JP2004265662A - Method of manufacturing inorganic oxide semiconductor electrode for photoelectric conversion - Google Patents
Method of manufacturing inorganic oxide semiconductor electrode for photoelectric conversion Download PDFInfo
- Publication number
- JP2004265662A JP2004265662A JP2003052916A JP2003052916A JP2004265662A JP 2004265662 A JP2004265662 A JP 2004265662A JP 2003052916 A JP2003052916 A JP 2003052916A JP 2003052916 A JP2003052916 A JP 2003052916A JP 2004265662 A JP2004265662 A JP 2004265662A
- Authority
- JP
- Japan
- Prior art keywords
- oxide semiconductor
- inorganic oxide
- photoelectric conversion
- electrode
- conductive layer
- 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.)
- Granted
Links
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 111
- 239000004065 semiconductor Substances 0.000 title claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 230000001235 sensitizing effect Effects 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 239000010410 layer Substances 0.000 description 138
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 48
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 46
- 239000000975 dye Substances 0.000 description 39
- 239000000463 material Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 29
- 238000012545 processing Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000017525 heat dissipation Effects 0.000 description 6
- 239000012327 Ruthenium complex Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000013021 overheating Methods 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000000191 radiation effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000009768 microwave sintering Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 230000009967 tasteless effect Effects 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 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
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-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
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005294 BK7 Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001856 aerosol method Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009699 high-speed sintering Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、無機酸化物多孔質状の無機酸化物半導体電極を作成する製造工程、および、当該無機酸化物半導体電極を用いた光電変換用電極、光電変換セルに関する。
【０００２】
【従来の技術】
太陽光発電は単結晶シリコン太陽電池、多結晶シリコン太陽電池、アモルファスシリコン太陽電池、テルル化カドミウムやセレン化インジウム銅などの化合物太陽電池が実用化、もしくは研究開発対象となっているが、普及させる上で製造コスト、原材料確保、エネルギーペイバックタイムが長い等の問題点を克服する必要がある。一方、大面積化や低価格を指向した有機材料を用いた太陽電池もこれまでに多く提案されているが変換効率が低く、耐久性も悪いという問題があった。
【０００３】
こうした状況の中で、色素によって増感された無機酸化物半導体多孔質を用いた光電変換用電極および光電変換セル、ならびにこれを作成するための材料および製造技術が開示された（非特許文献１および特許文献１参照）。提案された電池は、ルテニウム錯体等の増感色素によって分光増感された酸化チタン多孔質層を作用電極としヨウ素を主体とする電解質および対電極から成る色素増感型の光電変換セルである。この方式の第一の利点は酸化チタン等の安価な酸化物半導体を用いるため、安価な光電変換素子を提供できる点であり、第二の利点は用いられるルテニウム錯体が可視光域に幅広く吸収を有していることから比較的高い変換効率が得られる点である。
【０００４】
また、酸化チタンペーストで成膜後焼成してできた酸化チタン多孔質層に、トリピリジルカルボキシレート配位子を有するルテニウム錯体を吸着させた電極を用いてセルを作製し、変換効率１０．４％を達成したことが報告されている（非特許文献２参照）。
【０００５】
このような色素増感型光電変換セルの製造上の問題点のひとつとして、高温の焼結プロセスを必要とする問題点がある。酸化チタン多孔質層を形成する際に一般的に用いられる手法は酸化チタン粒子の分散ペーストを塗布して形成した酸化チタン粒子層に４００℃以上の温度を与えることによって粒子間にネッキングを生じさせることにより多孔質化させ、電子伝達性を向上させるものである。このため用いることができる基材がガラスのような耐熱性の高い材質に限られるので光電変換セルの基材材料費や製造時に消費するエネルギー費等の製造コストを高価な物にしている。樹脂を基材としてこれが溶解しない温度を与えて酸化チタン多孔質層を作る方法も試みられているが変換効率が低いものにとどまっていた。さらに低温焼成で作成された酸化チタン多孔質層はもろく、セルの耐久性が低いものであった（非特許文献３参照）。低温で焼成する焼結方法は焼結時間も比較的長時間となり、この点からも量産時のプロセスとしては問題があった。
【０００６】
樹脂を基材とした場合の無機酸化物多孔質層の製造方法として無機酸化物粒子層に加圧する方法がある（非特許文献７および特許文献４参照）。しかし、プレス処理単独の場合、用いられる圧力が数百ｋｇｆ／ｃｍ２と高圧であるため高圧の油圧装置が必要な上、ロールツーロールなどの連続生産装置では圧力を伝達するロールが磨耗、破壊しやすい、処理速度が遅い等、連続生産には不向きな方法であった。
【０００７】
無機酸化物を含むセラミクスの焼結にはマイクロ波が用いられることがある（非特許文献４および５参照）。
マイクロ波加熱の特徴の一つは、外部加熱と違い、マイクロ波エネルギーの吸収可能な誘電体が優先的に発熱する選択性を有することにある。基材に対してこれに製膜された無機酸化物粒子層を選択的に加熱することができれば樹脂基材を用いた光電変換セルのシート化に有効な手段として有用である。
【０００８】
色素増感型太陽電池の無機酸化物半導体電極処理におけるマイクロ波の適用としては、、様々なエネルギーや電磁波照射の列挙の一つとしてマイクロ波が登場するが、実施されたエネルギーおよび電磁波照射は加熱、紫外光、赤外光のみで、マイクロ波照射での実施例は無い上に、明細書中での説明も無い（特許文献２および３参照）。さらに透明電極、又はこれに酸化チタン粒子を塗布したものに一般的な家庭用電子レンジ（５００Ｗ、２．４５ＧＨｚ）でマイクロ波照射を行うと、数秒で基材や導電層の破壊に至ることから単純な電磁波処理では電極の処理が困難であることがわかる。
【０００９】
又、本発明を演者らが発表した学術会議（電気化学会 第７０回大会 ２００２年９月１２〜１３日 東京工芸大学厚木キャンパス）において、桐蔭横浜大学から電着法によって得られた一定の変換効率を既に有する酸化チタンの多孔質層に対しての効率向上効果として照射条件不明確ながら家庭用電子レンジでマイクロ波照射を行った例（５５０Ｗ、２．４５ＧＨｚ）が同時に発表された（非特許文献６参照）が、簡便で量産性の優れた塗布法によって得られた粒子層への応用で、粒子間のネッキングや透明導電層−粒子間の結着を生じさせた例は同発表においても無い。
同学術会議で演者らも家庭用電子レンジで酸化チタン粒子のみをマイクロ波処理した例を示したが、この条件では粒子径の収縮変化は無く、粒子間のネッキングを生じさせるような実質的な形態変化が確認できなかった（図２）。簡便で量産性の優れた塗布法によって製膜された酸化チタン粒子層から多孔質層を形成させるためのマイクロ波応用には条件検討が必要なことが示唆された。
【００１０】
【非特許文献１】Ｎａｔｕｒｅ（第３５３巻、第７３７〜７４０頁、１９９１年
【特許文献１】米国特許４９２７７２１号明細書
【非特許文献２】Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．（２００１），Ｖｏｌ．１２３，ｐ．ｐ．１６１３−１６２４
【非特許文献３】ＥＣＮ ｃｏｎｔｒｉｂｕｔｉｏｎｓ １６ｔｈ Ｅｕｒｏｐｅａｎ Ｐｈｏｔｏｖｏｌｔａｉｃ Ｓｏｌａｒ Ｅｎａｒｇｙ Ｃｏｎｆｅｒｅｎｃｅ ａｎｄ Ｅｘｈｉｂｉｔｉｏｎ， Ｍａｙ １−５，２０００ ａｂｓｔｒａｃｔ； Ｐ．Ｍ．Ｓｏｍｍｅｌｉｎｇ ｅｔ．ａｌ，”Ｆｌｅｘｉｂｌｅ ｄｙｅ−ｓｅｎｓｉｔｉｚｅｄ ｎａｎｏｃｒｉｓｔａｌｌｉｎｅ ＴｉＯ２ ｓｏｌａｒ ｃｅｌｌｓ”
【非特許文献４】「豊田中央研究所Ｒ＆Ｄレビュー、 Ｖｏｌ．３０ Ｎｏ．４（１９９５．１２）ｐ．２５ 機能性セラミックスのマイクロ波焼結」
【非特許文献５】「セラミックスの高速焼結技術 セラミックス電磁プロセッシング、 株式会社ティー・アイ・シー １９９８年 三宅正司編」
【特許文献２】特開２００１−３５７８９６号公報
【特許文献３】特開２００２‐１３４４３５号公報
【非特許文献６】電気化学会 第７０回大会 ２００２年９月１２〜１３日 東京工芸大学厚木キャンパス ２Ｅ１９
【非特許文献７】Ｎａｎｏｌｅｔｔｅｒｓ，１，（２００１），ｐ．ｐ．９７‐１００，Ｈ．Ｌｉｎｄｓｔｒｏｎ，ｅｔ．ａｌ．
【特許文献４】国際公開第００／７２３７３号パンフレット
【００１１】
【発明が解決しようとする課題】
色素増感型の光電変換セルの安価なプロセスを可能にするには、短時間の処理でかつ安価な樹脂基材を用いて高い変換効率有することのできる多孔質状の無機酸化物半導体層形成の技術が求められていた。
【００１２】
本発明の目的は、短時間の処理で、かつ樹脂基材を用いて高い変換効率を有した多孔質状の無機酸化物半導体層を形成できる製造工程を提供し、ひいては、当該無機酸化物半導体層を用いた光電変換用電極、光電変換セルの製造をも可能とすることである。
【００１３】
【課題を解決するための手段】
発明者らは、マイクロ波を低出力で使用することで上記課題を解決することを見出し、本発明に至った。
【００１４】
即ち、本発明は、透明導電層を具えた透明基材と、無機酸化物半導体多孔質層とを含む光電変換用無機酸化物半導体電極の製造方法であって、
平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子を透明導電層上に塗布して製膜して無機酸化物半導体多孔質層とする工程１、
透明導電層および無機酸化物半導体多孔質層に、周波数１ＧＨｚ以上３００ＧＨｚ以下のマイクロ波を１Ｗ以上、かつ、下記式の出力以下で照射して発熱させる工程２、
増感色素を無機酸化物半導体多孔質層と接触させる工程３を含む工程により製造されることを特徴とする光電変換用無機酸化物半導体電極の製造方法。
式 ｙ ＝ ２×１０−８ ｘ＋ ３００（式中、ｙは高周波出力（Ｗ）、ｘは高周波周波数（Ｈｚ）を表す。）
また、透明導電層を具えた透明基材と、無機酸化物半導体多孔質層とを含む光電変換用無機酸化物半導体電極の製造方法であって、
平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子を透明導電層上に塗布して製膜して無機酸化物半導体多孔質層とする工程１、
透明導電層および無機酸化物半導体多孔質層に周波数１ＧＨｚ以上３００ＧＨｚ以下のマイクロ波を照射して発熱させる工程であって、被照射体に放熱体を密着させながらマイクロ波を照射する工程４、
増感色素を無機酸化物半導体多孔質層と接触させる工程３を含む工程により製造されることを特徴とする光電変換用無機酸化物半導体電極の製造方法に関する。
【００１５】
また、本発明は、透明導電層を具えた透明基材と、無機酸化物半導体多孔質層とを含む光電変換用無機酸化物半導体電極の製造方法であって、
無機酸化物半導体多孔質層が、平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子を透明導電層上に塗布して製膜する工程１の後及び／又は前に、無機酸化物半導体多孔質層にプレス処理する工程５を行うことを特徴とする上記光電変換用無機酸化物半導体電極の製造方法に関する。
【００１６】
また、本発明は、無機酸化物半導体多孔質層に与えるプレス処理の圧力が０．０１Ｋｇｆ／ｃｍ２ 以上１００Ｋｇｆ／ｃｍ２未満であることを特徴とする上記光電変換用無機酸化物半導体電極の製造方法に関する。
【００１７】
また、本発明は、透明導電層が、酸化スズ、酸化インジウム、酸化亜鉛、炭素の少なくとも１つを含む上記光電変換用無機酸化物半導体電極の製造方法に関する。
【００１８】
また、本発明は、マイクロ波照射時に、マイクロ波の入射方向が透明基材面側からの照射することを特徴とする上記光電変換用無機酸化物半導体電極の製造方法に関する。
【００１９】
また、本発明は、マイクロ波照射時に、マイクロ波照射によって被照射体を５０℃以上１０００℃以下に昇温させることを特徴とする上記光電変換用無機酸化物半導体電極の製造方法に関する。
【００２０】
また、本発明は、マイクロ波照射時に、マイクロ波照射によって被照射体を２００℃／分以下の速度で昇温させることを特徴とする上記光電変換用無機酸化物半導体電極の製造方法に関する。
【００２１】
また、本発明は、上記光電変換用無機酸化物半導体電極と、電解質層と、導電性対極とを備えた光電変換用半導体セルに関する。
【００２２】
【発明の実施の形態】
（マイクロ波処理による無機酸化物半導体多孔質層の形成方法 工程２）
本発明では、被照射体である透明電極の透明導電層上に塗布法によって製膜された平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子から成る無機酸化物半導体粒子層および透明導電層に照射し、エネルギー吸収によりこれらを発熱させる工程を経て粒子間のネッキングおよび粒子−透明電極間に結着を生じさせることができる。とりわけ優先的に発熱するのは誘電損率の高い酸化スズ、酸化インジウム、酸化亜鉛、炭素などを含む透明導電層である。透明導電層に塗布された無機酸化物半導体粒子層は比較的誘電損率が低いので主として透明導電層から伝わる発熱により昇温し、粒子間のネッキングおよび粒子−透明導電層間に結着を生じる。図３は本発明のマイクロ波処理後の酸化チタン多孔質層の電子顕微鏡写真である。透明導電層の優先的な温度上昇の影響を受けた形で基材温度も上昇する。
【００２３】
表１は、予備試験として、（ａ）ガラス基材のみ、（ｂ）透明導電層（フッ素ドープ酸化スズ＝ＦＴＯ）付きガラス基材、（ｃ）酸化チタン粒子塗布層付きガラス基材、（ｄ）透明導電層付きガラス基材の透明導電層上に酸化チタン粒子塗布層を付けた物、の４種の被照射体に２８ＧＨｚ、５００Ｗのマイクロ波を５分間照射した後の被照射体温度である。マイクロ波照射に対して十分な発熱を得るには透明導電層の存在が必須であることがわかる。
【００２４】
表１ マイクロ波焼成の予備試験
周波数２８ＧＨｚ、５００Ｗのマイクロ波を５分間照射した後の被照射体温度。
透明導電層側にマイクロ波照射を行うことを表面照射と称する。
被照射体と熱電対やアルミナ台座との位置関係を表１（ｂ）裏面照射の場合を例として図４に示す。
【００２５】
【表１】
被照射体である誘電体が体積あたりに吸収されるエネルギーＰ（Ｗ／ｃｍ３）は、Ｐ＝ε０ε”ωＥ２／２（ここで、ε０は真空の誘電率、ε”（＝εｒｔａｎδ）は誘電体の誘電損率［εｒは比誘電率、ｔａｎδは誘電正接］、ωは角周波数、Ｅは電界強度）であり、電磁波の周波数と電界強度の双方がエネルギーの吸収強度に寄与するので、特定の誘電損率を有する被照射体に対して目的の処理状態に必要な温度になるようにエネルギーを調節するには照射電磁波の電界強度を変化させる方法と周波数を変化させる方法の２つの方法が存在する。電界強度の寄与は２乗で効いてくるのでこれを高くすることによるエネルギー増大の寄与は大きい。又、周波数の高い電磁波を用いると、誘電体の誘電損率もこれに依存して一般的に増大し、効率的なエネルギー吸収に繋がる。
【００２７】
無機酸化物をはじめとするセラミックスのマイクロ波焼結においては、被照射体の昇温に伴う誘電損率の増大によって生じる熱暴走（ｔｈｅｒｍａｌ ｒｕｎａｗａｙ）等に起因する局部的な過熱から生じる被照射体の破壊や歪み等がしばしば問題となる。被照射体が無機酸化物半導体電極である場合、照射条件が不適切であれば基材や導電層の破壊、クラック形成、部分的な溶解、変形等が生じる。
【００２８】
一般的な電子レンジ（２．４５ＧＨｚ、高周波出力５００Ｗ程度）で導電性ガラス（フッ素ドープ酸化スズ導電層で被覆）あるいはこの導電層側に酸化チタン粒子層を塗布して電磁波照射を行うと、数秒で基材の破壊が起こる。これは導電層に用いられる酸化スズの昇温が加速度的に起こり基材との間に熱分布の差が大きくなり歪が生じる為である。基材の面積が大きくなる程基材の破壊等は起こりやすくなる。たとえば２．４５ＧＨｚ高周波出力５００Ｗ家庭用電子レンジにおける電磁波照射において２．５ｃｍ×２．５ｃｍ×１．１ｍｍのＦＴＯガラスでは照射後３〜５秒で基材の破壊が起こり十分な昇温は得られない。基材を小さくカットしたり、照射面積を小さくするマスクを施したりすると破壊が起こるまでの照射時間を延長できるが、大面積を必要とする太陽電池の製造にとっては適切な方法ではない。塗布製膜された無機酸化物粒子層を有する導電層にマイクロ波照射を行って、焼成により粒子間のネッキングおよび粒子−透明導電層間に結着を生じさせるには適切な照射条件が必要である。
【００２９】
被照射体に温度差が生じた場合に熱暴走が生じないためには以下の条件を満足しなければならない。
Ｐｔ１−Ｐｔ２＜［（ｔ１−ｔ２）／ｌ］Ａ・Ｒ
（ここでＰｔ１−Ｐｔ２：温度ｔ１、ｔ２での吸収エネルギー、（ｔ１−ｔ２）／ｌ：温度勾配、Ａ：熱伝導断面積、Ｒ：熱伝導率 ；佐治他三郎、「セラミックスの高速焼成技術」（株）ティー・アイ・シー刊、第Ｉ部 第１章 第１節 ）
【００３０】
従って、熱伝導断面積が決まっている導電性基材に対して熱暴走を生じさせない対策は、高周波出力の比較的低い領域での連続照射を行うか、パルス状の高出力波を間欠的に照射する、熱伝導率の高い放熱板等の放熱体に密着させる等の放熱対策を行う、被照射体にプレヒートを行う等の均熱対策を行う等の熱分布を緩和するような工夫が必要となる。
又、高い周波数のマイクロ波を使用すると被照射体の誘電損率の温度依存性が小さくなり、式中Ｐｔ１−Ｐｔ２項を小さくすることに繋がるため効果的である。
【００３１】
２．４５ＧＨｚでのマイクロ波照射で、容易に入手可能な照射装置として家庭用電子レンジを用いる場合、同一のマグネトロンで可変出力を行おうとすると、汎用出力の５００Ｗ照射に比べて低出力の連続照射試験ではインバーターの周波数上昇に伴いフィラメント温度が低下しマグネトロンの発振が不安定となり、低出力領域での照射試験は行いづらいものがあった。入手可能な家庭用電子レンジでマグネトロンやインバーター回路を改良して１００Ｗ、２００Ｗの連続低出力照射の実験が可能なものは現在までに、２００１年発売の東芝社製ＥＲ−Ａ３０Ｓシリーズのみである（電波新聞２００１年５月２２日刊）。本発明での２．４５ＧＨｚ１００Ｗ照射は、当該装置を用いて照射試験を行った。その他の家庭用電子レンジでは解凍モード等で高周波出力の５００Ｗ付近の照射を間欠的に行うことで、１００Ｗ相当、２００Ｗ相当等と称している。周波数２．４５ＧＨｚでの低出力領域の試験検討が容易でなかったことがわかる。
【００３２】
さらに工業的な２．４５ＧＨｚのマイクロ波利用としては、木材の乾燥や冷凍品の加熱等の分野で出力１０００Ｗ以上の利用が先行し、医療や電子材料加工等の特殊途で１００Ｗ前後の低出力領域のマイクロ波が使われ始めたのは近年のことである。
【００３３】
（放熱体について 工程４）
マイクロ波照射処理時において、被照射体に放熱対策を行う場合はヒートシンクやシート状の放熱体および冷媒で冷却可能な放熱体等に酸化チタン電極を密着させる等の対策が挙げられる。密着面は被照射体の裏面でも表面でもかまわない。放熱体の材質は、使用温度での熱伝導率が１０Ｗ／ｍ・Ｋ以上であるものが好ましく、アルミ等の金属が好ましい。しかし、被照射体の急激な局部過熱を緩和する働きを行うものであれば、これに限らない。例えば、熱伝導率が１０Ｗ／ｍ・Ｋ未満の材質であっても、材質内部に冷媒を通すことにより本発明の放熱体とすることができる。高い熱伝導率を有する金属以外の材質の一例としてはグラファイト、ベリリア、窒化アルミ、炭化ケイ素等が挙げられる。放熱体として材質内部に冷媒を通す場合、冷媒の温度コントロールを行い安定な放熱効果を得ることがさらに望ましい。被照射体の放熱体への密着方法は器具による固定、圧着、粘着、接着、接触、吸引等が挙げられるが密着状態を生じさせることができれば他の方法でもかまわない。被照射体の放熱体の間に例えば１０ミリ以内の距離があっても放熱効果を及ぼすことができる配置関係であればこれに該当する。被照射体に気体、液体状の冷却冷媒を放熱体として直接接触させることも該当する。
【００３４】
図５は放熱体としてアルミ製のヒートシンクとテープを密着させた実施例である。
被照射体に対してマイクロ波を照射する方法として、マイクロ波照射器に対してシート状の被照射体が連続的に移動し巻き取り作業を伴って処理する方法は安価に製造する方法として有用である。この際、被照射体が放熱体に密着を保ちながら連続的に位置関係を変化させゆく工夫をすることにより連続的な放熱効果を得ることもできる。
【００３５】
（プレス処理について 工程５）
マイクロ波照射前に、無機酸化物半導体多孔質層にプレス処理を行うことは高い変換効率を得るために効果的である。とりわけ透明導電層を有した基材が樹脂製である場合は強い圧力をかけても基材の破壊に至ることなく効果を得ることができる。プレス処理単独での効果はＮａｎｏｌｅｔｔｅｒｓ，１，（２００１），ｐ．ｐ．９７‐１００，Ｈ．Ｌｉｎｄｓｔｒｏｎ，ｅｔ．ａｌ．および国際公開第００／７２３７３号パンフレットで述べられている。ただしプレス処理単独で処理を行う場合、用いられる圧力が数百ｋｇｆ／ｃｍ２と高圧であるため高圧の油圧装置が必要な上、ロールツーロールなどの連続生産装置では圧力を伝達するロールが磨耗、破壊しやすい、処理速度が遅い等、連続生産には不向きな方法である。圧力として量産製造工程上の観点からは一般的な印刷工程用のロール厚力で可能な０．０１Ｋｇｆ／ｃｍ２ 以上１００Ｋｇｆ／ｃｍ２未満の圧力で予備加圧として圧力を付与し、その後にマイクロ波処理を行う方法が初めて量産性を有しかつ高い変換効率を得るために最も有効な製造方法となる。圧力を付与する方法は加圧ジャッキ等で数秒〜数分間圧力をかけても良いし、ロール間で連続して加圧しても良い。加圧時には圧力シリンダーで直接圧力をかけると、無機酸化物の一部が基材から剥がれてシリンダー側へ付着するので、間にポリエチレン等のフィルム等を入れておくことが望ましい。プレス処理をマイクロ波処理前に行うと、無機酸化物半導体多孔質層を構成する粒子間や粒子−透明導電層間の距離を狭めてマイクロ波処理を行うことができるのでネッキングが形成しやすくなり、変換効率の向上等に特に有効であるが、プレス処理をマイクロ波処理後に行っても変換効率向上の効果を得ることができる。プレス処理をマイクロ波処理後に行うと、プレス処理時に起こりやすい無機酸化物層の剥がれなどが起こりにくくなる。
【００３６】
高い周波数のマイクロ波として２０ＧＨｚ以上の領域をミリ波領域と呼ぶことがある。
この領域にあたる高い周波数のマイクロ波による処理では、（１）処理容器内に一様な電界強度分布を作りやすい、（２）処理開始温度（たとえば室温）での誘電損率が一般に大きくなるのでエネルギー吸収が効率的である、（３）誘電損率の温度依存性が小さくなり加熱途上でしばしば発生する熱暴走を避けやすい、（４）非熱的作用から焼結に必要な温度そのものを下げることができる（Ｈ．Ｄ．Ｋｉｍｒｅｙ，ｅｔ．ａｌ．、ＭＲＳ．Ｓｙｍｐ．Ｐｒｏｃ．，１８９（１９９１）ｐ．ｐ．２４３−２５５）等特徴的な性質を有した電磁波領域であり、大面積での無機酸化物半導体電極の製造に有利な点を多く持つ。
【００３７】
本発明における検討においては、高い周波数のマイクロ波の電磁波加熱焼結装置として、富士電波工業株式会社製 ＦＭＳ‐１０‐２８（発振周波数 ２８ＧＨｚ）を用いた。本装置では１０ＫＷ以下の範囲で高周波出力を変化させて無機酸化物粒子層に電磁波照射を行うことができる。
【００３８】
２８ＧＨｚをはじめとする高い周波数での試験検討については、試験機の商品開発そのものが近年であり（佐治他三郎、ニューセラミックス，８［５］（１９９５）ｐ．２１； 三宅正司、「セラミックスの高速焼成技術」（株）ティー・アイ・シー刊、総論 第１節 ）、工業的な利用としてはこれからの状況である。
本発明におけるマイクロ波照射の実施例は周波数２８Ｈｚおよび２．４５ＧＨｚの電磁波において行ったが、１ＧＨｚ以上３００ＧＨｚ 以下の範囲であればこの周波数に限らない。この範囲での各周波数に対して、本発明で連続照射可能な高周波出力は、１Ｗ以上、ｙ ＝２×１０−８ ｘ＋ ３００（式中、ｙは高周波出力（Ｗ）、ｘは高周波周波数（Ｈｚ）を表す。）以下である。同式においては、周波数２．４５ＧＨｚのマイクロ波使用時においては１Ｗ以上約３５０Ｗ以下、周波数２８ＧＨｚのマイクロ波使用時においては１Ｗ以上約８５０Ｗ以下の高周波出力を使用することに該当する。この範囲以上の高周波出力を被照射体に照射すると、無機酸化物粒子層の粒子間のネッキングや粒子−透明導電層間の結着を形成する前に、被照射体の局部過熱のために基材や透明導電層および無機酸化物半導体層等に破壊、変形、溶解、クラック形成等が起こり、光電変換用無機酸化物電極を製造することができない。本発明の範疇として、これ以上の高周波出力を使用する場合は被照射体に金属性の放熱体を密着させる、適切な電磁波遮蔽物を設ける、マイクロ波照射装置から被照射体を遠ざける、照射方法を１０秒以下で１回以上の間欠照射にする等により実質的に照射強度を低下させる処置を行い、熱暴走を抑制することで光電変換用無機酸化物電極を製造することができる。
【００３９】
本発明においては、マイクロ波の照射の前後で、水を含む溶剤や、さらにオルトチタン酸テトライソプロピルを含む無味酸化物前駆体等、および有機、無機の処理剤で被照射体の前処理、後処理を行っても良い。
【００４０】
（無機酸化物半導体粒子層 工程１）
本発明で用いられる平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子層の材質は、酸化チタン、酸化スズ、酸化タングステン、酸化亜鉛、酸化インジウム、酸化ニオブ、酸化鉄、酸化ニッケル、酸化コバルト、酸化ストロンチウム、酸化タンタル、酸化アンチモン、酸化ランタノイド、酸化イットリウム、酸化バナジウム等を挙げることができるが、これらがマイクロ波処理後、無機酸化物半導体多孔質層を形成し、光励起された状態での電子電導性を有しさらに増感色素を連結することによって可視光および／又は近赤外光領域までの光電変換が可能となるものであればこれに限らない。無機酸化物半導体粒子の材質は複数種の無機酸化物同士の組合せ構成であってもかまわない。無機酸化物半導体多孔質層表面が増感色素によって増感されるためには無機酸化物半導体多孔質層の電導帯が増感色素の光励起順位から電子を受け取りやすい位置に存在することが望ましい。このため前記無機酸化物半導体粒子の中でも酸化チタン、酸化スズ、酸化亜鉛、酸化ニオブ等が特に用いられる。さらに、価格や環境衛生性等の点から、酸化チタンが特に用いられる。本発明においては平均粒子径径５ｎｍ以上５００ｎｍの無機酸化物半導体粒子から一種又は複数の種類を選択して組み合わせることができる。
【００４１】
無機酸化物半導体粒子層はたとえば溶剤中に無機酸化物半導体粒子を分散させたペーストを作成し、これを透明電極表面に塗布し、溶剤を蒸発させて形成する。ペースト作成時には必要に応じて、硝酸やアセチルアセトン等の酸やポリエチレングリコール、トリトンＸ−１００等の分散剤や有機物をペースト成分に混合しても良いが少量の使用が望ましい。無機酸化物半導体粒子層の製膜方法としては塗布法が簡便で量産性を有する方法として望ましい。スピンコーターによる塗布方法やスクリーン印刷を用いた塗布法、スキージーを用いた塗布方法、ディップ法、吹き付け法、転写法、ローラー法等を用いることができる。製膜後、基材を痛めない温度で乾燥させて揮発成分を除去することが望ましい。特開２００２−１８４４７７に開示されたエアロゾル方式等のように溶剤を用いない吹き付けの製膜法および吹き付け時に加熱等のエネルギー付与を併用する方法によっても良い。
【００４２】
無機酸化物半導体粒子層の製膜後、被照射体にマイクロ波照射をする前あるいは後に製膜層に対して加圧、光照射、加電圧処理、プラズマ処理、化学処理、超音波処理、電子線処理、オゾン処理等の別の処理方法を併用することもできる。又、マイクロ波の照射の前後で、水を含む溶剤や、さらにオルトチタン酸テトライソプロピル等のような無味酸化物前駆体等、および有機、無機の処理剤で被照射体の前処理、後処理を行っても良い。
【００４３】
（透明導電層）
用いられる透明導電層としては、太陽光の可視から近赤外領域に対して光吸収が少ない導電材料なら特に限定されないが、ＩＴＯ（インジウム−スズ酸化物）や酸化スズ（フッ素等がドープされた物を含む）、酸化亜鉛等の導電性の良好な金属酸化物や炭素が好適である。酸化スズ、酸化インジウム、酸化亜鉛、炭素などはマイクロ波照射時の誘電損率が高い材料でありのエネルギーを効率的に吸収し優先的に発熱し、透明導電層上に形成された無機酸化物粒子層にこの熱を伝え、粒子間のネッキングや粒子−透明導電層間の結着を形成することができる。本発明においては透明電極層と無機酸化物粒子層との間に結着を促進したり、電子伝達を改善したり、逆電子過程を防止する等の目的で他の層を追加しても良い。
【００４４】
（透明基材）
用いられる透明基材としては太陽光の可視から近赤外領域に対して光り吸収が少ない材料であれば特に限定されない。石英、並ガラス、ＢＫ７、鉛ガラス等のガラス基材、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリイミド、ポリエステル、ポリエチレン、ポリカーボネート、ポリビニルブチラート、ポリプロピレン、テトラアセチルセルロース、シンジオクタチックポリスチレン、ポリフェニレンスルフィド、ポリアリレート、ポリスルフォン、ポリエステルスルフォン、ポリエーテルイミド、環状ポリオレフィン、ブロム化フェノキシ、塩化ビニール等の樹脂基材等を用いることができる。
【００４５】
（光電変換用電極 工程３）
本発明においてマイクロ波処理によって得られた無機多孔質の無機酸化物半導体電極は、これを透明基材ごと増感色素を溶解させた溶液中に浸すことにより無機多孔質表面と増感色素の連結置換基の親和性を利用して増感色素を無機多孔質表面に接触・結合させる方法が一般的であるが、この方法に限定されない。
【００４６】
増感色素の溶液を作るための溶剤は、増感色素を溶解させ、無機酸化物層に色素吸着の仲立ちを行える溶剤である必要がある。増感色素を溶解させるために必要に応じて加熱、溶解助剤の添加および不溶分のろ過を行っても良い。溶剤は二種類以上の溶剤を混合して用いても良く、溶剤としてエタノール、イソプロピルアルコール、ベンジルアルコールなどのアルコール系溶剤、アセトニトリル、プロピオニトリルなどのニトリル系溶剤、クロロホルム、ジクロロメタン、クロロベンゼン等のハロゲン系溶剤、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶剤、酢酸エチル、サクサンブチル等のエステル系溶剤、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶剤、炭酸ジエチル、炭酸プロピレン等の炭酸エステル系溶剤、ヘキサン、オクタン、トルエン、キシレン等の炭水化物系位溶剤、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、１，３‐ジメチルイミダゾリノン、Ｎメチルピロリドン、水等を用いることができるがこれに限らない。溶剤は二種類以上の溶剤を混合して用いても良い。
【００４７】
透明基材の導電面上に形成される無機酸化物半導体多孔質層の膜厚は０．５μｍ以上２００μｍ以下であることが望ましい。膜厚がこの範囲未満である場合有効な変換効率が得られない。又膜厚がこの範囲より厚い場合成膜時に割れや剥がれが生じる等作成が困難になる反面、無機酸化物多孔質体表層と導電面との距離が増えるために発生電荷が導電面に有効に伝えられなくなるので、良好な変換効率を得にくくなる。
（
【００４８】
（光電変換用増感色素の説明）
本発明において用いられる光電変換用増感色素としては、式１に示した構造のルテニウム錯体色素が代表的である。ＳＯＬＡＲＯＮＩＸ社製 Ｒｕｔｈｅｎｉｕｍ ５３５、Ｒｕｔｈｅｎｉｕｍ ５３５−ｂｉｓＴＢＡなどがこれに該当する。
【００４９】
【化１】
【００５０】
さらに光電変換用増感色素としては、アゾ系色素、キナクリドン系色素、ジケトピロロピロール系色素、スクワリリウム系色素シアニン系色素、メロシアニン系色素、トリフェニルメタン系色素、キサンテン系色素、ポルフィン系色素、クロロフィル系色素、ルテニウム錯体系色素、インジゴ系色素、ペリレン系色素、オキサジン系色素、アントラキノン系色素、フタロシアニン系色素、ナフタロシアニン系色素等、およびその誘導体が挙げられるが光を吸収し無機酸化物半導体電極の伝導帯に励起電子を注入できる色素であればこれらに限定されない。これらの増感色素はその構造中に連結基を１個以上有する場合は、無機半導体多孔質体表面に連結することができ、光励起された色素の励起電子を無機半導体多孔質体の電導帯に迅速に伝えることができるので望ましい。
【００５１】
（光電変換セル）
本発明において用いられる光電変換用電極は、電解質層を介して導電性対極を組み合わせることによって光電変換セルを形成する。
【００５２】
（電解質層）
本発明で用いられる電解質層は電解質、媒体、および添加物から構成されることが好ましい。本発明の電解質はＩ２とヨウ化物（例としてＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＭｇＩ２、ＣａＩ２、ＣｕＩ、ーテルなどのアルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリンなどの多価アルコール類、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリルなどのニトリル化合物、エチレンカーボネート、プロピレンカーボネートなどのカーボネート化合物、３‐メチル‐２‐オキサゾリジノンなどの複素環化合物、ジメチルスルホキシド、スルホランなど非プロトン極性物質、水などを用いることができる。
【００５３】
又、固体状（ゲル状を含む）の媒体を用いる目的で、ポリマーを含ませることもできる。この場合、ポリアクリロニトリル、ポリフッ化ビニリデン等のポリマーを前記溶液状媒体中に添加したり、エチレン性不飽和基を有した多官能性モノマーを前記溶液状媒体中で重合させて媒体を固体状にする。
【００５４】
電解質層としてはこの他、ＣｕＩ、ＣｕＳＣＮ媒体を必要としない電解質および、Ｎａｔｕｒｅ，Ｖｏｌ．３９５， ８ Ｏｃｔ． １９９８，ｐ５８３−５８５記載の２，２’，７，７’‐テトラキス（Ｎ，Ｎ‐ジ‐ｐ‐メトキシフェニルアミン）９，９’‐スピロビフルオレンのような正孔輸送材料を用いることができる。
【００５５】
本発明に用いられる電解質層には光電変換セルの電気的出力を向上させたり、耐久性を向上させる働きをする添加物を添加することができる。電気的出力を向上させる添加物として４‐ｔ‐ブチルピリジンや、２‐ピコリン、２，６‐ルチジン等が挙げられる。耐久性を向上させる添加物としてＭｇＩ等が挙げられる。
【００５６】
（導電性対極）
本発明で用いられる導電性対極は光電変換セルの正極として機能するものである。具体的に対極に用いる導電性の材料としては金属（例えば白金、金、銀、銅、アルミニウム、ロジウム、インジウム等）、金属酸化物（ＩＴＯ（インジウム‐スズ酸化物）や酸化スズ（フッ素等がドープされた物を含む）、酸化亜鉛）、または炭素等が挙げられる。対極の膜厚は、特に制限はないが、５ｎｍ以上１０μｍ以下であることが好ましい。
【００５７】
（組み立て方）
前記の光電変換用電極と導電性対極を電解質層を介して組み合わせることによって光電変換セルを形成する。必要に応じて電解質層の漏れや揮発を防ぐために、光電変換セルの周囲に封止を行う。封止には熱可塑性樹脂、光硬化性樹脂、ガラスフリット等を封止材料として用いることができる。光電変換セルは必要に応じて小面積の光電変換セルを連結させて作る。光電変換セルを直列に組み合わせることによって起電圧を高くすることができる。
【００５８】
【実施例】
以下に実施例を具体的に示すが本発明は以下に限定されるものではない。
（実施例１）
・酸化チタン粒子層の調整
メタチタン酸スラリー（テイカ社製 ＴＫＳ２０２）を原料として水熱／オートクレーブ処理をして粒子径３０ｎｍの単分散コロイド粒子を作り、バインダー無添加のまま透明電極上に４ｍｍ×５ｍｍ角の大きさに塗布して製膜した。
・透明電極
導電膜を有した樹脂基材の透明電極として、日本板硝子社製ガラス基材透明電極（ＦＴＯ透明導電層）を使用した。
・放熱板の装着
透明電極基材を放熱板であるアルミ製ヒートシンクに貼り付けた。その際、透明導電膜側も酸化チタン粒子層以外の透明導電層の露出部分をアルミテープで覆った（図５）。
・電磁波照射処理（酸化チタン電極の作成）
高エネルギー照射用の電磁波加熱焼結装置として、富士電波工業株式会社製 ＦＭＳ‐１０‐２８（発振周波数 ２８ＧＨｚ、電磁波出力最大１０ＫＷ（出力可変））を用い、電磁波出力２ｋＷ、２分間の電磁波照射を行った。
【００５９】
・増感色素の吸着
増感色素としてＳＯＬＡＲＯＮＩＸ社製 Ｒｕｔｈｅｎｉｕｍ５３５−ｂｉｓＴＢＡを用い、エタノール溶剤に溶解し色素溶液酸化チタン電極を浸して色素を吸着させた。着色した電極表面をエタノールで洗浄して乾燥させ、光電変換用電極を得た。
・電解質溶液の調整
下記処方で電解質溶液を得た。
溶媒 メトキシアセトニトリル
ＬｉＩ ０．１Ｍ
Ｉ２ ０．０５Ｍ
４‐ｔ‐ブチルピリジン ０．５Ｍ
１‐プロピル‐２，３‐ジメチルイミダゾリウムヨージド ０．６Ｍ
【００６０】
・光電変換セルの組み立て
図１の様に光電変換セルの試験サンプルを組み立てた。
導電性対極にはフッ素ドープ酸化スズ層付ガラス基板の導電層上にスパッタリング法により白金層を積層した物を用いた。
樹脂フィルム製スペーサーとしては、三井・デュポンポリケミカル社製 「ハイミラン」フィルムの２５μｍ厚の物を用いた。
【００６１】
・変換効率の測定方法
分光計器社製ソーラーシュミレーター（ハイパーキセノンエキサイター）をエアマスフィルターとを組み合わせ、光量計で１００ｍＷ／ｃｍ２ の光量に調整して測定用光源とし、光電変換セルの試験サンプルに光照射をしながら Ｉ‐Ｖカーブトレーサーを使用してＩ‐Ｖカーブ特性を測定した（図６）。変換効率ηは、Ｉ‐Ｖカーブ特性測定から得られたＶｏｃ（開放電圧値）、Ｉｓｃ（短絡電流値）、ｆｆ（フィルファクター値）を用いて下式により算出した。
【００６２】
【式１】
・被照射体温度の測定
熱電対をマイクロ波照射側の反対側から被照射体に接するように配置して測定した。
【００６４】
・ネッキング形成の確認
ＳＥＭ観察を行ったところ粒子間のネッキング形成が確認された（図３）。
【００６５】
（実施例２）
導電性基板（日本板硝子社製）のみに対する２８ＧＨｚ電磁波の連続照射時における予備試験を行った上で焼成試験を行った。
・２８ＧＨｚ照射での予備試験
電磁波照射装置として富士電波工業株式会社製 ＦＭＳ‐１０‐２８を使用。透明電極を導電層上向きでアルミナ板上に置いた状態で、照射の高周波出力 ２００Ｗ、５００Ｗ、１０００Ｗ、２０００Ｗで基材への影響を調べた。照射時間に対する被照射体の温度変化を図７に示す。図にはＦＴＯ透明導電層のないガラス基材の温度変化も含めたが、これとの比較からも透明導電層がマイクロ波エネルギーを優先的に吸収して発熱に寄与していることが分かる。
【００６６】
【表２】
以上の結果から２８ＧＨｚの連続照射の実施例として１０００Ｗ未満で５分間の照射条件を用いた。
・照射面の予備試験
導電層表面に酸化チタン粒子層を製膜した透明電極を、酸化チタン粒子層上向きでアルミナ板上に置いた状態で電磁波照射した場合と裏面から照射した場合での焼成電極のセル特性を比較した。セル作成方法、評価方法等は実施例１と同様。裏面照射時の配置図を図８に示す。５００Ｗで５分間照射。
【００６８】
【表３】
以上の結果から本実験条件では裏面からの照射の方がより好ましいことがわかる。
【００７０】
・１０００Ｗ未満の出力領域での連続照射試験
導電層表面に酸化チタン粒子層を製膜した透明電極を、裏面から２００Ｗ、５００Ｗ、７００Ｗで５分間マイクロ波照射した場合の焼成電極のセル特性を比較した。セル作成方法、評価方法等は実施例１と同様。各高周波出力処理時の焼成電極を用いた場合の変換効率の変化を図９に示す。照射時間に対する被照射体の温度変化を図１０に示す。
【００７１】
【表４】
（実施例３）
導電性基板（日本板硝子社製）のみに対する２．４５ＧＨｚ電磁波の連続照射時における予備試験を行った上で焼成試験を行った。
・２．４５ＧＨｚ照射での予備試験
電磁波照射装置として東芝社製ＥＲ−Ａ３０Ｓ１を使用。
透明電極を導電層上向きでアルミナ板上に置いた状態で、照射の高周波出力 １００Ｗ、２００Ｗ、５００Ｗ、１０００Ｗで基材への影響を調べた。
【００７３】
【表５】
以上の結果から２．４５ＧＨｚの連続照射の実施例として２００Ｗ未満での連続照射条件を用いた。
【００７５】
・１００Ｗの出力領域での連続照射試験
導電層表面に酸化チタン粒子層を製膜した透明電極を、裏面から１００Ｗで照射した場合の焼成電極のセル特性を比較した。セル作成方法、評価方法等は実施例１と同様。
【００７６】
【表６】
（実施例４）
樹脂製導電性基板（王子トービ社製）のみに対する２８ＧＨｚ電磁波の連続照射時における予備試験を行った上で焼成試験を行った。
・２８ＧＨｚ照射での予備試験
電磁波照射装置として富士電波工業株式会社製 ＦＭＳ‐１０‐２８を使用。透明電極を導電層上向きでアルミ製放熱体に密着させた状態で、照射の高周波出力 ２００Ｗ、５００Ｗ、１０００Ｗで基材への影響を調べた。
【００７８】
【表７】
以上の結果から樹脂製導電性基板への２８ＧＨｚの連続照射の実施例として５００Ｗ未満で３０秒間の照射条件を用いた。
【００８０】
・２００Ｗの出力での連続照射試験
導電層表面に酸化チタン粒子層を製膜した樹脂製透明電極を、アルミ製放熱体に接触させた状態で表面から２００Ｗで照射した場合の焼成電極のセル特性を比較した。セル作成方法、評価方法等は実施例１と同様。
【００８１】
（実施例５）
樹脂製導電性基板（王子トービ社製）のみに対する２．４５ＧＨｚ電磁波の連続照射時における予備試験を行った上で焼成試験を行った。
・２．４５ＧＨｚ照射での予備試験
電磁波照射装置として東芝社製ＥＲ−Ａ３０Ｓ１を使用。
透明電極を導電層上向きで裏面にアルミ製放熱体（シート状）に粘着させた状態で、照射の高周波出力 １００Ｗ、２００Ｗ、５００Ｗ、１０００Ｗで基材への影響を調べた。
【００８２】
【表８】
以上の結果から樹脂製導電性基板への２．４５ＧＨｚの連続照射の実施例として５００Ｗ未満で３０秒間の照射条件を用いた。
【００８４】
・２００Ｗの出力での連続照射試験
導電層表面に酸化チタン粒子層を製膜した樹脂製透明電極を、裏面にアルミ製放熱体（シート状；エッジ部を丸く加工）に粘着させた状態で表面から２００Ｗで照射した場合の焼成電極のセル特性を比較した。セル作成方法、評価方法等は実施例１と同様。
【００８５】
（実施例６）実施例５で用いた酸化チタン粒子層を酸化スズ（Ｎａｎｏ Ｔｅｋ社製；平均粒子径約３０ｎｍを使用）粒子層に変更し同様の実験を行った。
【００８６】
（実施例７）実施例５で用いた酸化チタン粒子層を酸化亜鉛（Ｎａｎｏ Ｔｅｋ社製；平均粒子径約３０ｎｍを使用）粒子層に変更し同様の実験を行った。
【００８７】
（実施例８）実施例５で用いた酸化チタン粒子層を酸化チタンＰ−２５（日本アエロジル社製；平均粒子径約２５ｎｍを使用）粒子層に変更し、マイクロ波照射前に油圧ジャッキで９０Ｋｇｆ／ｃｍ２のプレス処理を行った以外は実施例５と同様の実験を行った。
【００８８】
（実施例９）実施例８で用いたマイクロ波を２８ＧＨｚ、２００Ｗに変えた以外は実施例８と同様の実験を行った。
【００８９】
（比較例１）実施例１で行った電磁波照射を行わなかった以外は実施例１と同様の方法で酸化チタン電極の作成を行い変換効率の測定を行った。セル作成方法、評価方法等は実施例１と同様。
【００９０】
（比較例２）実施例１で行った放熱板を装着せずに電磁波照射を行った以外は実施例１と同様の方法で酸化チタン電極の作成を行った。
【００９１】
（比較例３）実施例１で用いた電磁波照射装置を一般の家庭用電子レンジ（２．４５ＧＨｚ、高周波出力５００Ｗ）に代えて行った以外は実施例１と同様の方法で酸化チタン電極の作成を行った。
【００９２】
（比較例４）実施例４で行った電磁波照射を行わなかった以外は実施例４と同様の方法で酸化チタン電極の作成を行い変換効率の測定を行った。セル作成方法、評価方法等は実施例１と同様。
【００９３】
（比較例５）実施例４で行った電磁波照射を高周波出力２０００Ｗにした以外は実施例４と同様の方法で酸化チタン電極の作成を行い変換効率の測定を行った。セル作成方法、評価方法等は実施例１と同様。
【００９４】
（比較例６）実施例５で使用した放熱シートを用いない以外は実施例５と同様の方法で酸化チタン電極の作成を行い変換効率の測定を行った。セル作成方法、評価方法等は実施例１と同様。
【００９５】
（比較例７）実施例１で行った電磁波照射を電気炉加熱処理にした以外は実施例１と同様の方法で酸化チタン電極の作成を行い変換効率の測定を行った。セル作成方法、評価方法等は実施例１と同様。
（比較例８）実施例８で行った油圧ジャッキでの９０Ｋｇｆ／ｃｍ２のプレス処理を行った後、マイクロ波を行わなかった以外は実施例８と同様の実験を行った。セル作成方法、評価方法等は実施例１と同様。
【００９６】
【表９】
【発明の効果】
本発明において透明電極の無機酸化物半導体粒子層を製膜した透明導電層にマイクロ波照射を行うこと得られた発熱により、無機酸化物半導体多孔質層を形成し高い変換効率を得ることのできる無機酸化物半導体電極を作成することができた。低出力領域の照射を行う、高周波領域のマイクロ波照射を行う、放熱体を密着させながら照射を行う等の条件を取り入れることで、被照射体に生じる局部的な過熱に起因する基材や導電層の破壊、溶解、変形、クラック形成等を防ぎながら処理を行うことが可能となった。電気炉等を用いた外部加熱処理時に比べて処理時間を大幅に減じることができるため、バッチ処理によらない連続処理が可能となる。さらに基材として樹脂基材を用いることでコストを大幅に低減できる。当該製造方法をもちいることによりセルを安価に量産することが可能となった。
【図面の簡単な説明】
【図１】光電変換セル試験サンプル。
【図２】酸化チタン粒子のみに対する家庭用電子レンジによるマイクロ波照射時の粒径測定結果（酸化チタン：石原産業社製ＳＴ−０１、粒径測定方法：ＸＲＤ法により測定）。
【図３】実施例１におけるマイクロ波照射後の酸化チタン多孔質層の電子顕微鏡写真。
【図４】表１におけるマイクロ波焼成の予備試験時、被照射体と熱電対やアルミナ台座との位置関係（（ｂ）裏面照射の場合）。
【図５】実施例１における放熱対策。
【図６】実施例１と比較例１におけるセルのＩ−Ｖカーブ特性比較。
【図７】実施例２における透明電極に対する予備照射試験でマイクロ波照射時間に対する被照射体の温度変化。
【図８】実施例２におけるマイクロ波裏面照射時の配置図。
【図９】実施例２における各高周波出力処理時の焼成電極を用いた変換効率の変化。
【図１０】実施例２におけるマイクロ波照射時間に対する被照射体の温度変化。
【図１１】比較例２におけるマイクロ波照射後の被照射体の様子。
【図１２】比較例５におけるマイクロ波照射後の被照射体の様子。
【符号の説明】
１．酸化チタン多孔質層（光電変換用増感色素が吸着済）
２．電解質溶液層
３．透明導電層（ＩＴＯ又はＦＴＯ）
４．Ｐｔ電極層
５．ＰＥＴ基材、又はガラス基材
６．樹脂フィルム製スペーサー
７．変換効率測定用導線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a production process for producing a porous inorganic oxide semiconductor electrode, a photoelectric conversion electrode using the inorganic oxide semiconductor electrode, and a photoelectric conversion cell.
[0002]
[Prior art]
For solar power generation, single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, and compound solar cells such as cadmium telluride and indium copper selenide have been put into practical use or are subject to research and development. It is necessary to overcome problems such as manufacturing cost, securing raw materials, and long energy payback time. On the other hand, many solar cells using organic materials aimed at increasing the area and cost have been proposed, but there is a problem that conversion efficiency is low and durability is poor.
[0003]
Under such circumstances, a photoelectric conversion electrode and a photoelectric conversion cell using an inorganic oxide semiconductor porous material sensitized with a dye, and a material and a manufacturing technique for producing the electrode have been disclosed (Non-patent Document 1). And Patent Document 1). The proposed battery is a dye-sensitized photoelectric conversion cell comprising a titanium oxide porous layer spectrally sensitized with a sensitizing dye such as a ruthenium complex, an electrolyte mainly composed of iodine, and a counter electrode. The first advantage of this method is that an inexpensive oxide semiconductor such as titanium oxide is used, so that an inexpensive photoelectric conversion element can be provided. The second advantage is that the ruthenium complex used has a wide absorption in the visible light range. Therefore, a relatively high conversion efficiency can be obtained.
[0004]
In addition, a cell was produced using an electrode in which a ruthenium complex having a tripyridylcarboxylate ligand was adsorbed on a titanium oxide porous layer formed by baking after film formation with a titanium oxide paste, and a conversion efficiency of 10.4. % Has been reported (see Non-Patent Document 2).
[0005]
One of the problems in manufacturing such a dye-sensitized photoelectric conversion cell is that it requires a high-temperature sintering process. A commonly used method for forming a titanium oxide porous layer is to cause necking between particles by applying a temperature of 400 ° C. or higher to a titanium oxide particle layer formed by applying a dispersion paste of titanium oxide particles. This makes it porous and improves the electron transferability. For this reason, since the base material which can be used is restricted to the material with high heat resistance like glass, the manufacturing cost of the base material cost of a photoelectric conversion cell, the energy cost consumed at the time of manufacture, etc. is made expensive. Attempts have also been made to make a porous titanium oxide layer by applying a temperature at which the resin does not dissolve, but the conversion efficiency is low. Furthermore, the titanium oxide porous layer prepared by low-temperature firing was brittle and the cell durability was low (see Non-Patent Document 3). The sintering method for firing at a low temperature also has a relatively long sintering time, and from this point, there is a problem as a mass production process.
[0006]
As a method for producing an inorganic oxide porous layer using a resin as a base material, there is a method in which an inorganic oxide particle layer is pressurized (see Non-Patent
[0007]
Microwaves may be used for sintering ceramics containing inorganic oxides (see Non-Patent
One of the characteristics of microwave heating is that, unlike external heating, a dielectric capable of absorbing microwave energy has a selectivity that generates heat preferentially. If the inorganic oxide particle layer formed on the substrate can be selectively heated, it is useful as an effective means for forming a sheet of a photoelectric conversion cell using a resin substrate.
[0008]
As an application of microwaves in inorganic oxide semiconductor electrode processing of dye-sensitized solar cells, microwaves appear as one of the enumerations of various energy and electromagnetic wave irradiations. In addition, there is no example of microwave irradiation using only ultraviolet light and infrared light, and there is no description in the specification (see
[0009]
In addition, at the academic conference where the presenters presented the present invention (The Electrochemical Society 70th Conference, September 12-13, 2002, Atsugi Campus, Tokyo Polytechnic University), a certain amount obtained by the electrodeposition method from Toho Yokohama University An example (550 W, 2.45 GHz) in which microwave irradiation was performed in a home microwave oven with unclear irradiation conditions as an efficiency improvement effect for a porous layer of titanium oxide that already had conversion efficiency was simultaneously announced (non- Patent Document 6) is an application to a particle layer obtained by a simple and excellent mass productivity coating method, and examples in which necking between particles and binding between transparent conductive layers and particles are caused in the same announcement There is no.
At the same academic conference, the performers also showed an example in which only titanium oxide particles were microwaved in a home microwave oven, but under these conditions there was no change in the particle diameter shrinkage, and there was a substantial effect that would cause necking between particles. Morphological change could not be confirmed (FIG. 2). It was suggested that microwave application for forming a porous layer from a titanium oxide particle layer formed by a simple and excellent mass productivity coating method needs to be examined.
[0010]
[Non-Patent Document 1] Nature (Vol. 353, 737-740, 1991)
[Patent Document 1] US Pat. No. 4,927,721
[Non-Patent Document 2] Am. Chem. Soc. (2001), Vol. 123, p. p. 1613-1624
[Non-patent Document 3] ECN contributions 16 th European Photovoltaic Solar Energy Conference and Exhibition, May 1-5, 2000 abstract; M.M. Somemeling et. al, “Flexible dye-sensitized nanocrystalline TiO2 solar cells”
[Non-patent Document 4] “Toyota Central R & D Review, Vol. 30 No. 4 (1995.12) p. 25 Microwave sintering of functional ceramics”
[Non-patent document 5] "High-speed sintering technology for ceramics, electromagnetic processing of ceramics, TIS Co., Ltd. 1998, Masaji Miyake"
[Patent Document 2] Japanese Patent Laid-Open No. 2001-357896
[Patent Document 3] Japanese Patent Laid-Open No. 2002-134435
[Non-patent document 6] The 70th Annual Meeting of the Electrochemical Society of Japan September 12-13, 2002 Tokyo Institute of Technology Atsugi Campus 2E19
[Non-Patent Document 7] Nanoletters, 1, (2001), p. p. 97-100, H.C. Lindtron, et. al.
[Patent Document 4] International Publication No. 00/72373 Pamphlet
[0011]
[Problems to be solved by the invention]
In order to enable an inexpensive process for a dye-sensitized photoelectric conversion cell, a porous inorganic oxide semiconductor layer can be formed with a high conversion efficiency using an inexpensive resin base material in a short time. The technology of was requested.
[0012]
An object of the present invention is to provide a manufacturing process capable of forming a porous inorganic oxide semiconductor layer having a high conversion efficiency by using a resin base material in a short time, and consequently the inorganic oxide semiconductor. It is also possible to manufacture a photoelectric conversion electrode and a photoelectric conversion cell using the layer.
[0013]
[Means for Solving the Problems]
The inventors have found that the above problems can be solved by using microwaves at a low output, and have reached the present invention.
[0014]
That is, the present invention is a method for producing an inorganic oxide semiconductor electrode for photoelectric conversion comprising a transparent substrate comprising a transparent conductive layer and an inorganic oxide semiconductor porous layer,
A method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, comprising a step comprising a step 3 of bringing a sensitizing dye into contact with an inorganic oxide semiconductor porous layer.
Formula y = 2 × 10 -8 x + 300 (wherein y represents a high frequency output (W) and x represents a high frequency (Hz)).
Moreover, a method for producing an inorganic oxide semiconductor electrode for photoelectric conversion comprising a transparent substrate comprising a transparent conductive layer and an inorganic oxide semiconductor porous layer,
A step of irradiating the transparent conductive layer and the inorganic oxide semiconductor porous layer with microwaves having a frequency of 1 GHz or more and 300 GHz or less to generate heat, the step of irradiating the microwaves while adhering the radiator to the irradiated body;
The present invention relates to a method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, which is produced by a process including a process 3 in which a sensitizing dye is brought into contact with an inorganic oxide semiconductor porous layer.
[0015]
Further, the present invention is a method for producing an inorganic oxide semiconductor electrode for photoelectric conversion comprising a transparent substrate comprising a transparent conductive layer and an inorganic oxide semiconductor porous layer,
After and / or before the
[0016]
In the present invention, the pressure of the press treatment applied to the inorganic oxide semiconductor porous layer is 0.01 kgf / cm. 2 100 kgf / cm 2 It is related with the manufacturing method of the said inorganic oxide semiconductor electrode for photoelectric conversion characterized by being less than.
[0017]
Moreover, this invention relates to the manufacturing method of the said inorganic oxide semiconductor electrode for photoelectric conversions in which a transparent conductive layer contains at least 1 of a tin oxide, an indium oxide, a zinc oxide, and carbon.
[0018]
The present invention also relates to the above-described method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, wherein the microwave incident direction is irradiated from the transparent substrate surface side during microwave irradiation.
[0019]
The present invention also relates to the above-described method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, wherein the temperature of an irradiated object is raised to 50 ° C. or higher and 1000 ° C. or lower by microwave irradiation during microwave irradiation.
[0020]
The present invention also relates to the above-described method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, characterized in that, during microwave irradiation, the irradiated object is heated at a rate of 200 ° C./min or less by microwave irradiation.
[0021]
Moreover, this invention relates to the semiconductor cell for photoelectric conversion provided with the said inorganic oxide semiconductor electrode for photoelectric conversions, an electrolyte layer, and a conductive counter electrode.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
(Method of forming inorganic oxide semiconductor porous layer by microwave treatment, step 2)
In the present invention, an inorganic oxide semiconductor particle layer and a transparent conductive layer comprising inorganic oxide semiconductor particles having an average particle diameter of 5 nm or more and 500 nm or less formed by a coating method on a transparent conductive layer of a transparent electrode that is an object to be irradiated. Through the steps of irradiating and generating heat by absorbing energy, necking between the particles and binding between the particles and the transparent electrode can be caused. In particular, a transparent conductive layer containing tin oxide, indium oxide, zinc oxide, carbon or the like having a high dielectric loss factor preferentially generates heat. Since the inorganic oxide semiconductor particle layer applied to the transparent conductive layer has a relatively low dielectric loss factor, the temperature rises mainly due to heat generated from the transparent conductive layer, causing necking between particles and binding between the particle and the transparent conductive layer. FIG. 3 is an electron micrograph of the titanium oxide porous layer after the microwave treatment of the present invention. The substrate temperature also rises in the form affected by the preferential temperature rise of the transparent conductive layer.
[0023]
Table 1 shows, as preliminary tests, (a) glass substrate only, (b) glass substrate with transparent conductive layer (fluorine-doped tin oxide = FTO), (c) glass substrate with titanium oxide particle coating layer, (d ) At the temperature of the irradiated object after irradiating a microwave of 28 GHz and 500 W for 5 minutes to the four types of irradiated objects of the transparent conductive layer of the glass substrate with the transparent conductive layer and having the titanium oxide particle coating layer attached. is there. It can be seen that the presence of a transparent conductive layer is essential for obtaining sufficient heat generation with respect to microwave irradiation.
[0024]
Table 1 Preliminary tests for microwave firing
Temperature of irradiated object after irradiation with microwaves of frequency 28 GHz and 500 W for 5 minutes.
Performing microwave irradiation on the transparent conductive layer side is referred to as surface irradiation.
FIG. 4 shows the positional relationship between the object to be irradiated, the thermocouple, and the alumina pedestal as an example of the case of Table 1 (b) backside irradiation.
[0025]
[Table 1]
Energy P (W / cm) absorbed by the dielectric as the irradiated body per volume 3 ) Is P = ε 0 ε ”ωE 2 / 2 (where ε 0 Is the dielectric constant of vacuum, ε ″ (= ε r tan δ) is the dielectric loss factor of the dielectric [ε r Is the relative dielectric constant, tan δ is the dielectric tangent], ω is the angular frequency, and E is the electric field strength), and both the frequency of the electromagnetic wave and the electric field strength contribute to the energy absorption strength. There are two methods for adjusting the energy of the irradiated body so as to obtain a temperature necessary for a target processing state, that is, a method of changing the electric field intensity of the irradiated electromagnetic wave and a method of changing the frequency. Since the contribution of the electric field strength is effective by the square, the contribution of the energy increase by increasing this is large. In addition, when an electromagnetic wave having a high frequency is used, the dielectric loss factor of the dielectric generally increases depending on this, leading to efficient energy absorption.
[0027]
In microwave sintering of ceramics including inorganic oxides, the irradiated object caused by local overheating caused by thermal runaway caused by an increase in dielectric loss factor accompanying the temperature rise of the irradiated object Destruction or distortion of the material often becomes a problem. When the object to be irradiated is an inorganic oxide semiconductor electrode, if the irradiation condition is inappropriate, the base material or the conductive layer is destroyed, cracks are formed, partial dissolution, deformation, or the like occurs.
[0028]
When a general microwave oven (2.45 GHz, high frequency output of about 500 W) is coated with a conductive glass (covered with a fluorine-doped tin oxide conductive layer) or a titanium oxide particle layer on this conductive layer side and irradiated with electromagnetic waves, it takes several seconds. In this case, the base material is destroyed. This is because the temperature rise of tin oxide used for the conductive layer is accelerated and the difference in heat distribution with the base material is increased to cause distortion. The larger the area of the base material, the easier the destruction of the base material occurs. For example, in electromagnetic wave irradiation in a 2.45 GHz high frequency output 500 W household microwave oven, a 2.5 cm × 2.5 cm × 1.1 mm FTO glass breaks the substrate 3 to 5 seconds after irradiation, and a sufficient temperature rise is obtained. Absent. If the base material is cut small or a mask for reducing the irradiation area is applied, the irradiation time until destruction occurs can be extended, but this is not an appropriate method for manufacturing a solar cell requiring a large area. Appropriate irradiation conditions are necessary to perform microwave irradiation on the conductive layer having the inorganic oxide particle layer formed by coating and cause necking between particles and binding between particles and the transparent conductive layer by firing. .
[0029]
The following conditions must be satisfied so that thermal runaway does not occur when a temperature difference occurs in the irradiated object.
Pt 1 -Pt 2 <[(T 1 -T 2 / L] A ・ R
(Where Pt 1 -Pt 2 : Temperature t 1 , T 2 Absorbed energy at (t 1 -T 2 ) / L: temperature gradient, A: heat conduction cross section, R: heat conductivity; Saji et al. Saburo, “High-speed firing technology of ceramics”, Tea IC Co., Ltd.,
[0030]
Therefore, measures to prevent thermal runaway from occurring on conductive substrates with a fixed heat conduction cross-sectional area are either continuous irradiation in a relatively low region of high-frequency output or intermittent pulsed high-power waves. It is necessary to devise measures to alleviate the heat distribution, such as irradiating, heat dissipation measures such as close contact with a heat dissipation body such as a heat dissipation plate with high thermal conductivity, and preheating to the irradiated object. It becomes.
Also, if microwaves with a high frequency are used, the temperature dependence of the dielectric loss factor of the irradiated object is reduced, and Pt in the formula 1 -Pt 2 This is effective because it leads to a smaller term.
[0031]
2. When using a microwave oven for household use as an easily available irradiation device with microwave irradiation at 45 GHz, continuous output with low output compared to general-purpose output of 500 W when trying to perform variable output with the same magnetron In the test, the filament temperature decreased as the frequency of the inverter increased, and the oscillation of the magnetron became unstable, making it difficult to perform the irradiation test in the low output region. To date, only Toshiba ER-A30S series released in 2001 can be tested with 100W and 200W continuous low-power irradiation by improving the magnetron and inverter circuit with an available household microwave oven ( Denpa Shimbun, published May 22, 2001). In the present invention, 2.45 GHz 100 W irradiation was performed by an irradiation test using the apparatus. Other household microwave ovens are referred to as equivalent to 100 W, equivalent to 200 W, etc. by intermittently irradiating around 500 W of high frequency output in the decompression mode or the like. It turns out that examination examination of the low output region at a frequency of 2.45 GHz was not easy.
[0032]
Furthermore, industrial use of 2.45 GHz microwaves is preceded by over 1000 W output in fields such as drying of wood and heating of frozen products, and low output of around 100 W for medical and electronic material processing. It is only in recent years that microwaves in the area have begun to be used.
[0033]
(Regarding the radiator, step 4)
In the microwave irradiation process, when taking measures against heat radiation to the irradiated object, measures such as bringing a titanium oxide electrode into close contact with a heat sink, a sheet-like heat radiator, a heat radiator that can be cooled with a refrigerant, and the like can be given. The contact surface may be the back surface or the front surface of the irradiated object. The material of the radiator is preferably one having a thermal conductivity of 10 W / m · K or more at the operating temperature, and preferably a metal such as aluminum. However, the present invention is not limited to this as long as it functions to alleviate rapid local overheating of the irradiated object. For example, even if the material has a thermal conductivity of less than 10 W / m · K, the radiator of the present invention can be obtained by passing a coolant through the material. Examples of materials other than metals having high thermal conductivity include graphite, beryllia, aluminum nitride, silicon carbide and the like. When a refrigerant is passed through the material as a radiator, it is more desirable to obtain a stable heat radiation effect by controlling the temperature of the refrigerant. Examples of the method for adhering the irradiated body to the radiator include fixing by an instrument, pressure bonding, adhesion, adhesion, contact, suction, and the like, but other methods may be used as long as the adhesion state can be generated. For example, this is applicable to any arrangement relationship that can exert a heat radiation effect even if there is a distance of 10 mm or less between the heat radiators of the irradiated body. It is also applicable to bring a gas or liquid cooling refrigerant into direct contact with the irradiated body as a radiator.
[0034]
FIG. 5 shows an embodiment in which an aluminum heat sink and a tape are adhered to each other as a radiator.
As a method of irradiating the object to be irradiated with microwaves, a method in which the sheet-like object to be irradiated moves continuously with respect to the microwave irradiator and is processed with a winding operation is useful as a method for manufacturing at low cost. It is. At this time, it is also possible to obtain a continuous heat radiation effect by devising the object to continuously change the positional relationship while keeping the irradiated body in close contact with the heat radiator.
[0035]
(About press processing, step 5)
It is effective to press the inorganic oxide semiconductor porous layer before microwave irradiation in order to obtain high conversion efficiency. In particular, when the substrate having the transparent conductive layer is made of a resin, the effect can be obtained without destroying the substrate even when a strong pressure is applied. The effect of the press treatment alone is described in Nanoletters, 1, (2001), p. p. 97-100, H.C. Lindtron, et. al. And in WO 00/72373 pamphlet. However, when the press process is performed alone, the pressure used is as high as several hundred kgf / cm2, so a high pressure hydraulic device is required, and in a continuous production apparatus such as a roll-to-roll, the roll that transmits the pressure is worn, This method is not suitable for continuous production because it is easy to break and processing speed is slow. From the viewpoint of mass production process as pressure, 0.01Kgf / cm possible with roll thickness for
[0036]
A region of 20 GHz or more as a high frequency microwave may be referred to as a millimeter wave region.
In the processing by microwaves of high frequency corresponding to this region, (1) it is easy to create a uniform electric field intensity distribution in the processing container, and (2) the dielectric loss factor at the processing start temperature (for example, room temperature) generally increases, so that energy Absorption is efficient, (3) The temperature dependence of the dielectric loss factor is small, and thermal runaway that often occurs during heating is easy to avoid. (4) The temperature itself required for sintering is lowered from the non-thermal action. (HD Kimley, et.al., MRS.Symp.Proc., 189 (1991) pp. 243-255) and so on. It has many advantages for the production of inorganic oxide semiconductor electrodes.
[0037]
In the examination in the present invention, FMS-10-28 (oscillation frequency: 28 GHz) manufactured by Fuji Radio Industry Co., Ltd. was used as a microwave microwave heating and sintering apparatus of high frequency. In this apparatus, electromagnetic wave irradiation can be performed on the inorganic oxide particle layer by changing the high frequency output within a range of 10 KW or less.
[0038]
For high-frequency testing including 28 GHz, product development of testing machines has been in recent years (Saji et al. Saburo, New Ceramics, 8 [5] (1995) p.21; Miyake Shoji, “High-Speed Ceramics Baking technology "(published by TIC Co., Ltd., general remarks section 1).
Although the example of the microwave irradiation in this invention was performed in the electromagnetic waves of frequency 28Hz and 2.45GHz, if it is the range of 1 GHz or more and 300 GHz or less, it will not restrict to this frequency. For each frequency in this range, the high frequency output that can be continuously irradiated in the present invention is 1 W or more, and y = 2 × 10. -8 x + 300 (wherein y represents a high frequency output (W) and x represents a high frequency (Hz)). This equation corresponds to using a high frequency output of 1 W or more and about 350 W or less when using a microwave with a frequency of 2.45 GHz, and using a high frequency output of 1 W or more and about 850 W or less when using a microwave with a frequency of 28 GHz. When the object to be irradiated is irradiated with a high frequency output exceeding this range, the base material is used for local overheating of the object to be irradiated before necking between the particles of the inorganic oxide particle layer or binding between the particles and the transparent conductive layer. In addition, destruction, deformation, dissolution, crack formation, etc. occur in the transparent conductive layer and the inorganic oxide semiconductor layer, and the inorganic oxide electrode for photoelectric conversion cannot be produced. As a category of the present invention, when using a higher frequency output than this, an irradiation method is provided in which an appropriate electromagnetic wave shield is provided so that a metallic heat sink is closely attached to the irradiated body, and the irradiated body is moved away from the microwave irradiation apparatus. The inorganic oxide electrode for photoelectric conversion can be manufactured by performing a treatment for substantially reducing the irradiation intensity by, for example, making intermittent irradiation at least once in 10 seconds or less, and suppressing thermal runaway.
[0039]
In the present invention, before and after the microwave irradiation, pretreatment of the irradiated object with a solvent containing water, a tasteless oxide precursor containing tetraisopropyl orthotitanate, and an organic or inorganic treatment agent, and after Processing may be performed.
[0040]
(Inorganic oxide semiconductor particle layer, step 1)
The material of the inorganic oxide semiconductor particle layer having an average particle diameter of 5 nm to 500 nm used in the present invention is titanium oxide, tin oxide, tungsten oxide, zinc oxide, indium oxide, niobium oxide, iron oxide, nickel oxide, cobalt oxide, Examples include strontium oxide, tantalum oxide, antimony oxide, lanthanoid oxide, yttrium oxide, vanadium oxide, etc., but these form an inorganic oxide semiconductor porous layer after microwave treatment, and the electrons in a photoexcited state The present invention is not limited to this as long as it has electrical conductivity and can be converted into visible light and / or near-infrared light by connecting a sensitizing dye. The material of the inorganic oxide semiconductor particles may be a combination of a plurality of types of inorganic oxides. In order for the surface of the inorganic oxide semiconductor porous layer to be sensitized by the sensitizing dye, it is desirable that the conduction band of the inorganic oxide semiconductor porous layer be present at a position where electrons can be easily received from the photoexcitation order of the sensitizing dye. For this reason, titanium oxide, tin oxide, zinc oxide, niobium oxide and the like are particularly used among the inorganic oxide semiconductor particles. Further, titanium oxide is particularly used from the viewpoint of price and environmental hygiene. In the present invention, one or more kinds of inorganic oxide semiconductor particles having an average particle diameter of 5 nm to 500 nm can be selected and combined.
[0041]
The inorganic oxide semiconductor particle layer is formed, for example, by preparing a paste in which inorganic oxide semiconductor particles are dispersed in a solvent, applying this to the surface of the transparent electrode, and evaporating the solvent. When preparing the paste, if necessary, an acid such as nitric acid or acetylacetone, a dispersant such as polyethylene glycol or Triton X-100, or an organic substance may be mixed with the paste component, but a small amount is preferably used. As a method for forming the inorganic oxide semiconductor particle layer, a coating method is simple and desirable as a method having mass productivity. A coating method using a spin coater, a coating method using screen printing, a coating method using a squeegee, a dipping method, a spraying method, a transfer method, a roller method, or the like can be used. After film formation, it is desirable to remove volatile components by drying the substrate at a temperature that does not hurt. A spray film forming method that does not use a solvent, such as an aerosol method disclosed in Japanese Patent Application Laid-Open No. 2002-184477, and a method that uses energy application such as heating at the time of spraying may be used.
[0042]
After film formation of inorganic oxide semiconductor particle layer, before or after microwave irradiation to irradiated object, pressure, light irradiation, applied voltage treatment, plasma treatment, chemical treatment, ultrasonic treatment, electron Other treatment methods such as wire treatment and ozone treatment can be used in combination. In addition, before and after microwave irradiation, pre- and post-treatment of the irradiated object with a solvent containing water, a tasteless oxide precursor such as tetraisopropyl orthotitanate, and organic and inorganic treatment agents May be performed.
[0043]
(Transparent conductive layer)
The transparent conductive layer used is not particularly limited as long as it is a conductive material that absorbs little light from the visible to the near infrared region of sunlight, but ITO (indium-tin oxide) or tin oxide (fluorine or the like is doped) A metal oxide having good conductivity, such as zinc oxide, or carbon is preferable. Tin oxide, indium oxide, zinc oxide, carbon, etc. are inorganic oxides formed on a transparent conductive layer that absorbs energy efficiently and preferentially generates heat because it is a material with a high dielectric loss factor during microwave irradiation. This heat can be transferred to the particle layer to form a necking between the particles and a bond between the particles and the transparent conductive layer. In the present invention, another layer may be added for the purpose of promoting the binding between the transparent electrode layer and the inorganic oxide particle layer, improving the electron transfer, or preventing the reverse electron process. .
[0044]
(Transparent substrate)
The transparent substrate to be used is not particularly limited as long as it is a material that absorbs less light in the visible to near infrared region of sunlight. Glass substrates such as quartz, ordinary glass, BK7, lead glass, polyethylene terephthalate, polyethylene naphthalate, polyimide, polyester, polyethylene, polycarbonate, polyvinyl butyrate, polypropylene, tetraacetylcellulose, syndioctane polystyrene, polyphenylene sulfide, polyarylate Resin base materials such as polysulfone, polyester sulfone, polyetherimide, cyclic polyolefin, brominated phenoxy, and vinyl chloride can be used.
[0045]
(Photoelectric conversion electrode, step 3)
In the present invention, the inorganic porous inorganic oxide semiconductor electrode obtained by microwave treatment is immersed in a solution in which the sensitizing dye is dissolved together with the transparent base material, thereby connecting the inorganic porous surface and the sensitizing dye. A method of contacting and binding a sensitizing dye to an inorganic porous surface using the affinity of a substituent is common, but is not limited to this method.
[0046]
The solvent for preparing the sensitizing dye solution needs to be a solvent that can dissolve the sensitizing dye and mediate the dye adsorption to the inorganic oxide layer. In order to dissolve the sensitizing dye, heating, addition of a solubilizing agent, and filtration of insoluble matter may be performed as necessary. Two or more kinds of solvents may be used as a mixture, and alcohol solvents such as ethanol, isopropyl alcohol, and benzyl alcohol, nitrile solvents such as acetonitrile and propionitrile, and halogens such as chloroform, dichloromethane, and chlorobenzene. Solvents, ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate and succinbutyl, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, carbonate solvents such as diethyl carbonate and propylene carbonate, hexane and octane , Use of carbohydrate solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1,3-dimethylimidazolinone, N-methylpyrrolidone, water, etc. Kill is not limited to this. Two or more kinds of solvents may be mixed and used.
[0047]
The thickness of the inorganic oxide semiconductor porous layer formed on the conductive surface of the transparent substrate is desirably 0.5 μm or more and 200 μm or less. When the film thickness is less than this range, effective conversion efficiency cannot be obtained. If the film thickness is thicker than this range, it may be difficult to create such as cracking or peeling during film formation, but the distance between the inorganic oxide porous body surface layer and the conductive surface increases, so the generated charge is effectively applied to the conductive surface. Since it cannot be transmitted, it becomes difficult to obtain good conversion efficiency.
(
[0048]
(Description of sensitizing dye for photoelectric conversion)
As the sensitizing dye for photoelectric conversion used in the present invention, a ruthenium complex dye having a structure shown in
[0049]
[Chemical 1]
[0050]
Furthermore, as sensitizing dyes for photoelectric conversion, azo dyes, quinacridone dyes, diketopyrrolopyrrole dyes, squarylium dyes cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, porphine dyes, Examples include chlorophyll dyes, ruthenium complex dyes, indigo dyes, perylene dyes, oxazine dyes, anthraquinone dyes, phthalocyanine dyes, naphthalocyanine dyes, and derivatives thereof. The present invention is not limited to these as long as the dye can inject excited electrons into the conduction band of the electrode. If these sensitizing dyes have one or more linking groups in their structure, they can be connected to the surface of the inorganic semiconductor porous body, and the excited electrons of the photoexcited dye can be used as the conduction band of the inorganic semiconductor porous body. This is desirable because it can be communicated quickly.
[0051]
(Photoelectric conversion cell)
The photoelectric conversion electrode used in the present invention forms a photoelectric conversion cell by combining a conductive counter electrode through an electrolyte layer.
[0052]
(Electrolyte layer)
The electrolyte layer used in the present invention is preferably composed of an electrolyte, a medium, and an additive. The electrolyte of the present invention is I 2 And iodide (for example, LiI, NaI, KI, CsI, MgI 2 , CaI 2 , Alcohols such as CuI, -tel, polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, ethylene Carbonate compounds such as carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, aprotic polar substances such as dimethyl sulfoxide and sulfolane, water, and the like can be used.
[0053]
In addition, a polymer can be included for the purpose of using a solid (including gel) medium. In this case, a polymer such as polyacrylonitrile or polyvinylidene fluoride is added to the solution-like medium, or a polyfunctional monomer having an ethylenically unsaturated group is polymerized in the solution-like medium to make the medium solid. To do.
[0054]
As the electrolyte layer, an electrolyte that does not require a CuI or CuSCN medium, and Nature, Vol. 395, 8 Oct. A hole transport material such as 2,2 ′, 7,7′-tetrakis (N, N-di-p-methoxyphenylamine) 9,9′-spirobifluorene described in 1998, p583-585. it can.
[0055]
The electrolyte layer used in the present invention may contain an additive that functions to improve the electrical output of the photoelectric conversion cell or improve the durability. Examples of additives that improve electrical output include 4-t-butylpyridine, 2-picoline, and 2,6-lutidine. MgI etc. are mentioned as an additive which improves durability.
[0056]
(Conductive counter electrode)
The conductive counter electrode used in the present invention functions as a positive electrode of the photoelectric conversion cell. Specific examples of conductive materials used for the counter electrode include metals (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), metal oxides (ITO (indium-tin oxide), tin oxide (fluorine, etc.)). Including doped substances), zinc oxide), or carbon. The thickness of the counter electrode is not particularly limited, but is preferably 5 nm or more and 10 μm or less.
[0057]
(How to assemble)
A photoelectric conversion cell is formed by combining the photoelectric conversion electrode and a conductive counter electrode through an electrolyte layer. In order to prevent leakage and volatilization of the electrolyte layer as necessary, sealing is performed around the photoelectric conversion cell. For sealing, a thermoplastic resin, a photocurable resin, glass frit, or the like can be used as a sealing material. The photoelectric conversion cell is made by connecting small-area photoelectric conversion cells as necessary. The electromotive voltage can be increased by combining the photoelectric conversion cells in series.
[0058]
【Example】
Examples will be specifically shown below, but the present invention is not limited to the following examples.
Example 1
・ Titanium oxide particle layer adjustment
Mono-dispersed colloidal particles with a particle diameter of 30 nm are made by using hydrotitanium / autoclave treatment using metatitanic acid slurry (TKS 202 manufactured by Teika) as a raw material, and applied to a transparent electrode with a size of 4 mm x 5 mm square with no binder added. To form a film.
・ Transparent electrode
As a transparent electrode of a resin substrate having a conductive film, a glass substrate transparent electrode (FTO transparent conductive layer) manufactured by Nippon Sheet Glass Co., Ltd. was used.
・ Installation of heat sink
The transparent electrode substrate was affixed to an aluminum heat sink as a heat sink. At that time, the exposed portion of the transparent conductive layer other than the titanium oxide particle layer was also covered with aluminum tape on the transparent conductive film side (FIG. 5).
・ Electromagnetic wave irradiation treatment (creation of titanium oxide electrode)
As an electromagnetic heating and sintering apparatus for high energy irradiation, FMS-10-28 (oscillation frequency 28 GHz, electromagnetic wave output maximum 10 kW (variable output)) manufactured by Fuji Radio Industry Co., Ltd.,
[0059]
・ Adsorption of sensitizing dye
As a sensitizing dye, Ruthenium 535-bisTBA manufactured by SOLARONIX was used, dissolved in an ethanol solvent, and immersed in a dye solution titanium oxide electrode to adsorb the dye. The colored electrode surface was washed with ethanol and dried to obtain a photoelectric conversion electrode.
・ Preparation of electrolyte solution
An electrolyte solution was obtained according to the following formulation.
Solvent Methoxyacetonitrile
LiI 0.1M
I 2 0.05M
4-t-butylpyridine 0.5M
1-propyl-2,3-dimethylimidazolium iodide 0.6M
[0060]
・ Assembly of photoelectric conversion cell
A test sample of a photoelectric conversion cell was assembled as shown in FIG.
As the conductive counter electrode, a platinum layer laminated by a sputtering method on the conductive layer of the glass substrate with a fluorine-doped tin oxide layer was used.
As the resin film spacer, a 25 μm thick “High Milan” film manufactured by Mitsui DuPont Polychemical Co., Ltd. was used.
[0061]
・ Method of measuring conversion efficiency
A solar simulator (Hyper Xenon Exciter) manufactured by Spectrometer Co., Ltd. is combined with an air mass filter, and the light meter is 100 mW / cm 2 The IV curve characteristics were measured by using an IV curve tracer while irradiating the test sample of the photoelectric conversion cell with light. The conversion efficiency η was calculated by the following equation using Voc (open circuit voltage value), Isc (short circuit current value), and ff (fill factor value) obtained from the IV curve characteristic measurement.
[0062]
[Formula 1]
・ Measurement of irradiated object temperature
A thermocouple was placed from the opposite side of the microwave irradiation side so as to be in contact with the object to be measured.
[0064]
・ Confirmation of necking formation
SEM observation confirmed the formation of necking between the particles (FIG. 3).
[0065]
(Example 2)
A firing test was carried out after conducting a preliminary test at the time of continuous irradiation of 28 GHz electromagnetic waves only on a conductive substrate (manufactured by Nippon Sheet Glass Co., Ltd.).
・ Preliminary test at 28 GHz irradiation
FMS-10-28 manufactured by Fuji Radio Industry Co., Ltd. is used as the electromagnetic wave irradiation device. With the transparent electrode placed on the alumina plate with the conductive layer facing upward, the influence on the substrate was examined with high-frequency outputs of 200 W, 500 W, 1000 W, and 2000 W. FIG. 7 shows the temperature change of the irradiated object with respect to the irradiation time. Although the figure also includes the temperature change of the glass substrate without the FTO transparent conductive layer, it can be seen from the comparison with this that the transparent conductive layer preferentially absorbs microwave energy and contributes to heat generation.
[0066]
[Table 2]
From the above results, irradiation conditions of less than 1000 W for 5 minutes were used as an example of continuous irradiation at 28 GHz.
・ Preliminary test of irradiated surface
Comparison of the cell characteristics of the fired electrode when the transparent electrode with the titanium oxide particle layer formed on the surface of the conductive layer was irradiated with electromagnetic waves with the titanium oxide particle layer facing upward on the alumina plate and when irradiated from the back side . The cell creation method, evaluation method, etc. are the same as in Example 1. FIG. 8 shows a layout at the time of backside illumination. Irradiated at 500W for 5 minutes.
[0068]
[Table 3]
From the above results, it is understood that irradiation from the back surface is more preferable under the present experimental conditions.
[0070]
・ Continuous irradiation test in the output range of less than 1000W
The cell characteristics of the fired electrode were compared when a transparent electrode having a titanium oxide particle layer formed on the surface of the conductive layer was irradiated with microwaves at 200 W, 500 W, and 700 W for 5 minutes from the back surface. The cell creation method, evaluation method, etc. are the same as in Example 1. FIG. 9 shows the change in conversion efficiency when using the fired electrode during each high-frequency output process. FIG. 10 shows the temperature change of the irradiated object with respect to the irradiation time.
[0071]
[Table 4]
(Example 3)
A firing test was carried out after conducting a preliminary test at the time of continuous irradiation of 2.45 GHz electromagnetic waves only on a conductive substrate (manufactured by Nippon Sheet Glass Co., Ltd.).
・ Preliminary test at 2.45 GHz irradiation
ER-A30S1 manufactured by Toshiba is used as the electromagnetic wave irradiation device.
With the transparent electrode placed on the alumina plate with the conductive layer facing upward, the influence on the base material was examined with high frequency outputs of irradiation of 100 W, 200 W, 500 W, and 1000 W.
[0073]
[Table 5]
From the above results, continuous irradiation conditions of less than 200 W were used as an example of continuous irradiation at 2.45 GHz.
[0075]
・ Continuous irradiation test in 100 W output range
The cell characteristics of the fired electrode were compared when the transparent electrode having a titanium oxide particle layer formed on the surface of the conductive layer was irradiated at 100 W from the back surface. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0076]
[Table 6]
Example 4
A firing test was carried out after conducting a preliminary test at the time of continuous irradiation of a 28 GHz electromagnetic wave only on a resin conductive substrate (manufactured by Oji Tobi).
・ Preliminary test at 28 GHz irradiation
FMS-10-28 manufactured by Fuji Radio Industry Co., Ltd. is used as the electromagnetic wave irradiation device. With the transparent electrode facing upward on the conductive layer and in close contact with the aluminum heat sink, the influence on the substrate was examined with high-frequency irradiation powers of 200 W, 500 W, and 1000 W.
[0078]
[Table 7]
Based on the above results, irradiation conditions of less than 500 W for 30 seconds were used as an example of 28 GHz continuous irradiation to the resin conductive substrate.
[0080]
・ Continuous irradiation test at 200W output
The cell characteristics of the fired electrode were compared when a resin transparent electrode having a titanium oxide particle layer formed on the surface of the conductive layer was irradiated from the surface at 200 W while being in contact with an aluminum radiator. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0081]
(Example 5)
A firing test was carried out after conducting a preliminary test at the time of continuous irradiation of 2.45 GHz electromagnetic waves only on a resin conductive substrate (manufactured by Oji Tobi).
・ Preliminary test at 2.45 GHz irradiation
ER-A30S1 manufactured by Toshiba is used as the electromagnetic wave irradiation device.
With the transparent electrode facing upward and the back surface adhered to a heat sink made of aluminum (in the form of a sheet), the influence of the irradiation on the substrate was examined with high frequency outputs of 100 W, 200 W, 500 W, and 1000 W.
[0082]
[Table 8]
From the above results, an irradiation condition of less than 500 W for 30 seconds was used as an example of continuous irradiation of 2.45 GHz onto a resin conductive substrate.
[0084]
・ Continuous irradiation test at 200W output
A fired electrode when irradiated with 200 W from the surface in a state where a resin transparent electrode having a titanium oxide particle layer formed on the surface of the conductive layer is adhered to an aluminum radiator (sheet-like; the edge portion is rounded) on the back surface The cell characteristics were compared. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0085]
(Example 6) The titanium oxide particle layer used in Example 5 was changed to a tin oxide (manufactured by Nano Tek; average particle diameter of about 30 nm) particle layer, and a similar experiment was conducted.
[0086]
(Example 7) The titanium oxide particle layer used in Example 5 was changed to a zinc oxide (manufactured by Nano Tek; average particle diameter of about 30 nm) particle layer, and a similar experiment was conducted.
[0087]
(Example 8) The titanium oxide particle layer used in Example 5 was changed to a titanium oxide P-25 (manufactured by Nippon Aerosil Co., Ltd .; average particle diameter of about 25 nm) particle layer, and 90 kggf with a hydraulic jack before microwave irradiation. / Cm 2 The same experiment as in Example 5 was performed except that the press treatment was performed.
[0088]
(Example 9) An experiment similar to that of Example 8 was performed except that the microwave used in Example 8 was changed to 28 GHz and 200 W.
[0089]
(Comparative Example 1) A titanium oxide electrode was prepared in the same manner as in Example 1 except that the electromagnetic wave irradiation performed in Example 1 was not performed, and the conversion efficiency was measured. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0090]
(Comparative Example 2) A titanium oxide electrode was prepared in the same manner as in Example 1 except that the electromagnetic radiation was applied without mounting the heat dissipation plate used in Example 1.
[0091]
(Comparative Example 3) Preparation of a titanium oxide electrode in the same manner as in Example 1 except that the electromagnetic wave irradiation apparatus used in Example 1 was replaced with a general household microwave oven (2.45 GHz, high frequency output 500 W). Went.
[0092]
Comparative Example 4 A titanium oxide electrode was prepared in the same manner as in Example 4 except that the electromagnetic wave irradiation performed in Example 4 was not performed, and the conversion efficiency was measured. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0093]
(Comparative Example 5) A titanium oxide electrode was prepared in the same manner as in Example 4 except that the electromagnetic wave irradiation performed in Example 4 was changed to a high frequency output of 2000 W, and the conversion efficiency was measured. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0094]
(Comparative Example 6) A titanium oxide electrode was prepared in the same manner as in Example 5 except that the heat dissipation sheet used in Example 5 was not used, and the conversion efficiency was measured. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0095]
(Comparative Example 7) A titanium oxide electrode was prepared in the same manner as in Example 1 except that the electromagnetic wave irradiation performed in Example 1 was changed to electric furnace heat treatment, and the conversion efficiency was measured. The cell creation method, evaluation method, etc. are the same as in Example 1.
(Comparative example 8) 90 kgf / cm with the hydraulic jack performed in Example 8 2 After performing the pressing process, the same experiment as in Example 8 was performed except that microwaves were not performed. The cell creation method, evaluation method, etc. are the same as in Example 1.
[0096]
[Table 9]
【The invention's effect】
In the present invention, the transparent conductive layer formed with the inorganic oxide semiconductor particle layer of the transparent electrode can be irradiated with microwaves, and the heat generated can form an inorganic oxide semiconductor porous layer to obtain high conversion efficiency. An inorganic oxide semiconductor electrode could be prepared. Incorporating conditions such as irradiation in the low output area, microwave irradiation in the high frequency area, and irradiation while the heat sink is in close contact with the substrate and electrical conductivity due to local overheating generated in the irradiated object It became possible to perform processing while preventing destruction, dissolution, deformation, crack formation, etc. of the layer. Since the processing time can be greatly reduced as compared with the external heat treatment using an electric furnace or the like, continuous processing without batch processing is possible. Furthermore, the cost can be significantly reduced by using a resin base material as the base material. By using this manufacturing method, it became possible to mass-produce cells at low cost.
[Brief description of the drawings]
FIG. 1 shows a photoelectric conversion cell test sample.
FIG. 2 is a particle size measurement result during microwave irradiation with a household microwave oven for only titanium oxide particles (titanium oxide: ST-01 manufactured by Ishihara Sangyo Co., Ltd., particle size measurement method: measured by XRD method).
3 is an electron micrograph of a titanium oxide porous layer after microwave irradiation in Example 1. FIG.
FIG. 4 shows a positional relationship between an object to be irradiated and a thermocouple or an alumina pedestal during a microwave baking preliminary test in Table 1 ((b) in the case of backside irradiation).
FIG. 5 shows heat dissipation measures in Example 1.
6 is a comparison of cell IV curve characteristics between Example 1 and Comparative Example 1. FIG.
7 shows the temperature change of the irradiated object with respect to the microwave irradiation time in the preliminary irradiation test for the transparent electrode in Example 2. FIG.
8 is a layout diagram at the time of microwave backside irradiation in Example 2. FIG.
9 shows a change in conversion efficiency using a fired electrode during each high-frequency output process in Example 2. FIG.
10 shows the temperature change of the irradiated object with respect to the microwave irradiation time in Example 2. FIG.
11 shows a state of an irradiated object after microwave irradiation in Comparative Example 2. FIG.
12 shows a state of an irradiated object after microwave irradiation in Comparative Example 5. FIG.
[Explanation of symbols]
1. Titanium oxide porous layer (photosensitive sensitizing dye already adsorbed)
2. Electrolyte solution layer
3. Transparent conductive layer (ITO or FTO)
4). Pt electrode layer
5. PET substrate or glass substrate
6). Resin film spacer
7). Conversion efficiency measurement lead
Claims (9)
平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子を透明導電層上に塗布して製膜して無機酸化物半導体多孔質層とする工程１、
透明導電層および無機酸化物半導体多孔質層に、周波数１ＧＨｚ以上３００ＧＨｚ以下のマイクロ波を１Ｗ以上、かつ、下記式の出力以下で照射して発熱させる工程２、
増感色素を無機酸化物半導体多孔質層と接触させる工程３を含む工程により製造されることを特徴とする光電変換用無機酸化物半導体電極の製造方法。
式 ｙ ＝ ２×１０−８ ｘ＋ ３００（式中、ｙは高周波出力（Ｗ）、ｘは高周波周波数（Ｈｚ）を表す。）A method for producing an inorganic oxide semiconductor electrode for photoelectric conversion comprising a transparent substrate comprising a transparent conductive layer and an inorganic oxide semiconductor porous layer,
Step 1, by applying inorganic oxide semiconductor particles having an average particle diameter of 5 nm or more and 500 nm or less on a transparent conductive layer to form an inorganic oxide semiconductor porous layer,
Step 2 of generating heat by irradiating a transparent conductive layer and an inorganic oxide semiconductor porous layer with microwaves having a frequency of 1 GHz or more and 300 GHz or less at 1 W or more and an output of the following formula or less:
A method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, comprising a step comprising a step 3 of bringing a sensitizing dye into contact with an inorganic oxide semiconductor porous layer.
Expression y = 2 × 10 −8 x + 300 (where y represents a high frequency output (W) and x represents a high frequency frequency (Hz)).
平均粒子径５ｎｍ以上５００ｎｍ以下の無機酸化物半導体粒子を透明導電層上に塗布して製膜して無機酸化物半導体多孔質層とする工程１、
透明導電層および無機酸化物半導体多孔質層に周波数１ＧＨｚ以上３００ＧＨｚ以下のマイクロ波を照射して発熱させる工程であって、被照射体に放熱体を密着させながらマイクロ波を照射する工程４、
増感色素を無機酸化物半導体多孔質層と接触させる工程３を含む工程により製造されることを特徴とする光電変換用無機酸化物半導体電極の製造方法。A method for producing an inorganic oxide semiconductor electrode for photoelectric conversion comprising a transparent substrate comprising a transparent conductive layer and an inorganic oxide semiconductor porous layer,
Step 1, by applying inorganic oxide semiconductor particles having an average particle diameter of 5 nm or more and 500 nm or less on a transparent conductive layer to form an inorganic oxide semiconductor porous layer,
A step of irradiating the transparent conductive layer and the inorganic oxide semiconductor porous layer with microwaves having a frequency of 1 GHz or more and 300 GHz or less to generate heat, the step of irradiating the microwaves while adhering the radiator to the irradiated body;
A method for producing an inorganic oxide semiconductor electrode for photoelectric conversion, comprising a step comprising a step 3 of bringing a sensitizing dye into contact with an inorganic oxide semiconductor porous layer.
さらに、無機酸化物半導体多孔質層にプレス処理する工程５を行うことを特徴とする請求項１または２記載の光電変換用無機酸化物半導体電極の製造方法。A method for producing an inorganic oxide semiconductor electrode for photoelectric conversion comprising a transparent substrate comprising a transparent conductive layer and an inorganic oxide semiconductor porous layer,
Furthermore, the process 5 which press-processes to an inorganic oxide semiconductor porous layer is performed, The manufacturing method of the inorganic oxide semiconductor electrode for photoelectric conversion of Claim 1 or 2 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003052916A JP4461691B2 (en) | 2003-02-28 | 2003-02-28 | Method for producing inorganic oxide semiconductor electrode for photoelectric conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003052916A JP4461691B2 (en) | 2003-02-28 | 2003-02-28 | Method for producing inorganic oxide semiconductor electrode for photoelectric conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004265662A true JP2004265662A (en) | 2004-09-24 |
| JP4461691B2 JP4461691B2 (en) | 2010-05-12 |
Family
ID=33117670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003052916A Expired - Fee Related JP4461691B2 (en) | 2003-02-28 | 2003-02-28 | Method for producing inorganic oxide semiconductor electrode for photoelectric conversion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4461691B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005074068A1 (en) * | 2004-01-30 | 2005-08-11 | Teijin Dupont Films Japan Limited | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
| JP2006060064A (en) * | 2004-08-20 | 2006-03-02 | Ishikawajima Harima Heavy Ind Co Ltd | Method for heating thin film with microwave |
| EP1808928A1 (en) * | 2004-10-13 | 2007-07-18 | Teijin Dupont Films Japan Limited | Multilayer body for dye-sensitized solar cell, electrode for dye-sensitized solar cell and method for producing same |
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| JP2011222430A (en) * | 2010-04-14 | 2011-11-04 | Hitachi Zosen Corp | Method of forming photocatalyst film in dye-sensitized solar cell |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
-
2003
- 2003-02-28 JP JP2003052916A patent/JP4461691B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005074068A1 (en) * | 2004-01-30 | 2005-08-11 | Teijin Dupont Films Japan Limited | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
| US8039735B2 (en) | 2004-01-30 | 2011-10-18 | Teijin Dupont Films Japan Limited | Laminated film for dye-sensitized solar cell and electrode for dye-sensitized solar cell, and process for their production |
| JP2006060064A (en) * | 2004-08-20 | 2006-03-02 | Ishikawajima Harima Heavy Ind Co Ltd | Method for heating thin film with microwave |
| EP1808928A1 (en) * | 2004-10-13 | 2007-07-18 | Teijin Dupont Films Japan Limited | Multilayer body for dye-sensitized solar cell, electrode for dye-sensitized solar cell and method for producing same |
| EP1808928A4 (en) * | 2004-10-13 | 2009-07-08 | Teijin Dupont Films Japan Ltd | Multilayer body for dye-sensitized solar cell, electrode for dye-sensitized solar cell and method for producing same |
| US8604335B2 (en) | 2004-10-13 | 2013-12-10 | Teijin Dupont Films Japan Limited | Laminate for dye-sensitized solar cell, electrode for dye-sensitized solar cell and method for producing it |
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| EP2845882A2 (en) | 2008-10-29 | 2015-03-11 | Fujifilm Corporation | Dye, Photoelectric Conversion Element and Photoelectrochemical Cell |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| JP2011222430A (en) * | 2010-04-14 | 2011-11-04 | Hitachi Zosen Corp | Method of forming photocatalyst film in dye-sensitized solar cell |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4461691B2 (en) | 2010-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Solidifying liquid electrolytes with fluorine polymer and silica nanoparticles for quasi-solid dye-sensitized solar cells | |
| Sedghi et al. | Influence of TiO2 electrode properties on performance of dye-sensitized solar cells | |
| TWI480229B (en) | A battery electrode material, a battery electrode paste, a method for manufacturing an electrode material for a battery, a dye-sensitized solar cell, and a battery | |
| WO2012105581A1 (en) | Method for producing oxide semiconductor layer | |
| JP4881600B2 (en) | Dye-sensitized solar cell, method for producing the same, and dye-sensitized solar cell module | |
| KR20120129247A (en) | Sintering method of semiconductor oxide by using intense pulsed light | |
| Kouhestanian et al. | Investigating the effects of thickness on the performance of ZnO-based DSSC | |
| JP2012521622A (en) | Low temperature sintering of dye-sensitized solar cells | |
| JP4461691B2 (en) | Method for producing inorganic oxide semiconductor electrode for photoelectric conversion | |
| JP2004319439A (en) | Dye-sensitized solar cell and its manufacturing method | |
| Sudhagar et al. | Efficient performance of electrostatic spray-deposited TiO 2 blocking layers in dye-sensitized solar cells after swift heavy ion beam irradiation | |
| JP4982067B2 (en) | Method for producing photoelectrode for dye-sensitized solar cell | |
| JP2005302509A (en) | Dye-sensitized solar cell | |
| JP5636736B2 (en) | Photoelectric conversion device and manufacturing method thereof | |
| JP5657780B2 (en) | Photoelectric conversion element and photoelectric conversion module | |
| Wu et al. | Rapid dye-sensitized solar cell working electrode preparation using far infrared rapid thermal annealing | |
| Cai et al. | Porous acetylene-black spheres as the cathode materials of dye-sensitized solar cells | |
| JP2012043662A (en) | Metal oxide semiconductor electrode manufacturing method | |
| JP2004273770A (en) | Method for manufacturing inorganic oxide semiconductor electrode for photoelectric conversion | |
| Shinde et al. | Experimental and theoretical study of 1, 4-naphthoquinone based dye in dye-sensitized solar cells using ZnO photoanode | |
| Ho et al. | Enhanced efficiency via blocking layers at photocathode interfaces in cobalt-mediated tandem dye-sensitized solar cells | |
| Pervez et al. | Photoanode annealing effect on charge transport in dye-sensitized solar cell | |
| Raj et al. | Fabrication of low-cost carbon paste based counter electrodes for dye-sensitized solar cells | |
| Liu et al. | Operating temperature and temperature gradient effects on the photovoltaic properties of dye sensitized solar cells assembled with thermoelectric–photoelectric coaxial nanofibers | |
| Elangovan et al. | Performance of dye-sensitized solar cells based on various sensitizers applied on TiO 2-Nb 2 O 5 core/shell photoanode structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050915 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090616 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090807 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20090807 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100126 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100208 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130226 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4461691 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130226 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130226 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140226 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |