WO2012029659A1 - Novel fluorene compound, dye for dye-sensitized solar cell using the compound, electrode containing dye for dye-sensitized solar cell, and dye-sensitized solar cell - Google Patents
Novel fluorene compound, dye for dye-sensitized solar cell using the compound, electrode containing dye for dye-sensitized solar cell, and dye-sensitized solar cell Download PDFInfo
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- WO2012029659A1 WO2012029659A1 PCT/JP2011/069317 JP2011069317W WO2012029659A1 WO 2012029659 A1 WO2012029659 A1 WO 2012029659A1 JP 2011069317 W JP2011069317 W JP 2011069317W WO 2012029659 A1 WO2012029659 A1 WO 2012029659A1
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- dye
- group
- solar cell
- sensitized solar
- electrode
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- -1 fluorene compound Chemical class 0.000 title claims abstract description 58
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 13
- 239000007784 solid electrolyte Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 206010070834 Sensitisation Diseases 0.000 claims 1
- 230000008313 sensitization Effects 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 22
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 13
- 150000002220 fluorenes Chemical class 0.000 abstract description 12
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- 239000002904 solvent Substances 0.000 description 41
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 35
- 239000012043 crude product Substances 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 26
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical group OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 15
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 11
- 235000019341 magnesium sulphate Nutrition 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- RXACYPFGPNTUNV-UHFFFAOYSA-N 9,9-dioctylfluorene Chemical class C1=CC=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 RXACYPFGPNTUNV-UHFFFAOYSA-N 0.000 description 9
- 229920001940 conductive polymer Polymers 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- FXSCJZNMWILAJO-UHFFFAOYSA-N 2-bromo-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3CC2=C1 FXSCJZNMWILAJO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 0 CCCCCCC1=CC(c2c(*)cc(-c(cc3)cc4c3[n](CC)c3c4cccc3)[s]2)=S*1 Chemical compound CCCCCCC1=CC(c2c(*)cc(-c(cc3)cc4c3[n](CC)c3c4cccc3)[s]2)=S*1 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 230000008033 biological extinction Effects 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 2
- SZLOIDBLRICYBJ-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole;hydrochloride Chemical compound Cl.C1CC=PC1 SZLOIDBLRICYBJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical compound CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical group CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GEBYOCJZLPJAJK-UHFFFAOYSA-N [I+].C[N+]1=C(N(C=C1)CCC)C Chemical compound [I+].C[N+]1=C(N(C=C1)CCC)C GEBYOCJZLPJAJK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YSXKPIUOCJLQIE-UHFFFAOYSA-N biperiden Chemical compound C1C(C=C2)CC2C1C(C=1C=CC=CC=1)(O)CCN1CCCCC1 YSXKPIUOCJLQIE-UHFFFAOYSA-N 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
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
- 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
- C09B23/0008—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
- C09B23/10—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
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a novel fluorene compound, a dye-sensitized solar cell dye using the compound, a dye-sensitized solar cell dye-containing electrode adsorbing the fluorene compound, and a dye-sensitized dye having such an electrode. It relates to solar cells.
- a Ru metal complex dye As the sensitizing dye used in the dye-sensitized solar cell, a Ru metal complex dye is generally used. Such a Ru metal complex dye does not have a very high extinction coefficient and does not have a large light absorption ability as a single molecule. However, in a dye-sensitized solar cell, a nanoporous metal oxide can be used as an electrode. By increasing the film thickness, the amount of dye per unit area can be increased, and high photoelectric conversion efficiency can be realized by using such a function. However, since Ru, which is a rare metal, is used, there is anxiety in terms of stable supply in the future, and the amount of dye used increases in order to maintain high photoelectric conversion efficiency. Based on these backgrounds, organic dyes for dye-sensitized solar cells that do not use rare metals such as Ru complexes have attracted attention.
- organic sensitizing dyes have a higher molar extinction coefficient than Ru-based dyes, but conversely, even if the thickness of the anode electrode is increased, the photoelectric conversion efficiency is not greatly improved.
- the skeleton used for organic dyes requires a high conjugated structure in order to achieve both the light absorption ability and the charge transfer ability, but the development of these conjugated structures makes the solubility in solvents worse and the anode. It becomes difficult to dye the electrodes.
- organic dyes for dye-sensitized solar cells often use a heterocycle containing nitrogen element and / or an amine group as a donor skeleton in order to efficiently transfer charges from iodine anions used as an electrolyte.
- dye-sensitized solar cells usually use an electrolyte having redox ability such as I ⁇ / I 3 ⁇ (electrolyte capable of redox reaction) by combining iodine and an iodine anion such as lithium iodide. Is done.
- the solution of I ⁇ / I 3 ⁇ is widely used because of its excellent stability, but such an I ⁇ / I 3 ⁇ solution is related to cell durability. corrosion of the wiring material by iodine, degradation has become a problem, I - / I 3 - is a dye capable of performing redox redox alternative to the solution is required, good ones have been reported little.
- MK-2 was developed using N-ethylcarbazole as the donor part for the combination of oligo n-hexylthiophene (conjugated bond system) and cyanoacetic acid group (acceptor, anchor). Yes (see Non-Patent Document 1). MK-2 is an excellent dye that has a higher open-circuit voltage and higher conversion efficiency than conventional organic dyes, and has been confirmed to exhibit very high conversion efficiency as an organic dye. The structure of MK-2 is shown below as (MK-2).
- An object of the present invention is to provide a novel fluorene compound using a fluorene compound containing a nitrogen-containing heterocycle and no amine group as a donor, and has a solubility in a general-purpose solvent such as toluene as a dye dyeing solvent.
- An object of the present invention is to provide a sensitizing dye for a dye-sensitized solar cell which is good but has a high performance.
- Another object of the present invention is to provide a dye-containing electrode for a dye-sensitized solar cell having high performance by using the fluorene compound. It is another object of the present invention to provide a dye-containing electrode for a dye-sensitized solar cell that can generate power using a non-iodine redox solution by adjusting the HOMO-LUMO level.
- an object of the present invention is to provide a dye-sensitized solar cell having an electrode using the fluorene compound.
- novel fluorene compound of the present invention can be represented by the following formula (I).
- R 1 and R 2 each independently represents at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group, and X represents the following formula (1 ), At least one group selected from the group consisting of (2) and (3), and n is an integer from 1 to 12.
- R 3 and R 4 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group. Represents.
- the dye for dye-sensitized solar cells of the present invention uses the fluorene compound represented by the above formula (I) as the sensitizing dye of the dye-sensitized solar cell.
- the fluorene compound-coated metal oxide particles obtained by adsorbing the fluorene compound represented by the above formula (I) on the surface of the metal oxide particles are metal electrodes. It has the structure arrange
- the dye-sensitized solar cell of the present invention has a transparent electrode having a fluorene compound-coated metal oxide particle disposed on the surface as described above as one electrode and a catalyst electrode as the other electrode. And the catalyst electrode.
- the fluorene compound of the present invention is a novel compound.
- This fluorene compound can be effectively used as a dye used in a dye-sensitized solar cell.
- applying a fluorene compound containing a nitrogen element heterocycle and no amine group as a donor skeleton, and using a conjugated low-molecular oligothiophene having a side chain, etc. imparts solubility to general-purpose solvents such as toluene, dye As a dye to be used in dye-sensitized solar cells by controlling inter-stacking, suppressing charge leakage from photoelectrodes, etc., and adjusting the light absorption wavelength region and charge transferability by adjusting the conjugate length It can be used effectively.
- the electrode in which the dye comprising the fluorene compound of the present invention is adsorbed on titanium oxide can be effectively used as an electrode for a dye-sensitized solar cell.
- the dye-sensitized solar cell having this electrode has higher open-circuit voltage and short-circuit current density and higher conversion efficiency than the solar cell using MK-2.
- the fluorene compound of the present invention has a lower extinction coefficient than that of MK-2, and by utilizing this characteristic, the photoelectrode for dye-sensitized solar cell having high conversion efficiency by increasing the effective area of the photoelectrode Can be provided.
- an electrode containing a dye comprising the fluorene compound of the present invention it is possible to generate power with a non-iodine-based electrolyte, and in particular, a liquid electrolyte that has been an essential constituent requirement for dye-sensitized solar cells Instead of this, it is possible to generate electric power using a solid electrolyte such as a conductive polymer instead. Accordingly, it is possible to provide a new dye-sensitized solar cell that suppresses corrosion of cell wiring materials due to iodine redox and provides a long-life cell or does not cause leakage of electrolyte from the dye-sensitized solar cell. it can.
- FIG. 1 is a drawing schematically showing an example of a cross section of a dye-sensitized solar cell ⁇ liquid photoelectric conversion element>.
- FIG. 2 is a drawing schematically showing an example of a cross section of a dye-sensitized solar cell ⁇ fully solid-state photoelectric conversion element>.
- FIG. 3 is a 1 H-NMR spectrum of the compound represented by formula (H).
- FIG. 4 is an LC-MS spectrum of the compound represented by the formula (H).
- FIG. 5 is a 1 H-NMR spectrum of the compound represented by formula (K).
- FIG. 6 is an LC-MS spectrum of the compound represented by formula (K).
- a fluorene compound of the present invention a dye for a dye-sensitized solar cell comprising the fluorene compound, a dye-containing electrode for a dye-sensitized solar cell and a dye-sensitized solar cell using the dye will be specifically described. .
- the fluorene compound of the present invention can be represented by the following formula (I).
- R 1 and R 2 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an alkoxy group.
- both R 1 and R 2 are hydrogen atoms or alkyl groups, aryl groups and alkoxy groups having the same carbon number, and R 1 and R 2 are those having 1 to 12 carbon atoms.
- An alkyl group, an aryl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms is preferable.
- a compound in which R 1 and R 2 are both hydrogen atoms or alkyl groups is suitable as a fluorene compound that forms an electrode for a dye-sensitized solar cell.
- a fluorene compound using a substituent is used as a dye compound used as an electrode of a dye-sensitized solar cell
- an electrolyte that performs a redox reaction of the solar cell is, for example, I ⁇ / I 3 ⁇ .
- a liquid electrolyte but also a solid electrolyte such as a conductive polymer can be suitably used.
- n is an integer of 1 to 12, particularly preferably an integer of 2 to 10.
- X is any group of the following formulas (1), (2), and (3).
- R 3 and R 4 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group. Represents.
- R 3 and R 4 is a hydrogen atom
- the other group is an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
- the groups Preferably any of the groups.
- R 3 and R 4 are linear groups. It is preferable.
- X in the formula (I) is preferably the above formula (1) having a thiophene ring, and in this case, one of R 3 and R 4 bonded to the thiophene ring is It is preferably a hydrogen atom and the other is an alkyl group having 2 to 12 carbon atoms, an aryl group or an alkoxy group, and usually has 2 to 12 thiophene rings having such a substituent, preferably 3 It is particularly desirable that ⁇ 7 are bonded (that is, n in formula (I) is usually 2 to 12, preferably 3 to 7).
- the dye for a dye-sensitized solar cell of the present invention a compound represented by the following formula can be used.
- R 1 to R 4 and n are the same as described above.
- a compound having n of 3 is shown as follows.
- (II-1) having a thiophene ring is preferred as a dye for a dye-sensitized solar cell.
- R 1 and R 2 may be hydrogen atoms, but are preferably linear alkyl groups.
- R 1 and R 2 are alkyl groups having the same carbon number. Is particularly preferred.
- R 3 and R 4 are at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an alkoxy group, and either one of R 3 and R 4 Is a hydrogen atom, and the other is preferably an alkyl group, an aryl group and an alkoxy group.
- Such a compound can be synthesized using 2-bromofluorene or a derivative thereof as a starting material.
- the method for synthesizing the compound of the present invention will be described by taking 2-bromofluorene as an example where R 3 is a hydrogen atom and R 4 is a hexyl group.
- 2-bromofluorene is converted to 3-hexylthiophene-5-boronic acid ester. React.
- the mixture is refluxed in dimethoxyethane in the presence of bis (triphenylphosphine) palladium (II) dichloride and an aqueous sodium carbonate solution as a catalyst.
- the reflux time at this time is usually 3 to 12 hours.
- one fluorene ring having a hexyl group can be introduced into 2-bromofluorene. Then, using a brominating agent such as N-bromosuccinimide, it can be substituted with the bromine atom of the hydrogen atom to which the thiophene ring of the 3-hexylthiophene group is bonded.
- a coupling reaction Sudzuki coupling reaction
- thiophene rings can be bonded one after another.
- a desired alkyl group, aryl group, and alkoxy group can be introduce
- a hydrogen atom in the 9-position of the fluorene derivative is first used, by using the fluorene derivative substituted on R 1 and R 2, to give a compound wherein R 1 and R 2 is an alkyl group, an aryl group or an alkoxy group be able to.
- N, N-dimethylformamide (DMF) is added dropwise to cooled phospholine chloride to prepare a Vilsmeier reagent.
- An aldehyde group is introduced into the terminal thiophene ring by adding to the fluorene derivative bound with the thiophene ring prepared as described above.
- the fluorene derivative aldehyde having an aldehyde group introduced into the terminal thiophene ring thus obtained is reacted with cyanoacetic acid in the presence of piperidine, and the reaction product is extracted with chloroform, and the extracted organic phase is extracted with hydrochloric acid or the like.
- a cyano group and a carboxyl group that are both acceptors and anchors can be introduced into the terminal thiophene ring.
- Such a compound can be suitably used as a dye for a dye-sensitized solar cell. That is, an electrode in which the fluorene compound of the present invention is dissolved in an organic solvent and adsorbed on a metal oxide layer (for example, a TiO 2 film (or layer)) disposed on the surface of the transparent electrode is used as one electrode. By disposing the other electrode through a layer that performs a redox reaction, the dye-sensitized solar cell of the present invention can be obtained.
- a metal oxide layer for example, a TiO 2 film (or layer)
- Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
- a solid electrolyte such as a conductive polymer
- the metal oxide layer for example, a TiO 2 film (or layer)
- Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
- photosensitization can be achieved by adsorbing the above-described dye compound in a particle layer of a metal oxide such as titanium oxide laminated on the surface of a transparent electrode disposed on the anode. it can.
- the thickness (film thickness) of the metal oxide particles such as titanium oxide is usually 1 to 50 ⁇ m, preferably 10 to 30 ⁇ m.
- One electrode of the dye-sensitized solar cell is an electrode in which the dye is adsorbed on the surface of the transparent electrode as described above, but the other electrode is formed by sputtering or depositing a conductive metal such as Pt on the surface of the substrate.
- a catalyst electrode made of a laminated body having a thickness of 2 to 100 nm is used.
- an electrolyte is filled between the electrodes as described above.
- the electrolyte solution is formed from lithium iodide / iodine / t-butylpyridine / iodide 1,2-dimethyl-3-propyl imidazolium used conventionally I - / I 3 - as redox solution
- an iodine-based electrolytic solution can be used, in the present invention, by introducing an alkyl group or the like into the fluorene ring, a conductive polymer can be used instead of the liquid electrolytic solution.
- solid electrolyte examples include conductive polymers (polyaniline, polyethylenedioxythiophene, poly (3-hexylthiophene), polypyrrole, etc.) and international patent applications (PCT / JP2010 / 061514) filed earlier by the present applicant.
- Composition for solid electrolyte according to the present invention solid electrolyte comprising a polymer compound obtained by polymerizing a monomer containing a monomer having a chelating ability, and a charge transfer material which is a carbon material and / or a ⁇ -conjugated polymer) Composition
- solid electrolyte comprising a polymer compound obtained by polymerizing a monomer containing a monomer having a chelating ability, and a charge transfer material which is a carbon material and / or a ⁇ -conjugated polymer
- the width of the gap between the electrodes filled with the above redox solution or conductive polymer usually needs to be determined by the balance with the titania film thickness. It is preferable to adjust within a range of 50 ⁇ m, preferably 10 to 30 ⁇ m.
- the dye-sensitized solar cell using the conductive polymer as described above has a power generation efficiency equal to or higher than that of a dye-sensitized solar cell using a conventionally used dye.
- the dye-sensitized solar cell of the present invention will be described from the step of producing a fluorene compound with specific examples. These examples show one embodiment of the present invention, and the present invention is not limited to these examples.
- MK-2 was prepared according to the description in Example 2 of WO2007 / 119525.
- Example 1 2.50 g of 2-bromofluorene represented by the following formula (A) (manufactured by Sigma-Aldrich) and 4.29 g of 3-hexylthiophene-5-boronic acid ester represented by the following formula (B) were mixed, The mixture was refluxed with heating in dimethoxyethane for 8 hours in the presence of 0.36 g of bis (triphenylphosphine) palladium (II) dichloride and 13.00 g of 25% aqueous sodium carbonate solution.
- A 2-bromofluorene represented by the following formula (A) (manufactured by Sigma-Aldrich)
- 3-hexylthiophene-5-boronic acid ester represented by the following formula (B) were mixed, The mixture was refluxed with heating in dimethoxyethane for 8 hours in the presence of 0.36 g of bis (triphenylphosphine) palladium (II) dichloride and 13.00 g of 25%
- reaction solution was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water and saturated brine.
- the obtained washed product was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
- DMF N, N-dimethylformamide
- a fluorene derivative represented by the formula (D) was dissolved in 4 ml of DMF.
- the Vilsmeier reagent prepared by the above operation was added dropwise at room temperature and stirred at 70 ° C. for 1 hour. Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
- the obtained organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product.
- Example 2 In Example 1, 0.1 ml of phosphoryl chloride was cooled to 5 ° C., 0.21 ml of DMF was added dropwise, and the mixture was stirred for 1 hour to prepare a Vilsmeier reagent. 0.52 g of the fluorene derivative represented by the formula (E) was dissolved in 4 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature and stirred at 70 ° C. for 1 hour. Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and extraction was performed with ethyl acetate. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
- FIG. 5 shows the 1 H-NMR result of the compound represented by the formula (K), and FIG. 6 shows the LC-MS result.
- Example 3 0.06 ml of phosphoryl chloride was cooled to 5 ° C., 0.12 ml of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent. 0.35 g of the fluorene derivative represented by the formula (F) was dissolved in 3 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature, followed by stirring at 70 ° C. for 1 hour.
- Example 4 A dimethyl sulfoxide solution of 5.00 g of 2-bromofluorene represented by formula (A) (manufactured by Sigma-Aldrich), 13.79 g of 1-bromooctane represented by formula (N), and 0.66 g of tetrabutylammonium bromide was added with 10 ml of 50 wt% sodium hydroxide aqueous solution and stirred at 70 ° C. for 12 hours for reaction. After the reaction, ethyl acetate was added, and the organic phase was washed with 2N hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (solvent: hexane) to obtain 7.09 g of a 9,9-di-n-octylfluorene derivative represented by the formula (O). The yield was 70%.
- A 2-bromoflu
- Example 5 0.09 ml of phosphoryl chloride was cooled to 5 ° C., 0.18 ml of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent.
- Example 6 0.06 ml of sulforyl hydrochloride was cooled to 5 ° C., 0.12 m of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent.
- the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
- Example 7 (Creation of dye-sensitized solar cell using liquid electrolyte) (1) ⁇ Creation of photoelectrode> Using a FTO glass with an FTO electrode coating formed on one side as a transparent electrode substrate, a commercially available titanium oxide paste (manufactured by Solaronix) was applied to the FTO surface of this transparent electrode by a screen printing method. The average particle diameter of this titanium oxide is 13 ⁇ m. This was fired in air at 450 ° C. to prepare a titanium oxide porous film layer, and this was treated with titanium tetrachloride to prepare a titanium oxide photoelectrode.
- a commercially available titanium oxide paste manufactured by Solaronix
- Table 1 shows the performance of the dye-sensitized solar cell using a liquid electrolyte depending on the dye used.
- Jsc, Voc, FF, and Eff represent a short-circuit current, an open-circuit voltage, a fill factor, and conversion efficiency, respectively.
- the dye MK-2 shown in the above table is a compound having the following structure.
- Example 8 (Preparation of dye-sensitized solar cell using solid electrolyte) (1) ⁇ Creation of photoelectrode> Using FTO glass with an FTO electrode coating formed on one side as a transparent electrode substrate, an IPA solution of titanium alkoxide was applied to the FTO surface of this transparent electrode and heated to 120 ° C. to create a short-circuit prevention layer. On top of that, a commercially available titanium oxide paste (manufactured by Solaronix) was applied by screen printing. The average particle type of this titanium oxide is 37 ⁇ m. This was fired in air at 450 ° C. to prepare a titanium oxide porous film layer, and this was treated with titanium tetrachloride to prepare a titanium oxide photoelectrode.
- IPA solution of titanium alkoxide was applied to the FTO surface of this transparent electrode and heated to 120 ° C. to create a short-circuit prevention layer.
- a commercially available titanium oxide paste manufactured by Solaronix
- Jsc, Voc, FF, and Eff represent a short-circuit current, an open-circuit voltage, a fill factor, and conversion efficiency, respectively.
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Abstract
[Solution] The present invention provides a novel fluorene compound such as one represented by formula (I) and a fluorene derivative. An electrode for a dye-sensitized solar cell and a dye-sensitized solar cell using the electrode can be obtained by having the fluorene compound or a derivative thereof adsorbed on metal oxide particles such as titanium oxide particles that constitute a dye-sensitized solar cell.
[Effect] A dye-sensitized solar cell using this fluorene compound or a derivative thereof can be operated at high efficiency.
(In formula (I), R1 and R2 each represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group; X represents a cyclic structure such as a thiophene ring represented by formulae; and n represents an integer of 1-12.)
Description
本発明は新規なフルオレン化合物、この化合物を用いた色素増感型太陽電池用色素、このフルオレン化合物を吸着した色素増感型太陽電池用色素含有電極、および、このような電極を有する色素増感太陽電池に関する。
The present invention relates to a novel fluorene compound, a dye-sensitized solar cell dye using the compound, a dye-sensitized solar cell dye-containing electrode adsorbing the fluorene compound, and a dye-sensitized dye having such an electrode. It relates to solar cells.
色素増感太陽電池に用いられる増感色素としては、一般にＲｕ金属錯体系色素が用いられる。
このようなＲｕ金属錯体色素は吸光係数が余り高くなく、単分子として光吸収能は大きくは無いが、色素増感太陽電池においてはナノポーラスな金属酸化物を電極として用いる事が出来るためアノード電極の膜厚を厚くする事で、単位面積当たりの色素量を多くすることが可能であり、こうした機能を利用することにより高い光電変換効率を実現する事ができる。しかし、希少金属であるＲｕを用いているため将来的には供給安定面で不安さを有しており、また、高い光電変換効率を維持する為には色素使用量も増えてしまう。これら背景に基づきＲｕ錯体などの希少金属を用いない色素増感太陽電池用有機色素が注目されている。 As the sensitizing dye used in the dye-sensitized solar cell, a Ru metal complex dye is generally used.
Such a Ru metal complex dye does not have a very high extinction coefficient and does not have a large light absorption ability as a single molecule. However, in a dye-sensitized solar cell, a nanoporous metal oxide can be used as an electrode. By increasing the film thickness, the amount of dye per unit area can be increased, and high photoelectric conversion efficiency can be realized by using such a function. However, since Ru, which is a rare metal, is used, there is anxiety in terms of stable supply in the future, and the amount of dye used increases in order to maintain high photoelectric conversion efficiency. Based on these backgrounds, organic dyes for dye-sensitized solar cells that do not use rare metals such as Ru complexes have attracted attention.
このようなＲｕ金属錯体色素は吸光係数が余り高くなく、単分子として光吸収能は大きくは無いが、色素増感太陽電池においてはナノポーラスな金属酸化物を電極として用いる事が出来るためアノード電極の膜厚を厚くする事で、単位面積当たりの色素量を多くすることが可能であり、こうした機能を利用することにより高い光電変換効率を実現する事ができる。しかし、希少金属であるＲｕを用いているため将来的には供給安定面で不安さを有しており、また、高い光電変換効率を維持する為には色素使用量も増えてしまう。これら背景に基づきＲｕ錯体などの希少金属を用いない色素増感太陽電池用有機色素が注目されている。 As the sensitizing dye used in the dye-sensitized solar cell, a Ru metal complex dye is generally used.
Such a Ru metal complex dye does not have a very high extinction coefficient and does not have a large light absorption ability as a single molecule. However, in a dye-sensitized solar cell, a nanoporous metal oxide can be used as an electrode. By increasing the film thickness, the amount of dye per unit area can be increased, and high photoelectric conversion efficiency can be realized by using such a function. However, since Ru, which is a rare metal, is used, there is anxiety in terms of stable supply in the future, and the amount of dye used increases in order to maintain high photoelectric conversion efficiency. Based on these backgrounds, organic dyes for dye-sensitized solar cells that do not use rare metals such as Ru complexes have attracted attention.
一般的に有機増感色素はＲｕ系色素に比べ高いモル吸光係数を有するが、逆にアノード電極の膜厚を厚くしても光電変換効率は大きくは向上しない。また、有機系色素に用いる骨格には光吸収能と電荷移動能を両立するために高い共役構造が必要とされるが、これら共役構造が発達する事で溶剤等への溶解性が悪くなりアノード電極への染色が困難となる。更に、色素増感太陽電池用の有機色素には電解質として使用されるヨウ素アニオンからの電荷移動を効率よく行うために窒素元素を含むヘテロ環及び／またはアミン基をドナー骨格に用いる事が多い。有機色素としては、これら各要素を取り入れた設計が重要であるが、吸収波長領域がルテニウム錯体とほぼ同等である有機色素の場合でも、ルテニウム錯体に比べて開放電圧が低いため変換効率が低いとの問題があった。
Generally, organic sensitizing dyes have a higher molar extinction coefficient than Ru-based dyes, but conversely, even if the thickness of the anode electrode is increased, the photoelectric conversion efficiency is not greatly improved. In addition, the skeleton used for organic dyes requires a high conjugated structure in order to achieve both the light absorption ability and the charge transfer ability, but the development of these conjugated structures makes the solubility in solvents worse and the anode. It becomes difficult to dye the electrodes. Further, organic dyes for dye-sensitized solar cells often use a heterocycle containing nitrogen element and / or an amine group as a donor skeleton in order to efficiently transfer charges from iodine anions used as an electrolyte. As an organic dye, a design that incorporates these elements is important. However, even in the case of an organic dye whose absorption wavelength region is almost the same as that of a ruthenium complex, the conversion efficiency is low because the open-circuit voltage is lower than that of the ruthenium complex. There was a problem.
一方、色素増感太陽電池には電解質として通常はヨウ素及びヨウ化リチウムなどのヨウ素アニオンの組み合わせによるＩ-／Ｉ3
-のようなレドックス能を有する電解質（酸化還元反応が可能な電解質）が利用される。こうしたレドックス能を有する電解質のなかでも、Ｉ-／Ｉ3
-の溶液は安定性に優れている為に広汎に使用されているが、こうしたＩ-／Ｉ3
-溶液は、セル耐久性に関してはヨウ素による配線材料の腐食、劣化が問題となっており、Ｉ-／Ｉ3
-溶液に代わるレドックスとの酸化還元を行える色素が要求されているが、良好なものは殆ど報告されていない。
On the other hand, dye-sensitized solar cells usually use an electrolyte having redox ability such as I − / I 3 − (electrolyte capable of redox reaction) by combining iodine and an iodine anion such as lithium iodide. Is done. Among the electrolytes having such redox ability, the solution of I − / I 3 − is widely used because of its excellent stability, but such an I − / I 3 − solution is related to cell durability. corrosion of the wiring material by iodine, degradation has become a problem, I - / I 3 - is a dye capable of performing redox redox alternative to the solution is required, good ones have been reported little.
この問題を解決すべく開発されたのがオリゴｎ－ヘキシルチオフェン（共役結合系）、シアノ酢酸基（アクセプター、アンカー）の組み合わせに対して、ドナー部としてＮ－エチルカルバゾールを用いたＭＫ-２である（非特許文献１参照）。ＭＫ-２は従来の有機色素と比較して開放電圧が高く、また変換効率も高い優れた色素であり、有機色素としては非常に高い変換効率を発現する事が確認されている。ＭＫ-２の構造を下記に（ＭＫ－２）として示す。
To solve this problem, MK-2 was developed using N-ethylcarbazole as the donor part for the combination of oligo n-hexylthiophene (conjugated bond system) and cyanoacetic acid group (acceptor, anchor). Yes (see Non-Patent Document 1). MK-2 is an excellent dye that has a higher open-circuit voltage and higher conversion efficiency than conventional organic dyes, and has been confirmed to exhibit very high conversion efficiency as an organic dye. The structure of MK-2 is shown below as (MK-2).
本発明は、窒素元素を含むヘテロ環及びアミン基を持たないフルオレン化合物をドナーとした、新規フルオレン化合物を提供することを目的としており、色素染色溶剤としてトルエン等への汎用溶剤への溶解性が良好でありながら、高性能な色素増感太陽電池用増感色素を提供することを目的としている。
An object of the present invention is to provide a novel fluorene compound using a fluorene compound containing a nitrogen-containing heterocycle and no amine group as a donor, and has a solubility in a general-purpose solvent such as toluene as a dye dyeing solvent. An object of the present invention is to provide a sensitizing dye for a dye-sensitized solar cell which is good but has a high performance.
また本発明は、上記フルオレン化合物を用いる事で高性能な色素増感太陽電池用色素含有電極を提供することを目的としている。
更には、HOMO-LUMO準位の調整による非ヨウ素系レドックス溶液を用いて発電が可能となる色素増感太陽電池用色素含有電極を提供する事を目的としている。 Another object of the present invention is to provide a dye-containing electrode for a dye-sensitized solar cell having high performance by using the fluorene compound.
It is another object of the present invention to provide a dye-containing electrode for a dye-sensitized solar cell that can generate power using a non-iodine redox solution by adjusting the HOMO-LUMO level.
更には、HOMO-LUMO準位の調整による非ヨウ素系レドックス溶液を用いて発電が可能となる色素増感太陽電池用色素含有電極を提供する事を目的としている。 Another object of the present invention is to provide a dye-containing electrode for a dye-sensitized solar cell having high performance by using the fluorene compound.
It is another object of the present invention to provide a dye-containing electrode for a dye-sensitized solar cell that can generate power using a non-iodine redox solution by adjusting the HOMO-LUMO level.
さらに本発明は、上記フルオレン化合物を用いた電極を有する色素増感太陽電池を提供することを目的としている。
Furthermore, an object of the present invention is to provide a dye-sensitized solar cell having an electrode using the fluorene compound.
本発明の新規なフルオレン化合物は、次式（Ｉ）で表わすことができる。
The novel fluorene compound of the present invention can be represented by the following formula (I).
但し、上記式（１）、（２）および（３）において、Ｒ3およびＲ4はそれぞれ独立に水素原子、アルキル基、アリール基およびアルコキシ基よりなる群から選ばれる少なくとも一種類の原子あるいは基を表わす。
However, in the above formulas (1), (2) and (3), R 3 and R 4 are each independently at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an alkoxy group. Represents.
また、本発明の色素増感型太陽電池用色素は、上記式（Ｉ）で表されるフルオレン化合物を色素増感型太陽電池の増感色素として使用するものである。
さらに、本発明の色素増感型太陽電池用色素含有電極は、上記の式（Ｉ）で表わされるフルオレン化合物を金属酸化物粒子の表面に吸着させたフルオレン化合物被覆金属酸化物粒子が金属製電極表面に配置された構成を有する。 Moreover, the dye for dye-sensitized solar cells of the present invention uses the fluorene compound represented by the above formula (I) as the sensitizing dye of the dye-sensitized solar cell.
Further, in the dye-containing electrode for a dye-sensitized solar cell of the present invention, the fluorene compound-coated metal oxide particles obtained by adsorbing the fluorene compound represented by the above formula (I) on the surface of the metal oxide particles are metal electrodes. It has the structure arrange | positioned on the surface.
さらに、本発明の色素増感型太陽電池用色素含有電極は、上記の式（Ｉ）で表わされるフルオレン化合物を金属酸化物粒子の表面に吸着させたフルオレン化合物被覆金属酸化物粒子が金属製電極表面に配置された構成を有する。 Moreover, the dye for dye-sensitized solar cells of the present invention uses the fluorene compound represented by the above formula (I) as the sensitizing dye of the dye-sensitized solar cell.
Further, in the dye-containing electrode for a dye-sensitized solar cell of the present invention, the fluorene compound-coated metal oxide particles obtained by adsorbing the fluorene compound represented by the above formula (I) on the surface of the metal oxide particles are metal electrodes. It has the structure arrange | positioned on the surface.
また本発明の色素増感型太陽電池は、上記のように表面にフルオレン化合物被覆金属酸化物粒子が配置された透明電極を一方の電極とし、他方の電極として触媒電極を配置し、該透明電極と触媒電極との間に電解質を挟持してなる。
Further, the dye-sensitized solar cell of the present invention has a transparent electrode having a fluorene compound-coated metal oxide particle disposed on the surface as described above as one electrode and a catalyst electrode as the other electrode. And the catalyst electrode.
本発明のフルオレン化合物は新規な化合物である。このフルオレン化合物は色素増感型太陽電池に用いる色素として有効に利用することができる。
すなわち、窒素元素を含むヘテロ環及びアミン基を持たないフルオレン化合物をドナー骨格として適用し、側鎖を有する共役系低分子のオリゴチオフェン等を用いることでトルエン等の汎用溶剤に対する溶解性付与、色素間スタックの抑制、光電極等からの電荷の漏れの抑制を可能にし、共役長の調整によって光吸収波長領域および電荷移動能の調整等の設計を行うことで色素増感太陽電池に用いる色素として有効に利用することができる。 The fluorene compound of the present invention is a novel compound. This fluorene compound can be effectively used as a dye used in a dye-sensitized solar cell.
In other words, applying a fluorene compound containing a nitrogen element heterocycle and no amine group as a donor skeleton, and using a conjugated low-molecular oligothiophene having a side chain, etc., imparts solubility to general-purpose solvents such as toluene, dye As a dye to be used in dye-sensitized solar cells by controlling inter-stacking, suppressing charge leakage from photoelectrodes, etc., and adjusting the light absorption wavelength region and charge transferability by adjusting the conjugate length It can be used effectively.
すなわち、窒素元素を含むヘテロ環及びアミン基を持たないフルオレン化合物をドナー骨格として適用し、側鎖を有する共役系低分子のオリゴチオフェン等を用いることでトルエン等の汎用溶剤に対する溶解性付与、色素間スタックの抑制、光電極等からの電荷の漏れの抑制を可能にし、共役長の調整によって光吸収波長領域および電荷移動能の調整等の設計を行うことで色素増感太陽電池に用いる色素として有効に利用することができる。 The fluorene compound of the present invention is a novel compound. This fluorene compound can be effectively used as a dye used in a dye-sensitized solar cell.
In other words, applying a fluorene compound containing a nitrogen element heterocycle and no amine group as a donor skeleton, and using a conjugated low-molecular oligothiophene having a side chain, etc., imparts solubility to general-purpose solvents such as toluene, dye As a dye to be used in dye-sensitized solar cells by controlling inter-stacking, suppressing charge leakage from photoelectrodes, etc., and adjusting the light absorption wavelength region and charge transferability by adjusting the conjugate length It can be used effectively.
本発明のフルオレン化合物からなる色素を酸化チタンに吸着した電極は、色素増感型太陽電池用の電極として有効に使用することができる。この電極を有する色素増感型太陽電池は、ＭＫ-２を用いた太陽電池よりも開放電圧および短絡電流密度が高く、さらに変換効率も高い値を示す。また、本発明のフルオレン化合物は、ＭＫ-２より低い吸光係数を有しており、この特性を利用して光電極の有効面積を増やすことで高い変換効率を有する色素増感太陽電池用光電極の提供が可能となる。
The electrode in which the dye comprising the fluorene compound of the present invention is adsorbed on titanium oxide can be effectively used as an electrode for a dye-sensitized solar cell. The dye-sensitized solar cell having this electrode has higher open-circuit voltage and short-circuit current density and higher conversion efficiency than the solar cell using MK-2. Further, the fluorene compound of the present invention has a lower extinction coefficient than that of MK-2, and by utilizing this characteristic, the photoelectrode for dye-sensitized solar cell having high conversion efficiency by increasing the effective area of the photoelectrode Can be provided.
しかも、本発明のフルオレン化合物からなる色素を含有する電極を用いることにより、非ヨウ素系電解質での発電が可能になり、特に色素増感型の太陽電池では必須構成要件であった液体の電解液を使用せずに、これに代わって導電性ポリマーなどの固体電解質を用いて発電することが可能になる。従って、ヨウ素レドックスによるセル配線材料の腐食を抑制して高寿命なセルの提供又は色素増感型太陽電池からの電解液の漏れが発生しないという新たな色素増感型太陽電池を提供することができる。
Moreover, by using an electrode containing a dye comprising the fluorene compound of the present invention, it is possible to generate power with a non-iodine-based electrolyte, and in particular, a liquid electrolyte that has been an essential constituent requirement for dye-sensitized solar cells Instead of this, it is possible to generate electric power using a solid electrolyte such as a conductive polymer instead. Accordingly, it is possible to provide a new dye-sensitized solar cell that suppresses corrosion of cell wiring materials due to iodine redox and provides a long-life cell or does not cause leakage of electrolyte from the dye-sensitized solar cell. it can.
次の本発明のフルオレン化合物、このフルオレン化合物からなる色素増感型太陽電池用色素、この色素を用いた色素増感型太陽電池用色素含有電極および色素増感型太陽電池について具体的に説明する。
Next, a fluorene compound of the present invention, a dye for a dye-sensitized solar cell comprising the fluorene compound, a dye-containing electrode for a dye-sensitized solar cell and a dye-sensitized solar cell using the dye will be specifically described. .
本発明のフルオレン化合物は下記式（Ｉ)で表すことができる。
The fluorene compound of the present invention can be represented by the following formula (I).
特に本発明では、Ｒ1およびＲ2の両者が水素原子か、同一の炭素数を有するアルキル基、アリール基およびアルコキシ基であることが好ましく、Ｒ1およびＲ2が、炭素数１～１２のアルキル基、炭素数１～１２のアリール基、または、炭素数１～１２のアルコキシ基のいずれかであることが好ましい。
In particular, in the present invention, it is preferable that both R 1 and R 2 are hydrogen atoms or alkyl groups, aryl groups and alkoxy groups having the same carbon number, and R 1 and R 2 are those having 1 to 12 carbon atoms. An alkyl group, an aryl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms is preferable.
特に本発明では、Ｒ1およびＲ2が共に水素原子またはアルキル基である化合物は、色素増感型太陽電池用の電極を形成するフルオレン化合物として適している。このような置換基を用いたフルオレン化合物は、色素増感型太陽電池の電極として使用する色素化合物として使用した場合に、太陽電池の酸化還元反応を行う電解質は、Ｉ-／Ｉ3
-のような液体電解質のみならず、導電性ポリマーのような固体電解質でも好適に使用することが可能となる。
In particular, in the present invention, a compound in which R 1 and R 2 are both hydrogen atoms or alkyl groups is suitable as a fluorene compound that forms an electrode for a dye-sensitized solar cell. When such a fluorene compound using a substituent is used as a dye compound used as an electrode of a dye-sensitized solar cell, an electrolyte that performs a redox reaction of the solar cell is, for example, I − / I 3 − . Not only a liquid electrolyte but also a solid electrolyte such as a conductive polymer can be suitably used.
上記式（Ｉ）において、ｎは１～１２の整数であり、２～１０の整数であることが特に好ましい。
上記式（I)において、Xは、次式（１）、（２）、（３）のいずれかの基である。 In the above formula (I), n is an integer of 1 to 12, particularly preferably an integer of 2 to 10.
In the above formula (I), X is any group of the following formulas (1), (2), and (3).
上記式（I)において、Xは、次式（１）、（２）、（３）のいずれかの基である。 In the above formula (I), n is an integer of 1 to 12, particularly preferably an integer of 2 to 10.
In the above formula (I), X is any group of the following formulas (1), (2), and (3).
これらの中でもＲ3およびＲ4のいずれか一方が水素原子であり、他方の基は、炭素数１～１２のアルキル基、炭素数１～１２のアリール基、または、炭素数１～１２のアルコキシ基のいずれかであることが好ましい。
Among these, one of R 3 and R 4 is a hydrogen atom, and the other group is an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Preferably any of the groups.
また、Ｒ3およびＲ4のいずれか一方が水素原子であり、他方の基は、アルキル基、アリール基、または、アルコキシ基のいずれかである場合、これらの基は直鎖状の基であることが好ましい。
When either one of R 3 and R 4 is a hydrogen atom and the other group is an alkyl group, an aryl group, or an alkoxy group, these groups are linear groups. It is preferable.
特に本発明においては式（Ｉ）におけるＸはチオフェン環を有する上記式（１）であることが好ましく、この場合、チオフェン環に結合しているＲ3，Ｒ4の内のいずれか一方は、水素原子であり、他方が炭素数２～１２のアルキル基、アリール基またはアルコキシ基のいずれかであることが好ましく、このような置換基を有するチオフェン環が通常は２～１２個、好ましくは３～７個結合していること（即ち式（Ｉ）におけるｎが通常は２～１２、好ましくは３～７である）が特に望ましい。
In particular, in the present invention, X in the formula (I) is preferably the above formula (1) having a thiophene ring, and in this case, one of R 3 and R 4 bonded to the thiophene ring is It is preferably a hydrogen atom and the other is an alkyl group having 2 to 12 carbon atoms, an aryl group or an alkoxy group, and usually has 2 to 12 thiophene rings having such a substituent, preferably 3 It is particularly desirable that ˜7 are bonded (that is, n in formula (I) is usually 2 to 12, preferably 3 to 7).
さらに、本発明の色素増感型太陽電池用色素としては、以下に示す式で表す化合物を使用することができる。
Furthermore, as the dye for a dye-sensitized solar cell of the present invention, a compound represented by the following formula can be used.
このような本発明の色素増感型太陽電池用色素の具体的な例として、例えばｎが３の化合物を示せば次のようになる。
As a specific example of such a dye-sensitized solar cell dye of the present invention, for example, a compound having n of 3 is shown as follows.
また、Ｒ1およびＲ2は、水素原子であっても良いが、直鎖状のアルキル基であることが好ましく、この場合、Ｒ1およびＲ2は同一の炭素数を有するアルキル基であることが特に好ましい。このようにフルオレン構造中に同一炭素数の直鎖状の基が２個有する化合物を使用することにより、電解液を用いる代わりに導電性ポリマーなど固体の導電性物質を使用しやすくなる。
R 1 and R 2 may be hydrogen atoms, but are preferably linear alkyl groups. In this case, R 1 and R 2 are alkyl groups having the same carbon number. Is particularly preferred. Thus, by using a compound having two linear groups having the same carbon number in the fluorene structure, it becomes easy to use a solid conductive material such as a conductive polymer instead of using an electrolytic solution.
また、本発明において、Ｒ3およびＲ4は、水素原子、アルキル基、アリール基およびアルコキシ基よりなる群から選ばれる少なくとも一種類の原子あるいは基であるが、Ｒ3およびＲ4のいずれか一方が水素原子であり、他方がアルキル基、アリール基およびアルコキシ基であることが好ましい。
In the present invention, R 3 and R 4 are at least one atom or group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an alkoxy group, and either one of R 3 and R 4 Is a hydrogen atom, and the other is preferably an alkyl group, an aryl group and an alkoxy group.
このような化合物は、２－ブロモフルオレンあるいはその誘導体を出発物質として合成することができる。
２－ブロモフルオレンをＲ3が水素原子でＲ4がヘキシル基の場合を例にして本発明の化合物の合成方法を説明すると、まず２－ブロモフルオレンに３－ヘキシルチオフェン－５－ボロン酸エステルとを反応させる。このとき触媒としてビス（トリフェニルホスフィン）パラジウム（II)ジクロリドおよび炭酸ナトリウム水溶液の存在下にジメトキシエタン中で還流する。このときの還流時間は通常は３～１２時間である。 Such a compound can be synthesized using 2-bromofluorene or a derivative thereof as a starting material.
The method for synthesizing the compound of the present invention will be described by taking 2-bromofluorene as an example where R 3 is a hydrogen atom and R 4 is a hexyl group. First, 2-bromofluorene is converted to 3-hexylthiophene-5-boronic acid ester. React. At this time, the mixture is refluxed in dimethoxyethane in the presence of bis (triphenylphosphine) palladium (II) dichloride and an aqueous sodium carbonate solution as a catalyst. The reflux time at this time is usually 3 to 12 hours.
２－ブロモフルオレンをＲ3が水素原子でＲ4がヘキシル基の場合を例にして本発明の化合物の合成方法を説明すると、まず２－ブロモフルオレンに３－ヘキシルチオフェン－５－ボロン酸エステルとを反応させる。このとき触媒としてビス（トリフェニルホスフィン）パラジウム（II)ジクロリドおよび炭酸ナトリウム水溶液の存在下にジメトキシエタン中で還流する。このときの還流時間は通常は３～１２時間である。 Such a compound can be synthesized using 2-bromofluorene or a derivative thereof as a starting material.
The method for synthesizing the compound of the present invention will be described by taking 2-bromofluorene as an example where R 3 is a hydrogen atom and R 4 is a hexyl group. First, 2-bromofluorene is converted to 3-hexylthiophene-5-boronic acid ester. React. At this time, the mixture is refluxed in dimethoxyethane in the presence of bis (triphenylphosphine) palladium (II) dichloride and an aqueous sodium carbonate solution as a catalyst. The reflux time at this time is usually 3 to 12 hours.
この反応により２－ブロモフルオレンにヘキシル基を有するフルオレン環を一個導入することができる。
次いで、Ｎ－ブロモスクシンイミドのような臭素化剤を用いて、３－ヘキシルチオフェン基のチオフェン環の結合している水素原子のブロム原子に置換させることができ、このように臭素化したら上述のようにカップリング反応（スズキカップリング反応）を利用することにより、チオフェン環を次々と結合させることができる。そして、カップリングの際に使用するチオフェン環に結合している置換基を変えることにより、所望のアルキル基、アリール基、アルコキシ基を導入することができる。 By this reaction, one fluorene ring having a hexyl group can be introduced into 2-bromofluorene.
Then, using a brominating agent such as N-bromosuccinimide, it can be substituted with the bromine atom of the hydrogen atom to which the thiophene ring of the 3-hexylthiophene group is bonded. By using a coupling reaction (Suzuki coupling reaction), thiophene rings can be bonded one after another. And a desired alkyl group, aryl group, and alkoxy group can be introduce | transduced by changing the substituent couple | bonded with the thiophene ring used in the case of coupling.
次いで、Ｎ－ブロモスクシンイミドのような臭素化剤を用いて、３－ヘキシルチオフェン基のチオフェン環の結合している水素原子のブロム原子に置換させることができ、このように臭素化したら上述のようにカップリング反応（スズキカップリング反応）を利用することにより、チオフェン環を次々と結合させることができる。そして、カップリングの際に使用するチオフェン環に結合している置換基を変えることにより、所望のアルキル基、アリール基、アルコキシ基を導入することができる。 By this reaction, one fluorene ring having a hexyl group can be introduced into 2-bromofluorene.
Then, using a brominating agent such as N-bromosuccinimide, it can be substituted with the bromine atom of the hydrogen atom to which the thiophene ring of the 3-hexylthiophene group is bonded. By using a coupling reaction (Suzuki coupling reaction), thiophene rings can be bonded one after another. And a desired alkyl group, aryl group, and alkoxy group can be introduce | transduced by changing the substituent couple | bonded with the thiophene ring used in the case of coupling.
最初に使用するフルオレン誘導体の９位にある水素原子を、Ｒ1およびＲ2に置換したフルオレン誘導体を使用することにより、Ｒ1およびＲ2 がアルキル基、アリール基あるいはアルコキシ基である化合物を得ることができる。
A hydrogen atom in the 9-position of the fluorene derivative is first used, by using the fluorene derivative substituted on R 1 and R 2, to give a compound wherein R 1 and R 2 is an alkyl group, an aryl group or an alkoxy group be able to.
上記のようにして所望の数のチオフェン環を結合させた後、例えば、冷却した塩化ホスホリンにＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）を滴下してビルスマイヤー試薬を調製し、このビルスマイヤー試薬を上記のようにして調製したチオフェン環が結合したフルオレン誘導体に加えることにより、末端のチオフェン環にアルデヒド基を導入する。こうして得られた末端のチオフェン環にアルデヒド基が導入されたフルオレン誘導体アルデヒドとシアノ酢酸とを、ピペリジンの存在下に反応させ、反応物をクロロホルムなどで抽出して、抽出された有機相を塩酸などの鉱酸で処理することにより、末端のチオフェン環にアクセプターであると共にアンカーでもあるシアノ基およびカルボキシル基を導入することができる。
After a desired number of thiophene rings are bonded as described above, for example, N, N-dimethylformamide (DMF) is added dropwise to cooled phospholine chloride to prepare a Vilsmeier reagent. An aldehyde group is introduced into the terminal thiophene ring by adding to the fluorene derivative bound with the thiophene ring prepared as described above. The fluorene derivative aldehyde having an aldehyde group introduced into the terminal thiophene ring thus obtained is reacted with cyanoacetic acid in the presence of piperidine, and the reaction product is extracted with chloroform, and the extracted organic phase is extracted with hydrochloric acid or the like. By treating with a mineral acid, a cyano group and a carboxyl group that are both acceptors and anchors can be introduced into the terminal thiophene ring.
このような化合物は、色素増感型太陽電池用の色素として好適に使用することができる。すなわち、本発明のフロオレン化合物を有機溶媒に溶解して、透明電極の表面に配置した金属酸化物の層（例えばＴｉＯ2膜(或いは層)）に吸着させた電極を一方の電極とし、間に酸化還元反応を行う層を介して他方の電極を配置することにより、本発明の色素増感型太陽電池とすることができる。
Such a compound can be suitably used as a dye for a dye-sensitized solar cell. That is, an electrode in which the fluorene compound of the present invention is dissolved in an organic solvent and adsorbed on a metal oxide layer (for example, a TiO 2 film (or layer)) disposed on the surface of the transparent electrode is used as one electrode. By disposing the other electrode through a layer that performs a redox reaction, the dye-sensitized solar cell of the present invention can be obtained.
このような色素増感型太陽電池は、通常は図１に示すような断面構造を有している。
また、後述するように、酸化還元反応を行う層に導電性ポリマーなどのような固体電解質を用いる場合は、透明電極と金属酸化物の層（例えばＴｉＯ2膜(或いは層)）の間に電荷の漏れを防止する短絡防止層をもうけることができる。 Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
As will be described later, when a solid electrolyte such as a conductive polymer is used for the layer that performs the oxidation-reduction reaction, a charge is generated between the transparent electrode and the metal oxide layer (for example, a TiO 2 film (or layer)). It is possible to provide a short-circuit prevention layer that prevents leakage of the material.
また、後述するように、酸化還元反応を行う層に導電性ポリマーなどのような固体電解質を用いる場合は、透明電極と金属酸化物の層（例えばＴｉＯ2膜(或いは層)）の間に電荷の漏れを防止する短絡防止層をもうけることができる。 Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
As will be described later, when a solid electrolyte such as a conductive polymer is used for the layer that performs the oxidation-reduction reaction, a charge is generated between the transparent electrode and the metal oxide layer (for example, a TiO 2 film (or layer)). It is possible to provide a short-circuit prevention layer that prevents leakage of the material.
このような色素増感太陽電池は、通常は図２に示すような断面構造を有している。
色素増感型太陽電池では、上記のような色素化合物を陽極に配置された透明電極の表面に積層された酸化チタンなどの金属酸化物の粒子層中に吸着させることにより光増感させることができる。 Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
In dye-sensitized solar cells, photosensitization can be achieved by adsorbing the above-described dye compound in a particle layer of a metal oxide such as titanium oxide laminated on the surface of a transparent electrode disposed on the anode. it can.
色素増感型太陽電池では、上記のような色素化合物を陽極に配置された透明電極の表面に積層された酸化チタンなどの金属酸化物の粒子層中に吸着させることにより光増感させることができる。 Such a dye-sensitized solar cell usually has a cross-sectional structure as shown in FIG.
In dye-sensitized solar cells, photosensitization can be achieved by adsorbing the above-described dye compound in a particle layer of a metal oxide such as titanium oxide laminated on the surface of a transparent electrode disposed on the anode. it can.
このときの酸化チタンなどの金属酸化物粒子の粒子層の厚さ（膜厚）は通常は１～５０μｍ、好ましくは１０～３０μｍである。
色素増感型の太陽電池の一方の電極は、上記のように透明電極の表面に色素が吸着された電極であるが、他方の電極は基板の表面にＰｔなどの導電性金属をスパッタリング、蒸着などの方法により、例えば２～１００nmの厚さに積層した積層体からなる触媒電極を使用する。 In this case, the thickness (film thickness) of the metal oxide particles such as titanium oxide is usually 1 to 50 μm, preferably 10 to 30 μm.
One electrode of the dye-sensitized solar cell is an electrode in which the dye is adsorbed on the surface of the transparent electrode as described above, but the other electrode is formed by sputtering or depositing a conductive metal such as Pt on the surface of the substrate. For example, a catalyst electrode made of a laminated body having a thickness of 2 to 100 nm is used.
色素増感型の太陽電池の一方の電極は、上記のように透明電極の表面に色素が吸着された電極であるが、他方の電極は基板の表面にＰｔなどの導電性金属をスパッタリング、蒸着などの方法により、例えば２～１００nmの厚さに積層した積層体からなる触媒電極を使用する。 In this case, the thickness (film thickness) of the metal oxide particles such as titanium oxide is usually 1 to 50 μm, preferably 10 to 30 μm.
One electrode of the dye-sensitized solar cell is an electrode in which the dye is adsorbed on the surface of the transparent electrode as described above, but the other electrode is formed by sputtering or depositing a conductive metal such as Pt on the surface of the substrate. For example, a catalyst electrode made of a laminated body having a thickness of 2 to 100 nm is used.
上記のような電極間には通常は電解液が充填されている。この電解液としては従来から使用されているヨウ化リチウム/ヨウ素/ｔ-ブチルピリジン/ヨウ化1，2-ジメチル-3-プロピルイミダゾリウムから形成されるＩ-／Ｉ3
-レドックス溶液のようなヨウ素系の電解液を使用することもできるが、本発明では、フルオレン環にアルキル基などを導入することにより、液体である電解液の代わりに導電性ポリマーを使用することが可能になる。固体電解質としては、導電性ポリマー（ポリアニリン、ポリエチレンジオキシチオフェン、ポリ(３－ヘキシルチオフェン)、ポリピロールなど）や、本出願人が先に出願している国際特許出願（ＰＣＴ／ＪＰ２０１０／０６１５１４）に係る発明である固体電解質用組成物（キレート能を有するモノマーを含むモノマーを重合して得られる高分子化合物と、炭素材料および／またはπ共役系高分子である電荷移動性材料とを含む固体電解質用組成物）などを挙げることができる。このような固体電解質を用いると、液体であるＩ-／Ｉ3
-の溶液のような電解液のように液漏れを起こすことがないので、長寿命の色素増感型太陽電池を使用することができる。
Usually, an electrolyte is filled between the electrodes as described above. As the electrolyte solution is formed from lithium iodide / iodine / t-butylpyridine / iodide 1,2-dimethyl-3-propyl imidazolium used conventionally I - / I 3 - as redox solution Although an iodine-based electrolytic solution can be used, in the present invention, by introducing an alkyl group or the like into the fluorene ring, a conductive polymer can be used instead of the liquid electrolytic solution. Examples of the solid electrolyte include conductive polymers (polyaniline, polyethylenedioxythiophene, poly (3-hexylthiophene), polypyrrole, etc.) and international patent applications (PCT / JP2010 / 061514) filed earlier by the present applicant. Composition for solid electrolyte according to the present invention (solid electrolyte comprising a polymer compound obtained by polymerizing a monomer containing a monomer having a chelating ability, and a charge transfer material which is a carbon material and / or a π-conjugated polymer) Composition) and the like. When such a solid electrolyte is used, liquid leakage does not occur as in the case of an electrolyte such as a liquid I − / I 3 − solution. Therefore, a long-life dye-sensitized solar cell should be used. Can do.
本発明の色素増感型太陽電池において、上記のようなレドックス溶液あるいは導電性ポリマーを充填する電極間の間隙の幅は、通常チタニアの膜厚とのバランスで決定する必要があるが、１～５０μｍ、好ましくは１０～３０μｍの範囲内に調整するのが好ましい。
In the dye-sensitized solar cell of the present invention, the width of the gap between the electrodes filled with the above redox solution or conductive polymer usually needs to be determined by the balance with the titania film thickness. It is preferable to adjust within a range of 50 μm, preferably 10 to 30 μm.
しかも、このように導電性ポリマーを用いた色素増感型太陽電池は、従来から使用されている色素を用いた色素増感型太陽電池と同等若しくは同等以上の発電効率を有している。
Moreover, the dye-sensitized solar cell using the conductive polymer as described above has a power generation efficiency equal to or higher than that of a dye-sensitized solar cell using a conventionally used dye.
以下本発明の色素増感型太陽電池について、具体的に実施例を示してフルオレン化合物を製造する工程から説明する。
これらの実施例は、本発明の一態様を示すものであり、本発明は、これら実施例によって限定されるものではない。 Hereinafter, the dye-sensitized solar cell of the present invention will be described from the step of producing a fluorene compound with specific examples.
These examples show one embodiment of the present invention, and the present invention is not limited to these examples.
これらの実施例は、本発明の一態様を示すものであり、本発明は、これら実施例によって限定されるものではない。 Hereinafter, the dye-sensitized solar cell of the present invention will be described from the step of producing a fluorene compound with specific examples.
These examples show one embodiment of the present invention, and the present invention is not limited to these examples.
なお、本発明において、本発明の色素増感型太陽電池用色素の性能を評価させるために、ＭＫ-２を基準にして評価を行った。なお、ＭＫ－２は、ＷＯ２００７／１１９５２５の実施例２の記載に従って調製した。
In addition, in this invention, in order to evaluate the performance of the pigment | dye for dye-sensitized solar cells of this invention, it evaluated on the basis of MK-2. MK-2 was prepared according to the description in Example 2 of WO2007 / 119525.
次に本発明の実施例を示して本発明をさらに詳細に説明するが本発明はこれらによって限定されるものではない。
なお、1HNMRおよびLC-MSは、以下の装置および条件で測定した。
1HNMR（装置:JNM－ECX500M、５００MHz、溶媒:テトラヒドロフラン-d８）。
LC-MS（装置:LC部 Agilent １１００Series、MS部 Bruker Daltonics esquire4000、APCI法）。
また、太陽電池の性能は、以下の条件で測定した。
１ＳＵＮ、擬似太陽光（入射光強度１００ｍＷ／ｃｍ2 （AM1..5））を光源として、光電変換素子の色素増感電極側から入射させ、電圧/電流発生器（R6243, ADVANTEST）によって電圧印加し、電池特性を測定した。
〔実施例１〕
次式（Ａ）で表わされる２－ブロモフルオレン（シグマアルドリッチ社製）２．５０ｇと次式（Ｂ）で表わされる３－へキシルチオフェン－５－ボロン酸エステル４．２９ｇとを混合し、この混合物中にビス（トリフェニルホスフィン）パラジウム（II）ジクロリド０．３６ｇおよび、２５％炭酸ナトリウム水溶液１３．００ｇの存在下に、ジメトキシエタン中で8時間加熱環流を行った、 EXAMPLES Next, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited thereto.
1 HNMR and LC-MS were measured with the following apparatus and conditions.
1 HNMR (apparatus: JNM-ECX500M, 500 MHz, solvent: tetrahydrofuran-d8).
LC-MS (apparatus: LC part Agilent 1100Series, MS part Bruker Daltonics esquire4000, APCI method).
Moreover, the performance of the solar cell was measured under the following conditions.
1SUN, simulated sunlight (incident light intensity 100mW / cm 2 (AM1..5)) as a light source, incident from the dye-sensitized electrode side of the photoelectric conversion element, and voltage applied by voltage / current generator (R6243, ADVANTEST) The battery characteristics were measured.
[Example 1]
2.50 g of 2-bromofluorene represented by the following formula (A) (manufactured by Sigma-Aldrich) and 4.29 g of 3-hexylthiophene-5-boronic acid ester represented by the following formula (B) were mixed, The mixture was refluxed with heating in dimethoxyethane for 8 hours in the presence of 0.36 g of bis (triphenylphosphine) palladium (II) dichloride and 13.00 g of 25% aqueous sodium carbonate solution.
なお、1HNMRおよびLC-MSは、以下の装置および条件で測定した。
1HNMR（装置:JNM－ECX500M、５００MHz、溶媒:テトラヒドロフラン-d８）。
LC-MS（装置:LC部 Agilent １１００Series、MS部 Bruker Daltonics esquire4000、APCI法）。
また、太陽電池の性能は、以下の条件で測定した。
１ＳＵＮ、擬似太陽光（入射光強度１００ｍＷ／ｃｍ2 （AM1..5））を光源として、光電変換素子の色素増感電極側から入射させ、電圧/電流発生器（R6243, ADVANTEST）によって電圧印加し、電池特性を測定した。
〔実施例１〕
次式（Ａ）で表わされる２－ブロモフルオレン（シグマアルドリッチ社製）２．５０ｇと次式（Ｂ）で表わされる３－へキシルチオフェン－５－ボロン酸エステル４．２９ｇとを混合し、この混合物中にビス（トリフェニルホスフィン）パラジウム（II）ジクロリド０．３６ｇおよび、２５％炭酸ナトリウム水溶液１３．００ｇの存在下に、ジメトキシエタン中で8時間加熱環流を行った、 EXAMPLES Next, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited thereto.
1 HNMR and LC-MS were measured with the following apparatus and conditions.
1 HNMR (apparatus: JNM-ECX500M, 500 MHz, solvent: tetrahydrofuran-d8).
LC-MS (apparatus: LC part Agilent 1100Series, MS part Bruker Daltonics esquire4000, APCI method).
Moreover, the performance of the solar cell was measured under the following conditions.
1SUN, simulated sunlight (incident light intensity 100mW / cm 2 (AM1..5)) as a light source, incident from the dye-sensitized electrode side of the photoelectric conversion element, and voltage applied by voltage / current generator (R6243, ADVANTEST) The battery characteristics were measured.
[Example 1]
2.50 g of 2-bromofluorene represented by the following formula (A) (manufactured by Sigma-Aldrich) and 4.29 g of 3-hexylthiophene-5-boronic acid ester represented by the following formula (B) were mixed, The mixture was refluxed with heating in dimethoxyethane for 8 hours in the presence of 0.36 g of bis (triphenylphosphine) palladium (II) dichloride and 13.00 g of 25% aqueous sodium carbonate solution.
得られた粗生成物をガラムクロマトグラフィー（溶媒：ヘキサン/酢酸エチル＝50/1）で精製し、次式（Ｃ）で表わされるフルオレン誘導体２．６９ｇを得た。収率は７９％であった。
The obtained crude product was purified by galam chromatography (solvent: hexane / ethyl acetate = 50/1) to obtain 2.69 g of a fluorene derivative represented by the following formula (C). The yield was 79%.
攪拌後、溶媒を減圧下で留去し、残留物を酢酸エチルに溶解した。
有機相を１０％炭酸ナトリウム水溶液、水および飽和食塩水で洗浄し、この洗浄物を硫酸マグネシウムで乾燥させた後、溶媒を減圧下に除去し粗成生物を得た。 After stirring, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate.
The organic phase was washed with 10% aqueous sodium carbonate solution, water and saturated brine, and the washed product was dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product.
有機相を１０％炭酸ナトリウム水溶液、水および飽和食塩水で洗浄し、この洗浄物を硫酸マグネシウムで乾燥させた後、溶媒を減圧下に除去し粗成生物を得た。 After stirring, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate.
The organic phase was washed with 10% aqueous sodium carbonate solution, water and saturated brine, and the washed product was dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product.
この粗生成物から再結晶溶媒としてヘキサン/酢酸エチル＝25/1の混合溶媒を用いて再結晶を行うことにより次式（Ｃ－１）で表されるフルオレン誘導体１.９１ｇを得た。
収率は６４％であった。
From this crude product, 1.91 g of a fluorene derivative represented by the following formula (C-1) was obtained by recrystallization using a mixed solvent of hexane / ethyl acetate = 25/1 as a recrystallization solvent.
The yield was 64%.
収率は６４％であった。
The yield was 64%.
上記式（Ｂ）を用いたスズキカップリング反応および式（Ｃ）の化合物から式（Ｃ－１）の化合物を得た工程と同様の臭素化反応を繰り返すことにより、式（Ｄ）で表されるヘキシル置換チオフェンが三個連なったフルオレン誘導体、式（Ｅ）で表されるヘキシル置換チオフェンが四個連なったフルオレン誘導体、および式（Ｆ）で表されるヘキシル置換チオフェンが五個連なったフルオレン誘導体を合成することができた。
By repeating the Suzuki coupling reaction using the above formula (B) and the bromination reaction similar to the step of obtaining the compound of the formula (C-1) from the compound of the formula (C), it is represented by the formula (D). A fluorene derivative with three hexyl-substituted thiophenes, a fluorene derivative with four hexyl-substituted thiophenes represented by formula (E), and a fluorene derivative with five hexyl-substituted thiophenes represented by formula (F) Was able to be synthesized.
次に式（Ｄ）で表されるフルオレン誘導体０．５ｇをＤＭＦ４mlに溶解した。この溶液に上記の操作で調整したビルスマイヤー試薬を室温で滴下し、７０℃で１時間攪拌した。
その後、１０％の酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで抽出した。 Next, 0.5 g of a fluorene derivative represented by the formula (D) was dissolved in 4 ml of DMF. To this solution, the Vilsmeier reagent prepared by the above operation was added dropwise at room temperature and stirred at 70 ° C. for 1 hour.
Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
その後、１０％の酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで抽出した。 Next, 0.5 g of a fluorene derivative represented by the formula (D) was dissolved in 4 ml of DMF. To this solution, the Vilsmeier reagent prepared by the above operation was added dropwise at room temperature and stirred at 70 ° C. for 1 hour.
Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
得られた有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した後、溶媒を留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー（溶媒；ヘキサン/酢酸エチル＝４/１）で精製し、式（Ｇ）で表されるフルオレン誘導体アルデヒドを０．２９ｇ得た。収率は５６％であった。
The obtained organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain a crude product. The crude product was purified by column chromatography (solvent; hexane / ethyl acetate = 4/1) to obtain 0.29 g of a fluorene derivative aldehyde represented by the formula (G). The yield was 56%.
その後、反応液にクロロホルム５０mlを加え、有機相を１Ｎ-塩酸で処理し、水および飽和食塩水で洗浄し、硫酸ナトリウムで乾燥し、溶媒を減圧下で留去し粗生成物を得た。
得られた粗生成物をカラムクロマトグラフィー（溶媒：クロロホルム→クロロホルム/エタノール＝１０／１）により精製し、式（Ｈ）で表される色素化合物０．２７ｇを得た。収率は８４％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, the organic phase was treated with 1N hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product.
The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10/1) to obtain 0.27 g of a dye compound represented by the formula (H). The yield was 84%.
得られた粗生成物をカラムクロマトグラフィー（溶媒：クロロホルム→クロロホルム/エタノール＝１０／１）により精製し、式（Ｈ）で表される色素化合物０．２７ｇを得た。収率は８４％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, the organic phase was treated with 1N hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product.
The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10/1) to obtain 0.27 g of a dye compound represented by the formula (H). The yield was 84%.
得られた式（Ｈ）で表される化合物の1Ｈ-ＮＭＲの結果を図３に示すと共に、ＬＣ－ＭＳの結果を図４に示す。
The 1 H-NMR result of the obtained compound represented by the formula (H) is shown in FIG. 3, and the LC-MS result is shown in FIG.
実施例１において、塩化ホスホリル０．１mlを５℃に冷却し、ＤＭＦを０．２１ml滴下し、１時間攪拌し、ビルスマイヤー試薬を調製した。式（Ｅ）で表されるフルオレン誘導体０．５２ｇをＤＭＦ４mlで溶解し、そこへ上記で調製したビルスマイヤー試薬を室温で滴下し７０℃で１時間攪拌した。その後、１０％の酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで抽出を行った。有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。
In Example 1, 0.1 ml of phosphoryl chloride was cooled to 5 ° C., 0.21 ml of DMF was added dropwise, and the mixture was stirred for 1 hour to prepare a Vilsmeier reagent. 0.52 g of the fluorene derivative represented by the formula (E) was dissolved in 4 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature and stirred at 70 ° C. for 1 hour. Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and extraction was performed with ethyl acetate. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
得られた粗組成物を再結晶（溶媒：ヘキサン）で精製し、次式（Ｊ)で表されるフルオレン誘導体アルデヒドを０．４９ｇ得た。収率は９１％であった。
The obtained crude composition was purified by recrystallization (solvent: hexane) to obtain 0.49 g of a fluorene derivative aldehyde represented by the following formula (J). The yield was 91%.
その後、反応液にクロロホルム１００mlを加え、有機相を１N-塩酸で処理し、水および飽和食塩水で洗浄し、硫酸ナトリウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。得られた粗生成物をカラムクロマトグラフィー（溶媒：クロロホルム→クロロホルム／エタノール＝１０／１）により精製し、式（Ｋ)で表される色素化合物を得た。収率は８７％であった。
Thereafter, 100 ml of chloroform was added to the reaction solution, the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10/1) to obtain a dye compound represented by the formula (K). The yield was 87%.
得られた式（Ｋ）で表される化合物の1Ｈ-ＮＭＲの結果を図５に示すと共に、ＬＣ－ＭＳの結果を図６に示す。
FIG. 5 shows the 1 H-NMR result of the compound represented by the formula (K), and FIG. 6 shows the LC-MS result.
塩化ホスホリル０．０６mlを５℃に冷却し、ＤＭＦを０．１２ml滴下し、１時間攪拌し、ビルスマイヤー試薬を調製した。式（Ｆ)で表されるフルオレン誘導体０．３５ｇをDMF３mlで溶解し、そこに上記で調製したビルスマイヤー試薬を室温で滴下し、７０℃で１時間攪拌した。
0.06 ml of phosphoryl chloride was cooled to 5 ° C., 0.12 ml of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent. 0.35 g of the fluorene derivative represented by the formula (F) was dissolved in 3 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature, followed by stirring at 70 ° C. for 1 hour.
その後、１０％の酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで中和した。
有機相を水および飽和食塩水で洗浄し、酢酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。 Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and neutralized with ethyl acetate.
The organic phase was washed with water and saturated brine, dried over magnesium acetate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
有機相を水および飽和食塩水で洗浄し、酢酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。 Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and neutralized with ethyl acetate.
The organic phase was washed with water and saturated brine, dried over magnesium acetate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
その粗生成物を再結晶（溶媒：ヘキサン）で精製し、式（Ｌ)で表されるフルオレン誘導体アルデヒドを０．２５ｇ得た。収率は７０％であった。
The crude product was purified by recrystallization (solvent: hexane) to obtain 0.25 g of a fluorene derivative aldehyde represented by the formula (L). The yield was 70%.
その後、粗生成物をカラムクロマトグラフィー（溶媒：クロロホルム→クロロホルム／エタノール＝１０／１）により精製し、式（Ｍ)で表される色素化合物０．２１ｇを得た。収率は８０％であった。
Thereafter, the crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10/1) to obtain 0.21 g of a dye compound represented by the formula (M). The yield was 80%.
式（Ａ)で表される２-ブロモフルオレン（シグマアルドリッチ社製）５．００ｇ、式(Ｎ)で表される1-ブロモオクタン１３．７９ｇ、またテトラブチルアンモニウムブロミド０．６６ｇのジメチルスルホキシド溶液に、５０ｗｔ％水酸化ナトリウム水溶液10mlを加え、７０℃で１２時間攪拌し反応させた。反応後、酢酸エチルを加え、有機相を２N塩酸、水、及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した後、溶媒を減圧下で留去し粗生成物を得た。その粗生成物をカラムクロマトグラフィー（溶媒：ヘキサン）により精製し、式（Ｏ）で表される9，9-ジ-n-オクチルフルオレン誘導体７．０９ｇを得た。収率は７０％であった。
A dimethyl sulfoxide solution of 5.00 g of 2-bromofluorene represented by formula (A) (manufactured by Sigma-Aldrich), 13.79 g of 1-bromooctane represented by formula (N), and 0.66 g of tetrabutylammonium bromide Was added with 10 ml of 50 wt% sodium hydroxide aqueous solution and stirred at 70 ° C. for 12 hours for reaction. After the reaction, ethyl acetate was added, and the organic phase was washed with 2N hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (solvent: hexane) to obtain 7.09 g of a 9,9-di-n-octylfluorene derivative represented by the formula (O). The yield was 70%.
室温に冷却後、酢酸エチルで希釈し、有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。
得られた粗組成物をカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル＝５０：１）で精製し、式（Ｐ)で表される９，９-ジ-n-オクチルフルオレン誘導体３．８９ｇを得た。収率は７８％である。 After cooling to room temperature, the mixture was diluted with ethyl acetate, the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product.
The obtained crude composition was purified by column chromatography (solvent: hexane / ethyl acetate = 50: 1) to obtain 3.89 g of a 9,9-di-n-octylfluorene derivative represented by the formula (P). It was. The yield is 78%.
得られた粗組成物をカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル＝５０：１）で精製し、式（Ｐ)で表される９，９-ジ-n-オクチルフルオレン誘導体３．８９ｇを得た。収率は７８％である。 After cooling to room temperature, the mixture was diluted with ethyl acetate, the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product.
The obtained crude composition was purified by column chromatography (solvent: hexane / ethyl acetate = 50: 1) to obtain 3.89 g of a 9,9-di-n-octylfluorene derivative represented by the formula (P). It was. The yield is 78%.
攪拌後、溶媒を減圧下で留去し、酢酸エチルで溶解した。有機相を１０％炭酸ナトリウム、水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去して粗生成物を得た。
After stirring, the solvent was distilled off under reduced pressure and dissolved with ethyl acetate. The organic phase was washed with 10% sodium carbonate, water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
得られた粗生成物から再結晶（溶媒：ヘキサン／酢酸エチル＝２５／１）により、式（Ｑ)で表される粗生成物２．９１ｇを得た。収率は６７％であった。
2.91 g of the crude product represented by the formula (Q) was obtained by recrystallization (solvent: hexane / ethyl acetate = 25/1) from the obtained crude product. The yield was 67%.
式（Ｒ)で表される9，9-ジ-n-オクチルフルオレン誘導体０．４０ｇをDMF４mlで溶解し、上記で調製したビルスマイヤー試薬を室温で滴下し、７０℃で１時間攪拌した。
その後、１０％酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで抽出した。 0.49 g of the 9,9-di-n-octylfluorene derivative represented by the formula (R) was dissolved in 4 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise at room temperature, followed by stirring at 70 ° C. for 1 hour.
Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
その後、１０％酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで抽出した。 0.49 g of the 9,9-di-n-octylfluorene derivative represented by the formula (R) was dissolved in 4 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise at room temperature, followed by stirring at 70 ° C. for 1 hour.
Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下に留去して粗生成物を得た。
得られた粗生成物をカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル＝４／１）で精製し、式（Ｕ)で得られる9，9-n-ジ-オクチルフルオレン誘導体アルデヒド０．２８ｇを得た。収率は６７％であった。 The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
The resulting crude product was purified by column chromatography (solvent: hexane / ethyl acetate = 4/1) to obtain 0.28 g of the 9,9-n-di-octylfluorene derivative aldehyde obtained by the formula (U). It was. The yield was 67%.
得られた粗生成物をカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル＝４／１）で精製し、式（Ｕ)で得られる9，9-n-ジ-オクチルフルオレン誘導体アルデヒド０．２８ｇを得た。収率は６７％であった。 The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
The resulting crude product was purified by column chromatography (solvent: hexane / ethyl acetate = 4/1) to obtain 0.28 g of the 9,9-n-di-octylfluorene derivative aldehyde obtained by the formula (U). It was. The yield was 67%.
その後、反応液にクロロホルム５０mlを加え有機相を１N-塩酸で処理し、水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。
得られた粗生成物をカラムクロマトグラフィー（溶媒；クロロホルム→クロロホルム／エタノール＝１０：１）により精製し、式（Ｖ)で表される色素化合物０．２３ｇを得た。収率は７８％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, and the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10: 1) to obtain 0.23 g of a dye compound represented by the formula (V). The yield was 78%.
得られた粗生成物をカラムクロマトグラフィー（溶媒；クロロホルム→クロロホルム／エタノール＝１０：１）により精製し、式（Ｖ)で表される色素化合物０．２３ｇを得た。収率は７８％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, and the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10: 1) to obtain 0.23 g of a dye compound represented by the formula (V). The yield was 78%.
塩化ホスホリル０．０９mlを５℃に冷却し、DMFを０．１８ml滴下し、１時間攪拌してビルスマイヤー試薬を調製した。
0.09 ml of phosphoryl chloride was cooled to 5 ° C., 0.18 ml of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent.
式（Ｓ)で表される9，9-ジ-n-オクチルフルオレン誘導体０．５２ｇをDMF５mlで溶解し、そこへ上記で調製したビルスマイヤー試薬を室温で滴下して、７０℃で１時間攪拌した。
Dissolve 0.52 g of the 9,9-di-n-octylfluorene derivative represented by the formula (S) with 5 ml of DMF, drop the Vilsmeier reagent prepared above at room temperature, and stir at 70 ° C. for 1 hour. did.
その後、１０％酢酸ナトリウム水溶液を５０ｇ加えて中和し、酢酸エチルで抽出をした。
有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し、粗生成物を得た。 Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し、粗生成物を得た。 Thereafter, 50 g of 10% aqueous sodium acetate solution was added for neutralization, and the mixture was extracted with ethyl acetate.
The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
得られた粗生成物をカラムクロマトグラフィー（溶媒；ヘキサン／酢酸エチル＝４／１）で精製し、式(Ｗ)で表される9，9-ジ-n-オクチルフルオレン誘導体アルデヒドを０，３５ｇ得た。収率は６５％であった。
The resulting crude product was purified by column chromatography (solvent: hexane / ethyl acetate = 4/1), and 0.35 g of a 9,9-di-n-octylfluorene derivative aldehyde represented by the formula (W) was obtained. Obtained. The yield was 65%.
その後、反応液にクロロホルム５０mlを加えて、有機相を１N-塩酸で処理し、水および飽和食塩水で洗浄し、硫酸ナトリウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。
得られた粗生成物をカラムクロマトグラフィー（溶媒：クロロホルム／エタノール＝１０／１）により精製し、式（Ｘ)で表される色素化合物０．２３ｇを得た。収率は８１％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, and the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. .
The obtained crude product was purified by column chromatography (solvent: chloroform / ethanol = 10/1) to obtain 0.23 g of a dye compound represented by the formula (X). The yield was 81%.
得られた粗生成物をカラムクロマトグラフィー（溶媒：クロロホルム／エタノール＝１０／１）により精製し、式（Ｘ)で表される色素化合物０．２３ｇを得た。収率は８１％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, and the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. .
The obtained crude product was purified by column chromatography (solvent: chloroform / ethanol = 10/1) to obtain 0.23 g of a dye compound represented by the formula (X). The yield was 81%.
塩酸スルホリル０．０６mlを５℃に冷却し、DMFを０．１２m;滴下し、１時間攪拌し、ビルスマイヤー試薬を調製した。
0.06 ml of sulforyl hydrochloride was cooled to 5 ° C., 0.12 m of DMF was added dropwise and stirred for 1 hour to prepare Vilsmeier reagent.
式（Ｔ)で示される9，9-ジ-n-オクチルフルオレン誘導体０．３９ｇをDMF５mlに溶解し、そこに上記で調製したビルスマイヤー試薬を室温で滴下し、７０℃で１時間攪拌した。
その後１０％酢酸ナトリウム水溶液５０ｇを加えて中和し、酢酸エチルで抽出を行った。 0.39 g of the 9,9-di-n-octylfluorene derivative represented by the formula (T) was dissolved in 5 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature, followed by stirring at 70 ° C. for 1 hour.
Thereafter, 50 g of a 10% aqueous sodium acetate solution was added for neutralization, and extraction was performed with ethyl acetate.
その後１０％酢酸ナトリウム水溶液５０ｇを加えて中和し、酢酸エチルで抽出を行った。 0.39 g of the 9,9-di-n-octylfluorene derivative represented by the formula (T) was dissolved in 5 ml of DMF, and the Vilsmeier reagent prepared above was added dropwise thereto at room temperature, followed by stirring at 70 ° C. for 1 hour.
Thereafter, 50 g of a 10% aqueous sodium acetate solution was added for neutralization, and extraction was performed with ethyl acetate.
有機相を水および飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧下で留去し粗生成物を得た。
得られた粗生成物をカラムクロマトグラフィー（溶媒；ヘキサン／酢酸エチル＝４／１）で精製し、式（Ｙ）で表される9,9-ジ-n-オクチルフルオレン誘導体アルデヒド０．２９ｇを得た。収率は７２％であった。 The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
The obtained crude product was purified by column chromatography (solvent: hexane / ethyl acetate = 4/1), and 0.29 g of 9,9-di-n-octylfluorene derivative aldehyde represented by the formula (Y) was obtained. Obtained. The yield was 72%.
得られた粗生成物をカラムクロマトグラフィー（溶媒；ヘキサン／酢酸エチル＝４／１）で精製し、式（Ｙ）で表される9,9-ジ-n-オクチルフルオレン誘導体アルデヒド０．２９ｇを得た。収率は７２％であった。 The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.
The obtained crude product was purified by column chromatography (solvent: hexane / ethyl acetate = 4/1), and 0.29 g of 9,9-di-n-octylfluorene derivative aldehyde represented by the formula (Y) was obtained. Obtained. The yield was 72%.
その後、反応液にクロロホルム５０mlを加え、有機相を１Ｎ－塩酸で処理し、水および飽和食塩水で洗浄し、硫酸ナトリウムで乾燥後、溶媒を減圧下で留去して粗生成物を得た。
得られた粗生成物をカラムクロマトグラフィー（溶媒；クロロホルム→クロロホルム／エタノール＝１０／１）により精製し、式（Ｚ)で表される色素化合物０．２５ｇを得た。収率は８５％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. .
The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10/1) to obtain 0.25 g of a dye compound represented by the formula (Z). The yield was 85%.
得られた粗生成物をカラムクロマトグラフィー（溶媒；クロロホルム→クロロホルム／エタノール＝１０／１）により精製し、式（Ｚ)で表される色素化合物０．２５ｇを得た。収率は８５％であった。 Thereafter, 50 ml of chloroform was added to the reaction solution, the organic phase was treated with 1N-hydrochloric acid, washed with water and saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. .
The obtained crude product was purified by column chromatography (solvent: chloroform → chloroform / ethanol = 10/1) to obtain 0.25 g of a dye compound represented by the formula (Z). The yield was 85%.
（液体電解質を用いた色素増感型太陽電池の作成）
（１）＜光電極の作成＞
透明電極基材として、片面にFTO電極被膜が形成されたFTOガラスを用いて、この透明電極のFTO面に市販の酸化チタンペースト（Solaronix社製）をスクリーン印刷法により塗布した。この酸化チタンの平均粒子径は１３μｍである。
これを空気中で４５０℃で焼成することにより、酸化チタンの多孔膜層を作成し、これを四塩化チタン処理することにより酸化チタン光電極を作成した。
(Creation of dye-sensitized solar cell using liquid electrolyte)
(1) <Creation of photoelectrode>
Using a FTO glass with an FTO electrode coating formed on one side as a transparent electrode substrate, a commercially available titanium oxide paste (manufactured by Solaronix) was applied to the FTO surface of this transparent electrode by a screen printing method. The average particle diameter of this titanium oxide is 13 μm.
This was fired in air at 450 ° C. to prepare a titanium oxide porous film layer, and this was treated with titanium tetrachloride to prepare a titanium oxide photoelectrode.
（２）＜色素の吸着＞
上記のようにして調製した色素化合物を濃度が０．１～０．５mMになるようにトルエンに溶解させ、この色素溶液に上記で作成した酸化チタン光電極を室温で、１８時間浸漬させて色素を酸化チタンに吸着させた。
色素を吸着させた後、光電極をトルエンで充分に洗浄し室温で乾燥して色素吸着酸化チタン光電極を得た。 (2) <Dye adsorption>
The dye compound prepared as described above is dissolved in toluene so as to have a concentration of 0.1 to 0.5 mM, and the titanium oxide photoelectrode prepared above is immersed in this dye solution for 18 hours at room temperature. Was adsorbed on titanium oxide.
After adsorbing the dye, the photoelectrode was thoroughly washed with toluene and dried at room temperature to obtain a dye-adsorbed titanium oxide photoelectrode.
上記のようにして調製した色素化合物を濃度が０．１～０．５mMになるようにトルエンに溶解させ、この色素溶液に上記で作成した酸化チタン光電極を室温で、１８時間浸漬させて色素を酸化チタンに吸着させた。
色素を吸着させた後、光電極をトルエンで充分に洗浄し室温で乾燥して色素吸着酸化チタン光電極を得た。 (2) <Dye adsorption>
The dye compound prepared as described above is dissolved in toluene so as to have a concentration of 0.1 to 0.5 mM, and the titanium oxide photoelectrode prepared above is immersed in this dye solution for 18 hours at room temperature. Was adsorbed on titanium oxide.
After adsorbing the dye, the photoelectrode was thoroughly washed with toluene and dried at room temperature to obtain a dye-adsorbed titanium oxide photoelectrode.
（３）＜電解液の作成＞
ヨウ化リチウム／ヨウ素／t-ブチルピリジン／ヨウ化1,2-ジメチル-3-プロピルイミダゾリウムをそれぞれ、０．１M/０．０５M/０．５M/０．６Mの濃度になるようにアセトニトリルに溶解させて電解液を調製した。 (3) <Creation of electrolyte solution>
Lithium iodide / iodine / t-butylpyridine /iodine 1,2-dimethyl-3-propylimidazolium in acetonitrile to a concentration of 0.1M / 0.05M / 0.5M / 0.6M respectively. The electrolyte was prepared by dissolving.
ヨウ化リチウム／ヨウ素／t-ブチルピリジン／ヨウ化1,2-ジメチル-3-プロピルイミダゾリウムをそれぞれ、０．１M/０．０５M/０．５M/０．６Mの濃度になるようにアセトニトリルに溶解させて電解液を調製した。 (3) <Creation of electrolyte solution>
Lithium iodide / iodine / t-butylpyridine /
（４）＜液体電解質を用いた色素増感型太陽電池の作成＞
前記（１）および（２）で作成した色素吸着酸化チタン光電極とFTOガラスにスパッタ法により作成したPt電極を、ポリエチレンフィルムスペーサーを介して重ね併せて、両者の間隙に電解液を注入し、クリップで止め液体電解質を用いた色素増感型太陽電池を得た。 (4) <Preparation of dye-sensitized solar cell using liquid electrolyte>
The dye-adsorbed titanium oxide photoelectrode prepared in (1) and (2) above and the Pt electrode prepared by sputtering on the FTO glass are overlapped via a polyethylene film spacer, and an electrolyte is injected into the gap between the two, A dye-sensitized solar cell using a liquid electrolyte was obtained by stopping with a clip.
前記（１）および（２）で作成した色素吸着酸化チタン光電極とFTOガラスにスパッタ法により作成したPt電極を、ポリエチレンフィルムスペーサーを介して重ね併せて、両者の間隙に電解液を注入し、クリップで止め液体電解質を用いた色素増感型太陽電池を得た。 (4) <Preparation of dye-sensitized solar cell using liquid electrolyte>
The dye-adsorbed titanium oxide photoelectrode prepared in (1) and (2) above and the Pt electrode prepared by sputtering on the FTO glass are overlapped via a polyethylene film spacer, and an electrolyte is injected into the gap between the two, A dye-sensitized solar cell using a liquid electrolyte was obtained by stopping with a clip.
使用した色素による液体電解質を用いた色素増感型太陽電池の性能を表１に示す。
Table 1 shows the performance of the dye-sensitized solar cell using a liquid electrolyte depending on the dye used.
また、上記表において示した色素ＭＫ－２は下記の構造を有する化合物である。
In addition, the dye MK-2 shown in the above table is a compound having the following structure.
（固体電解質を用いた色素増感型太陽電池の作成）
（１）＜光電極の作成＞
透明電極基材として、片面にFTO電極被膜が形成されたFTOガラスを用いて、この透明電極のFTO面にチタンアルコキシドのIPA溶液を塗布、１２０℃に加熱し短絡防止層を作成した。その上に、市販の酸化チタンペースト（Solaronix社製）をスクリーン印刷法により塗布した。この酸化チタンの平均粒子型は３７μｍである。
これを空気中で４５０℃で焼成することにより、酸化チタンの多孔膜層を作成し、これを四塩化チタン処理することにより酸化チタン光電極を作成した。
(Preparation of dye-sensitized solar cell using solid electrolyte)
(1) <Creation of photoelectrode>
Using FTO glass with an FTO electrode coating formed on one side as a transparent electrode substrate, an IPA solution of titanium alkoxide was applied to the FTO surface of this transparent electrode and heated to 120 ° C. to create a short-circuit prevention layer. On top of that, a commercially available titanium oxide paste (manufactured by Solaronix) was applied by screen printing. The average particle type of this titanium oxide is 37 μm.
This was fired in air at 450 ° C. to prepare a titanium oxide porous film layer, and this was treated with titanium tetrachloride to prepare a titanium oxide photoelectrode.
（２）＜色素の吸着＞
上記のようにして調製した色素を濃度が０．１～０．５mMになるようにトルエンに溶解させ、この色素溶液に上記で作成した酸化チタン光電極を室温で、１８時間浸漬させて色素を酸化チタンに吸着させた。
色素を吸着させた後、光電極をトルエンで充分に洗浄し室温で乾燥して色素吸着酸化チタン光電極を得た。 (2) <Dye adsorption>
The dye prepared as described above is dissolved in toluene to a concentration of 0.1 to 0.5 mM, and the titanium oxide photoelectrode prepared above is immersed in this dye solution for 18 hours at room temperature. Adsorbed on titanium oxide.
After adsorbing the dye, the photoelectrode was thoroughly washed with toluene and dried at room temperature to obtain a dye-adsorbed titanium oxide photoelectrode.
上記のようにして調製した色素を濃度が０．１～０．５mMになるようにトルエンに溶解させ、この色素溶液に上記で作成した酸化チタン光電極を室温で、１８時間浸漬させて色素を酸化チタンに吸着させた。
色素を吸着させた後、光電極をトルエンで充分に洗浄し室温で乾燥して色素吸着酸化チタン光電極を得た。 (2) <Dye adsorption>
The dye prepared as described above is dissolved in toluene to a concentration of 0.1 to 0.5 mM, and the titanium oxide photoelectrode prepared above is immersed in this dye solution for 18 hours at room temperature. Adsorbed on titanium oxide.
After adsorbing the dye, the photoelectrode was thoroughly washed with toluene and dried at room temperature to obtain a dye-adsorbed titanium oxide photoelectrode.
（３）＜固体電解質層の作成＞
ポリ(3-ヘキシルチオフェン)（P3HT、Rieke Metals.Inc. Mw=50000）をo-ジクロロベンゼンに溶解し、1 wt％溶液とした。この溶液を用いて、前記の（１）～（２）で作成した色素吸着酸化チタン光電極上に、スピンコート法によりP3HT膜の電解質層を形成した。 (3) <Creation of solid electrolyte layer>
Poly (3-hexylthiophene) (P3HT, Rieke Metals. Inc. Mw = 50000) was dissolved in o-dichlorobenzene to obtain a 1 wt% solution. Using this solution, an electrolyte layer of a P3HT film was formed on the dye-adsorbed titanium oxide photoelectrode prepared in the above (1) and (2) by spin coating.
ポリ(3-ヘキシルチオフェン)（P3HT、Rieke Metals.Inc. Mw=50000）をo-ジクロロベンゼンに溶解し、1 wt％溶液とした。この溶液を用いて、前記の（１）～（２）で作成した色素吸着酸化チタン光電極上に、スピンコート法によりP3HT膜の電解質層を形成した。 (3) <Creation of solid electrolyte layer>
Poly (3-hexylthiophene) (P3HT, Rieke Metals. Inc. Mw = 50000) was dissolved in o-dichlorobenzene to obtain a 1 wt% solution. Using this solution, an electrolyte layer of a P3HT film was formed on the dye-adsorbed titanium oxide photoelectrode prepared in the above (1) and (2) by spin coating.
（４）＜Pt電極の形成、及び固体電解質を用いた色素増感型太陽電池の作成＞
前記（３）で作成した素子のP3HT上にPtをスパッタしPt電極を形成し、固体電解質を用いた色素増感型太陽電池を作成した。
使用した色素による固体電解質を用いた色素増感型太陽電池の性能を表２に示す。 (4) <Formation of Pt electrode and creation of dye-sensitized solar cell using solid electrolyte>
Pt was sputtered on P3HT of the device prepared in the above (3) to form a Pt electrode, and a dye-sensitized solar cell using a solid electrolyte was prepared.
Table 2 shows the performance of the dye-sensitized solar cell using the solid electrolyte depending on the dye used.
前記（３）で作成した素子のP3HT上にPtをスパッタしPt電極を形成し、固体電解質を用いた色素増感型太陽電池を作成した。
使用した色素による固体電解質を用いた色素増感型太陽電池の性能を表２に示す。 (4) <Formation of Pt electrode and creation of dye-sensitized solar cell using solid electrolyte>
Pt was sputtered on P3HT of the device prepared in the above (3) to form a Pt electrode, and a dye-sensitized solar cell using a solid electrolyte was prepared.
Table 2 shows the performance of the dye-sensitized solar cell using the solid electrolyte depending on the dye used.
１・・・透明電極基材(光電極)
２・・・酸化チタン層
３・・・色素
４・・・電解液
５・・・スペーサー
６・・・Pt
７・・・電極基材(対極)
１１・・・透明電極基材(光電極)
１２・・・短絡防止層
１３・・・酸化チタン層
１４・・・色素
１５・・・固体電解層
１６・・・スペーサー
１７・・・Pt
１８・・・電極基材(対極) 1 ... Transparent electrode substrate (photoelectrode)
2 ...Titanium oxide layer 3 ... Dye 4 ... Electrolyte 5 ... Spacer 6 ... Pt
7 ... Electrode substrate (counter electrode)
11 ... Transparent electrode substrate (photoelectrode)
12 ... Short-circuit prevention layer 13 ... Titanium oxide layer 14 ... Dye 15 ... Solid electrolytic layer 16 ... Spacer 17 ... Pt
18 ... Electrode substrate (counter electrode)
２・・・酸化チタン層
３・・・色素
４・・・電解液
５・・・スペーサー
６・・・Pt
７・・・電極基材(対極)
１１・・・透明電極基材(光電極)
１２・・・短絡防止層
１３・・・酸化チタン層
１４・・・色素
１５・・・固体電解層
１６・・・スペーサー
１７・・・Pt
１８・・・電極基材(対極) 1 ... Transparent electrode substrate (photoelectrode)
2 ...
7 ... Electrode substrate (counter electrode)
11 ... Transparent electrode substrate (photoelectrode)
12 ... Short-
18 ... Electrode substrate (counter electrode)
Claims (5)
- 次式（Ｉ）で表わす新規なフルオレン化合物；
- 上記式（I）で表わさせるフルオレン化合物からなることを特徴とする色素増感型太陽電池用色素；
- 次式（I）で表わされるフルオレン化合物を金属酸化物粒子に吸着させたフルオレン化合物被覆金属酸化物粒子が金属製又は金属酸化物電極表面に配置された構成を有することを特徴とする色素増感型太陽電池用電極；
- 表面を次式（I）で表わされるフルオレン化合物で被覆されたフルオレン化合物被覆金属酸化物粒子が電極表面に配置された透明電極を一方の電極とし、他方の電極として触媒電極を配置し、該透明電極と触媒電極との間に電解質が挟持されていることを特徴とする色素増感型太陽電池；
- 前記電解質が固体電解質であることを特徴とする請求項第４項記載の色素増感型太陽電池。 The dye-sensitized solar cell according to claim 4, wherein the electrolyte is a solid electrolyte.
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| WO2013042699A1 (en) * | 2011-09-20 | 2013-03-28 | 日本電気株式会社 | Spirobifluorene compound, colorant for photoelectric transducer, and photoelectric transducer using same |
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| JP2006004736A (en) * | 2004-06-17 | 2006-01-05 | Sumitomo Chemical Co Ltd | Photoelectric transducer and colorant for photoelectric transducer |
| WO2007119525A1 (en) * | 2006-03-31 | 2007-10-25 | National Institute Of Advanced Industrial Science And Technology | Organic compound, semiconductor thin film electrode using the same, photoelectric transducer, and photoelectrochemical solar cell |
| JP2009266633A (en) * | 2008-04-25 | 2009-11-12 | Konica Minolta Business Technologies Inc | Photoelectric conversion element and solar battery |
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| JP2006004736A (en) * | 2004-06-17 | 2006-01-05 | Sumitomo Chemical Co Ltd | Photoelectric transducer and colorant for photoelectric transducer |
| WO2007119525A1 (en) * | 2006-03-31 | 2007-10-25 | National Institute Of Advanced Industrial Science And Technology | Organic compound, semiconductor thin film electrode using the same, photoelectric transducer, and photoelectrochemical solar cell |
| JP2009266633A (en) * | 2008-04-25 | 2009-11-12 | Konica Minolta Business Technologies Inc | Photoelectric conversion element and solar battery |
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