JP4081149B2 - Wet solar cells using phthalocyanine compounds - Google Patents
Wet solar cells using phthalocyanine compounds Download PDFInfo
- Publication number
- JP4081149B2 JP4081149B2 JP02181496A JP2181496A JP4081149B2 JP 4081149 B2 JP4081149 B2 JP 4081149B2 JP 02181496 A JP02181496 A JP 02181496A JP 2181496 A JP2181496 A JP 2181496A JP 4081149 B2 JP4081149 B2 JP 4081149B2
- Authority
- JP
- Japan
- Prior art keywords
- phthalocyanine
- tetra
- compound
- solar cell
- carboxymethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title description 9
- -1 phthalocyanine compound Chemical class 0.000 claims description 123
- 239000003504 photosensitizing agent Substances 0.000 claims description 23
- 230000002165 photosensitisation Effects 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 61
- 239000004408 titanium dioxide Substances 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920006391 phthalonitrile polymer Polymers 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000004424 polypyridyl Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000000872 2-diethylaminoethoxy group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])O* 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910006111 GeCl2 Inorganic materials 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
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- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
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- ZUNKQZLMIFINMI-UHFFFAOYSA-N ethyl 2-(3,4-dicyanophenoxy)acetate Chemical compound CCOC(=O)COC1=CC=C(C#N)C(C#N)=C1 ZUNKQZLMIFINMI-UHFFFAOYSA-N 0.000 description 1
- PXHVVDKOTBHTJY-UHFFFAOYSA-N ethyl 2-(3,4-dicyanophenyl)sulfanylacetate Chemical compound CCOC(=O)CSC1=CC=C(C#N)C(C#N)=C1 PXHVVDKOTBHTJY-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
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- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQZZGEUJERGRIN-UHFFFAOYSA-N manganese;pentane-2,4-dione Chemical compound [Mn].CC(=O)CC(C)=O SQZZGEUJERGRIN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WWECJGLXBSQKRF-UHFFFAOYSA-N n,n-dimethylformamide;methanol Chemical compound OC.CN(C)C=O WWECJGLXBSQKRF-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- 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
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明はフタロシアニン化合物を用いる湿式太陽電池に関する。さらに詳しくは有機溶剤に対する溶解性があり、二酸化チタン表面と強固な吸着結合状態を形成するフタロシアニン化合物を光増感色素として用いる湿式太陽電池に関する。
【０００２】
【従来の技術】
化石燃料に代るエネルギー源として太陽光を利用する太陽電池が注目され、種々研究が行われてきた。現在実用化されている太陽電池の主流は多結晶又はアモルファスシリコンをセルとするものであるが、経済コストや製造プロセスにおけるエネルギーコストが高く、又ガリウムやヒ素などの毒性の高い材料を使用することには問題がないとも言えない。
【０００３】
新しいタイプの太陽電池として特表平５−５０４０２３号公報、特表平７−５００６３０号公報、国際公開９４／０５０２５号公報等に金属錯体の光誘起電子移動を応用した湿式太陽電池が開示されている。
【０００４】
この湿式太陽電池は、電解液を介して隔てられた少なくとも一方が実質的に透明である２つの電極を有し、この透明な電極は光増感色素が吸着された多孔質の二酸化チタン層を有している。
【０００５】
この湿式太陽電池の原理は、半導体としての二酸化チタンに、これよりも高い位置に電子の最低空軌道を有する光増感色素を吸着させ、更に電子供与体から光増感色素の最高被占軌道への速い電子移動を構成することによって、励起電子の速やかな電子移動によりアノード電流が流れることを応用したものである。
【０００６】
この湿式太陽電池は、低コスト、高効率、構造が単純で製造が容易である等の長所を有する。
【０００７】
前記特表平５−５０２０４３号公報及び特表平７−５００６３０号公報、国際公開９４／０５０２５号報においては、電子供与体としてヨウ素を、電子受容体（半導体）として二酸化チタンを使用し、光増感色素としてはポリピリジル化合物のルテニウム錯体を使用しており、国際公開９４／０５０２５号報においては光増感色素としてカルボキシル基を有するフタロシアニン化合物、ナフタロシアニン化合物等も使用されている。
【０００８】
しかしながら、このポリピリジル化合物のルテニウム錯体は耐光堅牢度が十分でない、製法が複雑である、ルテニウムが高価である等の問題がある。またカルボキシル基を有するフタロシアニン化合物はこのような欠点はないが、有機溶剤に対する溶解性が極端に低いため、二酸化チタン層に対する吸着効率が低い。湿式太陽電池においては、光増感色素を溶解した溶液に二酸化チタン薄膜を浸漬して吸着処理するため、光増感色素の有機溶剤に対する溶解度が二酸化チタンへの吸着量、ひいては発電効率に影響する。
【０００９】
光増感色素に要求される特性としては下記が挙げられる。
１）最低空軌道の準位（励起状態の酸化還元電位）が半導体のConduction-bandの下端より高いこと。
２）最高被占軌道の準位（酸化還元電位）が半導体のValence-bandの上端より高いこと。
３）二酸化チタンの表面に対する吸着性が高いこと。
４）有機溶剤に対する溶解性が高いこと。
５）耐久性に優れること。
６）経済性に優れること。
【００１０】
これらの諸点を満足する光増感色素は未だ見い出さていない。
【００１１】
なお、特表平２−５０２０９９（国際公開番号Ｗ０８８／６１７５）号公報には、一般式としては本発明のフタロシアニン化合物を含有する広範囲のフタロシアニン化合物とこれを使用する液晶光学ディスプレイが開示されているが、本発明のフタロシアニン化合物の具体的開示及び説明はない。
【００１２】
【発明が解決しようとする課題】
本発明の課題は、光増感色素として前記した諸特性に優れる新規なフタロシアニン化合物を使用した湿式太陽電池を提供することである。
【００１３】
【課題を解決するための手段】
本発明者らは、鋭意検討した結果、特定の置換基を有するフタロシアニン化合物が、太陽光を効率的に吸収し、有機溶媒に対する溶解性が良好で、二酸化チタンに対する吸着性に優れていることを見い出した。即ち、本発明は一般式(Ｉ)で表わされるフタロシアニン化合物を光増感色素として用いる湿式太陽電池に関する。
【００１４】
【化２】
【００１５】
【発明の実施の形態】
前記一般式（I）において、Ｍは２個の水素原子、金属又は金属誘導体であり、金属であるものとしては、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｐｂ、Ｒｈ、Ｐｄ、Ｐｔ、Ｍｎ、Ｓｎが好ましく、金属誘導体であるものとしては、ＡｌＣｌ、ＩｎＣｌ、ＦｅＣｌ、ＭｎＯＨ、ＳｉＣｌ2、ＳｎＣｌ2、ＧｅＣｌ2、Ｓｉ（ＯＨ）2、Ｓｎ（ＯＨ）2、Ｇｅ（ＯＨ）2、ＶＯ、ＴｉＯが好ましい。特にＭとしては、Ｚｎ、Ｍｇ、Ｃｕ、Ａｌ、Ｆｅ、２個の水素原子が好ましい。
【００１６】
Ｘは酸素原子或いは硫黄原子であり、ｎは１〜３の整数である。
【００１７】
本発明のフタロシアニン化合物の好ましい具体例を以下に示す。
（１）テトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニン
（２）テトラ（カルボキシメトキシ）−Ｍｇ−フタロシアニン
（３）テトラ（カルボキシメトキシ）−Ｃｕ−フタロシアニン
（４）テトラ（カルボキシメトキシ）−ＡｌＣｌ−フタロシアニン
（５）テトラ（カルボキシメトキシ）−ＦｅＣｌ−フタロシアニン
（６）テトラ（カルボキシメトキシ）−Ｈ2−フタロシアニン
（７）テトラ（カルボキシメトキシ）−Ｃｏ−フタロシアニン
（８）テトラ（カルボキシメトキシ）−Ｎｉ−フタロシアニン
（９）テトラ（カルボキシメトキシ）−Ｒｕ−フタロシアニン
（10）テトラ（カルボキシメトキシ）−Ｐｂ−フタロシアニン
【００１８】
（11）テトラ（カルボキシメトキシ）−Ｒｈ−フタロシアニン
（12）テトラ（カルボキシメトキシ）−Ｐｄ−フタロシアニン
（13）テトラ（カルボキシメトキシ）−Ｐｔ−フタロシアニン
（14）テトラ（カルボキシメトキシ）−ＭｎＯＨ−フタロシアニン
（15）テトラ（カルボキシメトキシ）−Ｓｎ−フタロシアニン
（16）テトラ（カルボキシメトキシ）−ＩｎＣｌ−フタロシアニン
（17）テトラ（カルボキシメトキシ）−ＳｉＣｌ2−フタロシアニン
（18）テトラ（カルボキシメトキシ）−ＳｎＣｌ2−フタロシアニン
（19）テトラ（カルボキシメトキシ）−ＧｅＣｌ2−フタロシアニン
（20）テトラ（カルボキシメトキシ）−Ｓｉ（ＯＨ）2−フタロシアニン
（21）テトラ（カルボキシメトキシ）−Ｓｎ（ＯＨ）2−フタロシアニン
（22）テトラ（カルボキシメトキシ）−Ｇｅ（ＯＨ）2−フタロシアニン
（23）テトラ（カルボキシメトキシ）−ＶＯ−フタロシアニン
（24）テトラ（カルボキシメトキシ）−ＴｉＯ−フタロシアニン
（25）テトラ（カルボキシメチルチオ）−Ｚｎ−フタロシアニン
（26）テトラ（カルボキシメチルチオ）−Ｍｇ−フタロシアニン
（27）テトラ（カルボキシメチルチオ）−Ｃｕ−フタロシアニン
（28）テトラ（カルボキシメチルチオ）−ＡｌＣｌ−フタロシアニン
（29）テトラ（カルボキシメチルチオ）−ＦｅＣｌ−フタロシアニン
（30）テトラ（カルボキシメチルチオ）−Ｈ2−フタロシアニン
【００１９】
（31）テトラ（カルボキシメチルチオ）−Ｃｏ−フタロシアニン
（32）テトラ（カルボキシメチルチオ）−Ｎｉ−フタロシアニン
（33）テトラ（カルボキシメチルチオ）−Ｒｕ−フタロシアニン
（34）テトラ（カルボキシメチルチオ）−Ｐｂ−フタロシアニン
（35）テトラ（カルボキシメチルチオ）−Ｒｈ−フタロシアニン
（36）テトラ（カルボキシメチルチオ）−Ｐｄ−フタロシアニン
（37）テトラ（カルボキシメチルチオ）−Ｐｔ−フタロシアニン
（38）テトラ（カルボキシメチルチオ）−ＭｎＯＨ−フタロシアニン
（39）テトラ（カルボキシメチルチオ）−Ｓｎ−フタロシアニン
（40）テトラ（カルボキシメチルチオ）−ＩｎＣｌ−フタロシアニン
（41）テトラ（カルボキシメチルチオ）−ＳｉＣｌ2−フタロシアニン
（42）テトラ（カルボキシメチルチオ）−ＳｎＣｌ2−フタロシアニン
（43）テトラ（カルボキシメチルチオ）−ＧｅＣｌ2−フタロシアニン
（44）テトラ（カルボキシメチルチオ）−Ｓｉ（ＯＨ）2−フタロシアニン
（45）テトラ（カルボキシメチルチオ）−Ｓｎ（ＯＨ）2−フタロシアニン
（46）テトラ（カルボキシメチルチオ）−Ｇｅ（ＯＨ）2−フタロシアニン
（47）テトラ（カルボキシメチルチオ）−ＶＯ−フタロシアニン
（48）テトラ（カルボキシメチルチオ）−ＴｉＯ−フタロシアニン
（49）テトラ（２−カルボキシエトキシ）−Ｚｎ−フタロシアニン
（50）テトラ（２−カルボキシエトキシ）−Ｍｇ−フタロシアニン
【００２０】
（51）テトラ（２−カルボキシエトキシ）−Ｃｕ−フタロシアニン
（52）テトラ（２−カルボキシエトキシ）−ＡｌＣｌ−フタロシアニン
（53）テトラ（２−カルボキシエトキシ）−ＦｅＣｌ−フタロシアニン
（54）テトラ（２−カルボキシエトキシ）−Ｈ2−フタロシアニン
（55）テトラ（３−カルボキシプロポキシ）−Ｚｎ−フタロシアニン
（56）テトラ（３−カルボキシプロポキシ）−Ｍｇ−フタロシアニン
（57）テトラ（３−カルボキシプロポキシ）−Ｃｕ−フタロシアニン
（58）テトラ（３−カルボキシプロポキシ）−ＡｌＣｌ−フタロシアニン
（59）テトラ（３−カルボキシプロポキシ）−ＦｅＣｌ−フタロシアニン
（60）テトラ（３−カルボキシプロポキシ）−Ｈ2−フタロシアニン
（61）テトラ（２−カルボキシエチルチオ）−Ｚｎ−フタロシアニン
（62）テトラ（２−カルボキシエチルチオ）−Ｍｇ−フタロシアニン
（63）テトラ（２−カルボキシエチルチオ）−Ｃｕ−フタロシアニン
（64）テトラ（２−カルボキシエチルチオ）−ＡｌＣｌ−フタロシアニン
（65）テトラ（２−カルボキシエチルチオ）−ＦｅＣｌ−フタロシアニン
（66）テトラ（２−カルボキシエチルチオ）−Ｈ2−フタロシアニン
（67）テトラ（３−カルボキシプロピルチオ）−Ｚｎ−フタロシアニン
（68）テトラ（３−カルボキシプロピルチオ）−Ｍｇ−フタロシアニン
（69）テトラ（３−カルボキシプロピルチオ）−Ｃｕ−フタロシアニン
（70）テトラ（３−カルボキシプロピルチオ）−ＡｌＣｌ−フタロシアニン
（71）テトラ（３−カルボキシプロピルチオ）−ＦｅＣｌ−フタロシアニン
（72）テトラ（３−カルボキシプロピルチオ）−Ｈ2−フタロシアニン
上記化合物（１）〜（７２）を代表例とする本発明の一般式（I）で表わされるフタロシアニン化合物は、例えば下記の方法に従って製造される。
【００２１】
一般式（II）で表わされるフタロニトリル化合物と一般式（III）で表わされる金属誘導体とを反応させて一般式（IV）で表わされるフタロシアニン化合物を製造し、更にこれを溶媒中、アルカリで加水分解することにより、前記一般式（I）で表わされるフタロシアニン化合物とする。
【００２２】
【化３】
Ｍ'-(Ｙ)d (III)
（式中、Ｍ’は１価〜４価の金属原子を表わし、Ｙはハロゲン原子、酢酸陰イオン、アセチルアセテート、酸素などの１価又は２価の配位子を示し、ｄは１〜４の整数を示す。）
【００２３】
【化４】
（式中、Ｘ、Ｍ及びｎは一般式（I）の式のＸ、Ｍ及びｎと同一であり、Ｒは一般式（II）の式のＲと同一である。）
式（III）で表わされる金属誘導体としては、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇｅ、Ｒｕ、Ｒｈ、Ｐｄ、Ｉｎ、Ｓｎ、Ｐｔ、Ｐｂのハロゲン化物、酢酸塩、アセチルアセトネート、酸化物、硫酸塩、硝酸塩、錯体等が挙げられる。具体例としては塩化銅、臭化銅、ヨウ化銅、塩化ニッケル、臭化ニッケル、酢酸ニッケル、塩化コバルト、臭化コバルト、酢酸コバルト、塩化鉄、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、酢酸亜鉛、塩化バナジウム、オキシ三塩化バナジウム、塩化パラジウム、酢酸パラジウム、塩化アルミニウム、塩化マンガン、酢酸マンガン、アセチルアセトンマンガン、塩化鉛、酢酸鉛、塩化インジウム、塩化チタン、塩化スズ等が挙げられる。
【００２５】
反応は通常、溶媒の存在下に行われる。溶媒としては、沸点８０℃以上、好ましくは１００℃以上の有機溶媒が用いられる。例えばｎ−ペンタノール、ｎ−ヘキサノール、シクロヘキサノール、２−メチル−１−ペンタノール、１−ヘプタノール、１−オクタノール、２−エチルヘキサノール、ベンジルアルコール、エチレングリコール、プロピレングリコール、エトキシエタノール、プロポキシエタノール、ブトキシエタノール、ジメチルアミノエタノール、ジエチルアミノエタノール、トリクロロベンゼン、クロロナフタレン、スルフォラン、ニトロベンゼン、キノリン、尿素等がある。溶媒の使用量はフタロニトリル化合物の１重量部に対して１〜１００重量部、好ましくは５〜５０重量部である。
【００２６】
反応において触媒として水素化ナトリウム、１，４−ジアザビシクロ［２，２，２］オクタン、１，５−ジアザビシクロ［４，３，０］−５−ノネン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢＵ）、モリブデン酸アンモニウム等を添加しても良い。添加量はフタロニトリル化合物１モルに対して、０．１〜１０モル、好ましくは０．５〜５モルである。
【００２７】
反応温度は８０〜３００℃、好ましくは１００〜２５０℃である。８０℃以下では反応速度が極端に遅い。３００℃以上ではフタロシアニン化合物の分解が起こる可能性がる。
【００２８】
反応時間は１〜４０時間、好ましくは２〜２０時間である。１時間以下では未反応原料が多く存在し、４０時間以上ではフタロシアニンの分解が起こる可能性がある。
【００２９】
反応後、反応液より溶媒を濃縮するか、又は反応液をフタロシアニン化合物に対する貧溶媒（メタノール等）に排出し、析出物を濾取することによって式（IV）で表わされるフタロシアニン化合物が得られる。また必要に応じて得られたフタロシアニン化合物を更に再結晶或いはカラムクロマトグラフィー処理により精製することができる。
【００３０】
金属誘導体とフタロニトリル化合物の使用量は、モル比で１：３〜１：６が好ましい。
【００３１】
無金属フタロシアニン化合物は金属誘導体としてナトリウムアルコラート或いはリチウムアルコラートを用いて製造したＮａ2フタロシアニン化合物或いはＬｉ2フタロシアニン化合物を酸で処理、脱金属することにより得ることができる。
【００３２】
式（IV）で表わされるフタロシアニン化合物を加水分解して式（I）で表わされるフタロシアニン化合物を製造する際の溶媒としては水或いはメタノール、エタノール、ｎ−プロパノール、イソプロパノール、２−エチルヘキサノール等のアルコールが用いられる。
【００３３】
アルカリとしては水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム等が使用できるが、水酸化ナトリウムが特に好ましい。
【００３４】
加水分解時の反応温度は５０℃〜溶媒の沸点温度であり、８０〜１２０℃が特に好ましい。
【００３５】
加水分解終了後、目的物の水溶液に或いはアルコール溶媒の場合はこれを水に排出したものに酸を加えて目的物を析出させる。酸としては塩酸、硫酸、酢酸等を使用するが、塩酸が特に好ましい。
【００３６】
一般式（II）のフタロニトリル化合物は、例えば下記の方法に従って製造できる。
【００３７】
ニトロフタロニトリルとグリコール酸アルキルエステル類或いはチオグリコール酸アルキルエステル類とを、反応溶媒として非プロトン性極性溶媒、例えばジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡＣ）、ジメチルスルホキシド（ＤＭＳＯ）等を用い、触媒として例えば１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢＵ）等の存在下、５０〜１２０℃にて反応させる。反応物を水に排出、トルエン等の有機溶剤で抽出し、必要に応じて再結晶等により精製することによって目的物が得られる。
【００３８】
本発明のフタロシアニン化合物を光増感色素として含有する湿式太陽電池について下記に説明する。
【００３９】
本発明の湿式太陽電池は、電解液を介して少なくとも一方が実質的に透明である２つの電極を有し、この透明電極が光増感色素として本発明のフタロシアニン化合物が吸着された二酸化チタン層を有していることが特徴である。
【００４０】
本発明の湿式太陽電池の構造の一例として、実施例において作製した湿式太陽電池の略図を図１に示す。
【００４１】
図１において、１は導電性ガラスからなる透明電極、２は光増感色素として本発明のフタロシアニン化合物を担持した二酸化チタン層、３は電解液、４は対極である。
【００４２】
導電性ガラスとしては例えば、フッ素をドープしたＳｎＯ2等を導電層として有するＴＣＯガラス（旭硝子社製）、或いは酸化スズをドープした酸化インジウムを導電層として有するＩＴＯガラス（Ｂａｌｚｅｒｓ社製）等を使用できる。また透明な電極として、ガラスの代りにポリマーを使用することもできる。
【００４３】
二酸化チタン層の二酸化チタンは多孔質であることが望ましく、その粗さ度は好ましくは１０〜５０００であり、より好ましくは５０〜１０００である。なお、粗さ度は真の表面積に対する見かけの表面積の比で定義される。
【００４４】
二酸化チタン層を導電性ガラスの表面に形成する方法としてはゾルゲル法、コロイド法等がある。
【００４５】
二酸化チタン層の厚さは好ましくは５〜５０μｍ、より好ましくは１０〜３０μｍである。
【００４６】
二酸化チタン層に光増感色素としてのフタロシアニン化合物を担持（吸着）させるには、例えば、フタロシアニン化合物をＤＭＦ、アルコール類等の有機溶剤に溶解させて、これに二酸化チタン層を一定時間浸漬した後乾燥する方法が用いられる。
【００４７】
電解液としては、ヨウ素／ヨウ素溶液、臭素／臭素溶液、ハイドロキノン溶液、遷移金属錯体溶液等のレドックス系が好ましい。電解液に使用される溶媒としては、水、アルコール、３−メチル−（２−オキサゾリジノン）、１，３−ジメチル−２−イミダゾリジノン、プロピレンカーボネート、エチレンカーボネート、ＴＨＦ、ジメチルスルホオキシド、ジクロロエタン等や、これらの相溶性混合物がある。
【００４８】
対極としては白金等が用いられる。
【００４９】
【実施例】
以下に実施例を示すが、本発明はこの実施例に限定されるものではない。
【００５０】
［製造例１］テトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニンの合成
４−（エトキシカルボニルメトキシ）フタロニトリル１１.５ｇ、塩化亜鉛(II)２.１ｇ、ＤＢＵ７．６ｇ、ｎ−ペンチルアルコール１００ｍＬを混合した後、１２０〜１３０℃にて８時間撹拌した。冷却後、反応混合物をメタノール１０００ｍＬに排出し、析出物を濾取、乾燥し、テトラ（エトキシカルボニルメトキシ）−Ｚｎ−フタロシアニン１１.２ｇを濃緑色粉末物として得た。
【００５１】
この生成物９．７ｇを２％水酸化ナトリウム水溶液５００ｍＬ中で６時間還流撹拌した。冷却後、１０％塩酸で酸析し、析取物を濾取、水洗、乾燥して濃緑色粉末６．２ｇを得た。
【００５２】
下記分析結果より目的物であることを確認した。なお、元素分析値中、Ｚｎの値は原子吸光法による。
【００５３】
【００５４】
［製造例２］ テトラ（カルボキシメチルチオ）−Ｚｎ−フタロシアニンの合成
４−（エトキシカルボニルメチルチオ）フタロニトリル１２．３ｇ、塩化亜鉛（II）２．１ｇ、ＤＢＵ７．６ｇ、ｎ−ペンチルアルコール１００ｍＬを混合した後、１２０〜１３０℃にて８時間撹拌した。冷却後、反応混合物をメタノール１０００ｍＬに排出し、析出物を濾取、乾燥し、テトラ(エトキシカルボニルメチルチオ)−Ｚｎ−フタロシアニン１０.０ｇを濃緑色粉末物として得た。
【００５５】
この生成物８．４ｇを２％水酸化ナトリウム５００ｍＬ中で６時間還流撹拌した。冷却後、１０％塩酸で酸析し、析取物を濾取、水洗、乾燥して濃録色粉末３．０ｇを得た。
【００５６】
下記分析結果より目的物であることを確認した。
【００５７】
［実施例１］ 湿式太陽電池の作製
１）二酸化チタン層の作製
硫酸チタン（IV）の加水分解により調整した二酸化チタン超微粒子５ｇ(平均粒経１２ｎｍ、アナターゼ）に硝酸（ｐＨ＝０.５〜１）２０ｍＬを加え、十分に撹拌した後、ポリエチレングリコール（ＭＷ＝２００００）３.２ｇを加え撹拌して二酸化チタンの分散液を作製した。この分散液をエタノールで十分洗浄した導電性ガラス（フッ素をドープしたＳｎＯ２を導電層として有するもの）上に塗布し、自然乾燥後、空気中、４５０℃で３０分間焼結した後、アルゴン雰囲気下、室温まで放冷した。
【００５８】
２）光増感色素の二酸化チタンへの吸着
１）で作製した二酸化チタン薄膜を空気中、４５０℃で３０分間再加熱した後、この二酸化チタン薄膜を、製造例１で合成したテトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニンを３×１０−４Ｍ（ｍｏｌ／Ｌ）の濃度に溶解したＤＭＦ溶液中に５時間浸漬した。次いで脱水処理したＤＭＦ、エタノールで洗浄し、真空乾燥して色素担持二酸化チタン薄膜を調整した。
【００５９】
３）湿式太陽電池の作製
２）で作製した色素担持二酸化チタン薄膜を有するガラス電極を使用して図１のような湿式太陽電池を作製した。対極には白金電極を用い、電解液には０．５Ｍヨウ化テトラプロピルアンモニウム及び０．０４Ｍヨウ素を電解質として含む炭酸エチレン／アセトニトリル混合溶液（８０／２０ｖｏｌ％）を用いた。
【００６０】
［実施例２］ 湿式太陽電池の作製
実施例１における光増感色素であるテトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニンの代りに製造例２で合成したテトラ（カルボキシメチルチオ）−Ｚｎ−フタロシアニンを用いた以外は実施例１と同様の操作を行って、湿式太陽電池を作製した。
【００６１】
［比較例１］ 湿式太陽電池の作製
実施例１における光増感色素であるテトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニンの代りにテトラ（２−ジエチルアミノエトキシ）−Ｚｎ−フタロシアニン（化合物１）を用いた以外は実施例１と同様の操作を行って、湿式太陽電池を作製した。
【００６２】
［比較例２］ 湿式太陽電池の作製
実施例１における光増感色素であるテトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニンの代りにテトラ（ｔｅｒｔ−ブチル）−Ｚｎ−フタロシアニン（化合物２）を用いた以外は実施例１と同様の操作を行って、湿式太陽電池を作製した。
【００６３】
［比較例３］ 湿式太陽電池の作製
実施例１における光増感色素であるテトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニンの代りにテトラカルボキシ−Ｚｎ−フタロシアニン（化合物３、国際公開９４／０５０２５号公報に開示の化合物）を用いた以外は実施例１と同様の操作を行って、湿式太陽電池を作製した。
【００６４】
評価１ 溶解性試験
製造例１で合成したテトラ（カルボキシメトキシ）−Ｚｎ−フタロシアニン、製造例２で合成したテトラ（カルボキシメチルチオ）−Ｚｎ−フタロシアニン、化合物１、化合物２及び化合物３についてそれぞれメタノール、ＤＭＦ及びＤＭＳＯに対する溶解性を確認した。結果を下記表１に示す。
【００６５】
【表１】
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
メタノール ＤＭＦ ＤＭＳＯ
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
製造例１の化合物 △ ○ ○
製造例２の化合物 ○ ○ ○
化合物１（比較物質） ○ ○ ○
化合物２（比較物質） ○ ○ ○
化合物３（比較物質） × △ △
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
但し○は易溶、△は難溶、×は不溶を示す。
【００６６】
評価２ フタロシアニン化合物の酸化還元電位及び０−０バンドエネルギーの測定
酸化還元電位の測定
ＤＭＦに本発明のフタロシアニン化合物１ｍＭと、支持電解質テトラ−ｎ−ブチルアンモニウムヘキサフルオロホスファート０．１Ｍを溶解してＣＶ測定を行った。酸化還元電位を決定した結果を表２に示す。電極として作用電極にグラッシーカーボン、対電極にプラチナ電極、参照電極に硝酸銀電極を用いた。
【００６７】
０−０バンドエネルギーの測定
本発明のフタロシアニン化合物をメタノールに溶解して蛍光測定を行い、得られた励起スペクトルと蛍光スペルトルの交点０−０バンドから、０−０バンドエネルギーを算出した。
これらの結果を表２に示す。
【００６８】
【表２】
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
0-0バンド 0-0バンドエネルギー 酸化還元電位
（ｎｍ） （ｅＶ） （Ｖｖｓ．ＮＨＥ）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
製造例１の化合物 ６９３ １.７９ １.１０
製造例２の化合物 ６８８ １.８０ １.０２
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
これら本発明のフタロシアニン化合物は電子のドナーとなるヨウ素よりも正電位側にあり、励起準位はアクセプターとなる二酸化チタンの伝導帯よりも負電位側にあることがあることが確認できた。即ち半導体よりも高い位置に色素の最低空軌道が存在し色素の励起準位から伝導帯への電子注入が可能であり、電子供与体から色素の最高被占軌道への電子移動が生じえる性能が確認できた。
【００６９】
評価３ 二酸化チタン超微粒子膜に対する色素吸着量の測定
実施例１、２及び比較例１、２、３で作製した二酸化チタン薄膜のＵＶ〜可視吸収スペクトルを測定し、エタノール中の各フタロシアニン化合物の極大吸収波長における吸光係数を用いて色素の吸着密度を算出した。結果を表３に示す。
【００７０】
【表３】
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
担持フタロシアニン化合物 色素吸着量（×１０−９ mol．cm−２）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
製造例１の化合物 ２３
製造例２の化合物 ４７
化合物１（比較物質） ６
化合物２（比較物質） ３
化合物３（比較物質） １
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
以上の結果より、本発明のフタロシアニン化合物は他の置換基を有するフタロシアニン化合物に比べ二酸化チタンに効果的に吸着されていることが確認できた。
【００７１】
評価４ 湿式太陽電池の光電変換効率の測定
実施例１、２及び比較例１、２、３で作製した湿式太陽電池について下記のごとく光電変換効率を測定した。光源に５００ＷのＸｅランプを用い、紫外線カットフィルターを通した光（４００ｎｍ以上の光を照射、照射光強度は２２ｍＷ／ｃｍ２）をモノクロメーターにより分光照射して、それぞれの波長光における短絡電流を測定した。また、それぞれの波長における光強度を測定し、次式により変換効率を算出した。
【００７２】
ＩＰＣＥ＝１．２４×１０2×Ｉｓｃ／Ｐ×λ
ここでＩＰＣＥは入射光に対する変換効率（％）、Ｉscは短絡電流（ｍＡ／ｃｍ2）、Ｐは照射光強度（μＷ／ｃｍ2）、λは単色光の波長（ｎｍ）を示す。
次いで次式より、吸収極大波長付近での吸収光に対する光電変換効率ＬＨＥ（％）を算出した。
【００７３】
ＬＨＥ＝ＩＣＰＥ／（１−Ｔ／１００）
ここでＴ（％）はＱ−ｂａｎｄにおける太陽電池モジュールの透過率を示す。
結果を表４に示す。
【００７４】
【表４】
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ＬＨＥ（％：Ｑ−ｂａｎｄ）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１の太陽電池 ６.３７
実施例２の太陽電池 ９.９２
比較例１の太陽電池 ２.３５
比較例２の太陽電池 １.４１
比較例３の太陽電池 ０.５
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
以上の結果より本発明のフタロシアニンを光増感色素として用いた湿式太陽電池は高い光電変換効率を示すことが判った。
【００７５】
【発明の効果】
本発明の新規なフタロシアニン化合物は有機溶剤への溶解性に優れ、半導体に用いられる二酸化チタン表面と強固な結合状態を形成し、半導体よりも高い位置に色素の最低空軌道が存在し色素の励起準位から伝導帯への電子注入が可能であり、電子供与体から色素の最高被占軌道への電子移動が生じえる性能に優れるとともに耐久性に優れるので、これを光増感剤として使用する湿式太陽電池に好適に用いることができる。
【図面の簡単な説明】
【図１】本発明の湿式太陽電池の一具体例の概略図である。
【符号の説明】
１ 透明電極
２ 二酸化チタン層
３ 電解液
４ 対極[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a phthalocyanine compoundThingsThe present invention relates to a wet solar cell to be used. More specifically, it is soluble in organic solvents and forms a strong adsorption bond with the titanium dioxide surface.ThingsThe present invention relates to a wet solar cell used as a photosensitizing dye.
[0002]
[Prior art]
Solar cells that use sunlight as an energy source to replace fossil fuels have attracted attention and various studies have been conducted. The mainstream of solar cells that are currently in practical use is cells that use polycrystalline or amorphous silicon, but use high-toxic materials such as gallium and arsenic that have high economic costs and energy costs in the manufacturing process. It can not be said that there is no problem.
[0003]
As a new type of solar cell, a wet solar cell using photo-induced electron transfer of a metal complex is disclosed in JP-T-5-504023, JP-A-7-500630, WO94 / 05025, and the like. Yes.
[0004]
This wet solar cell has two electrodes separated by an electrolyte solution, at least one of which is substantially transparent. This transparent electrode has a porous titanium dioxide layer on which a photosensitizing dye is adsorbed. Have.
[0005]
The principle of this wet solar cell is that titanium dioxide as a semiconductor adsorbs a photosensitizing dye having the lowest empty orbit of electrons at a position higher than this, and further, the highest occupied orbit of the photosensitizing dye from the electron donor. This is an application of the fact that the anode current flows due to the rapid electron transfer of the excited electrons by configuring the fast electron transfer to the.
[0006]
This wet solar cell has advantages such as low cost, high efficiency, simple structure, and easy manufacture.
[0007]
In the above Japanese National Publication No. 5-502043, Japanese National Publication No. 7-500630, and International Publication No. 94/05025, iodine is used as an electron donor and titanium dioxide is used as an electron acceptor (semiconductor). As the sensitizing dye, a ruthenium complex of a polypyridyl compound is used. In International Publication No. 94/05025, a phthalocyanine compound having a carboxyl group, a naphthalocyanine compound and the like are also used as a photosensitizing dye.
[0008]
However, the ruthenium complex of this polypyridyl compound has problems such as insufficient light fastness, complicated production methods, and expensive ruthenium. Moreover, although the phthalocyanine compound which has a carboxyl group does not have such a fault, since the solubility with respect to an organic solvent is extremely low, the adsorption efficiency with respect to a titanium dioxide layer is low. In wet solar cells, a titanium dioxide thin film is immersed in a solution in which a photosensitizing dye is dissolved and adsorbed. Therefore, the solubility of the photosensitizing dye in an organic solvent affects the amount of titanium dioxide adsorbed and, in turn, the power generation efficiency. .
[0009]
The characteristics required for the photosensitizing dye include the following.
1) The level of the lowest unoccupied orbit (the redox potential in the excited state) is higher than the lower end of the semiconductor conduction-band.
2) The level of the highest occupied orbit (redox potential) is higher than the upper end of the semiconductor Valence-band.
3) Adsorbability on the surface of titanium dioxide is high.
4) High solubility in organic solvents.
5) Excellent durability.
6) Excellent economy.
[0010]
A photosensitizing dye satisfying these points has not yet been found.
[0011]
In addition, Japanese National Publication No. 2-502099 (International Publication No. W088 / 6175) discloses a wide range of phthalocyanine compounds containing the phthalocyanine compound of the present invention as a general formula and a liquid crystal optical display using the same. However, there is no specific disclosure or explanation of the phthalocyanine compound of the present invention.
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel phthalocyanine compound having excellent properties as described above as a photosensitizing dye.ThingsIt is to provide a wet solar cell used.
[0013]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a phthalocyanine compound having a specific substituent efficiently absorbs sunlight, has good solubility in organic solvents, and has excellent adsorptivity to titanium dioxide. I found it. That is, the present invention relates to a phthalocyanine compound represented by the general formula (I).ThingsThe present invention relates to a wet solar cell used as a photosensitizing dye.
[0014]
[Chemical formula 2]
[0015]
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I), M is two hydrogen atoms, a metal or a metal derivative, and examples of the metal include Cu, Zn, Fe, Co, Ni, Ru, Pb, Rh, Pd, Pt, Mn and Sn are preferable, and examples of the metal derivative include AlCl, InCl, FeCl, MnOH, SiCl.2, SnCl2, GeCl2, Si (OH)2, Sn (OH)2, Ge (OH)2, VO, and TiO are preferable. In particular, M is preferably Zn, Mg, Cu, Al, Fe, or two hydrogen atoms.
[0016]
X is an oxygen atom or a sulfur atom, and n is an integer of 1 to 3.
[0017]
Preferred specific examples of the phthalocyanine compound of the present invention are shown below.
(1) Tetra (carboxymethoxy) -Zn-phthalocyanine
(2) Tetra (carboxymethoxy) -Mg-phthalocyanine
(3) Tetra (carboxymethoxy) -Cu-phthalocyanine
(4) Tetra (carboxymethoxy) -AlCl-phthalocyanine
(5) Tetra (carboxymethoxy) -FeCl-phthalocyanine
(6) Tetra (carboxymethoxy) -H2-Phthalocyanine
(7) Tetra (carboxymethoxy) -Co-phthalocyanine
(8) Tetra (carboxymethoxy) -Ni-phthalocyanine
(9) Tetra (carboxymethoxy) -Ru-phthalocyanine
(10) Tetra (carboxymethoxy) -Pb-phthalocyanine
[0018]
(11) Tetra (carboxymethoxy) -Rh-phthalocyanine
(12) Tetra (carboxymethoxy) -Pd-phthalocyanine
(13) Tetra (carboxymethoxy) -Pt-phthalocyanine
(14) Tetra (carboxymethoxy) -MnOH-phthalocyanine
(15) Tetra (carboxymethoxy) -Sn-phthalocyanine
(16) Tetra (carboxymethoxy) -InCl-phthalocyanine
(17) Tetra (carboxymethoxy) -SiCl2-Phthalocyanine
(18) Tetra (carboxymethoxy) -SnCl2-Phthalocyanine
(19) Tetra (carboxymethoxy) -GeCl2-Phthalocyanine
(20) Tetra (carboxymethoxy) -Si (OH)2-Phthalocyanine
(21) Tetra (carboxymethoxy) -Sn (OH)2-Phthalocyanine
(22) Tetra (carboxymethoxy) -Ge (OH)2-Phthalocyanine
(23) Tetra (carboxymethoxy) -VO-phthalocyanine
(24) Tetra (carboxymethoxy) -TiO-phthalocyanine
(25) Tetra (carboxymethylthio) -Zn-phthalocyanine
(26) Tetra (carboxymethylthio) -Mg-phthalocyanine
(27) Tetra (carboxymethylthio) -Cu-phthalocyanine
(28) Tetra (carboxymethylthio) -AlCl-phthalocyanine
(29) Tetra (carboxymethylthio) -FeCl-phthalocyanine
(30) Tetra (carboxymethylthio) -H2-Phthalocyanine
[0019]
(31) Tetra (carboxymethylthio) -Co-phthalocyanine
(32) Tetra (carboxymethylthio) -Ni-phthalocyanine
(33) Tetra (carboxymethylthio) -Ru-phthalocyanine
(34) Tetra (carboxymethylthio) -Pb-phthalocyanine
(35) Tetra (carboxymethylthio) -Rh-phthalocyanine
(36) Tetra (carboxymethylthio) -Pd-phthalocyanine
(37) Tetra (carboxymethylthio) -Pt-phthalocyanine
(38) Tetra (carboxymethylthio) -MnOH-phthalocyanine
(39) Tetra (carboxymethylthio) -Sn-phthalocyanine
(40) Tetra (carboxymethylthio) -InCl-phthalocyanine
(41) Tetra (carboxymethylthio) -SiCl2-Phthalocyanine
(42) Tetra (carboxymethylthio) -SnCl2-Phthalocyanine
(43) Tetra (carboxymethylthio) -GeCl2-Phthalocyanine
(44) Tetra (carboxymethylthio) -Si (OH)2-Phthalocyanine
(45) Tetra (carboxymethylthio) -Sn (OH)2-Phthalocyanine
(46) Tetra (carboxymethylthio) -Ge (OH)2-Phthalocyanine
(47) Tetra (carboxymethylthio) -VO-phthalocyanine
(48) Tetra (carboxymethylthio) -TiO-phthalocyanine
(49) Tetra (2-carboxyethoxy) -Zn-phthalocyanine
(50) Tetra (2-carboxyethoxy) -Mg-phthalocyanine
[0020]
(51) Tetra (2-carboxyethoxy) -Cu-phthalocyanine
(52) Tetra (2-carboxyethoxy) -AlCl-phthalocyanine
(53) Tetra (2-carboxyethoxy) -FeCl-phthalocyanine
(54) Tetra (2-carboxyethoxy) -H2-Phthalocyanine
(55) Tetra (3-carboxypropoxy) -Zn-phthalocyanine
(56) Tetra (3-carboxypropoxy) -Mg-phthalocyanine
(57) Tetra (3-carboxypropoxy) -Cu-phthalocyanine
(58) Tetra (3-carboxypropoxy) -AlCl-phthalocyanine
(59) Tetra (3-carboxypropoxy) -FeCl-phthalocyanine
(60) Tetra (3-carboxypropoxy) -H2-Phthalocyanine
(61) Tetra (2-carboxyethylthio) -Zn-phthalocyanine
(62) Tetra (2-carboxyethylthio) -Mg-phthalocyanine
(63) Tetra (2-carboxyethylthio) -Cu-phthalocyanine
(64) Tetra (2-carboxyethylthio) -AlCl-phthalocyanine
(65) Tetra (2-carboxyethylthio) -FeCl-phthalocyanine
(66) Tetra (2-carboxyethylthio) -H2-Phthalocyanine
(67) Tetra (3-carboxypropylthio) -Zn-phthalocyanine
(68) Tetra (3-carboxypropylthio) -Mg-phthalocyanine
(69) Tetra (3-carboxypropylthio) -Cu-phthalocyanine
(70) Tetra (3-carboxypropylthio) -AlCl-phthalocyanine
(71) Tetra (3-carboxypropylthio) -FeCl-phthalocyanine
(72) Tetra (3-carboxypropylthio) -H2-Phthalocyanine
The phthalocyanine compound represented by the general formula (I) of the present invention using the above compounds (1) to (72) as representative examples is produced, for example, according to the following method.
[0021]
A phthalocyanine compound represented by general formula (IV) is produced by reacting a phthalonitrile compound represented by general formula (II) with a metal derivative represented by general formula (III). By decomposing, a phthalocyanine compound represented by the general formula (I) is obtained.
[0022]
[Chemical Formula 3]
M '-(Y)d (III)
(In the formula, M ′ represents a monovalent to tetravalent metal atom, Y represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetate, or oxygen, and d represents 1-4. Indicates an integer.)
[0023]
[Formula 4]
(In the formula, X, M and n are the same as X, M and n in the formula of the general formula (I), and R is the same as R in the formula of the general formula (II).)
Examples of the metal derivative represented by the formula (III) include halides of Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, and Pb. , Acetate, acetylacetonate, oxide, sulfate, nitrate, complex and the like. Specific examples include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, acetic acid. Examples include zinc, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.
[0025]
The reaction is usually performed in the presence of a solvent. As the solvent, an organic solvent having a boiling point of 80 ° C. or higher, preferably 100 ° C. or higher is used. For example, n-pentanol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, Examples include butoxyethanol, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, and urea. The usage-amount of a solvent is 1-100 weight part with respect to 1 weight part of a phthalonitrile compound, Preferably it is 5-50 weight part.
[0026]
Sodium hydride, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0 as catalysts in the reaction ] -7-undecene (DBU), ammonium molybdate or the like may be added. The addition amount is 0.1 to 10 mol, preferably 0.5 to 5 mol, relative to 1 mol of the phthalonitrile compound.
[0027]
The reaction temperature is 80 to 300 ° C, preferably 100 to 250 ° C. Below 80 ° C, the reaction rate is extremely slow. Above 300 ° C, the phthalocyanine compound may be decomposed.
[0028]
The reaction time is 1 to 40 hours, preferably 2 to 20 hours. If it is 1 hour or less, there are many unreacted raw materials, and if it is 40 hours or more, phthalocyanine may be decomposed.
[0029]
After the reaction, the phthalocyanine compound represented by the formula (IV) is obtained by concentrating the solvent from the reaction solution or discharging the reaction solution into a poor solvent (such as methanol) for the phthalocyanine compound and collecting the precipitate by filtration. Moreover, the phthalocyanine compound obtained as needed can be further purified by recrystallization or column chromatography.
[0030]
As for the usage-amount of a metal derivative and a phthalonitrile compound, 1: 3 to 1: 6 are preferable by molar ratio.
[0031]
Metal-free phthalocyanine compounds are prepared by using sodium alcoholate or lithium alcoholate as metal derivatives.2Phthalocyanine compound or Li2It can be obtained by treating a phthalocyanine compound with an acid and demetalizing it.
[0032]
As a solvent for hydrolyzing the phthalocyanine compound represented by the formula (IV) to produce the phthalocyanine compound represented by the formula (I), water or alcohol such as methanol, ethanol, n-propanol, isopropanol, 2-ethylhexanol Is used.
[0033]
As the alkali, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like can be used, and sodium hydroxide is particularly preferable.
[0034]
The reaction temperature at the time of hydrolysis is from 50 ° C to the boiling point of the solvent, with 80 to 120 ° C being particularly preferred.
[0035]
After completion of the hydrolysis, an acid is added to the aqueous solution of the target product or, in the case of an alcohol solvent, discharged into water to precipitate the target product. As the acid, hydrochloric acid, sulfuric acid, acetic acid and the like are used, and hydrochloric acid is particularly preferable.
[0036]
The phthalonitrile compound of the general formula (II) can be produced, for example, according to the following method.
[0037]
Nitrophthalonitrile and glycolic acid alkyl esters or thioglycolic acid alkyl esters are used as reaction solvents using aprotic polar solvents such as dimethylformamide (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), etc. The reaction is carried out at 50 to 120 ° C. in the presence of, for example, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) as a catalyst. The target product is obtained by discharging the reaction product into water, extracting it with an organic solvent such as toluene, and purifying the product by recrystallization as required.
[0038]
The wet solar cell containing the phthalocyanine compound of the present invention as a photosensitizing dye will be described below.
[0039]
The wet solar cell of the present invention has two electrodes, at least one of which is substantially transparent via an electrolytic solution, and the transparent electrode is a titanium dioxide layer on which the phthalocyanine compound of the present invention is adsorbed as a photosensitizing dye. It is characteristic that it has.
[0040]
As an example of the structure of the wet solar cell of the present invention, a schematic diagram of the wet solar cell produced in the example is shown in FIG.
[0041]
In FIG. 1, 1 is a transparent electrode made of conductive glass, 2 is a titanium dioxide layer carrying the phthalocyanine compound of the present invention as a photosensitizing dye, 3 is an electrolytic solution, and 4 is a counter electrode.
[0042]
Examples of the conductive glass include SnO doped with fluorine.2TCO glass (made by Asahi Glass Co., Ltd.) having a conductive layer or the like, or ITO glass (made by Balzers) having indium oxide doped with tin oxide as a conductive layer can be used. A polymer can also be used as a transparent electrode instead of glass.
[0043]
The titanium dioxide of the titanium dioxide layer is desirably porous, and the roughness is preferably 10 to 5000, more preferably 50 to 1000. The roughness is defined by the ratio of the apparent surface area to the true surface area.
[0044]
Examples of the method for forming the titanium dioxide layer on the surface of the conductive glass include a sol-gel method and a colloid method.
[0045]
The thickness of the titanium dioxide layer is preferably 5 to 50 μm, more preferably 10 to 30 μm.
[0046]
In order to support (adsorb) the phthalocyanine compound as a photosensitizing dye on the titanium dioxide layer, for example, the phthalocyanine compound is dissolved in an organic solvent such as DMF or alcohol, and the titanium dioxide layer is immersed in this for a predetermined time. A drying method is used.
[0047]
The electrolyte solution is preferably a redox system such as an iodine / iodine solution, a bromine / bromine solution, a hydroquinone solution, or a transition metal complex solution. Solvents used in the electrolyte include water, alcohol, 3-methyl- (2-oxazolidinone), 1,3-dimethyl-2-imidazolidinone, propylene carbonate, ethylene carbonate, THF, dimethyl sulfoxide, dichloroethane, etc. Or a compatible mixture of these.
[0048]
Platinum or the like is used as the counter electrode.
[0049]
【Example】
Examples are shown below, but the present invention is not limited to these examples.
[0050]
[ManufacturingExample 1] Synthesis of tetra (carboxymethoxy) -Zn-phthalocyanine
4- (Ethoxycarbonylmethoxy) phthalonitrile (11.5 g), zinc (II) chloride (2.1 g), DBU (7.6 g) and n-pentyl alcohol (100 mL) were mixed, and the mixture was stirred at 120 to 130 ° C. for 8 hours. After cooling, the reaction mixture was discharged into 1000 mL of methanol, and the precipitate was collected by filtration and dried to obtain 11.2 g of tetra (ethoxycarbonylmethoxy) -Zn-phthalocyanine as a dark green powder.
[0051]
9.7 g of this product was stirred under reflux in 500 mL of 2% aqueous sodium hydroxide solution for 6 hours. After cooling, acid precipitation was performed with 10% hydrochloric acid, and the precipitate was collected by filtration, washed with water and dried to obtain 6.2 g of a dark green powder.
[0052]
From the following analysis results, it was confirmed to be the target product. In the elemental analysis values, the value of Zn is determined by the atomic absorption method.
[0053]
[0054]
[ManufacturingExample 2] Synthesis of tetra (carboxymethylthio) -Zn-phthalocyanine
After mixing 12.3 g of 4- (ethoxycarbonylmethylthio) phthalonitrile, 2.1 g of zinc (II) chloride, 7.6 g of DBU, and 100 mL of n-pentyl alcohol, the mixture was stirred at 120 to 130 ° C. for 8 hours. After cooling, the reaction mixture was discharged into 1000 mL of methanol, and the precipitate was collected by filtration and dried to obtain 10.0 g of tetra (ethoxycarbonylmethylthio) -Zn-phthalocyanine as a dark green powder.
[0055]
8.4 g of this product was stirred at reflux in 500 mL of 2% sodium hydroxide for 6 hours. After cooling, acid precipitation was performed with 10% hydrochloric acid, and the precipitate was collected by filtration, washed with water and dried to obtain 3.0 g of a dark color powder.
[0056]
From the following analysis results, it was confirmed to be the target product.
[0057]
[Example1] Fabrication of wet solar cells
1) Preparation of titanium dioxide layer
After adding 20 mL of nitric acid (pH = 0.5-1) to 5 g of titanium dioxide ultrafine particles (average particle size 12 nm, anatase) prepared by hydrolysis of titanium (IV) sulfate, and sufficiently stirring, polyethylene glycol (MW = 20000) 3.2 g was added and stirred to prepare a dispersion of titanium dioxide. This dispersion was thoroughly washed with ethanol to be conductive glass (fluorine-doped SnO2After being naturally dried, sintered in air at 450 ° C. for 30 minutes, and then allowed to cool to room temperature under an argon atmosphere.
[0058]
2) Adsorption of photosensitizing dye onto titanium dioxide
After reheating the titanium dioxide thin film produced in 1) at 450 ° C. for 30 minutes in the air,ManufacturingTetra (carboxymethoxy) -Zn-phthalocyanine synthesized in Example 1 was 3 × 10-4It was immersed for 5 hours in a DMF solution dissolved in a concentration of M (mol / L). Subsequently, it was washed with dehydrated DMF and ethanol, and vacuum-dried to prepare a dye-supported titanium dioxide thin film.
[0059]
3) Fabrication of wet solar cells
A wet solar cell as shown in FIG. 1 was prepared using the glass electrode having the dye-supported titanium dioxide thin film prepared in 2). A platinum electrode was used as the counter electrode, and an ethylene carbonate / acetonitrile mixed solution (80/20 vol%) containing 0.5M tetrapropylammonium iodide and 0.04M iodine as the electrolyte was used as the electrolyte.
[0060]
[Example2] Fabrication of wet solar cells
Example1Instead of tetra (carboxymethoxy) -Zn-phthalocyanine, a photosensitizing dye inManufacturingExample except that tetra (carboxymethylthio) -Zn-phthalocyanine synthesized in Example 2 was used1A wet solar cell was produced by performing the same operation as in Example 1.
[0061]
[Comparative Example 1] Fabrication of wet solar cell
Example1Example 1 except that tetra (2-diethylaminoethoxy) -Zn-phthalocyanine (Compound 1) was used instead of tetra (carboxymethoxy) -Zn-phthalocyanine which is a photosensitizing dye in1A wet solar cell was produced by performing the same operation as in Example 1.
[0062]
[Comparative Example 2] Fabrication of wet solar cell
Example1Example 4 except that tetra (tert-butyl) -Zn-phthalocyanine (Compound 2) was used instead of tetra (carboxymethoxy) -Zn-phthalocyanine which is a photosensitizing dye in1A wet solar cell was produced by performing the same operation as in Example 1.
[0063]
[Comparative Example 3] Fabrication of wet solar cell
Example1Example 4 except that tetracarboxy-Zn-phthalocyanine (
[0064]
Evaluation 1 Solubility test
ManufacturingTetra (carboxymethoxy) -Zn-phthalocyanine synthesized in Example 1;ManufacturingThe tetra (carboxymethylthio) -Zn-phthalocyanine synthesized in Example 2, Compound 1,
[0065]
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Methanol DMF DMSO
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ManufacturingCompound of Example 1 △ ○ ○
ManufacturingCompound of Example 2 ○ ○ ○
Compound 1 (Comparative substance) ○ ○ ○
Compound 2 (Comparative substance) ○ ○ ○
Compound 3 (Comparative substance) × △ △
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
However, (circle) shows easy solubility, (triangle | delta) is hardly soluble, and x shows insoluble.
[0066]
Measurement of redox potential
CV measurement was performed by dissolving 1 mM of the phthalocyanine compound of the present invention and 0.1 M of the supporting electrolyte tetra-n-butylammonium hexafluorophosphate in DMF. The results of determining the redox potential are shown in Table 2. As electrodes, glassy carbon was used as the working electrode, platinum electrode was used as the counter electrode, and silver nitrate electrode was used as the reference electrode.
[0067]
Measurement of 0-0 band energy
The phthalocyanine compound of the present invention was dissolved in methanol to measure fluorescence, and 0-0 band energy was calculated from the intersection 0-0 band of the obtained excitation spectrum and fluorescence spectrum.
These results are shown in Table 2.
[0068]
[Table 2]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
0-0 band 0-0 band energy Redox potential
(Nm) (eV) (Vvs.NHE)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ManufacturingCompound of Example 1 693 1.79 1.10
ManufacturingCompound of Example 2 688 1.80 1.02
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
It has been confirmed that these phthalocyanine compounds of the present invention are on the positive potential side with respect to iodine serving as an electron donor, and the excitation level is on the negative potential side with respect to the conduction band of titanium dioxide serving as an acceptor. In other words, the lowest unoccupied orbital of the dye exists at a position higher than that of the semiconductor, and electrons can be injected from the excitation level of the dye to the conduction band, and electron transfer from the electron donor to the highest occupied orbital of the dye can occur. Was confirmed.
[0069]
Example1, 2And the UV-visible absorption spectrum of the titanium dioxide thin film produced in Comparative Examples 1, 2, and 3 was measured, and the adsorption density of the dye was calculated using the extinction coefficient at the maximum absorption wavelength of each phthalocyanine compound in ethanol. The results are shown in Table 3.
[0070]
[Table 3]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Supported phthalocyanine compound Dye adsorption amount (× 10-9 mol. cm-2)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ManufacturingCompound of Example 1 23
ManufacturingCompound of Example 2 47
Compound 1 (Comparative substance) 6
Compound 2 (Comparative substance) 3
Compound 3 (Comparative substance) 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
From the above results, it was confirmed that the phthalocyanine compound of the present invention was more effectively adsorbed on titanium dioxide than phthalocyanine compounds having other substituents.
[0071]
Evaluation 4 Measurement of photoelectric conversion efficiency of wet solar cells
Example1, 2And the photoelectric conversion efficiency was measured as follows about the wet solar cell produced by Comparative Examples 1, 2, and 3. FIG. Using a 500 W Xe lamp as the light source, light passing through an ultraviolet cut filter (irradiates light of 400 nm or more, irradiation light intensity is 22 mW / cm2) Was spectrally irradiated with a monochromator, and the short-circuit current at each wavelength was measured. Moreover, the light intensity in each wavelength was measured, and the conversion efficiency was calculated by the following formula.
[0072]
IPCE = 1.24 × 102× Isc / P × λ
Where IPCE is the conversion efficiency (%) for incident light, Isc is the short circuit current (mA / cm)2), P is irradiation light intensity (μW / cm2), Λ represents the wavelength (nm) of monochromatic light.
Next, the photoelectric conversion efficiency LHE (%) for the absorbed light near the absorption maximum wavelength was calculated from the following equation.
[0073]
LHE = ICPE / (1-T / 100)
Here, T (%) indicates the transmittance of the solar cell module in Q-band.
The results are shown in Table 4.
[0074]
[Table 4]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
LHE (%: Q-band)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example1Solar cell 6.37
Example2Solar cell 9.92
Solar cell of Comparative Example 1. 2.35
Solar cell of Comparative Example 2 1.41
Solar cell of Comparative Example 3 0.5
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
From the above results, it was found that the wet solar cell using the phthalocyanine of the present invention as a photosensitizing dye exhibits high photoelectric conversion efficiency.
[0075]
【The invention's effect】
The novel phthalocyanine compound of the present invention has excellent solubility in organic solvents, forms a strong bond with the surface of titanium dioxide used in semiconductors, and has the lowest free orbital of the dye at a position higher than the semiconductor, thus exciting the dye. Electrons can be injected from the level to the conduction band, and the electron transfer from the electron donor to the highest occupied orbital of the dye is excellent and the durability is excellent. Use this as a photosensitizer. It can be suitably used for wet solar cells.
[Brief description of the drawings]
FIG. 1 is a schematic view of a specific example of a wet solar cell according to the present invention.
[Explanation of symbols]
1 Transparent electrode
2 Titanium dioxide layer
3 Electrolytic solution
4 Counter electrode
Claims (2)
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| JP02181496A JP4081149B2 (en) | 1996-01-12 | 1996-01-12 | Wet solar cells using phthalocyanine compounds |
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| JP02181496A JP4081149B2 (en) | 1996-01-12 | 1996-01-12 | Wet solar cells using phthalocyanine compounds |
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