WO2006038495A1 - 色素増感太陽電池及びその製造方法 - Google Patents
色素増感太陽電池及びその製造方法 Download PDFInfo
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- WO2006038495A1 WO2006038495A1 PCT/JP2005/017744 JP2005017744W WO2006038495A1 WO 2006038495 A1 WO2006038495 A1 WO 2006038495A1 JP 2005017744 W JP2005017744 W JP 2005017744W WO 2006038495 A1 WO2006038495 A1 WO 2006038495A1
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- WO
- WIPO (PCT)
- Prior art keywords
- dye
- solar cell
- conductive film
- metal oxide
- side electrode
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 17
- 230000003746 surface roughness Effects 0.000 claims abstract description 15
- 238000005498 polishing Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 10
- 238000009499 grossing Methods 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 206010070834 Sensitisation Diseases 0.000 claims 3
- 230000008313 sensitization Effects 0.000 claims 3
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 25
- 239000004065 semiconductor Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 13
- 239000011521 glass Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- -1 etc. Chemical compound 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- KQNVWRXGMSYLDH-UHFFFAOYSA-N 2-methyl-3-propyl-1h-imidazol-3-ium;iodide Chemical compound [I-].CCC[N+]=1C=CNC=1C KQNVWRXGMSYLDH-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
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJLPWIOVCYTBQS-UHFFFAOYSA-N [NH+]1=CNC=C1.I(=O)(=O)[O-] Chemical compound [NH+]1=CNC=C1.I(=O)(=O)[O-] KJLPWIOVCYTBQS-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 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
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Definitions
- the present invention relates to a dye-sensitized solar cell formed from a metal oxide semiconductor electrode, a dye for absorbing light, and an electrolyte.
- a solar cell that can be manufactured at low cost, for example, a dye-sensitized solar cell using a material in which a photosensitizing dye such as a ruthenium metal complex is adsorbed on an oxide semiconductor such as titanium oxide. Proposed and reproved.
- a photosensitizing dye such as a ruthenium metal complex
- the dye-sensitized solar cell is formed on the transparent conductive layer side of a transparent insulating material such as a transparent glass plate or a transparent resin plate provided with a transparent conductive layer such as indium-added tin oxide.
- Electrolyte liquid is sealed between transparent insulating materials.
- the electrons of the dye that absorbed the light are excited in the negative electrode, the excited electrons move to the semiconductor layer, and are further guided to the transparent electrode, and from the conductive layer in the positive electrode.
- the electrolyte is reduced by the coming electrons.
- the reduced electrolyte is oxidized by transferring electrons to the dye, and the dye-sensitized solar cell is thought to generate electricity during this cycle.
- dye-sensitized solar cells have lower generator energy efficiency with respect to irradiation light energy than silicon solar cells, and it is important to increase the efficiency to produce effective dye-sensitized solar cells. It has become a challenge.
- the efficiency of dye-sensitized solar cells constitute it Various characteristics are considered to be affected by the characteristics of each element and the combination of these elements, and various attempts have been made.
- Patent Document 1 JP 2002-151168 A
- Patent Document 2 Japanese Patent Laid-Open No. 2003-142169
- Patent Document 3 JP 2004-193321 A
- Patent Document 4 Japanese Patent Laid-Open No. 2000-150005
- Patent Document 5 Japanese Patent Laid-Open No. 2003-92417
- JP2002-151168A describes a semiconductor layer in which a dye functioning as a photosensitizer is adsorbed on a semiconductor such as titanium oxide titanium, and this semiconductor layer includes a reverse electron injection preventing layer and a photoelectric conversion layer. Consists of layers. Here, it is described that the photoelectric conversion layer has a surface roughness coefficient of 100 to 3000 and a film thickness of 1 to 50 ⁇ m.
- JP2003-142169A discloses that a dye-sensitized metal oxide semiconductor electrode is formed by a vapor deposition method on an electrode composed of a substrate, a transparent electrode, and a dye-sensitized metal oxide semiconductor electrode.
- JP2004-193321A describes a semiconductor electrode in which a base material, a transparent conductive film, and a porous titanium oxide film are laminated in this order. This titanium oxide hydrolyzes titanium isopropoxide.
- titanium oxide fine particles are added to the solution and mixed to form a coating solution, which is applied to the surface of the transparent conductive film, baked, and then impregnated with the Ru complex solution.
- the titanium oxide film is formed by aggregation of titanium oxide particles, and the particle diameter is 10-50.
- these documents do not teach the surface roughness of the transparent conductive film.
- JP2000-150005A has an electrode plate in which one surface of a conductive substrate is etched to have a surface roughness of 10 to 10 and a dye-containing metal oxide film is formed thereon, and a transparent conductive film.
- a solar cell having a structure in which an electrolyte is injected between a substrate and a substrate is described.
- JP2003-92417 A describes smoothness of a transparent conductive film, but this relates to a dry solar cell that does not require an electrolyte, and prevents protrusions from protruding the barrier layer. To solve the peculiar problems of dry solar cells of a specific structure. The
- the present invention relates to a dye having an electrolyte disposed between a surface-side electrode obtained by laminating a substrate, a transparent conductive film, and a sensitizing dye-adsorbing metal oxide in this order, and a counter-surface-side electrode provided to face the electrode. It aims at improving the energy conversion efficiency of a sensitized solar cell.
- the present inventors have found that the contact between the transparent conductive film and the sensitizing dye-adsorbing metal oxide is important, and that the surface roughness of the transparent conductive film is within a certain range.
- the present inventors have found that energy conversion efficiency can be improved and have completed the present invention.
- the dye-sensitized solar cell of the present invention includes a surface-side electrode in which a substrate, a transparent conductive film, and a sensitizing dye-adsorbing metal oxide are stacked in this order, and a counter-surface-side electrode provided to face the surface-side electrode.
- the surface roughness Ra of the surface in contact with the sensitizing dye adsorbing metal oxide of the transparent conductive film of the surface side electrode is smoothed in the range of 0.1 to 10 mm. It is characterized by being.
- a transparent conductive film is formed by forming a transparent conductive film on a substrate by a vapor deposition method or a spray method, and then smoothing the surface thereof.
- the smoothing treatment is performed by polishing treatment, and 3) the sensitizing dye adsorbing metal oxide, the physical strength, the sensitizing dye adsorbing titanium oxide, and having an average particle diameter of 5 to 500 nm. It is preferable to satisfy at least 1 or more.
- a transparent conductive film is formed on a substrate by a vapor deposition method, and then the surface is smoothed to have a surface roughness Ra in the range of 0.1 to 10 nm. It can be produced by providing a layer of sensitized dye-adsorbed metal oxide.
- the basic structure of the dye-sensitized solar cell according to the present invention includes a surface electrode 10 in which a conductive layer 2 and a dye-adsorbing metal oxide layer 3 are laminated in this order on a substrate 1, and a conductive material on the substrate 4.
- the counter electrode 11 provided with the layer 5 is provided, and the electrolyte 6 is disposed between the two electrodes.
- the dye adsorbing metal oxide layer 3 is provided on the inner surface side of the surface electrode 10 and is referred to as a semiconductor electrode.
- the dye-adsorbing metal oxide layer also has a sensitizing dye power that exists so as to fill a gap between metal oxide particles such as titanium oxide particles and the particles or to cover the surface of the particles. Light enters from the surface electrode 10 side.
- the substrate 1 used in the dye-sensitized solar cell is not particularly limited as long as it is a transparent insulating material.
- examples thereof include a normal glass plate and a plastic plate, and the base material is flexible.
- the base material is flexible.
- it is a heat resistant material that can withstand the process of baking titanium oxide on a base material with an upper limit of about 500 ° C. Is mentioned.
- a conductive layer 2 is provided on the surface of the substrate 1 so as not to impair the transparency of the base material.
- ITO, FTO, ATO or so-called transparent electrodes known as so-called transparent electrodes are used.
- a metal layer having a thickness that does not impair the transparency may be used.
- the method of providing these conductive layers is not particularly limited, and includes sputtering, vapor deposition VD, and PVD), spraying, laser ablation, or pasting materials for spin coating, bar coating, and screen printing. A known method such as a method can be used. However, spraying or sputtering or vapor deposition performed in the gas phase is suitable.
- the surface roughness Ra of the transparent conductive layer 2 formed in this way is set to a range of 0.1 to 10 nm, preferably 1 to 10 nm, more preferably 1 to 5 nm.
- Such surface roughness may be achieved by selecting a method or conditions for providing a conductive layer.
- a surface roughness Ra exceeding 10 nm is required. It is preferable to create first and then smooth this.
- As a smoothing treatment method ultrafine such as alumina Although there are methods of polishing using a slurry of particles and other chemical treatments such as mechanical treatment and etching, polishing is preferred.
- the surface of the transparent conductive film 2 formed on the glass substrate 1 has irregularities, which increases the surface roughness. Therefore, a smoothing process is performed to reduce the unevenness. As a result, a transparent conductive film 2 having a flat surface as shown in FIG. 3 is obtained.
- the same reference numerals mean the same unless otherwise specified.
- a dye-adsorbing metal oxide layer 3 that is, a semiconductor electrode is provided.
- a sensitizing dye is adsorbed thereto.
- the metal oxide what is known as a photoelectric conversion material can be used, and titanium oxide, zinc oxide, acid-tandane, and the like are preferable.
- the acid titanium may be an anatase type, a rutile type, or the like, titanium hydroxide, or a hydrous acid titanium.
- at least one of Nb, V, or Ta may be doped so as to have a weight concentration (as a metal element) of 30 ppm to 5% with respect to titanium oxide.
- Such metal oxides can be used in the present invention, but fine particles having an average particle size of ⁇ 500 nm, preferably 10-200 nm are preferred. In the case of such a particle diameter, it is considered that the contact area between the conductive film subjected to the smoothing treatment and the metal oxide particles is increased, thereby reducing the resistance. However, since the adhesive strength between the transparent conductive film 2 and the dye-adsorbed metal oxide layer 3 is reduced when the smoothing treatment is performed, conventionally, the smoothing treatment for such a purpose is performed! It was a thing.
- the force for forming the metal oxide film on the transparent electrode 2 is not particularly limited.
- a paste-coated metal oxide is spin coated, printed, spray coated, etc. These methods may be used. It is also possible to sinter for the purpose of sintering a metal oxide such as titanium oxide after film formation.
- a dye is adsorbed on the metal oxide to obtain a dye adsorbed acid titanium.
- the dye enters the periphery of the metal oxide particles, but also enters the inside of the metal oxide particles if the metal oxide particles are porous.
- the type of sensitizing dye is not particularly limited! /, But cis-L-bis (2,2'-bibilidyl-4,4'-dicarboxylate) ruthenium (II) complex
- it is a ruthenium complex such as L (where L is halogen, CN or SCN).
- the method for adsorbing the dye is not particularly limited, but the one in which the conductive film 2 and the metal oxide layer are formed on the substrate 1 is immersed in a dye solution in which the dye is dissolved in an appropriate solvent. , And so-called impregnation method.
- This surface electrode 10 acts as a negative electrode.
- the other electrode (counter electrode) 11 acting as the positive electrode is disposed to face the surface electrode 10 as shown in FIG.
- the electrode to be the positive electrode may be a conductive metal or the like, or may be a substrate 4 such as a normal glass plate or plastic plate provided with a conductive film 5 such as a metal film or carbon film.
- An electrolyte layer is provided between the surface electrode 10 serving as the negative electrode and the counter electrode 11 serving as the positive electrode.
- the type of the electrolyte layer is not particularly limited as long as it contains an acid-reducing species for reducing the dye after photoexcitation and electron injection into the semiconductor, and even if it is a liquid electrolyte Well, it may be a gel electrolyte obtained by adding a known gelling agent (polymer or low molecular weight gelling agent) to this.
- examples of the electrolyte used for the solution electrolyte include iodine and iodide (metal iodides such as Lil, Nal, KI, Csl, and Cal, tetraalkylammo-moydide, pyridi-mu-mo
- quaternary ammonium compounds such as ammonium bromide and pyridinium bromide
- iodo compounds such as sodium polysulfide, alkylthiol, and alkyldisulfide
- viologen dyes hydroquinones, quinones, etc. It is done.
- the electrolyte may be used as a mixture.
- the compound When a solvent is used for the electrolytic solution, it is desirable that the compound has a low viscosity and high ion mobility, and can exhibit excellent ion conductivity.
- solvents include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, and etherification such as dioxane and jetyl ether.
- chain ethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, methanol, ethanol, ethylene glycol monoethanolateolene, propyleneglycololenoethanol Alcohols such as quinoleateol, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, acetonitrile, glutarodiene -Tolyl compounds such as tolyl, methoxyacetonitrile, propio-tolyl, benzo-tolyl, dimethylsulfur Kishido, aprotic polar substances such as sulfolane, water and the like. These solvents can also be used as a mixture.
- a molten salt electrolyte having a high boiling point is preferred.
- the molten salt electrolyte composition includes a molten salt.
- the molten salt electrolyte composition is preferably liquid at room temperature.
- the main component, molten salt is a liquid at room temperature or a low melting point electrolyte, a common example of which is ⁇ Electrochemistry '', 1997, 65, 11, p. Pyridinium salts, imidazolium salts, triazolium salts and the like described in No. 923.
- the molten salt may be used alone or in combination of two or more.
- alkalis such as Lil, Nal, KI, LiBF, CF COOLi ⁇ CF COONa ⁇ LiSCN ⁇ NaSCN
- the molten salt electrolyte composition contains iodine.
- the molten salt electrolyte composition preferably has low volatility and preferably does not contain a solvent.
- the molten salt electrolyte composition may be used after gelation.
- the solar cell of the present invention exhibits excellent battery characteristics by combining the above negative electrode with a molten salt electrolyte consisting of methyl propyl imidazolium iodide, iodine, tert-butyl pyridine, and lithium iodide.
- the method of providing such an electrolyte layer is not particularly limited.
- a glass substrate with a transparent conductive film of 30 mm X 25 mm X 3 mm a glass substrate with FTO (fluorine-doped tin oxide) film made by Nippon Sheet Glass (trade name: Low-E glass) was used.
- FTO fluorine-doped tin oxide
- Low-E glass Low-E glass
- This FTO film was polished manually using an ultrafine slurry abrasive mainly composed of alumina and a fiber polishing pad.
- Four types of substrates with conductive films were obtained in which the polishing time was changed to 3, 6, 9, and 12 minutes.
- the average roughness Ra was determined by AFM, and each Ra was 8.65 nm (Example 1), 2.17 nm (Example 2), 1.96 nm (Example 3) and 1.72 (Example). 4).
- Fig. 4 shows AFM observations of the surface of each substrate when the polishing time is 0 minutes, 3 minutes, 6 minutes, 9 minutes, or 12 minutes.
- titanium oxide As the titanium oxide, a commercially available acid titanium paste (D paste made by Solaro-Tas Co.) was used.
- thermoplastic adhesive made of ionomer resin having a thickness of 50 ⁇ m on four sides of a 20mm x 5mm outer circumference on which a titanium oxide film is formed (trade name of Mitsui DuPont Polychemicals; Himira)
- the sheet was attached so that a gap of about 1 mm was provided at two locations on the outer periphery so that the electrolyte could be injected.
- This thermoplastic adhesive is not only a sealing material but also a spacer between both electrodes.
- a glass substrate on which a platinum film having a thickness of 10 nm serving as a positive electrode was formed by a sputtering method was bonded through the thermoplastic adhesive film so that the platinum side was opposed to the titanium oxide side.
- thermoplastic adhesive films From the gap between the thermoplastic adhesive films, 0.5 M Lil 0.5 M t-butylpyridine and a acetonitrile solution containing 0.05 M iodine as a main component were filled between the base material and the positive electrode using capillary action. . After filling the electrolyte, the gap was immediately sealed with an epoxy resin adhesive to obtain a dye-sensitized solar cell.
- a dye-sensitized solar cell was prepared in the same manner as in Example 1 except that the substrate with the conductive film prepared under the same conditions as in Example 1 was not polished (polishing time: 0 minutes) and was used as it was. Created.
- Example 1 Example 2
- Example 3 Example 4 Comparative Example 1 Transparent conductive film F T O F T O F T O F T O F T O F T O F T O
- Polishing time 3 minutes 6 minutes 9 minutes 12 minutes 1 Abrasive Alumina Alumina Alumina Alumina 1 Average roughness Ra 8.6onm 2.17nm 1.96nm 1.72 18.32nm Photoelectric conversion efficiency 7.56% 7.97% 8.10% 8.62% 7.21%
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JP2007042494A (ja) * | 2005-08-04 | 2007-02-15 | Fujikura Ltd | 作用極及びその製造方法、並びに太陽電池及びその製造方法 |
JP2008277249A (ja) * | 2006-12-21 | 2008-11-13 | Fujifilm Corp | 導電膜およびその製造方法 |
FR2961955A1 (fr) * | 2010-06-29 | 2011-12-30 | Saint Gobain | Cellule photovoltaique a colorant |
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JP2001085722A (ja) * | 1999-09-17 | 2001-03-30 | Mitsubishi Heavy Ind Ltd | 透明電極膜の製造方法及び太陽電池 |
JP2003142169A (ja) * | 2001-10-31 | 2003-05-16 | Bridgestone Corp | 有機色素増感型金属酸化物半導体電極及びこの半導体電極を有する太陽電池 |
JP2005317225A (ja) * | 2004-04-27 | 2005-11-10 | Enplas Corp | 色素増感型太陽電池、及び色素増感型太陽電池の光電極基板 |
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JP2001085722A (ja) * | 1999-09-17 | 2001-03-30 | Mitsubishi Heavy Ind Ltd | 透明電極膜の製造方法及び太陽電池 |
JP2003142169A (ja) * | 2001-10-31 | 2003-05-16 | Bridgestone Corp | 有機色素増感型金属酸化物半導体電極及びこの半導体電極を有する太陽電池 |
JP2005317225A (ja) * | 2004-04-27 | 2005-11-10 | Enplas Corp | 色素増感型太陽電池、及び色素増感型太陽電池の光電極基板 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007042494A (ja) * | 2005-08-04 | 2007-02-15 | Fujikura Ltd | 作用極及びその製造方法、並びに太陽電池及びその製造方法 |
JP2008277249A (ja) * | 2006-12-21 | 2008-11-13 | Fujifilm Corp | 導電膜およびその製造方法 |
FR2961955A1 (fr) * | 2010-06-29 | 2011-12-30 | Saint Gobain | Cellule photovoltaique a colorant |
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