JP2006155907A - Counter electrode for dye-sensitized solar cell, and dye-sensitized solar cell using this - Google Patents
Counter electrode for dye-sensitized solar cell, and dye-sensitized solar cell using this Download PDFInfo
- Publication number
- JP2006155907A JP2006155907A JP2004340120A JP2004340120A JP2006155907A JP 2006155907 A JP2006155907 A JP 2006155907A JP 2004340120 A JP2004340120 A JP 2004340120A JP 2004340120 A JP2004340120 A JP 2004340120A JP 2006155907 A JP2006155907 A JP 2006155907A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- solar cell
- transparent conductive
- sensitized solar
- 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
- 239000002985 plastic film Substances 0.000 claims abstract description 32
- 229920006255 plastic film Polymers 0.000 claims abstract description 32
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 26
- 229920000728 polyester Polymers 0.000 abstract description 11
- 229920000128 polypyrrole Polymers 0.000 abstract description 4
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000123 polythiophene Polymers 0.000 abstract description 3
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000767 polyaniline Polymers 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 76
- 239000010408 film Substances 0.000 description 29
- 239000006185 dispersion Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 239000004065 semiconductor Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- -1 fluororesin Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 239000012327 Ruthenium complex Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- FGSUUFDRDVJCLT-UHFFFAOYSA-N 3-methylazepan-2-one Chemical compound CC1CCCCNC1=O FGSUUFDRDVJCLT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZAOCWQZQPKGTRN-UHFFFAOYSA-N nitrous acid;sodium Chemical compound [Na].ON=O ZAOCWQZQPKGTRN-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer 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
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は色素増感型太陽電池の対極およびこれを用いた色素増感型太陽電池に関する。 The present invention relates to a counter electrode of a dye-sensitized solar cell and a dye-sensitized solar cell using the same.
色素増感型太陽電池は、色素増感半導体微粒子を用いた光電変換素子が提案されて以来(「ネイチャー(Nature)」 第353巻、第737〜740ページ、(1991年))、シリコン系太陽電池に替る新たな太陽電池として注目されている。シリコン系太陽電池と比較すると製造時の低コスト化が可能であり、注目されている。 The dye-sensitized solar cell has been proposed since a photoelectric conversion element using dye-sensitized semiconductor fine particles was proposed (“Nature”, Vol. 353, pages 737-740, (1991)). It is attracting attention as a new solar battery that replaces batteries. Compared to silicon-based solar cells, it is possible to reduce the manufacturing cost, and is attracting attention.
色素増感型太陽電池の多くは、ガラス上の透明導電層に多孔酸化チタン膜を積層し、表面に増感色素で吸着させることによって得られる作用電極と、電解質、対極を備える。現在知られている色素増感型太陽電池に使用される対極は、その多くがITOガラスなどの透明導電性材料に白金を坦持させたものである。しかし、白金は貴金属であり高価であることから、より安価な導電性高分子を用い、これをガラス基板に設けられた透明導電層のうえに担持させることが検討されている。
従来の技術において、色素増感型太陽電池の対極に導電性高分子を用いる際には、導電性高分子の分散液もしくはそのモノマーの分散液を、ガラス基材上の透明導電層のうえに塗布し、乾燥もしくは重合させる方法がとられていた。しかし、導電性高分子やそのモノマーは溶解性が低く極性の高い溶媒を用いる必要があり、基材への濡れ性が悪く、均一に塗布するためにはスピンコートといった限られた塗布方法が必要であった。。さらに太陽電池に組み立てた際、電解質を溶液として用いた場合において、透明導電層からの剥離を抑制するために十分な接着性が必要とされる。
また基材としてガラスを用いた場合、耐衝撃性が低く、太陽電池としたときの耐衝撃性も低いものであった。
In the conventional technique, when using a conductive polymer for the counter electrode of the dye-sensitized solar cell, the conductive polymer dispersion or the monomer dispersion is placed on the transparent conductive layer on the glass substrate. The method of applying, drying or polymerizing was taken. However, it is necessary to use a highly polar solvent with low solubility for the conductive polymer and its monomers, and the wettability to the base material is poor, so a limited coating method such as spin coating is required for uniform coating. Met. . Furthermore, when the electrolyte is used as a solution when assembled into a solar cell, sufficient adhesiveness is required to suppress peeling from the transparent conductive layer.
Moreover, when glass was used as the substrate, the impact resistance was low, and the impact resistance when a solar cell was obtained was also low.
本発明は、かかる従来技術の問題を解決することを課題とする。すなわち本発明の目的は、耐衝撃性が高く、なおかつ濡れ性の悪い基材と十分に高い接着強度で接着した導電性高分子からなる、色素増感型太陽電池の対極およびこれを用いた耐衝撃性の高い色素増感型太陽電池を提供することにある。 An object of the present invention is to solve the problems of the prior art. That is, the object of the present invention is to provide a counter electrode for a dye-sensitized solar cell, which is composed of a conductive polymer bonded with a substrate having high impact resistance and poor wettability with sufficiently high adhesive strength, and resistance resistance using the same. The object is to provide a dye-sensitized solar cell with high impact.
すなわち本発明は、プラスチックフィルム、そのうえに設けられた透明導電層、および透明導電層のうえに設けられた導電性高分子層からなる、色素増感型太陽電池の対極であり、また、この色素増感型太陽電池の対極を用いた色素増感型太陽電池である。 That is, the present invention is a counter electrode of a dye-sensitized solar cell comprising a plastic film, a transparent conductive layer provided thereon, and a conductive polymer layer provided on the transparent conductive layer. This is a dye-sensitized solar cell using the counter electrode of the sensitive solar cell.
本発明によれば、耐衝撃性が高く、基材と十分に高い接着強度で接着した、色素増感型太陽電池用対極を提供することにある。 According to the present invention, there is provided a counter electrode for a dye-sensitized solar cell that has high impact resistance and is bonded to a substrate with sufficiently high adhesive strength.
以下、本発明を詳細に説明する。
[プラスチックフィルム]
本発明におけるプラスチックフィルムはプラスチックから構成される。プラスチックとしては、ポリエステル、ポリカーボネート、非晶質オレフィン、ポリエーテル、ポリエーテルエーテルケトン、ポリフェニレンエーテル、ポリメタクリレート、ポリスチレン、アクリル、ポリアミド、ポリアリレート、ポリスルホン酸、ポリエーテルスルホン、ポリアリーレンスルフィド、フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、ジアリルフタレート、ポリウレタン、ケイ素樹脂、フッ素樹脂、ポリイミド、ポリエーテルイミド、ポリアミドイミドを例示することができる。就中、ポリエステルが好ましい。
Hereinafter, the present invention will be described in detail.
[Plastic film]
The plastic film in the present invention is made of plastic. Plastics include polyester, polycarbonate, amorphous olefin, polyether, polyether ether ketone, polyphenylene ether, polymethacrylate, polystyrene, acrylic, polyamide, polyarylate, polysulfonic acid, polyethersulfone, polyarylene sulfide, phenol resin, Examples include urea resin, melamine resin, epoxy resin, diallyl phthalate, polyurethane, silicon resin, fluororesin, polyimide, polyetherimide, and polyamideimide. Of these, polyester is preferred.
ポリエステルとしては、芳香族ポリエステルを用い、ポリエチレンナフタレンジカルボキシレート、ポリエチレンテレフタレートを例示することができる。就中ポリエチレンナフタレンジカルボキシレートが好ましい。 As polyester, aromatic polyester is used, and polyethylene naphthalene dicarboxylate and polyethylene terephthalate can be exemplified. In particular, polyethylene naphthalene dicarboxylate is preferred.
本発明におけるプラスチックフィルムの厚みは、好ましくは10〜500μm、さらに好ましくは20〜400μm、特に好ましくは50〜300μmである。10μm未満であるとハンドリングが困難となりその後の太陽電池組み立て工程に支障をきたすため好ましくない。500μmより厚いと色素増感型太陽電池の柔軟性が落ちるため好ましくない。
プラスチックとしてポリエステルを用いる場合には、ポリエステルは延伸されたフィルム、特に二軸延伸されたフィルムとして用いることが、機械的強度の観点から好ましい。
The thickness of the plastic film in the present invention is preferably 10 to 500 μm, more preferably 20 to 400 μm, and particularly preferably 50 to 300 μm. If the thickness is less than 10 μm, handling becomes difficult and the subsequent solar cell assembly process is hindered. A thickness of more than 500 μm is not preferable because the flexibility of the dye-sensitized solar cell is lowered.
When polyester is used as the plastic, it is preferable from the viewpoint of mechanical strength that the polyester is used as a stretched film, particularly a biaxially stretched film.
[易接着層]
プラスチックフィルムのうえには透明導電層が設けられるが、プラスチックフィルムと透明導電層との密着性を向上させるために、プラスチックフィルムと透明導電層の間に易接着層を設けてもよい。易接着層を設ける場合、その厚みは、好ましくは10〜200nm、さらに好ましくは20〜150nmである。易接着層の厚みが10nm未満であると密着性を向上させる効果が乏しく好ましくなく、200nmを超えると易接着層の凝集破壊が発生しやすくなり密着性が低下することがあり好ましくない。
[Easily adhesive layer]
A transparent conductive layer is provided on the plastic film, but an easy-adhesion layer may be provided between the plastic film and the transparent conductive layer in order to improve the adhesion between the plastic film and the transparent conductive layer. When providing an easily bonding layer, the thickness becomes like this. Preferably it is 10-200 nm, More preferably, it is 20-150 nm. If the thickness of the easy-adhesion layer is less than 10 nm, the effect of improving the adhesion is poor, which is not preferable. If the thickness exceeds 200 nm, the easy-adhesion layer tends to cause cohesive failure and the adhesion may be lowered.
易接着層は、プラスチックフィルムが形成された後に設けてもよく、プラスチックフィルムの製造過程で塗工により設けてもよい。プラスチックフィルムの製造過程で塗工により設けることが好ましく、特に、プラスチックフィルムが延伸されて製造される場合には、プラスチックフィルムの製造工程において延伸および熱固定の工程が完了する前に塗布することが好ましい。 The easy adhesion layer may be provided after the plastic film is formed, or may be provided by coating during the production process of the plastic film. It is preferably provided by coating during the production process of the plastic film. In particular, when the plastic film is produced by being drawn, it may be applied before the drawing and heat setting steps are completed in the production process of the plastic film. preferable.
ここで、結晶配向が完了する前のプラスチックフィルムとは、未延伸フィルム、未延伸フィルムを縦方向または横方向の何れか一方に配向せしめた一軸配向フィルム、さらには縦方向および横方向の二方向に低倍率延伸配向せしめたもの(最終的に縦方向また横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム)を包含する。 Here, the plastic film before crystal orientation is completed is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in two directions, the longitudinal direction and the transverse direction. And a film that has been stretched and oriented at a low magnification (a biaxially stretched film before it is finally re-stretched in the machine direction or the transverse direction to complete oriented crystallization).
易接着層の構成材としては、プラスチックフィルムと透明導電層の双方に優れた接着性を示す構成材であることが好ましく、具体的には、ポリエステル樹脂、アクリル樹脂、ウレタンアクリル樹脂、シリコンアクリル樹脂、メラミン樹脂、ポリシロキサン樹脂が例示できる。これらの樹脂は単独で用いてもよく、2種以上を例えば混合物として用いてもよい。 The constituent material of the easy-adhesion layer is preferably a constituent material that exhibits excellent adhesion to both the plastic film and the transparent conductive layer. Specifically, polyester resin, acrylic resin, urethane acrylic resin, silicon acrylic resin And melamine resin and polysiloxane resin. These resins may be used alone, or two or more kinds thereof may be used as a mixture, for example.
[ハードコート層]
さらに、プラスチックフィルムと透明導電層との密着性、特に密着の耐久性を向上させるために、易接着層と透明導電層との間にハードコート層を設けてもよい。
ハードコート層は、易接着層を設けたプラスチックフィルム上に塗工する方法で設けることが好ましい。ハードコート層は、易接層および透明導電層の双方に優れた密着性を示す材料で構成されることが好ましく、熱硬化性やエネルギー線硬化性樹脂が工業的な生産性の観点から、アクリル樹脂、ウレタン樹脂、シリコン樹脂、エポキシ樹脂といった樹脂成分や、これらとアルミナ、シリカ、マイカといった無機粒子の混合物が好ましい。ハードコート層の厚みは、好ましくは0.01〜20μm、さらに好ましくは1〜10μmである。
[Hard coat layer]
Furthermore, a hard coat layer may be provided between the easy-adhesion layer and the transparent conductive layer in order to improve the adhesion between the plastic film and the transparent conductive layer, particularly the durability of the adhesion.
The hard coat layer is preferably provided by a method of coating on a plastic film provided with an easy adhesion layer. The hard coat layer is preferably composed of a material that exhibits excellent adhesion to both the easy-contact layer and the transparent conductive layer. From the viewpoint of industrial productivity, thermosetting and energy ray curable resins are acrylic. A resin component such as resin, urethane resin, silicon resin, and epoxy resin, and a mixture of these with inorganic particles such as alumina, silica, and mica are preferable. The thickness of the hard coat layer is preferably 0.01 to 20 μm, more preferably 1 to 10 μm.
[透明導電層]
本発明において、透明導電層は、導電性の金属酸化物を用いて形成する。例えば、フッ素ドープ酸化スズ、インジウム−スズ複合酸化物(ITO)、インジウム−亜鉛複合酸化物、金属の薄膜(例えば白金、金、銀、銅、アルミニウムなど)、炭素材料を例示することができる。透明導電層は1種を用いてもよく、2種以上を用いて積層したり、複合化させてもよい。就中、ITOおよびインジウム−亜鉛複合酸化物は、光線透過率が高く低抵抗であるため特に好ましい。
[Transparent conductive layer]
In the present invention, the transparent conductive layer is formed using a conductive metal oxide. Examples thereof include fluorine-doped tin oxide, indium-tin composite oxide (ITO), indium-zinc composite oxide, metal thin films (eg, platinum, gold, silver, copper, aluminum, etc.), and carbon materials. One type of transparent conductive layer may be used, or two or more types may be laminated or combined. In particular, ITO and indium-zinc composite oxide are particularly preferable because of high light transmittance and low resistance.
透明導電層の表面抵抗は、好ましくは100Ω/□以下、さらに好ましくは40Ω/□以下である。100Ω/□を超えると太陽電池の内部抵抗が上がり、十分に電流が流れないため好ましくない。
透明導電層の厚みは好ましくは100〜500nmである。これより薄いと十分に表面抵抗値を低くすることができず、厚いと透明導電層がわれやすくなり、好ましくない。
The surface resistance of the transparent conductive layer is preferably 100Ω / □ or less, more preferably 40Ω / □ or less. Exceeding 100Ω / □ is not preferable because the internal resistance of the solar cell increases and current does not sufficiently flow.
The thickness of the transparent conductive layer is preferably 100 to 500 nm. If it is thinner than this, the surface resistance value cannot be lowered sufficiently, and if it is thick, the transparent conductive layer is easily broken, which is not preferable.
透明導電層の表面エネルギーは、好ましくは40〜72mN/mである。表面エネルギーが40mN/m未満であると、導電性高分子およびモノマーの分散液を塗布することが困難となり好ましくなく、表面エネルギーが72mN/mを超えると、表面エネルギーを必要なレベルでフィルムに付与する工程で透明導電層表面が破壊される可能性があり好ましくない。 The surface energy of the transparent conductive layer is preferably 40 to 72 mN / m. When the surface energy is less than 40 mN / m, it becomes difficult to apply a dispersion of conductive polymer and monomer, and when the surface energy exceeds 72 mN / m, the surface energy is applied to the film at a necessary level. This is not preferable because the surface of the transparent conductive layer may be destroyed in the step of performing.
上記の表面エネルギーを達成するための手段としては、例えば(1)透明導電性薄膜を酸性もしくはアルカリ性溶液で表面を活性化する方法、(2)紫外線や電子線を薄膜表面に照射して活性化する方法、(3)コロナ処理やプラズマ処理を施して表面を活性化する方法、を適用することができる。この中でコロナ処理やプラズマ処理、特にプラズマ処理を施して表面を活性化する方法は、高い表面エネルギーが得られるため特に好ましい。 Means for achieving the above surface energy include, for example, (1) a method of activating the surface of a transparent conductive thin film with an acidic or alkaline solution, and (2) activation by irradiating the surface of the thin film with ultraviolet rays or an electron beam. And (3) a method of activating the surface by performing corona treatment or plasma treatment can be applied. Among these, a method of activating the surface by performing corona treatment or plasma treatment, particularly plasma treatment, is particularly preferable because high surface energy can be obtained.
[導電性高分子層]
本発明における導電性高分子としては、ポリチオエフェン、ポリピロールおよびポリアニリンを例示することができる。
ポリチオフェンとしては、下記式に示すものを用いることができる。なお、ポリチオフェンは、共重合体でもよく、混合体でもよい。
[Conductive polymer layer]
Examples of the conductive polymer in the present invention include polythioephene, polypyrrole and polyaniline.
As the polythiophene, those represented by the following formula can be used. Polythiophene may be a copolymer or a mixture.
また、ポリピロールとしては下記式に示すものを用いることができる。なお、ポリピロールは、共重合体でもよく、混合体でもよい。 Moreover, what is shown to a following formula can be used as a polypyrrole. Polypyrrole may be a copolymer or a mixture.
導電層高分子層を形成するには、1)導電性高分子を含む分散液をプラスチックフィルム上の透明導電層に塗布し溶媒を除去する方法、2)導電性高分子のモノマーおよび重合触媒を含む分散液を、プラスチックフィルム上の透明導電層に塗布した後に重合を進め、最終的に溶媒を除去する方法を例示することができる。 In order to form a conductive polymer layer, 1) a method of applying a dispersion containing a conductive polymer to a transparent conductive layer on a plastic film and removing the solvent, 2) a monomer of the conductive polymer and a polymerization catalyst An example is a method in which the dispersion is applied to the transparent conductive layer on the plastic film and then polymerized to finally remove the solvent.
1)、2)の溶媒としては、上記導電性高分子およびモノマーまた重合触媒等を十分に分散し、さらにプラスチックフィルムを溶解、侵食しない溶媒であればよい。例えば、水、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、2−ブタノール、t−ブタノール、エチレングリコール、ジエチレングリコールといったプロトン系溶媒、アセトニトリル、プロピロニトリル、3−メトキシプロピロニトリル、ブチロニトリルといったニトリル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン、ヘキサメチルホスホルアミド、1,3−ジメチルイミダゾリジノン、テトラメチルウレア、1,3−ジピロピルイミダゾリジノン、Nーメチルカプロラクタム、ジメチルスルホキシド、ジメチルスルホン、テトラメチルスルホンといった非プロトン性極性溶媒、塩化メチレン、クロロホルム、テトラクロロエタン、といったハロゲン溶媒、テトラヒドロフランを用いることができる。これらの溶媒は、単独で用いてもよく、また混合物として用いてもよい。 The solvent of 1) and 2) may be any solvent that sufficiently disperses the conductive polymer, monomer, polymerization catalyst, etc., and that does not dissolve or erode the plastic film. For example, proton solvents such as water, methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, t-butanol, ethylene glycol, diethylene glycol, nitrile solvents such as acetonitrile, propironitrile, 3-methoxypropironitrile, butyronitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, 1,3-dimethylimidazolidinone, tetramethylurea, 1,3-dipyropyrimidazolidinone, N --Aprotic polar solvents such as methyl caprolactam, dimethyl sulfoxide, dimethyl sulfone and tetramethyl sulfone; halogen solvents such as methylene chloride, chloroform and tetrachloroethane; Rahidorofuran can be used. These solvents may be used alone or as a mixture.
2)における重合触媒としては、塩化鉄や有機スルホン酸鉄およびこれらの水和物を例示することができる。触媒の添加量は十分に反応を進めるだけの量があれば良いが、例えばモノマーに対し0.1〜5倍モル量、好ましくは0.5〜3倍モルである。0.1倍未満であると反応が十分に進行しないため好ましくなく、5倍を超えると大過剰であり工業的に好ましくない。 Examples of the polymerization catalyst in 2) include iron chloride, iron organic sulfonate, and hydrates thereof. The catalyst may be added in an amount sufficient to allow the reaction to proceed sufficiently. For example, the amount is 0.1 to 5 times, preferably 0.5 to 3 times the amount of the monomer. If it is less than 0.1 times, the reaction does not proceed sufficiently. This is not preferable, and if it exceeds 5 times, it is excessively large and not industrially preferable.
2)において造膜性を向上させるため、重合制御剤を添加してもよい。重合制御剤としては、例えばイミダゾール、芳香族オキシスルホン酸を例示することができる。重合制御剤の添加量は造膜性をたかめつつ十分に重合反応を進めるだけの量があれば良く、この観点からモノマーに対し例えば9倍モル以下、好ましくは5倍モル以下である。9倍モルを超えると、重合反応が十分進行せず好ましくない。 In order to improve the film-forming property in 2), a polymerization controller may be added. Examples of the polymerization control agent include imidazole and aromatic oxysulfonic acid. The polymerization controller may be added in an amount sufficient to allow the polymerization reaction to proceed sufficiently while increasing the film-forming property. From this viewpoint, it is, for example, 9 times mol or less, preferably 5 times mol or less with respect to the monomer. If it exceeds 9 moles, the polymerization reaction does not proceed sufficiently, which is not preferable.
1)において必要に応じて分散性向上のために分散剤を用いてもよい。分散剤としては、スルホン酸系化合物もしくは重合体を例示することができる。
添加量としては導電性高分子の繰り返し単位数あたり0.01〜5倍モル、好ましくは0.5〜3倍モルである。0.01倍モル未満であると分散性は十分に改善されず、5倍モルを超えると内部抵抗があがり、導電性高分子としての機能を発揮できないため好ましくない。
In 1), a dispersant may be used as necessary to improve dispersibility. Examples of the dispersant include sulfonic acid compounds or polymers.
The addition amount is 0.01 to 5 times mol, preferably 0.5 to 3 times mol per the number of repeating units of the conductive polymer. If the amount is less than 0.01 moles, the dispersibility is not sufficiently improved, and if it exceeds 5 moles, the internal resistance is increased and the function as a conductive polymer cannot be exhibited.
さらに、1)および2)において得られる導電性高分子膜の剥離を抑える目的でバインダーを添加してもよい。バインダーとしては、例えばアクリル樹脂、ウレタン樹脂、シリコン樹脂、エポキシ樹脂を用いることができる。これらの樹脂成分は、樹脂成分のみで用いてもよいが、これらとアルミナ、シリカ、マイカといった無機粒子との混合物として用いることもできる。 Furthermore, you may add a binder in order to suppress peeling of the conductive polymer film obtained in 1) and 2). As the binder, for example, an acrylic resin, a urethane resin, a silicon resin, or an epoxy resin can be used. These resin components may be used alone, but can also be used as a mixture of these and inorganic particles such as alumina, silica, and mica.
添加するバインダーの量は、導電性高分子に対し好ましくは5倍重量以下である。5倍重量を超えて添加すると、内部抵抗があがり、導電性高分子としての機能を発揮できないため好ましくない。 The amount of the binder to be added is preferably 5 times or less by weight based on the conductive polymer. Addition exceeding 5 times the weight is not preferable because the internal resistance is increased and the function as a conductive polymer cannot be exhibited.
これら1)および2)の場合、分散液に含まれる導電性高分子およびそのモノマーの重量含有率は、例えば0.01〜50重量%、好ましくは0.05〜40重量%、さらに好ましくは0.1〜30重量%である。0.01重量%未満であると十分な膜厚が取れないため、太陽電池に用いた際電子の移動が十分行われず好ましくない。50重量%を超えると、分散液の粘度が上がり均一に塗布することができず好ましくない。 In the case of these 1) and 2), the weight content of the conductive polymer and its monomer contained in the dispersion is, for example, 0.01 to 50% by weight, preferably 0.05 to 40% by weight, more preferably 0. .1 to 30% by weight. If the amount is less than 0.01% by weight, a sufficient film thickness cannot be obtained. Therefore, when used in a solar cell, electrons are not sufficiently transferred, which is not preferable. If it exceeds 50% by weight, the viscosity of the dispersion is increased, and uniform application cannot be achieved.
上記1)の導電性高分子の分散液および2)のモノマー分散液の透明導電層上への塗布は、スピンコート、キャスト法、スプレーコート、ディップコート、ロールコート、ビードコートといった公知の塗布方法により行うことができる。 The above-mentioned dispersion of the conductive polymer of 1) and the dispersion of the monomer of 2) are applied onto the transparent conductive layer by known coating methods such as spin coating, casting, spray coating, dip coating, roll coating, and bead coating. Can be performed.
塗布後、加熱、必要があれば減圧することで溶媒を除去することで目的とする導電性高分子膜を形成することができる。この際の温度は、1)の場合溶媒が揮発する温度以上であり、2)の場合重合が進行し溶媒が揮発する温度で以上であり、さらにプラスチックフィルムが変形する温度以下である。 After the application, the target conductive polymer film can be formed by removing the solvent by heating and, if necessary, reducing the pressure. The temperature at this time is equal to or higher than the temperature at which the solvent volatilizes in the case of 1), and is equal to or higher than the temperature at which the polymerization proceeds and the solvent volatilizes in the case of 2).
上記2)の場合、重合後に過剰の重合触媒を取り除くことが好ましい。除去方法としては洗浄が挙げられる。洗浄時の溶媒としては重合触媒を溶解しなおかつ導電性高分子を溶解しないものであればよい。好ましくは水、メタノール、エタノール、イソプロパノールを用いる。また、洗浄後は乾燥することが好ましい。乾燥温度はプラスチックフィルムおよび導電性高分子が劣化しない温度未満であればよい。 In the case of 2), it is preferable to remove excess polymerization catalyst after polymerization. An example of the removal method is washing. The solvent for washing may be any solvent that dissolves the polymerization catalyst and does not dissolve the conductive polymer. Preferably, water, methanol, ethanol and isopropanol are used. Moreover, it is preferable to dry after washing. The drying temperature may be lower than the temperature at which the plastic film and the conductive polymer are not deteriorated.
こうして得られた導電性高分子層の厚みは、好ましくは0.1〜500nm、好ましくは1〜200nmである。0.1nm未満であると目的とする電子の受け渡しが不十分となるため好ましくない。500nmを超えると、フィルムの剥離等が問題となるため好ましくない。 The thickness of the conductive polymer layer thus obtained is preferably 0.1 to 500 nm, preferably 1 to 200 nm. If it is less than 0.1 nm, it is not preferable because the intended delivery of electrons becomes insufficient. If it exceeds 500 nm, peeling of the film or the like becomes a problem, which is not preferable.
[色素増感型太陽電池の作成]
本発明の電極を用いて色素増感型太陽電池を作成するには、公知の方法を用いることができる。具体的には例えば下記の方法で作成することができる。
[Creation of dye-sensitized solar cell]
In order to produce a dye-sensitized solar cell using the electrode of the present invention, a known method can be used. Specifically, for example, it can be created by the following method.
(1)多孔質半導体の作成
プラスチックフィルムのうえに透明導電層を形成し、そのうえに多孔質半導体層を形成する。多孔質半導体層の形成は、水、アルコールといった溶媒に分散された酸化チタン結晶微粒子の分散液を、電極の透明導電層のうえにスピンコート、キャスト法、スプレーコート、ディップコート、ロールコート、ビードコートといった公知方法により塗布し、溶媒を除去することにより行うことができる。
(1) Creation of porous semiconductor A transparent conductive layer is formed on a plastic film, and a porous semiconductor layer is formed thereon. The porous semiconductor layer is formed by applying a dispersion of titanium oxide crystal fine particles dispersed in a solvent such as water or alcohol on the transparent conductive layer of the electrode by spin coating, casting, spray coating, dip coating, roll coating, or beading. It can apply by apply | coating by well-known methods, such as a coating, and removing a solvent.
また、多孔質半導体層の形成には、電着によって粒子の薄膜を担持する方法を用いてもよい。すなわち、半導体微粒子を適当な低伝導度の溶媒、例えば純水、アルコールやアセトニトリル、THFなどの極性有機溶媒、ヘキサン、クロロホルムなどの非極性有機溶媒、あるいはこれらの混合溶媒に添加し、凝集のないよう均一に分散し、電着すべき導電性樹脂シート電極と対極とを一定の間隔で平行に対向させ、この間隙に上記の分散液を注入し、両電極間に直流電圧を印加する。分散液の濃度と電極間隔を選択することにより、基板電極に一定かつ均一な厚みの電着膜である多孔質半導体層を形成することができる。 In addition, for forming the porous semiconductor layer, a method of supporting a thin film of particles by electrodeposition may be used. That is, the semiconductor fine particles are added to an appropriate low-conductivity solvent such as pure water, polar organic solvents such as alcohol, acetonitrile and THF, nonpolar organic solvents such as hexane and chloroform, or a mixed solvent thereof, so that there is no aggregation. The conductive resin sheet electrode to be electrodeposited and the counter electrode are made to face each other in parallel at a constant interval, the dispersion liquid is injected into the gap, and a DC voltage is applied between the electrodes. By selecting the concentration of the dispersion and the electrode spacing, a porous semiconductor layer that is an electrodeposited film having a constant and uniform thickness can be formed on the substrate electrode.
塗設した多孔質半導体層に対し、半導体粒子同士の電子的接触の強化と、支持体との密着性の向上のために、さらに高温処理をしてもよい。また、半導体粒子に対して該粒子が強く吸収する紫外光などを照射する、マイクロ波を照射して微粒子層を加熱する、半導体粒子のアモルファス成分を添加することにより微粒子の間の物理的接合を強める、といった処理を行ってもよい。 The coated porous semiconductor layer may be further subjected to a high temperature treatment in order to enhance the electronic contact between the semiconductor particles and improve the adhesion to the support. In addition, the semiconductor particles are irradiated with ultraviolet light or the like that the particles strongly absorb, the microwave layer is irradiated to heat the fine particle layer, and the amorphous component of the semiconductor particles is added to form a physical bond between the fine particles. Processing such as strengthening may be performed.
(2)作用電極の作成
上記(1)で作成した多孔質半導体層に色素を吸着させる。色素としては、可視光領域および赤外光領域の光を吸収する特性を有する色素、例えば、ルテニウムビピリジン系錯体(ルテニウム錯体)に代表される有機金属錯体色素、シアニン系色素、クマリン系色素、キサンテン系色素、ポルフィリン系色素を用いることができる。これらをアルコールやトルエンなどの溶媒に溶解させて色素溶液を作成し、多孔質半導体層を浸漬するか、多孔質半導体層に噴霧または塗布する。
(2) Production of working electrode A dye is adsorbed to the porous semiconductor layer produced in (1) above. Examples of the dye include a dye having a characteristic of absorbing light in the visible light region and the infrared light region, for example, an organometallic complex dye represented by a ruthenium bipyridine complex (ruthenium complex), a cyanine dye, a coumarin dye, and a xanthene. System dyes and porphyrin dyes can be used. These are dissolved in a solvent such as alcohol or toluene to prepare a dye solution, and the porous semiconductor layer is immersed, or sprayed or applied to the porous semiconductor layer.
(3)シール
上記(2)で作成した作用電極と、本発明の対極とを、熱圧着性のポリエチレンフィルム製フレーム型スペーサー(厚さ20μm)を挟んで重ね合わせ、スペーサー部を加熱し、両電極を圧着する。さらに、そのエッジ部をエポキシ樹脂接着剤でシールする。
シートのコーナー部にあらかじめ設けた電解液注入用の小孔を通して、ヨウ化リチウムとヨウ素(モル比3:2)ならびにスペーサーとして平均粒径20μmのナイロンビーズを3重量%含む電解質水溶液を注入する。内部の脱気を十分に行い、最終的に小孔をエポキシ樹脂接着剤で封じる。
(3) Seal The working electrode prepared in (2) above and the counter electrode of the present invention are overlapped with a thermocompressible polyethylene film frame spacer (thickness 20 μm) sandwiched between them, and the spacer portion is heated. Crimp the electrode. Further, the edge portion is sealed with an epoxy resin adhesive.
An electrolyte aqueous solution containing lithium iodide and iodine (molar ratio 3: 2) and 3% by weight of nylon beads having an average particle diameter of 20 μm as a spacer is injected through a small hole for injecting an electrolyte provided in the corner of the sheet in advance. Thoroughly deaerate the inside and finally seal the small holes with an epoxy resin adhesive.
次に、実施例により本発明をさらに詳細に説明する。なお、例中の各特性値は、下記の方法により測定した。
(1)フィルム厚み
マイクロメーター(アンリツ(株)製のK−402B型)を用いて、フィルムの連続製膜方向および幅方向に各々10cm間隔で測定を行い、全部で300ヶ所のフィルム厚みを測定した。得られた300ヶ所のフィルム厚みの平均値を算出してフィルム厚みとした。
Next, the present invention will be described in more detail with reference to examples. In addition, each characteristic value in an example was measured with the following method.
(1) Film thickness Using a micrometer (K-402B type manufactured by Anritsu Co., Ltd.), the film thickness is measured at 10 cm intervals in the continuous film-forming direction and the width direction of the film, and the film thickness is measured at a total of 300 locations. did. The average value of the film thicknesses of the obtained 300 locations was calculated and used as the film thickness.
(2)表面抵抗値
4探針式表面抵抗率測定装置(三菱化学(株)製、ロレスタGP)を用いて任意の5点を測定し、その平均値を代表値として用いた。
(2) Surface resistance value Any five points were measured using a 4-probe type surface resistivity measuring device (Made by Mitsubishi Chemical Corporation, Loresta GP), and the average value was used as a representative value.
(3)表面エネルギー
表面エネルギーが既知である水、およびヨウ化メテレンの透明導電性薄膜に対する接触角:θw、θyを接触角計(協和界面科学社製「CA−X型」)を使用し、25℃、50%RHの条件で測定した。これらの測定値を用い、以下の様にして透明導電性薄膜の表面エネルギーγsを算出した。
透明導電性薄膜の表面エネルギーγsは、分散性成分γsdと極性成分γspとの和である。即ち、
γs=γsd+γsp (式1)
また、Youngの式より、
γs=γsw+γw・cosθw (式2)
γs=γsy+γy・cosθy (式3)
ここで、γswは透明導電性薄膜と水との間に働く張力、γswは透明導電性薄膜とヨウ化メチレンとの間に働く張力、γwは水の表面エネルギー、γyはヨウ化メチレンの表面エネルギーである。
また、Fowkesの式より、
γsw=γs+γw−2×(γsd・γwd)1/2−2×(γsp・γwp)1/2 (式4)
γsy=γs+γy−2×(γsd・γyd)1/2−2×(γsp・γyp)1/2 (式5)
である。ここで、γwdは水の表面エネルギーの分散性成分、γwpは水の表面エネルギーの極性成分、γydはヨウ化メテレンの表面エネルギーの分散性成分、γypはヨウ化メチレンの表面エネルギーの極性成分である。
(3) Surface energy Contact angle: θw, θy of water having a known surface energy and methylene iodide with respect to the transparent conductive thin film using a contact angle meter (“CA-X type” manufactured by Kyowa Interface Science Co., Ltd.) It measured on 25 degreeC and 50% RH conditions. Using these measured values, the surface energy γs of the transparent conductive thin film was calculated as follows.
The surface energy γs of the transparent conductive thin film is the sum of the dispersive component γsd and the polar component γsp. That is,
γs = γsd + γsp (Formula 1)
From the Young equation,
γs = γsw + γw · cos θw (Formula 2)
γs = γsy + γy · cos θy (Formula 3)
Here, γsw is the tension acting between the transparent conductive thin film and water, γsw is the tension acting between the transparent conductive thin film and methylene iodide, γw is the surface energy of water, and γy is the surface energy of methylene iodide. It is.
From the Fowkes equation,
γ sw = γ s + γ w −2 × (γ sd · γ wd ) 1/2 −2 × (γ sp · γ wp ) 1/2 (Formula 4)
γ sy = γ s + γ y −2 × (γ sd · γ yd ) 1/2 −2 × (γ sp · γ yp ) 1/2 (Formula 5)
It is. Where γ wd is the dispersive component of the surface energy of water, γ wp is the polar component of the surface energy of water, γ yd is the dispersive component of the surface energy of methyl iodide, and γ yp is the surface energy of methylene iodide. It is a polar component.
式1〜5の連立方程式を解くことにより、透明導電性薄膜の表層張力γs=γsd+γspを算出できる。この時、水の表面エネルギー(γw):72.8mN/m、よう化メチレンの表面エネルギー(γy):50.5mN/m、水の表面エネルギーの分散性成分(γwd):21.8mN/m、水の表面エネルギーの極性成分(γwp):51.0mN/m、ヨウ化メチレンの表面エネルギーの分散性成分(γyd):49.5mN/m、ヨウ化メテレンの表面エネルギーの極性成分(γyp):1.3mN/mを用いた。 By solving the simultaneous equations of Equations 1 to 5, the surface tension γ s = γ sd + γ sp of the transparent conductive thin film can be calculated. At this time, the surface energy of water (γ w ): 72.8 mN / m, the surface energy of methylene iodide (γ y ): 50.5 mN / m, the dispersive component of the surface energy of water (γ wd ): 21. 8 mN / m, polar component of surface energy of water (γ wp ): 51.0 mN / m, dispersive component of surface energy of methylene iodide (γ y d): 49.5 mN / m, surface energy of methylene iodide Polar component (γ yp ): 1.3 mN / m was used.
(4)I−V特性(光電流−電圧特性)
15mm2大の色素増感型太陽電池を形成し、下記の方法で光発電効率を算出した。ぺクセルテクノロジーズ社製ソーラーシュミレーター(PEC-L10)を用い入射光強度が100mW/cm2の模擬太陽光を、気温25℃、湿度50%の雰囲気で測定した。電流電圧測定装置(PECK 2400)を用いて、システムに印加するDC電圧を10mV/secの定速でスキャンし、素子の出力する光電流を計測することにより、光電流−電圧特性を測定し、光発電効率を算出した。
(4) IV characteristics (photocurrent-voltage characteristics)
A 15 mm 2 large dye-sensitized solar cell was formed, and the photovoltaic power generation efficiency was calculated by the following method. Using a solar simulator (PEC-L10) manufactured by Pexel Technologies, simulated sunlight with an incident light intensity of 100 mW / cm 2 was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 50%. Using a current-voltage measuring device (PECK 2400), the DC voltage applied to the system is scanned at a constant speed of 10 mV / sec, and the photocurrent output from the device is measured to measure the photocurrent-voltage characteristics. Photovoltaic efficiency was calculated.
[実施例1]
<易接着層の組成物(塗剤A)の作成>
2,6−ナフタレンジカルボン酸ジメチル66部、イソフタル酸ジメチル47部、5−ナトリウムスルホイソフタル酸ジメチル8部、エチレングリコール54部、ジエチレングリコール62部を反応器に仕込み、これにテトラブトキシチタン0.05部を添加して窒素雰囲気下で温度を230℃にコントロールして加熱し、生成するメタノールを留去させてエステル交換反応を行った。次いで反応系の温度を徐々に255℃まで上昇させ系内を1mmHgの減圧にして重縮合反応を行い、ポリエステルを得た。このポリエステル25部をテトラヒドロフラン75部に溶解させ、得られた溶液に10000回転/分の高速攪拌下で水75部を滴下して乳白色の分散体を得、次いでこの分散体を20mmHgの減圧下で蒸留し、テトラヒドロフランを留去し、固形分が25重量%のポリエステルの水分散体を得た。
[Example 1]
<Creation of easy-adhesion layer composition (Coating A)>
66 parts of dimethyl 2,6-naphthalenedicarboxylate, 47 parts of dimethyl isophthalate, 8 parts of dimethyl 5-sodium sulfoisophthalate, 54 parts of ethylene glycol and 62 parts of diethylene glycol were charged into the reactor, and 0.05 parts of tetrabutoxy titanium Was added and heated under a nitrogen atmosphere while controlling the temperature at 230 ° C., and the produced methanol was distilled off to conduct a transesterification reaction. Subsequently, the temperature of the reaction system was gradually raised to 255 ° C., and the pressure inside the system was reduced to 1 mmHg to carry out a polycondensation reaction to obtain a polyester. 25 parts of this polyester was dissolved in 75 parts of tetrahydrofuran, and 75 parts of water was dropped into the resulting solution under high-speed stirring at 10,000 rpm to obtain a milky white dispersion, and then this dispersion was subjected to a reduced pressure of 20 mmHg. Distillation was performed, and tetrahydrofuran was distilled off to obtain an aqueous dispersion of polyester having a solid content of 25% by weight.
次に、四つ口フラスコに、界面活性剤としてラウリルスルホン酸ナトリウム3部、およびイオン交換水181部を仕込んで窒素気流中で60℃まで昇温させ、次いで重合開始剤として過硫酸アンモニウム0.5部、亜硝酸水素ナトリウム0.2部を添加し、更にモノマー類である、メタクリル酸メチル30.1部、2−イソプロペニル−2−オキサゾリン21.9部、ポリエチレンオキシド(n=10)メタクリル酸39.4部、アクリルアミド8.6部の混合物を3時間にわたり、液温が60〜70℃になるよう調整しながら滴下した。滴下終了後も同温度範囲に2時間保持しつつ、攪拌下に反応を継続させ、次いで冷却して固形分が35%重量のアクリルの水分散体を得た。 Next, 3 parts of sodium lauryl sulfonate as a surfactant and 181 parts of ion-exchanged water are charged into a four-necked flask and the temperature is raised to 60 ° C. in a nitrogen stream, and then 0.5% ammonium persulfate is used as a polymerization initiator. Part, 0.2 part of sodium hydrogen nitrite is added, and further monomers 30.1 parts of methyl methacrylate, 21.9 parts of 2-isopropenyl-2-oxazoline, polyethylene oxide (n = 10) methacrylic acid A mixture of 39.4 parts and 8.6 parts of acrylamide was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. After completion of dropping, the reaction was continued with stirring while maintaining the same temperature range for 2 hours, and then cooled to obtain an acrylic aqueous dispersion having a solid content of 35% by weight.
一方で、シリカフィラー(平均粒径:100nm)(日産化学株式会社製 商品名スノーテックスZL)を0.2重量%、濡れ剤として、ポリオキシエチレン(n=7)ラウリルエーテル(三洋化成株式会社製 商品名ナロアクティーN−70)の0.3重量%添加した水溶液を作成した。
上記のポリエステルの水分散体8重量部、アクリルの水分散体7重量部と水溶液85重量部を混合して、塗剤Aを作成した。
On the other hand, 0.2% by weight of silica filler (average particle size: 100 nm) (trade name Snowtex ZL manufactured by Nissan Chemical Co., Ltd.), polyoxyethylene (n = 7) lauryl ether (Sanyo Chemical Co., Ltd.) as a wetting agent An aqueous solution containing 0.3% by weight of the trade name NAROACTY N-70) was prepared.
A coating agent A was prepared by mixing 8 parts by weight of the polyester aqueous dispersion, 7 parts by weight of the acrylic water dispersion, and 85 parts by weight of the aqueous solution.
<プラスチックフィルムの作成>
固有粘度が0.63で、実質的に粒子を含有しないポリエチレン−2,6−ナフタレンジカルボキシレートのペレットを170℃で6時間乾燥後、押出機ホッパーに供給し、溶融温度305℃で溶融し、平均目開きが17μmのステンレス鋼細線フィルターで濾過し、3mmのスリット状ダイを通して表面温度60℃の回転冷却ドラム上で押出し、急冷して未延伸フィルムを得た。このようにして得られた未延伸フィルムを120℃にて予熱し、さらに低速、高速のロール間で15mm上方より850℃のIRヒーターにて加熱して縦方向に3.1倍に延伸した。この縦延伸後のフィルムの片面に上記の塗剤Aを乾燥後の塗膜厚みが0.25μmになるようにロールコーターで塗工し易接層を形成した。
<Creation of plastic film>
Polyethylene-2,6-naphthalene dicarboxylate pellets having an intrinsic viscosity of 0.63 and containing substantially no particles are dried at 170 ° C. for 6 hours, then fed to an extruder hopper, and melted at a melting temperature of 305 ° C. Then, it was filtered through a stainless steel fine wire filter having an average opening of 17 μm, extruded through a 3 mm slit die on a rotary cooling drum having a surface temperature of 60 ° C., and rapidly cooled to obtain an unstretched film. The unstretched film thus obtained was preheated at 120 ° C., and further heated by an IR heater at 850 ° C. from above 15 mm between low-speed and high-speed rolls and stretched 3.1 times in the longitudinal direction. The easy-coating layer was formed by applying the coating agent A on one side of the film after the longitudinal stretching with a roll coater so that the coating thickness after drying was 0.25 μm.
続いてテンターに供給し、140℃にて横方向に.3.3倍に延伸した。得られた二軸配向フィルムを245℃の温度で5秒間熱固定し、固有粘度が0.58dl/g、厚み125μmのフィルムとし、その後、このフィルムを懸垂状態で、弛緩率0.7%、温度205℃で熱弛緩させて、プラスチックフィルムとした。このプラスチックフィルムの易接層側に、UV硬化性ハードコート剤(JSR製 デソライトR7501)を厚さ約5μmになるよう塗布し、UV硬化させてハードコート層を形成した。 Subsequently, it was supplied to the tenter and laterally at 140 ° C. 3. Stretched 3 times. The obtained biaxially oriented film was heat-fixed at a temperature of 245 ° C. for 5 seconds to form a film having an intrinsic viscosity of 0.58 dl / g and a thickness of 125 μm, and then the film was suspended, with a relaxation rate of 0.7%, It was heat relaxed at a temperature of 205 ° C. to obtain a plastic film. A UV curable hard coat agent (Desolite R7501 from JSR) was applied to the easy-contact layer side of the plastic film so as to have a thickness of about 5 μm, and UV cured to form a hard coat layer.
<透明導電層形成>
ハードコート層が形成された面のうえに、ITOターゲット(錫濃度は二酸化錫換算で10重量%)を用いた直流マグネトロンスパッタリング法により、膜厚400nmのITOからなる透明導電層を形成した。透明導電層のスパッタリング法による形成は、プラズマの放電前にチャンバー内を5×10−4Paまで排気した後、チャンバー内にアルゴンと酸素の混合ガス(酸素濃度は0.5体積%)を導入して圧力を0.3Paとし、ITOターゲットに1000W印加して行った。透明導電層の表面抵抗値は15Ω/□であり、表面エネルギーは30.0mN/mであった。
<Transparent conductive layer formation>
On the surface on which the hard coat layer was formed, a transparent conductive layer made of ITO having a film thickness of 400 nm was formed by a direct current magnetron sputtering method using an ITO target (tin concentration is 10% by weight in terms of tin dioxide). The transparent conductive layer is formed by sputtering, after the inside of the chamber is evacuated to 5 × 10 −4 Pa before plasma discharge, and then a mixed gas of argon and oxygen (oxygen concentration is 0.5% by volume) is introduced into the chamber. Then, the pressure was set to 0.3 Pa, and 1000 W was applied to the ITO target. The surface resistance value of the transparent conductive layer was 15Ω / □, and the surface energy was 30.0 mN / m.
次いで、常圧プラズマ表面処理装置(積水化学工業製AP−T03−L)を用いて、窒素気流下(60L/分)、1m/分にて、透明導電層表面にプラズマ処理を施し、透明導電層を有するプラスチックフィルムを得た。透明導電層の表面抵抗値は16Ω/□、表面エネルギーは70.5mN/mであった。 Next, using a normal pressure plasma surface treatment apparatus (AP-T03-L, manufactured by Sekisui Chemical Co., Ltd.), the surface of the transparent conductive layer is subjected to plasma treatment at 1 m / min under a nitrogen stream (60 L / min) to obtain a transparent conductive layer. A plastic film with a layer was obtained. The transparent conductive layer had a surface resistance value of 16Ω / □ and a surface energy of 70.5 mN / m.
<対極の形成>
分散剤としてポリスチレンスルホン酸を用いたポリエチレンジオキシチオフェン(以下「PEDOT−PSS」という)の水分散液であるアグファ製S-300に、イソプロパノールを添加し、PEDOT−PSSを1重量%含有する分散液とした。乾燥厚みが50nmになるようにメイヤバーを用いてこのPEDOT−PSS分散液を、上記透明導電層を有するプラスチックフィルムの透明導電層のうえに塗布し、110℃で1分乾燥することで対極を形成した。PEDOT−PSS分散液は均一に塗布することが可能であった。
<Formation of counter electrode>
Dispersion containing 1% by weight of PEDOT-PSS by adding isopropanol to S-300 manufactured by Agfa, which is an aqueous dispersion of polyethylene dioxythiophene (hereinafter referred to as “PEDOT-PSS”) using polystyrene sulfonic acid as a dispersant. Liquid. The PEDOT-PSS dispersion is applied onto the transparent conductive layer of the plastic film having the transparent conductive layer using a Mayer bar so that the dry thickness is 50 nm, and the counter electrode is formed by drying at 110 ° C. for 1 minute. did. The PEDOT-PSS dispersion could be applied uniformly.
<作用電極の形成>
ぺクセルテクノロジーズ社製の酸化チタン分散液PECC01をよく攪拌したのち、100μmのドクターブレードを用い、上記透明導電層を有するプラスチックフィルムの透明導電層のうえに塗布し、その後大気中150℃で5分乾燥することで多孔質半導体層を形成し、これを、ルテニウム錯体(Ru535bisTBA、Solaronix製)の300μMエタノール溶液中に24時間浸漬し、表面にルテニウム錯体を吸着させることで作用電極を作成した。
<Formation of working electrode>
After thoroughly stirring Peccel Technologies' titanium oxide dispersion PECC01, using a 100 μm doctor blade, it was applied on the transparent conductive layer of the plastic film having the transparent conductive layer, and then at 150 ° C. in the atmosphere for 5 minutes. The porous semiconductor layer was formed by drying, and this was immersed in a 300 μM ethanol solution of ruthenium complex (Ru535bisTBA, manufactured by Solaronix) for 24 hours, and the working electrode was prepared by adsorbing the ruthenium complex on the surface.
<色素増感型太陽電池の作成>
上記の対極と作用電極とを、熱圧着性のポリエチレンフィルム製フレーム型スペーサー(厚さ20μm)を介して重ね合わせ、スペーサー部を120℃に加熱し、両電極を圧着する。さらに、そのエッジ部をエポキシ樹脂接着剤でシールする。電解質溶液(0.5Mのヨウ化リチウムと0.05Mのヨウ素と0.5Mのtert−ブチルピリジン、平均粒径20μmのナイロンビーズ3重量%を含む3−メトキシプロピオニトリル溶液)を注入した後、エポキシ系接着剤でシールした。
<Creation of dye-sensitized solar cell>
The counter electrode and the working electrode are overlapped via a thermocompression-bondable polyethylene film frame spacer (thickness 20 μm), the spacer portion is heated to 120 ° C., and both electrodes are pressure-bonded. Further, the edge portion is sealed with an epoxy resin adhesive. After injecting an electrolyte solution (3-methoxypropionitrile solution containing 0.5% lithium iodide, 0.05M iodine, 0.5M tert-butylpyridine, 3% by weight of nylon beads having an average particle size of 20 μm) And sealed with an epoxy adhesive.
完成した色素増感型太陽電池のI−V特性の測定(有効面積25mm2)を行った結果、開放電圧、短絡電流密度、曲線因子はそれぞれ、0.70V、6.2mA/cm2、0.30であり、その結果、光発電効率は1.4%であった。 As a result of measuring the IV characteristics of the completed dye-sensitized solar cell (effective area 25 mm 2 ), the open circuit voltage, short circuit current density, and fill factor were 0.70 V, 6.2 mA / cm 2 , 0, respectively. As a result, the photovoltaic power generation efficiency was 1.4%.
[実施例2]
実施例1と同様に、プラスチックフィルムを作成し、ハードコート、透明導電層、多孔質半導体層を形成した。対極を作成する際に、PEDOT−PSSの乾燥時の厚みが100nmになるようにメイヤーバーを変えた以外は、実施例1と同様とし色素増感型太陽電池を作成した。完成した色素増感型太陽電池のI−V特性の測定(有効面積25mm2)を行った結果、開放電圧、短絡電流密度、曲線因子はそれぞれ、0.70V、7.5mA/cm2、0.32であり、その結果、光発電効率は1.6%であった。
[Example 2]
Similar to Example 1, a plastic film was prepared, and a hard coat, a transparent conductive layer, and a porous semiconductor layer were formed. A dye-sensitized solar cell was prepared in the same manner as in Example 1 except that the Meyer bar was changed so that the thickness when PEDOT-PSS was dried was 100 nm when the counter electrode was prepared. As a result of measuring the IV characteristics (effective area 25 mm 2 ) of the completed dye-sensitized solar cell, the open circuit voltage, short circuit current density, and fill factor were 0.70 V, 7.5 mA / cm 2 , 0, respectively. As a result, the photovoltaic power generation efficiency was 1.6%.
[比較例1]
実施例1と同様に、プラスチックフィルムを作成し、ハードコートを作成した。透明導電層を形成する際にスパッタ処理を行わなかったこと以外は、実施例1と同様の方法でPEDOT−PSSを透明導電層に塗布した。結果PEDOT−PSS分散液は透明導電層上で凝集し均一に塗布することができなかった。
[Comparative Example 1]
As in Example 1, a plastic film was prepared and a hard coat was prepared. PEDOT-PSS was applied to the transparent conductive layer in the same manner as in Example 1 except that the sputtering process was not performed when forming the transparent conductive layer. Results The PEDOT-PSS dispersion liquid aggregated on the transparent conductive layer and could not be applied uniformly.
本発明は、色素増感型太陽電池の対極として好適に利用することができる。 The present invention can be suitably used as a counter electrode of a dye-sensitized solar cell.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004340120A JP4647292B2 (en) | 2004-11-25 | 2004-11-25 | Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004340120A JP4647292B2 (en) | 2004-11-25 | 2004-11-25 | Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2006155907A true JP2006155907A (en) | 2006-06-15 |
JP4647292B2 JP4647292B2 (en) | 2011-03-09 |
Family
ID=36633963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004340120A Active JP4647292B2 (en) | 2004-11-25 | 2004-11-25 | Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4647292B2 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009041269A1 (en) * | 2007-09-26 | 2009-04-02 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
WO2010095651A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
WO2010095648A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
WO2010095649A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
WO2010095650A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Complex conductive polymer composition, manufacturing method thereof, solution containing said composition, and applications for said composition |
WO2010095652A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
CN101923958A (en) * | 2010-09-08 | 2010-12-22 | 天津大学 | Method for preparing energy storage electrode of dye-sensitized solar battery |
US20110062829A1 (en) * | 2008-05-29 | 2011-03-17 | Murata Manufacturing Co., Ltd. | Sheet-type vibrator and acoustic apparatus |
KR101156585B1 (en) | 2009-11-03 | 2012-06-20 | 국립대학법인 울산과학기술대학교 산학협력단 | Dye-sensitized sollar cell and its fabrication method |
KR101193969B1 (en) | 2011-02-22 | 2012-10-24 | 한양대학교 산학협력단 | Fabrication method of counter electrode for dye-sensitized solar cells using polypyrrole nanoparticles and counter electrode for dye-sensitized solar cells fabricated by the method |
US8363863B2 (en) | 2008-05-29 | 2013-01-29 | Murata Manufacturing Co., Ltd. | Piezoelectric speaker, speaker apparatus, and tactile feedback apparatus |
CN103050289A (en) * | 2013-01-18 | 2013-04-17 | 中国海洋大学 | Transparent polyaniline counter electrode-base two-sided dye-sensitized solar cell as well as preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004319131A (en) * | 2003-04-11 | 2004-11-11 | Sony Corp | Manufacturing method of photoelectric transfer element, photoelectric transfer element, manufacturing method of electronic device, electronic device and forming method of metal membrane and laminate structure |
JP2004319130A (en) * | 2003-04-11 | 2004-11-11 | Sony Corp | Manufacturing method of photoelectric transfer device, photoelectric transfer element, manufacturing method of electronic device, electronic device and forming method of semiconductor particulate layer and laminate structure |
-
2004
- 2004-11-25 JP JP2004340120A patent/JP4647292B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004319131A (en) * | 2003-04-11 | 2004-11-11 | Sony Corp | Manufacturing method of photoelectric transfer element, photoelectric transfer element, manufacturing method of electronic device, electronic device and forming method of metal membrane and laminate structure |
JP2004319130A (en) * | 2003-04-11 | 2004-11-11 | Sony Corp | Manufacturing method of photoelectric transfer device, photoelectric transfer element, manufacturing method of electronic device, electronic device and forming method of semiconductor particulate layer and laminate structure |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2192650A1 (en) * | 2007-09-26 | 2010-06-02 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
WO2009041269A1 (en) * | 2007-09-26 | 2009-04-02 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
TWI424601B (en) * | 2007-09-26 | 2014-01-21 | Dai Ichi Kogyo Seiyaku Co Ltd | A method for manufacturing a conductive polymer electrode and a dye-sensitized solar cell provided with the same |
JP5215314B2 (en) * | 2007-09-26 | 2013-06-19 | 第一工業製薬株式会社 | Method for producing conductive polymer electrode and dye-sensitized solar cell provided with the same |
US8377504B2 (en) | 2007-09-26 | 2013-02-19 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Method for producing electroconductive polymer electrode, and dye-sensitized solar cell equipped with the same |
KR101177188B1 (en) * | 2007-09-26 | 2012-08-24 | 다이이치 고교 세이야쿠 가부시키가이샤 | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
EP2192650A4 (en) * | 2007-09-26 | 2011-07-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
US8148879B2 (en) * | 2008-05-29 | 2012-04-03 | Murata Manufacturing Co., Ltd. | Sheet-type vibrator and acoustic apparatus |
US8363863B2 (en) | 2008-05-29 | 2013-01-29 | Murata Manufacturing Co., Ltd. | Piezoelectric speaker, speaker apparatus, and tactile feedback apparatus |
US20110062829A1 (en) * | 2008-05-29 | 2011-03-17 | Murata Manufacturing Co., Ltd. | Sheet-type vibrator and acoustic apparatus |
JP5435436B2 (en) * | 2009-02-17 | 2014-03-05 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition |
US9034211B2 (en) | 2009-02-17 | 2015-05-19 | Soken & Chemical & Engineering Co., Ltd. | Composite conductive polymer composition, method of manufacturing the same, solution containing the composition, use of the composition |
JP5869880B2 (en) * | 2009-02-17 | 2016-02-24 | 綜研化学株式会社 | Composite conductive polymer solution and method for producing the same |
JP5869881B2 (en) * | 2009-02-17 | 2016-02-24 | 綜研化学株式会社 | Composite conductive polymer solution and method for producing the same |
JPWO2010095650A1 (en) * | 2009-02-17 | 2012-08-30 | 綜研化学株式会社 | Composite conductive polymer composition, production method thereof, solution containing the composition, and use of the composition |
JP5738178B2 (en) * | 2009-02-17 | 2015-06-17 | 綜研化学株式会社 | Composite conductive polymer composition, production method thereof, solution containing the composition, and use of the composition |
WO2010095652A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
WO2010095650A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Complex conductive polymer composition, manufacturing method thereof, solution containing said composition, and applications for said composition |
US9058916B2 (en) | 2009-02-17 | 2015-06-16 | Soken Chemical & Engineering Co., Ltd. | Composite conductive polymer composition, method of manufacturing the same, solution containing the composition, use of the composition |
WO2010095649A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
WO2010095648A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
WO2010095651A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
JP5435437B2 (en) * | 2009-02-17 | 2014-03-05 | 綜研化学株式会社 | COMPOSITE CONDUCTIVE POLYMER COMPOSITION, PROCESS FOR PRODUCING THE SAME, SOLUTION CONTAINING THE COMPOSITION, AND USE OF THE COMPOSITION |
CN102224197A (en) * | 2009-02-17 | 2011-10-19 | 综研化学株式会社 | Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition |
KR101156585B1 (en) | 2009-11-03 | 2012-06-20 | 국립대학법인 울산과학기술대학교 산학협력단 | Dye-sensitized sollar cell and its fabrication method |
CN101923958A (en) * | 2010-09-08 | 2010-12-22 | 天津大学 | Method for preparing energy storage electrode of dye-sensitized solar battery |
KR101193969B1 (en) | 2011-02-22 | 2012-10-24 | 한양대학교 산학협력단 | Fabrication method of counter electrode for dye-sensitized solar cells using polypyrrole nanoparticles and counter electrode for dye-sensitized solar cells fabricated by the method |
CN103050289A (en) * | 2013-01-18 | 2013-04-17 | 中国海洋大学 | Transparent polyaniline counter electrode-base two-sided dye-sensitized solar cell as well as preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
JP4647292B2 (en) | 2011-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hashmi et al. | Review of materials and manufacturing options for large area flexible dye solar cells | |
JP4600284B2 (en) | Transparent conductive laminate, manufacturing method thereof, and device using transparent conductive laminate | |
TWI390743B (en) | Pigment for a dye-sensitized solar cell, an electrode for a dye-sensitized solar cell, and a method of manufacturing the same | |
JP4647292B2 (en) | Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell using the same | |
JP4660252B2 (en) | Dye-sensitized solar cell laminated film and dye-sensitized solar cell electrode using the same | |
US8039735B2 (en) | Laminated film for dye-sensitized solar cell and electrode for dye-sensitized solar cell, and process for their production | |
Keothongkham et al. | Electrochemically deposited polypyrrole for dye‐sensitized solar cell counter electrodes | |
WO2008007448A1 (en) | Dye-sensitized solar cell, and electrode and laminated film therefor | |
US20230104362A1 (en) | Dye sensitized photovoltaic cells | |
JP5154743B2 (en) | Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell using the same | |
JP4710251B2 (en) | Method for producing metal oxide film | |
JP4456894B2 (en) | Dye-sensitized solar cell laminated film and dye-sensitized solar cell electrode using the same | |
JP5015467B2 (en) | Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell | |
JP4456883B2 (en) | Dye-sensitized solar cell laminate film and dye-sensitized solar cell electrode using the same | |
JP2007149600A (en) | Laminated film for dye-sensitized solar cell and electrode for dye-sensitized solar cell using it | |
JP2007018951A (en) | Electrode for dye-sensitized solar cell | |
JP5031997B2 (en) | Electrode for dye-sensitized solar cell and method for producing the same | |
JP5059289B2 (en) | Dye-sensitized solar cell laminate, dye-sensitized solar cell electrode, and method for producing the same | |
JP2011040288A (en) | Method of manufacturing semiconductor film, the semiconductor film, and dye-sensitized solar cell | |
JP2005251605A (en) | Dye-sensitized solar cell, module, and manufacturing method of dye-sensitized solar cell | |
CN105070510A (en) | Flexible dye-sensitized solar cell and preparation method thereof | |
TW200947789A (en) | Electrode with electrode-protection partition wall and dye-sensitized solar cell comprising the electrode | |
JP4922568B2 (en) | Dye-sensitized solar cell electrode | |
JP4456933B2 (en) | Method for producing dye-sensitized solar cell electrode | |
CN110431648A (en) | The manufacturing method of laminated body and organic system solar battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070508 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100720 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100916 |
|
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: 20101109 |
|
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: 20101208 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131217 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4647292 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |