrent density) and photoelectric conversion efficiency compared to dyes of the prior art, and thus it can greatly improve solar cell efficiency. And, it
can dramatically decrease dye synthesis cost because the dye of the present invention can be purified without using expensive columns. [Description of Drawings]
Fig. 1 shows absorption and emission spectrums of each of the dye compounds Ia to Ic of the present invention in ethanol , and emission spectrums of the dye compounds supported on ΗO2 layer.
Fig. 2 (a), (b) and (c) are diagrams respectively showing the optimized structure of each of the dye compounds Ia to Ic of the present invention (TD-DFT (time-dependent density functional theory) computation at B3LYP/3-21G) .
Fig. 3 (a) and (b) are diagrams respectively showing the geometrical structure of each of the dye compounds Ia to Ic of the present invention (HOMO and LUMO molecular orbitals, TD-DFT computation at B3LYP/3-21G) . Fig. 4 shows IPCE(incident photon-to-current conversion efficiency) spectrums of the solar cells respectively prepared using each of the dye compounds Ia to Ic of the present invention.
Fig. 5 shows photocurrent voltage curves of the solar cell respectively prepared using each of the dye compounds Ia to Ic of the present invention (under AM 1.5 radiation).
[Mode for Invention] The present invention will now be explained in detail.
The present inventors have discovered that a dye-sensitized solar cell prepared by supporting, on oxide semiconductor particles, a compounds of the Formula 1, which has a novel organic dye structure of using julolidine as an electron donor, introducing bithiophene unit in the middle linking part for increasing molar absorptivity and stability of the element, and using cyanoacrylic acid which is closely connected with Tiθ2 reforming and has the best electron transport capacity as an electron acceptor, has high photoelectric conversion efficiency, Jsc(short circuit photocurrent density) and molar absorptivity, and thus has superior efficiency to the existing dye-sensitized solar cells, and completed the present invention.
The julolidine-based organic dye of the present invention has the following Formula 1, and preferably one of the following Formulas Ia to Ic.
[Formula 1]
[Formula Ia]
[Formula Ib]
[Formula Ic]
The dye of the above Formula 1 can be prepared by the process comprising the steps of:
(1) subjecting bromojulolidine to a Suzuki coupling reaction with a compound of the following Formula 2 (1.2 equivalent) to form a compound of the following Formula 3;
(2) lithiating the compound of the Formula 3 with n- butyllithium(1.2 equivalent), and then continuously cooling it with dimethylformamide to form a compound of the following Formula 4; and
(3) reacting the compound of the Formula 4 with cyanoacetic acid in CH3CN in the presence of piperidine (see the reaction Formula 1).
[Formula 2]
[Formula 3]
[Formula 4]
[Reaction Formula 1]
2a R1=H, R2=H 3a R1=H, R2=H 2b R1=H, R2=CH3 3b R1=H, R2=CH3 2CR1-OCH2CH2O-R2 3c R1-OCH2CH2O-R2
4a R1=H, R2=H 1a R1=H, R2=H 4b R1=H, R2=CH3 1b R1=H1 R2=CH3 4c R1-OCH2CH2O-R2 1o R1-OCH2CH2O-R2
wherein, each Ri, R2 and n has the same meaning as defined above. In the Reaction Formula 1, the bromojulolidine used as starting material for the preparation of the dye of the Formula 1 can be obtained by bromination of julol idine with NBS in CHCI3.
And, the present invention provides a dye-sensitized photoelectric conversion element, wherein the dye of the Formula 1 is supported on oxide semiconductor particles. For the preparation of the dye-sensitized photoelectric conversion element of the present invention, any processes for preparing a dye-sensitized photoelectric conversion element for solar cells of the prior art can be applied, except using the dye of the above Formula 1. Preferably, the dye- sensitized photoelectric conversion element of the present invention is prepared by forming an oxide semiconductor thin film on a substrate, using oxide semiconductor particles, and then supporting the dye of the present invention on the thin film.
As the substrate on which the oxide semiconductor thin film is formed, a substrate having conductive surface is preferably used, but any commercially available substrates can be used. For examples, a substrate wherein a thin film of metal such as copper, silver, gold, etc. or conductive metal oxide such as tin oxide coated with indium, fluorine, or antimony, etc. is formed on the surface of glass or transparent polymer such as polyethyleneterephthalate or
polyethersulfone, etc. The conductivity is preferably 1000Ω or less, and more preferably 100Ω or less.
As the oxide semiconductor particles, a metal oxide is preferably used. For examples, oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, itrium, niobium, tantalum, vanadium, etc. can be used. Specifically, an oxide of titanium, tin, zinc, niobium, or indium is preferable, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferable. The oxide semiconductor can be used alone or in combination, and can be coated on the surface of the semiconductor.
And, the oxide semiconductor particles preferably have an average particle size of 1 ~ 500 nm, and more preferably 1 ~ 100 run. And, oxide semiconductor particles having large particle size and those having small particle size can be mixed, or they can be used in multi-layers.
The oxide semiconductor thin film can be prepared by directly forming a thin film of oxide semiconductor particles by spraying, etc.; by electrically depositing semiconductor thin film using a substrate as an electrode; or by coating on a substrate a paste
containing semiconductor particles which is obtained by hydrolyzing a precursor of semiconductor particles such as a slurry of semiconductor particles or semiconductor alkoxide, etc., and then drying, curing or calcining. Preferably, a process of coating a paste on a substrate is used, wherein a slurry can be obtained by dispersing secondary condensed oxide semiconductor particles in a dispersion medium by a common method so that a first average particle size is 1 ~ 200 nm.
As the dispersion medium for dispersing the slurry, any dispersion medium capable of dispersing semiconductor particles can be used without limitation. For examples, water, alcohol such as ethanol, etc., ketone such as acetone, acetylacetone, etc., or hydrocarbon such a hexane, etc. can be used. They can be used in combination, and water is preferable because it reduces viscosity change of the slurry. And, a dispersion stabilizer can be used for stabilizing the dispersion state of the oxide semiconductor particles. Examples of the dispersion stabilizer include acid such as acetic acid, hydrochloric acid, nitric acid, etc. acetylacetone, acrylic acid, polyethyleneglycol , polyvinylalcohol, etc.
The substrate coated with the slurry can be subjected to calcination. The calcination temperature is 100 "C or more, preferably 200 °C or more, and the upper limit of the calcination temperature is melting point(softening point) of the substrate or less, commonly 900 °C , preferably 600 °C or less. In the present invention, the calcination time is not specifically limited, but preferably within 4 hours.
In the present invention, the thickness of the thin film on the substrate is suitably 1 ~ 200 μm, and preferably 1 ~ 50 μm. When subjected to calcination, a thin layer of the oxide semiconductor particles is partly welded, which does not specifically cause any troubles in the present invention.
And, a secondary treatment can be conducted on the oxide semiconductor thin film. For example, the thin film can be immersed in a solution of alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor, and dried or re-calcined, thereby improving the performance of the semiconductor thin film. The metal alkoxide includes titanium ethoxide, titanium isoproepoxide, titanium t-butoxide, n-dibutyl-diacetyl tin, etc., and the alcohol solution
thereof can be used. The chloride includes titanium chloride, tin chloride, zinc chloride, etc., and the aqueous solution thereof can be used. Thus obtained oxide semiconductor thin film consists of oxide semiconductor particles. And, the method for supporting dye on the oxide semiconductor thin film is not specifically limited in the present invention. For example, a substrate on which the oxide semiconductor thin film is formed can be immersed in a solution obtained by dissolving the dye of the Formula 1 in a solvent capable of dissolving it, or in a dispersion obtained by dispersing the dye. The concentration of the dye in the solution or dispersion can be appropriately determined according to the dye. The immersion temperature is generally from a room temperature to a boiling point of the solvent, and the immersion time is from about 1 minute to 48 hours. The solvent for dissolving the dye includes methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, acetone, t-butanol, etc. The concentration of the dye in the solution is suitably Ix 10~6 M- IM, and preferably lx 10"5 M - IX 1O-1 M. Thus, the dye-sensitized photoelectric
conversion element of the present invention comprising oxide semiconductor particles in the form of a thin film can be obtained.
One kind of the dye of the Formula 1 can be supported, or some kinds of the dyes can be mixed and supported. And, the dye of the present invention can be mixed with other dyes or metal complex dyes. The examples of the metal complex dyes which can be mixed with the dye of the present invention are not specifically limited, but ruthenium complex or the quaternary salt thereof, phthalocyanine, or porphyrin is preferable. And, the examples of the organic dyes which can be mixed with the dye of the present invention include metal-free phthalocyanine, porphyrin or cyanine, merocyanine, oxonol, triphenylmethane-based dyes, methyne-based dyes such as acrylic acid based dyes described in W02002/011213, xanthene-based, azo-based, anthraquinone-based, or perylene-based dyes (see the literature [M.K.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 case two or more kinds of dyes are used, the dyes can be sequentially absorbed to the semiconductor thin film, or they can be mixed, dissolved and absorbed.
And, when the dye is supported on the thin film of the oxide semiconductor particles, it is preferable to support the dye in the presence of an inclusion compound in order to prevent bonding between the dyes. As the inclusion compound, cholic acid such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, cholic acid methyl ester, sodium cholic acid, etc., steroid-based compound, crown ether, cyclodextrin, calix arene, polyethylene oxide, etc. can be used.
After the dye is supported, the electrode surface of the semiconductor can be treated with amine compound such as pyridine, etc., or compounds having acid group such as acetic acid, propionic acid, etc. For example, a substrate on which a dye-supported semiconductor thin film is formed can be immersed in an ethanol solution of amine. The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention. For the manufacture of the dye-sensitized solar cell, commonly used methods for preparing a solar cell using a photoelectric conversion element of the prior art can be applied,
except using the dye-sensitized photoelectric conversion element comprising oxide semiconductor particles on which the dye of the Formula 1 is supported. For example, the dye-sensitized solar cell may consist of a photoelectric conversion element electrode(anode), a counter electrode(cathode), redox electrolyte, hole transport material or p-type semiconductor, etc.
Preferably, the dye-sensitized solar cell of the present invention can be prepared by a process comprising the steps of coating a titanium oxide on a transparent conductive substrate; subjecting the coated substrate to calcination so as to form a titanium oxide thin film; impregnating the titanium oxide thin film with a mixed solution in which the dye of the Formula 1 is dissolved, so as to form a dye-absorbed titanium oxide film electrode; providing a second glass substrate on which a counter electrode is formed; forming a hole through the second glass substrate and the counter electrode; placing a thermoplastic polymer film between the counter electrode and the dye-absorbed titanium oxide film electrode, and conducting heat pressing, so as to join the counter electrode and the titanium oxide film electrode! injecting an electrolyte in the
thermoplastic polymer film placed between the counter electrode and the titanium oxide film electrode through the hole; and, sealing the thermoplastic polymer.
The redox electrolyte, hole transport material, p-type semiconductor, etc. can be a liquid, condensed(gel and gel-type), or solid type. The liquid type includes those prepared by dissolving redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor in a solvent, or a room temperature dissolved salt. The condensed type (gel and gel-type) includes those containing redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor in a polymer matrix or low molecule gelling agent. The solid type includes redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor.
As the hole transport material, those using discotic liquid crystal phase such as amine derivatives, conductive polymer such as polyacetylene, polyaniline, polythiophene, etc., or triphenylene- based compounds can be used. As the p-type semiconductor, CuI, CuSCN, etc. can be used. The counter electrode preferably has conductivity, and functions as a catalyst for the reduction of oxidation-reduction
electrolyte. For example, those prepared by depositing platinum, carbon, rhodium, ruthenium, etc. on a glass or polymer film, or by coating conductive particles on a glass or polymer film can be used.
As the redox electrolyte used for the solar cell of the present invention, halogen redox electrolyte consisting of a halogen compound with halogen ions as a counter ion and a halogen molecule, metal redox electrolyte such as ferrocyanide-ferricyanide, ferrocene- ferricinium ion, metal complex such as cobalt complex, etc., organic redox electrolyte such as alkylthiol-alkyldisulfide, vologen dye, hydroquinone-quinone, etc. can be used. Specifically, halogen redox electrolyte is preferable. As the halogen molecule for the halogen redox electrolyte, iodine molecule is preferably used. And, as the halogen compound, halogenated metal salt such as LiI, NaI, KI, Cal2, Mgl2, CuI, etc., or organic ammonium salt of halogen such as tetraalkyl ammonium iodide, imidazolium iodide, pyridium iodide, etc., or I2 can be used.
In case the redox electrolyte is a solution comprising the same, an electrochemical Iy inert solvent can be used. For examples, acetonitrile, propylene carbonate, ethylene carbonate, 3-
methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethylcarbonate, 1,3-dioxolane, methylformate, 2- methyl tetrahydrofurane, 3-methoxy-oxazolidin-2-on, sulfolane, tetrahydrofurance, water, etc. can be used. Specifically, acetonitri Ie, propylene carbonate, ethylene carbonate, 3- methoxypropionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-on, or butyrolactone is preferable. One kind of solvent can be used or some kinds of solvents can be mixed and used. As a gel-type positive electrolyte, those containing electrolyte or electrolyte solution in a matrix of oligomer or polymer, or those containing an electrolyte or an electrolyte solution in a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01 - 99 wt%, and more preferably 0.1 - 30 wt%. The solar cell of the present invention can be obtained by placing on a substrate, a photoelectric conversion element (anode) where the dye of the Formula 1 is supported on the oxide semiconductor particles and a counter electrode (cathode), and filling a solution comprising a redox electrolyte therebetween.
The present invention will be explained with reference to the following examples. However, these examples are only intended to illustrate the present invention and the scope of the present invention is not limited thereto. [Example]
[Example 1] Synthesis of dye
All the reactions were conducted under argon atmosphere, and a solvent was distilled with suitable agent purchased from Sigma- Aldrich Company. IH and 13C NMR spectrums were measured by Varian Mercury 300 spectrometer, elementary analysis was measured by Carlo Elba Instruments CHNS-O EA 1108 spectrometer, and mass spectrum was measured by JEOL JMS-SX102A apparatus. Absorption and emission spectrums were respectively measured by Perkin-Elmer Lambda 2S UV- visible spectrometer and Perkin LS fluorescence spectrometer. < Cyclic voltammetry > BAS 10OB(Bioanalytical Systems, Inc.) was used as a cyclic voltammeter. A 3-electrode system consisting of a gold disc, a working electrode and a platinum wire electrode was used. The redox potential of dye on Tiθ2 was measured at a scan ratio of 50 mV s'Hvs. Fc/Fc+) using 0.1M OC4Hg)4N-PF6 in CH3CN.
I ) 9-br omo- cys , cys- 1 , 7-d i et hoxy-3- i sopr opy 1 j u 1 o 1 i d i ne cjs,ςFs-l,7-diethoxy-3-isopropyljulolidine (5g, 16.47mmol) and N- bromosuccinimide(2.91g, 16.47mmol) were mixed in chloroform( 100ml) for 2 hours. Water (30ml) and brine were added to the mixed solution. Then, an organic layer was separated and dried with magnesium sulfate. After the solvent was removed under vacuum, the obtained solid was subjected to chromatography (eluant MC:Hx=l:l, 7?/=0.5) to obtain a colorless oily title compound (yield 70%).
IH NMR (CDC13): δ 7.27 (s, IH), 7.17 (s, IH), 4.34 (t, J=6.0 Hz, IH), 4.19 (t, J=3.9 Hz, IH), 3.72 (m, 2H), 3.57 (m, 2H), 3.22 (m, 2H), 3.00 (m, IH), 2.36 (oct, J=6.6 Hz, IH), 1.97 (m, 4H), 1.26 (q, J=6.6 Hz, 6H), 0.97 (d, J=6.6 Hz, 3H), 0.85 (d, J=6.9 Hz, 3H).13C1H NMR (CDCl3): δ 141.0, 131.3, 130.3, 125.0, 124.1, 107.2, 73.8, 64.2, 63.7, 61.9, 42.9, 28.8, 27.4, 27.1, 20.5, 17.0, 15.7, 15.6. MS: m/z 381 [M+]. Anal. Calcd for Ci9H28BrNO2: C, 59.69; H, 7.38. Found: C, 59.42; H, 7.24.
II) 9-(2 , 2 ' -bi thi ophen-5-y 1 )~cys, cys-1 , 7-di ethoxy-3- isopropyljulolidine (compound 3a)
The compound obtained in the above step I)(Ig, 2.61mmol), 2- (2,2'-biothiophen-5-yl)-4,4,5,5,-tetramethyl-l,3,2-dioxaborolane (0.915g, 3.132mmol), Pd(PPh3)4(0.150g, 0.13mmol) and 2M K2CO3 aqueous solution(2ml) were refluxed in THF(IOOmI) for 12 hours. The reaction solution was cooled, and water(30ml) and brine were added thereto. Then, an organic layer was separated and dried with magnesium sulfate. After the solvent was removed under vacuum, the obtained solid was subjected to chromatograρhy(eluant MC:Hx=l:l, Rf=O.3) to obtain an yellow solid title compound (yield 70%). Mp: 189 °C . IH NMR (CDCl3): δ 7.42 (s, IH), 7.32 (s, IH), 7.15 (t,
J=6.3 Hz, IH), 7.08 (d, J=3.9 Hz, IH), 7.03 (d, J=3.9 Hz, IH), 7.00 (d, J=3.3 Hz, IH), 6.99 (d, J=3.3 Hz, IH), 4.42 (t, J=5.1 Hz, IH)1 4.30 (t, J=3.9 Hz, IH), 3.75 (m, 2H), 3.67 (m, 2H), 3.27 (m, 2H), 3.05 (m, IH), 2.42 (oct, J=6.9 Hz, IH), 2.06 (m, 4H), 1.29 (q, J=7.1 Hz, 6H), 0.99 (d, J=6.6 Hz, 3H), 0.88 (d, J=6.9 Hz, 3H). 13C1H NMR (CDCl3): δ 139.8,
138.7, 136.4, 135.5, 133.9, 133.3, 132.2, 131.5, 130.3, 128.2, 127.4,
124.8, 122.1, 109.8, 72.7, 70.8, 65.8, 63.8, 62.7, 42.8, 28.8, 27.4, 27.2, 20.4, 19.3, 15.4, 15.2. MS: m/z 467 [M+ ]. Anal. Calcd for C27H33NO2S2=C, 69.34; H, 7.11. Found: C, 69.12; H, 6.95.
III) 9-(3,3'-dimethyl-2,2'-bithiophen-5-y1)~cys,cys-l,7-diethoxy- 3-isopropyljulolidine (compound 3b)
The same process as the above step II) was conducted, except that 2-(3,3'-dimethyl-2,2'-bithiophen-5-yl)-4,4,5,5,-tetramethyl-1,3,2- dioxaborolane was used instead of 2-(2,2'-bithiophen-5-yl)-4,4,5,5,- tetramethyl-l,3,2-dioxaborolane, to obtain a title compound (yield 65%) .
Mp: 187 °C . IH NMR (CDCl3): δ 7.40 (s, IH), 7.29 (s, IH), 7.24 (d, J=5.1 Hz, IH), 6.95 (s, IH), 6.91 (d, J=5.1 Hz, IH), 4.42 (t, J=5.1 Hz, IH), 4.29 (t, J=3.9 Hz, IH), 3.77 (m, 2H), 3.63 (m, 2H), 3.26 (m, 2H), 3.05 (m, IH), 2.40 (oct, J=6.9 Hz, IH), 2.22 (s, 3H), 2.17 (s, 3H), 2.01 (m, 4H), 1.27 (q, J=6.9 Hz, 6H), 0.99 (d, J=6.6 Hz, 3H), 0.89 (d, J=6.1 Hz, 3H). 13CUH} NMR (CDCl3): δ 139.0, 138.5, 137.3, 135.8, 134.1, 133.3, 130.5, 130.3, 129.4, 125.9, 125.3, 122.1, 121.0, 109.8, 72.1, 70.7, 65.8, 64.5, 63.8, 48.0, 31.9, 31.5, 29.2, 27.2, 27.1, 20.4, 19.4, 15.5, 15.1. MS: m/z 467 [M+ ] . Anal. Calcd for C29H37NO2S2: C, 70.26; H, 7.52. Found: C, 69.89; H, 7.13.
IV) 9-(2,2'-bis(3,4-ethylenedioxythiophene)-5-yl)-cys, cys-l, 7- diethoxy-3-isopropyljulolidine (compound 3c)
The same process as the above step II) was conducted, except that 4,4,5,5,-tetramethyl-2-(2,2' ,3,3'-tetrahydro-5,7'-bithieno[3,4- Z>][l,4]dioxin-7-yl)-l,3,2-dioxaborolane(1.278g, 3.132mmol) was used instead of 2-(2,2'-bithiophen-5-yl )-4, 4,5,5, -tetramethyl-1,3,2- dioxaborolane, to obtain a title compound (yield 77%).
Mp: 198°C. IH NMR (CDCl3): δ 7.55 (s, IH), 7.42 H. Choi et al. / Tetrahedron 63 (2007) 1553.1559 (s, IH), 6.23 (s, IH), 4.43 (t, J=5.1 Hz, IH), 4.34.4.25 (m, 8H), 4.24 (t, J=3.7 Hz, IH), 3.74 (m, 2H), 3.66 (m, 2H), 3.26 (m, 2H), 3.03 (m, IH), 2.41 (oct, J=6.9 Hz, IH), 2.06 (m, 4H), 1.26 (q, J=7.2 Hz, 6H), 0.98 (d, J=6.9 Hz, 3H), 0.88 (d, J=6.3 Hz, 3H). 13C1H NMR (CDCl3): δ 141.4, 137.8, 136.5, 136.0, 127.9, 126.8, 122.5, 121.5, 119.8, 116.9, 110.6, 105.4, 97.0, 92.9, 73.9, 73.1, 65.9, 65.1, 65.0, 64.7, 63.7, 63.3, 62.3, 42.9, 29.2, 27.5, 25.7, 20.6, 17.6, 15.8, 15.7. MS: m/z 583 [M+]. Anal. Calcd for C3IH37NO6S2: C, 63.78; H, 6.39. Found: C, 63.55; H, 6.18.
V) θ-tδ'-formyl^^'-bithiophen-δ-yO-o^c^lJ-diethoxy-S- isopropyljulolidine (compound 4a)
To an anhydrous ethanol solution of the compound 3a obtained in the above step II) (0.22g,0.47mmol), /T-BuLi (0.35ml , 1.6M solution in hexane) was added under argon. After 3 hours, DMF(O.05g,0.7mmol) was added thereto at 0°C under argon and washed with 5% KOH. The reaction solution was dried with magnesium sulfate. After the solvent was removed, the obtained solid was subjected to silica gel chromatography (eluant MC:Hx=l:l, Rf=O.2) to obtain a title compound (yield 75%).
Mp: 186°C. IH NMR (CDCl3): δ 9.82 (s, IH), 7.64 (d, J=3.9 Hz, IH), 7.43 (s, IH), 7.33 (s, IH), 7.28 (d, J=3.9 Hz, IH), 7.28 (d, J=3.9 Hz, IH), 7.20 (d, J=3.9 Hz, IH), 7.08 (d, J=3.9 Hz, IH), 4.41 (t, J=5.4 Hz, IH), 4.30 (t, J=3.7 Hz, IH), 3.77 (m, 2H), 3.65 (m, 2H), 3.28 (m, 2H), 3.08 (m, IH), 2.41 (oct, J=6.3 Hz, IH), 2.02 (m, 4H), 1.29 (q, J=6.9 Hz, 6H), 0.99 (d, J=6.6 Hz, 3H), 0.88 (d, J=6.3 Hz, 3H).13C1H NMR (CDCl3): δ 182.6, 145.8, 143.2, 136.2, 134.5, 133.9, 133.3, 132.2, 131.5, 130.8, 128.2, 127.4, 124.8, 122.1, 111.8, 72.5, 70.1, 65.8, 63.8, 62.7, 42.8, 28.8, 27.4,
27.2, 20.4, 19.3, 15.4, 15.2. MS: m/z 495 [M+ ] . Anal. Calcd for C28H33NO3S2=C, 67.84; H, 6.71. Found: C, 67.36; H, 6.24.
VI ) θ-Cδ' -formyl-S.S' -dimethyl^^' -bithiophen-δ-yl -cys^ cj^-l,?- diethoxy-3-i sopropyl julol idine (compound 4b)
The same process as the above step V) was conducted, except that a compound 3b was used instead of the compound 3a , to obtain a t i t le compound (yield 72%) .
Mp: 179 °C . IH NMR (CDCl3): δ 9.82 (s, IH), 7.58 (s, IH), 7.40 (s, IH), 7.29 (d, J=5.1 Hz, IH), 6.98 (s, IH), 4.41 (t, J=5.1 Hz, IH), 4.29 (t,
J=3.9 Hz, IH), 3.74 (m, 2H), 3.63 (m, 2H), 3.27 (m, 2H), 3.07 (m, IH),
2.41 (oct, J=6.9 Hz, IH), 2.31 (s, 3H), 2.25 (s, 3H), 2.00 (m, 4H), 1.28 (q,
J=7.2 Hz, 6H), 0.99 (d, J=6.9 Hz, 3H), 0.88 (d, J=6.3 Hz1 3H). 13C1H
NMR (CDCl3): δ 182.8, 143.0, 141.2, 140.4, 139.2, 138.4, 137.0, 130.5, 127.1, 126.0, 125.0, 122.9, 122.0, 120.6, 112.1, 73.7, 73.1, 64.0, 63.5,
62.3, 42.9, 31.9, 31.5, 29.1, 27.2, 27.1, 22.6, 17.4, 15.8, 15.7. MS: m/z
523 [M+ ] . Anal. Calcd. for C30H37NO3S2: C, 68.80; H, 7.12. Found: C,
68.55; H, 6.89.
VII) θ-Cδ'-forrayl^^'-bisCS^-ethylenedioxythiophe^-δ-yl)- cys, cys-l,7-diethoxy-3-isopropyljulolidine (compound 4c)
The same process as the above step V) was conducted, except that a compound 3c was used instead of the compound 3a, to obtain a title compound (yield 75%).
Mp: 186 °C. IH NMR (CDCl3): δ 9.86 (s, IH), 7.58 (s, IH), 7.45 (s, IH), 4.42 (m, 9H), 4.31 (t, J=3.7 Hz, IH), 3.73 (m, 2H), 3.64 (m, 2H)1 3.27 (m, 2H), 3.04 (m, IH), 2.41 (oct, J=6.3 Hz, IH), 2.08 (m, 4H)11.27 (q, J=7.5 Hz, 6H), 0.99 (d, J=6.6 Hz, 3H), 0.88 (d, J=6.0 Hz, 3H).13C1H NMR (CDCl3): δ 179.6, 159.0, 156.0, 138.9, 137.7, 136.5, 133.4, 132.1, 130.5, 129.8, 128.7, 125.9, 124.9, 121.0, 106.9, 73.7, 73.3, 65.8, 65.4, 65.1, 64.7, 63.7, 63.3, 62.3, 42.3, 29.1, 27.2, 25.5, 20.7, 17.6, 15.8, 15.7. MS: m/z 611 [M+]. Anal. Calcd for C32H37NO7S2: C, 62.82; H, 6.10. Found: C, 62.55; H, 5.95.
II 11 ) 2-cyano-3-(5 ' -( cys, cys-1 , 7-diethoxy-3-i sopropyl julol idinyl )- 2,2'-bithiophen-5-yl)acrylic acid (compound Ia)
After a mixture of the compound 4a(0.38g, 0.76mmol) and cyanoacetic acid(0.13g, 1.53mmol) was vacuum dried, it was added to
MeCN(60ml) and piperidine(0.07ml , 0.76mmol), and the mixed solution was refluxed for 6 hours. The reaction solution was cooled and an organic layer was removed under vacuum. Then, the obtained solid was subjected to silica gel chromatography (eluant: MC:MeOH=-2: 1, /?/=0.6) to obtain a title compound (yield 51%).
Mp: 225°C. IH NMR (DMSC-cfc): δ 8.12 (s, IH), 7.65 (d, J=3.3 Hz, IH), 7.39 (d, J=3.6 Hz, IH), 7.37 (d, J=3.6 Hz, IH), 7.35 (s, IH), 7.32 (s, IH), 7.22 (d, J=3.3 Hz, IH), 4.37 (t, J=5.8 Hz, IH), 4.28 (t, J=3.9 Hz, IH), 3.70 (m, 2H), 3.61 (m, 2H), 3.20 (m, 2H), 3.06 (m, IH), 2.25 (oct, J=6.3 Hz, IH), 1.90 (m, 4H), 1.19 (q, J=6.9 Hz, 6H), 0.94 (d, J==6.9 Hz, 3H), 0.82 (d, J=6.9 Hz, 3H). 13C1H NMR (DMSO-cfc): δ 164.3, 150.6, 145.8, 142.3, 142.0, 141.7, 140.6, 136.6, 135.3, 134.8, 131.7, 126.9, 123.6, 122.5, 122.0, 119.1, 118.7, 73.7, 72.8, 64.2, 63.0, 62.5, 41.4, 29.7, 28.6, 28.2, 22.5, 17.0, 15.4, 15.3. MS: m/z 562 [M+ ]. Anal. Calcd for C3IH34N2O4S2: C, 66.16; H, 6.09. Found: C, 65.78; H, 5.87.
IX) 2-cyano-3-(5'-(cys, ςys^l,7-diethoxy-3-isopropyljulol idinyl )- 3,3'-dimethyl-2,2 ' -bithiophen-5-yl )acryl ic acid (compound Ib)
The same process as the above step VIII) was conducted, except that a compound 4b was used instead of the compound 4a, to obtain a title compound (yield 56%).
Mp: 212TC. IH NMR (DMS(W6): δ 8.03 (s, IH), 7.55 (s, IH), 7.32 (s, IH), 7.28 (s, IH), 7.15 (s, IH), 4.37 (t, J=5.3 Hz, IH)14.28 (t, J=3.9 Hz, IH), 3.69 (m, 2H), 3.57 (m, 2H), 3.27 (m, 2H), 3.08 (m, IH), 2.35 (oct, J=6.8 Hz, IH), 2.20 (s, 3H), 2.17 (s, 3H), 1.90 (m, 4H), 1.18 (q, J=7.2 Hz, 6H), 0.94 (d, J=6.9 Hz, 3H), 0.83 (d, J=6.9 Hz, 3H). 13C{1H} NMR (DMSO-cfe> δ 163.3, 149.0, 145.4, 144.8, 141.5, 137.8, 136.1, 135.6, 135.3, 134.8, 132.2, 128.9, 127.3, 125.5, 124.6, 124.1, 119.0, 73.8, 72.8, 64.3, 63.1, 61.5, 41.4, 40.4, 38.6, 29.7, 28.6, 28.4, 23.0, 17.2, 15.4, 15.1. MS: m/z 523 [M+]. Anal. Calcd. for C33H38N2O4S2: C, 67.09; H, 6.48. Found: C, 66.79; H, 6.33.
X) 2-cyano-3-(5 ' -( cys, cys-1 , 7-diethoxy-3-i sopropyl julol idinyl )-
2,2'-bis(3,4-ethylene-dioxythiophene)-5-yl)acrylic acid (compound Ic)
The same process as the above step VIII) was conducted, except that a compound 4c was used instead of the compound 4a, to obtain a title compound (yield 60%).
Mp: 232°C . IH NMR (DMSO-cfc): δ 8.03 (s, IH), 7.44 (s, IH), 7.35 (s, IH), 4.42 (m, 8H), 4.35 (t, J=5.9 Hz, IH), 4.27 (t, J=3.8 Hz, IH), 3.70 (m, 2H), 3.57 (m, 2H), 3.16 (m, 2H), 3.10 (m, IH), 2.35 (oct, J=6.8 Hz, IH), 1.93 (m, 4H), 1.17 (q, J=7.3 Hz, 6H), 0.95 (d, J=6.3 Hz, 3H), 0.83 (d, J=6.9 Hz, 3H). 13C1H NMR (DMSO-cfc): δ 161.8, 155.9, 144.6, 140.9, 140.4, 135.9, 126.1, 125.4, 122.4, 120.1, 118.4, 118.1, 115.3, 109.1, 108.1, 104.7, 103.8, 72.5, 72.1, 67.2, 65.2, 64.4, 63.0, 61.2, 59.6, 47.3, 28.6, 23.0, 22.5, 20.1, 17.2, 15.5, 15.4. MS: m/z 678 [M+ ]. Anal. Calcd for C35H38N2O8S2: C, 61.93; H, 5.64. Found: C, 61.56; H, 5.34.
[Example 2j Preparation of a dye-sensitized solar cell
In order to evaluate the current-voltage properties of the dye compound, a solar cell was prepared using a 12+8 μm T1O2 transparent layer. A UO2 paste(Solaronix, 13nm paste) was screen printed to prepare a first TiU2 layer having a thickness of 12 μm, and a second
Tiθ2 layer having a thickness of 8 μm was prepared using another pasteCCCIC, HWP-400) for light diffusion. The TiO2 bi-layered film was treated with a 4OmM TiCU solution and dried at 500 °C for
30minutes. The treated film was cooled to 60 "C, and then impregnated
with each solution of the dye compounds Ia to Ic of the present invention which were prepared in the above steps VIII) to X) (0.3 mM dye in ethanol containing 10 mM kenodioxycholic acid). A high temperature melting film (Surlyn 1702, 25 μm thickness) was placed as a spacer between the dye-absorbed Tiθ2 electrode and a platinum- counter electrode, and heated to prepare a sealed sandwich cell. As an electrolyte solution, 0.6 M 3-hexyl-l,2-dimethylimidazolium iodide, 0.04 M I2, 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert- butylpyridine dissolved in acetonitrile were used.
[Example 3] Measurement of the prepared dye and dye-sensitized solar cell
Absorption and emission spectrums of each of the dye compounds Ia to Ic of the present invention prepared in the above step VIII) to X) in ethanol (Ia: solid line, Ib: bar line, Ic: dotted line), and absorption spectrums of the dye compounds supported on TiO2 layer(Ia: bar line-dotted line, Ib: bar line-dotted line-dotted line, Ic: short bar line) were shown in Fig. 1. The emission spectrums were obtained
by exciting the compound Ia at 450nm, the compound Ib at 410 nm, and the compound Ic at 500nm at 298K.
The graphs as shown in Fig. 1 indicate that the absorption spectrum of the compound Ib was blue shifted, and the absorption spectrum of the compound Ic was red shifted, compared to the absorption spectrum of the compound Ia.
Such differences result from the molecular structures of the dye compounds, and the optimized structure of each of the compounds Ia to Ic (TD-DFT computation at B3LYP/3-21G) were shown in Fig. 2 ((a): Ia, (b): Ib, (c): Ic). In Fig. 2 (a) and (b), the angle observed at the upper part is a twist angle between julolidine and thienyl unit, and the angle observed at the lower part is a facial angle between two thienyl units. In Fig. 2 (c), the angle observed at the upper part is a facial angle of julolidine and 3,4-ethylenedioxytbiophene, and the angle observed at the lower part is a facial angle of bis(3,4- ethylenedioxythiophene). The molecular structures as shown in Fig. 2 indicate that the compound Ib more twisted, and the compound Ic is less twisted and close to a plane, compared to the compound Ia.
And, the geometrical structures of the compounds Ia and Ic (HOMO and LUMO molecular orbitals, TD-DFT computation at B3LYP/3-21G) were shown in Fig. 3. The structures as shown in Fig. 3 indicate that HOMO-LUMO excitation moves electron distribution from aniline unit to cyanoacrylic acid, and the change in electron distribution caused by light excitation results in efficient charge separation.
The optical performance and oxidation-reduction performance of each of the dye compounds of Ia to Ic of the present invention, and photoelectrochemical characteristics and IPCE spectrum of the solar cell prepared using each of the dye compound were shown in Fig. 4,
Fig. 5 and the following Table 1.
[Table 1]
In the above Table 1, ε is absorption coefficient, E0x is an oxidation potential, Eo-o is a voltage at the intersection of absorption and emission spectrums, Jsc is a short-circuit photocurrent density, Voc is an open circuit photovoltage, ff is a fill factor, η, is total photo-conversion efficiency. And, a means that an absorption spectrum is measured in an ethanol solution, b means that oxidation-reduction potential of the dye on Tiθ2 is measured at a scan ratio of 50 mVs~1(vs. Fc/Fc+) using O. IM (72-C4Hg)4N- PFβ in CH3CN, c means that Eo-o is determined at the intersection of absorption and emission spectrums in ethanol, d means that Enmo is
calculated by E0x-Eo-O, e means that the performance of dye-sensitized solar cell is measured on the working area of 0.18cm2.
The IPCE graph of a solar cell as shown in Fig. 4 and the photocurrent voltage curve (under AM 1.5 radiation) of a solar cell as shown in Fig. 5 (Ia: solid line, Ib: bar line, Ic: dotted line, N719: bar line-dotted line) indicate that IPCE maximum of the compound Ic is lower than those obtained from the compounds Ia and Ib, and total conversion efficiency of the compound Ic is low.
These results indicate that the efficiency of dye largely depends on the condensation degree of dye on TiU2 layer rather than dye absorption amount, and that it is also related to a twisted non- planar structure of the dye compound of the present invention. Namely, it is suggested that the photoelectric conversion efficiency of dye largely change according to the structural transformation of bithiophene linking moiety, and that the photoelectric conversion efficiency becomes higher as the degree of twist between julolidine and thienyl unit is high. [Industrial Applicability]
The novel julolidine-based dye of the present invention shows improved molar absorptivity, Jsc (short circuit photocurrent density) and photoelectric conversion efficiency, compared to the metal complex dye of the prior art, and thus can largely improve the efficiency of a solar cell. And, it can dramatically decrease dye synthesis cost because it can be purified without using expensive columns.
Claims
[CLAIMS] [Claim 1]
Julolidine-based dye of the following Formula 1: [Formula 1]
The julolidine-based dye according to claim 1, wherein the dye is represented by one of the following Formula Ia to Ic: [Formula Ia] 
[Formula Ic] 
[Claim 3] A process for preparing the julolidine-based dye of the Formula 1 as described in claim 1, comprising the steps of:
(1) subjecting bromojulolidine to a Suzuki coupling reaction with a compound of the following Formula 2 to form a compound of the following Formula 3;
(2) lithiating the compound of the Formula 3 with n-butyl lithium, and then continuously cooling it with dimethylformamide to form a compound of the following Formula 4:
(3) reacting the compound of the Formula 4 with cyanoacetic acid in CH3CN in the presence of piperidine:
[Formula 2]
[Formula 3] 
[Formula 4]
[Claim 4]
A dye-sensitized photoelectric conversion element comprising oxide semiconductor particles on which the julolidine-based dye as described in claim 1 is supported.
[Claim 5] The dye-sensitized photoelectric conversion element according to claim 4, wherein the julolidine-based dye is supported on the oxide semiconductor particles in the presence of an inclusion compound.
[Claim 6] The dye-sensitized photoelectric conversion element according to claim 4, wherein the oxide semiconductor particles comprise titanium dioxide as an essential element. [Claim 7]
The dye-sensitized photoelectric conversion element according to claim 4, wherein the oxide semiconductor particles have an average particle size of 1 ~ 500 nm. [Claim 8]
A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element as described in claim 4 as an electrode. [Claim 9]
The dye-sensitized solar cell according to claim 8, wherein the dye-sensitized solar cell is prepared by a process comprising the steps of: coating a titanium oxide on a transparent conductive substrate; subjecting the coated substrate to calcination so as to form a titanium oxide thin film; impregnating the titanium oxide thin film with a mixed solution in which the dye of the Formula 1 is dissolved, so as to form a dye- absorbed titanium oxide film electrode! providing a second glass substrate on which a counter electrode is formed; forming a hole through the second glass substrate and the counter electrode; placing a thermoplastic polymer film between the counter electrode and the dye-absorbed titanium oxide film electrode, and conducting heat pressing, so as to join the counter electrode and the titanium oxide film electrode; injecting an electrolyte in the thermoplastic polymer film placed between the counter electrode and the titanium oxide film electrode through the hole; and sealing the thermoplastic polymer.
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| JP2016119471A (en) * | 2014-12-19 | 2016-06-30 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Compound for organic photoelectric element, organic photoelectric element including the same, image sensor, and electronic apparatus including the same |
| EP3176221A4 (en) * | 2014-08-02 | 2018-04-18 | LG Chem, Ltd. | Dye complex, photoconversion film and electronic element including same |
| CN112961151A (en) * | 2021-02-05 | 2021-06-15 | 浙江工业大学 | Julolidine compound and preparation method and application thereof |
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| KR101555843B1 (en) | 2013-12-09 | 2015-09-25 | 재단법인대구경북과학기술원 | Dye for dye-sensitized solar cell and a dye sensitized solar cell using the same |
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| JP2003086257A (en) * | 2001-09-07 | 2003-03-20 | Nippon Kayaku Co Ltd | Dye sensitizing photoelectric conversion element |
| JP2003109676A (en) * | 2001-09-27 | 2003-04-11 | Konica Corp | Semiconductor for photoelectric conversion material, photoelectric conversion element and solar battery |
| WO2004082061A1 (en) * | 2003-03-14 | 2004-09-23 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2005078888A (en) * | 2003-08-29 | 2005-03-24 | Konica Minolta Holdings Inc | Semiconductor for photoelectric conversion material, photoelectric conversion element and solar cell |
| JP2006134649A (en) * | 2004-11-04 | 2006-05-25 | Nippon Kayaku Co Ltd | Photoelectric conversion element |
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| JP2003086257A (en) * | 2001-09-07 | 2003-03-20 | Nippon Kayaku Co Ltd | Dye sensitizing photoelectric conversion element |
| JP2003109676A (en) * | 2001-09-27 | 2003-04-11 | Konica Corp | Semiconductor for photoelectric conversion material, photoelectric conversion element and solar battery |
| WO2004082061A1 (en) * | 2003-03-14 | 2004-09-23 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2005078888A (en) * | 2003-08-29 | 2005-03-24 | Konica Minolta Holdings Inc | Semiconductor for photoelectric conversion material, photoelectric conversion element and solar cell |
| JP2006134649A (en) * | 2004-11-04 | 2006-05-25 | Nippon Kayaku Co Ltd | Photoelectric conversion element |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3176221A4 (en) * | 2014-08-02 | 2018-04-18 | LG Chem, Ltd. | Dye complex, photoconversion film and electronic element including same |
| JP2016119471A (en) * | 2014-12-19 | 2016-06-30 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Compound for organic photoelectric element, organic photoelectric element including the same, image sensor, and electronic apparatus including the same |
| CN112961151A (en) * | 2021-02-05 | 2021-06-15 | 浙江工业大学 | Julolidine compound and preparation method and application thereof |
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