WO2009157175A1 - 色素増感太陽電池 - Google Patents
色素増感太陽電池 Download PDFInfo
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- WO2009157175A1 WO2009157175A1 PCT/JP2009/002840 JP2009002840W WO2009157175A1 WO 2009157175 A1 WO2009157175 A1 WO 2009157175A1 JP 2009002840 W JP2009002840 W JP 2009002840W WO 2009157175 A1 WO2009157175 A1 WO 2009157175A1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a dye-sensitized solar cell.
- This application claims priority based on Japanese Patent Application No. 2008-164418 filed in Japan on June 24, 2008, the contents of which are incorporated herein by reference.
- a dye-sensitized solar cell is a solar cell that generates electricity by absorbing light and releasing electrons by a dye that absorbs sunlight.
- EPFL Michael Gratzel of autoimmune Polytechnique Federale de Lausanne
- the mechanism is that when light strikes the battery, the dye in the battery is excited and emits electrons. The electrons reach the transparent electrode via titanium oxide (TiO 2 ) and flow to the outside.
- the dye that has become a cation by emitting electrons receives the electrons supplied from the other electrode via iodine (I) in the electrolyte and returns to the original state.
- I iodine
- Requirement for the transparent electrode used in such a solar cell includes low resistance, thermal stability, chemical stability, high permeability, moisture resistance, low cost, and the like.
- a transparent conductive film for an electrode satisfying such conditions a tin oxide film (FTO) film doped with fluorine that is resistant to heat and chemical conditions is generally preferable to an indium oxide film (ITO film) doped with tin. .
- the inventors of the present invention are formed by laminating an FTO film having an orthorhombic part of the surface crystal structure on the surface of the ITO film as an electrode of a dye-sensitized solar cell. It has been found that when a transparent conductive film is used, high conversion efficiency and high output are exhibited, and the present invention has been completed.
- the present invention relates to the following.
- the electrode is a transparent conductive film formed by laminating an ITO film and an FTO film, and part or all of the crystal structure on the surface of the FTO film is orthorhombic.
- a dye-sensitized solar cell characterized by (2) The dye-sensitized solar cell according to (1), wherein the transparent conductive film has a sheet resistance value of 300 ⁇ / ⁇ or less.
- the transparent conductive film comprising the FTO / ITO laminated film of the present invention has an orthorhombic crystal structure on part or all of the FTO film surface, it has excellent heat resistance even when the film thickness is as thin as 5 to 20 nm. In addition, a dye-sensitized solar cell with high efficiency and high output can be obtained.
- a photoelectric conversion element 1 has a configuration in which a charge transport layer 4 is sandwiched between a substrate 2 (first substrate 2) and a substrate 3 (second substrate 3).
- the outer periphery of the transport layer 4 is sealed with a sealing material 5.
- the substrate 2 includes a base 6 (first base 6), an electrode layer 7 formed on the surface of the base 6, and a porous semiconductor layer 8 formed on the surface of the electrode layer 7. And facing the substrate 3 on the semiconductor layer 8 side.
- the substrate 3 has a base material 9 (second base material 9) and a counter electrode layer 10 formed on the surface of the base material 9, and faces the substrate 2 on the counter electrode layer 10 side.
- a sensitizing dye is carried on the porous semiconductor layer 8 formed on the surface of the electrode layer 7.
- One or both of the base material 6 and the electrode layer 7 formed on the surface thereof, or the base material 9 and the counter electrode layer 10 formed on the surface thereof are formed to be transparent, and light is incident on the semiconductor layer 8. It is possible.
- the transparent conductive film of the present invention is used for at least one of the electrode layer 7 and the counter electrode layer 10, and an ITO film is provided on the transparent substrate side, and an FTO film is laminated thereon. is there.
- Part or all of the surface (on the semiconductor layer 8 side) of the FTO film has an orthorhombic crystal structure.
- a part of the surface is orthorhombic means that at least the amount of orthorhombic crystal necessary for the change rate of the sheet resistance value to be within 1.5 times is included.
- the “sheet resistance change rate” can be obtained by dividing the sheet resistance value after heating the transparent conductive film at 350 ° C. for 1 hour by the sheet resistance value before heating.
- the orthorhombic crystal is one of seven crystal systems commonly used in the field of crystallography (cubic, hexagonal, rhombohedral, tetragonal, orthorhombic, monoclinic, and triclinic).
- the identification of the crystal system is performed by X-ray diffraction, neutron diffraction, electron diffraction or the like of single crystals and powders.
- the film thickness of the ITO film and the FTO film is not limited as long as it can be used as a transparent electrode of a solar cell, but the advantages of FTO and ITO can be utilized and the film of the FTO film can be used from the viewpoint of cost.
- the thickness is preferably 5 to 20 nm, and more preferably 10 to 20 nm.
- the thickness of the ITO film is preferably 20 to 60 nm, and more preferably 30 to 50 nm.
- Each of the FTO film and the ITO film is composed of at least one layer and can be laminated in multiple layers as long as the film thickness is not exceeded.
- the film thickness of ITO is 100 to 1000 nm, and the film thickness of FTO is 30 nm to 350 nm.
- the film thickness of the FTO film is required to be at least 30 nm for the protection of ITO, and the transparent conductive film of the present invention is characterized in that the film thickness of both ITO and FTO can be reduced. .
- the transparent conductive film of the present invention has excellent heat resistance against a temperature of 350 ° C. or higher even when the FTO film is as thin as 5 to 20 nm, and the rate of change in sheet resistance after heating for 1 hour at a temperature of 350 ° C. is 1. .5 times or less, preferably 1.2 times or less.
- the sheet resistance value is required to be 300 ⁇ / ⁇ or less especially when used as a transparent electrode of a dye-sensitized solar cell, but it should be 300 ⁇ / ⁇ or less by adjusting the film thickness. Is possible.
- the transparent conductive film of the present invention is laminated on a transparent substrate.
- the transparent substrate include glass such as alkali glass and quartz glass, polyester such as polycarbonate, polyethylene terephthalate, and polyarylate, polyethersulfone resin, amorphous polyolefin, polystyrene, and acrylic resin. These materials are appropriately selected according to the intended use of the final product.
- An inorganic oxide film can be formed between the transparent base material and the transparent conductive film as needed to prevent an alkali component or the like from entering the transparent conductive film.
- Transparent conductive film manufacturing method As a method for producing the transparent conductive film, any method can be used as long as it can form a film having the object physical property value of the present invention. Specifically, a sputtering method, an electron beam method, an ion plating method, a screen printing method. Or a chemical vapor deposition method (CVD method), a spray pyrolysis method, a pyrosol method, etc. can be illustrated, but especially a pyrosol method can be illustrated preferably.
- CVD method chemical vapor deposition method
- spray pyrolysis method a spray pyrolysis method
- a pyrosol method etc.
- the indium compound contained in the ITO film forming solution is preferably a substance that is thermally decomposed into indium oxide. Specifically, indium trisacetylacetonate (In (CH 3 COCHCOCH 3 ) 3 ), indium trisbenzoyl meta sulfonate (In (C 6 H 5 COCHCOC 6 H 5) 3), indium trichloride (InCl 3), indium nitrate (In (NO 3) 3) , indium triisopropoxide (In (OPr-i) 3 ) , etc. Can be illustrated.
- stannic chloride dimethyltin dichloride, dibutyltin dichloride, Examples thereof include tetrabutyltin, stania octoate (Sn (OCOC 7 H 15 ) 2 ), dibutyltin maleate, dibutylzuzuacetate, dibutyltin bisacetylacetonate, and the like.
- a periodic table group 2 element such as Mg, Ca, Sr and Ba, a group 3 element such as Sc and Y, La, Ce, Nd, Lanthanoids such as Sm and Gd, Group 4 elements such as Ti, Zr and Hf, Group 5 elements such as V, Nb and Ta, Group 6 elements such as Cr, Mo and W, Group 7 elements such as Mn Group elements such as Co, Co, Group 10 elements such as Ni, Pd, and Pt, Group 11 elements such as Cu and Ag, Group 12 elements such as Zn and Cd, and Group 13 elements such as B, Al, and Ga
- An ITO film can be formed by adding a simple substance such as a group element, a group 14 element such as Si, Ge or Pb, a group 15 element such as P, As or Sb, a group 16 element such as Se or Te, or a compound thereof. It can also be formed.
- a tin compound contained in the FTO film forming solution a tin compound used for the production of the ITO film can be used.
- the fluorine compound contained in the FTO film forming solution include hydrogen fluoride, sodium fluoride, trifluoroacetic acid, difluoroethane, bromotrifluoromethane, and the like.
- the above compounds are dissolved in alcohols such as methanol and ethanol, and organic solvents such as acetone, methyl butyl ketone and ketones such as acetylacetone to prepare ITO film forming solution and FTO film forming solution, respectively.
- alcohols such as methanol and ethanol
- organic solvents such as acetone, methyl butyl ketone and ketones such as acetylacetone to prepare ITO film forming solution and FTO film forming solution, respectively.
- a film is prepared by bringing the substrate into contact with the surface of the substrate and thermally decomposing it. The film thickness can be adjusted by changing the speed of the conveyor.
- By connecting three or more film forming furnaces at least one of the ITO film and the FTO film can be a multilayer film.
- another inorganic oxide film such as a SiO 2 film can be formed as the first substrate.
- the transparent conductive film of the present invention is used for at least one of the electrode layer 7 and the counter electrode layer 10, and one of these may be formed of an opaque electrode.
- the electrode may be formed of a metal itself or may be formed by laminating a conductive material layer on a film.
- Preferred conductive materials include metals such as platinum, gold, silver, copper, aluminum, rhodium and indium, or carbon or conductive metal oxides such as indium-tin composite oxide, tin oxide doped with antimony, fluorine Doped tin oxide, etc., or composites of the above compounds, or carbon materials such as graphite, carbon nanotubes, platinum-supported carbon, or silicon oxide, tin oxide, titanium oxide, zirconium oxide, aluminum oxide on the above compounds, etc. Can be mentioned.
- the preferable surface resistance range is 200 ⁇ / ⁇ or less, more preferably 50 ⁇ / ⁇ or less.
- the lower limit of the surface resistance is not particularly limited, but is usually 0.1 ⁇ / ⁇ .
- an inorganic semiconductor material or an organic semiconductor material can be used as a semiconductor material for forming the semiconductor layer 8.
- Inorganic semiconductor materials include metals such as Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si, and Cr. Elemental oxide, perovskite such as SrTiO 3 , CaTiO 3 , CdS, ZnS, In 2 S 3 , PbS, Mo 2 S, WS 2 , Sb 2 S 3 , Bi 2 S 3 , ZnCdS 2 , Cu 2 S, etc.
- Metal chalcogenides such as sulfide, CdSe, In 2 Se 3 , WSe 2 , HgS, PbSe, CdTe, etc., GaAs, Si, Se, Cd 2 P 3 , Zn 2 P 3 , InP, AgBr, PbI 2 , HgI 2 , BiI 3 or the like can be used.
- a composite containing at least one selected from these semiconductor materials for example, CdS / TiO 2 , CdS / AgI, Ag 2 S / AgI, CdS / ZnO, CdS / HgS, CdS / PbS, ZnO / ZnS, ZnO / ZnSe, CdS / HgS, CdS x / CdSe 1-x (0 ⁇ X ⁇ 1), CdS x / Te 1-x (0 ⁇ X ⁇ 1), CdSe x / Te 1-x (0 ⁇ X ⁇ 1), ZnS / CdSe, ZnSe / CdSe, CdS / ZnS, TiO 2 / Cd 3 P 2 , CdS / CdSeCd y Zn 1-y S (0 ⁇ Y ⁇ 1), CdS / HgS / CdS, etc.
- the film thickness of the semiconductor layer 8 is preferably in the range of 0.1 to 100 ⁇ m. This is because, within this range, a sufficient photoelectric conversion effect can be obtained, and the transparency to visible light and near infrared light is not deteriorated.
- a more preferable range of the thickness of the semiconductor layer 8 is 1 to 50 ⁇ m, a particularly preferable range is 5 to 30 ⁇ m, and a most preferable range is 10 to 20 ⁇ m.
- the semiconductor layer 8 is porous, and each pore diameter is about 1 to 100 nm.
- the semiconductor layer 8 may be formed by a known method.
- a mixed solution of semiconductor particles and a binder may be formed by a known method such as a coating method using a doctor blade or a bar coater, a spray method, a dip coating method,
- a coating method using a doctor blade or a bar coater a spray method, a dip coating method
- the substrate 6 is a glass substrate, it is heated and fired at around 500 ° C., and when the substrate 6 is a film substrate, the pressure is applied with a press. It can be formed by adding.
- any dye that is commonly used in conventional dye-sensitized solar cells can be used.
- Such dyes are, for example, RuL 2 (H 2 O) 2 type ruthenium-cis-diaqua-bipyridyl complexes or ruthenium-tris (RuL 3 ), ruthenium-bis (RuL 2 ), osmium-tris (OsL 3 ), Examples thereof include an osmium-bis (OsL 2 ) type transition metal complex, zinc-tetra (4-carboxyphenyl) porphyrin, iron-hexocyanide complex, and phthalocyanine.
- Organic dyes include 9-phenylxanthene dyes, coumarin dyes, acridine dyes, triphenylmethane dyes, tetraphenylmethane dyes, quinone dyes, azo dyes, indigo dyes, cyanine dyes, merocyanine dyes Examples thereof include dyes and xanthene dyes.
- ruthenium-bis (RuL 2 ) derivatives are particularly preferable because they have a broad absorption spectrum in the visible light region.
- the amount of the sensitizing dye supported on the semiconductor layer 8 is preferably in the range of 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 6 mol / cm 2 , particularly 0.1 ⁇ 10 ⁇ 7 to 9.0 ⁇ .
- a range of 10 ⁇ 7 mol / cm 2 is more preferable. Within this range, the effect of improving the photoelectric conversion efficiency can be obtained economically and sufficiently.
- Examples of the method of supporting the sensitizing dye on the semiconductor layer 8 include a method of immersing the substrate 6 including the electrode 7 on which the semiconductor layer 8 is deposited in a solution in which a metal complex dye is dissolved.
- a solvent of this solution any solvent that can dissolve metal complex dyes such as water, alcohol, toluene, and dimethylformamide can be used.
- heating and refluxing or applying ultrasonic waves may be performed when the substrate 6 provided with the electrode 7 having the semiconductor layer 8 deposited on the metal complex dye solution is dipped for a certain time. it can.
- the charge transport layer 4 can be formed using an electrolyte.
- the electrolyte is not particularly limited as long as it is a pair of redox constituents composed of an oxidant and a reductant, but a redox constituent that has the same charge as the oxidant and the reductant is preferable.
- a redox system constituent material means a pair of substances that reversibly exist in the form of an oxidant and a reductant in a redox reaction. Examples of such a redox system constituent material include chlorine compounds.
- iodine compounds-iodine are preferable.
- iodine compounds include metal iodides such as lithium iodide and potassium iodide, quaternary ammonium iodide compounds such as tetraalkylammonium iodide and pyridinium iodide, and dimethyl iodide.
- metal iodides such as lithium iodide and potassium iodide
- quaternary ammonium iodide compounds such as tetraalkylammonium iodide and pyridinium iodide
- dimethyl iodide Particularly preferred are imidazolium iodide compounds such as propyl imidazolium.
- the iodine (I 3 ⁇ ) concentration contained in the charge transport layer 4 is preferably more than 0 mol / dm 3 and 0.02 mol / dm 3 or less.
- iodine (I 3 ⁇ ) concentration is within the range, iodine or I 3 ⁇ absorbs a part of light in the visible region, and the coloration of the electrolyte, and the light absorption efficiency due to the coloration. The decrease and the output decrease can be suppressed. In particular, when used indoors, a dye-sensitized solar cell with better output characteristics can be provided.
- the solvent used for dissolving the electrolyte is preferably a compound that dissolves the redox constituents and has excellent ion conductivity.
- the solvent any of an aqueous solvent and an organic solvent can be used, but an organic solvent is preferable in order to further stabilize the redox component.
- carbonate compounds such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, ester compounds such as methyl acetate, methyl propionate, ⁇ -butyrolactone, diethyl ether, 1,2-dimethoxyethane, 1,3 -Ether compounds such as dioxosilane, tetrahydrofuran, 2-methyl-tetrahydrofuran, heterocyclic compounds such as 3-methyl-2-oxazodilinone, 2-methylpyrrolidone, nitrile compounds such as acetonitrile, methoxyacetonitrile, propionitrile, sulfolane, dimethylsulfone Examples include aprotic polar compounds such as foxoxide and dimethylformamide.
- carbonate compounds such as ethylene carbonate and propylene carbonate
- heterocyclic compounds such as ⁇ -butyrolactone, 3-methyl-2-oxazodilinone and 2-methylpyrrolidone
- acetonitrile methoxyacetonitrile
- propionitrile 3-methoxypropio Nitrile compounds
- nitrile and valeric nitrile are preferred.
- an ionic liquid as the solvent is effective from the viewpoint of non-volatility and flame retardancy.
- all known ionic liquids can be used.
- imidazolium-based, pyridine-based, alicyclic amine-based, aliphatic amine-based, azonium amine-based ionic liquids and European Patent No. 718288 specification , International Publication No. 95/18456, Electrochemical Vol. 65, No. 11, 923 (1997), J. Am. Electrochem. Soc. 143, 10, 3099 (1996), Inorg. Chem. 35, page 1168 (1996).
- the charge transport layer 4 can also be formed using a gelled electrolyte or a polymer electrolyte.
- the gelling agent include a gelling agent by a technique such as a polymer or a polymer crosslinking reaction, a gelling agent by a polyfunctional monomer that can be polymerized, and an oil gelling agent.
- Generally used gelling electrolytes and polymer electrolytes can be applied, but vinylidene fluoride polymers such as polyvinylidene fluoride, acrylic acid polymers such as polyacrylic acid, and acrylonitrile systems such as polyacrylonitrile.
- Polymers and polyether polymers such as polyethylene oxide, or compounds having an amide structure in the structure are preferred.
- the outer peripheral portion (the outer peripheral portion in plan view) of the charge transport layer 4 provided to be sandwiched between the semiconductor layer 8 and the counter electrode layer 10 is sealed with a sealing material 5.
- the sealing material 5 includes a thermoplastic resin, such as an olefin resin. Among these, DuPont's binel is particularly preferably used.
- the encapsulant 5 surrounds the periphery of the semiconductor layer 8 carrying the sensitizing dye (peripheral portion in plan view), and is a charge transport layer between the semiconductor layer 8 and the counter electrode layer 10. 4 is provided with a gap for forming the gap 4. At this time, it is preferable that the sealing material 5 is sandwiched between the electrode layer 7 and the counter electrode layer 10 as shown in FIG.
- the sealing material 5 arranged in this way is fixed so as to be sandwiched between the substrates 2 and 3 by, for example, a hot press method.
- the conditions of the hot press method are not particularly limited, but it is preferable to heat and press the film under conditions of 150 to 250 ° C. and 0.5 to 2 MPa.
- the electrolyte that forms the charge transport layer 4 is injected into the gap between the sealing material 5 fixed in this way, for example, by a reduced pressure injection method, and is sealed by the sealing material 5 to form the charge transport layer 4. .
- a laminate was continuously produced by blowing it into a conveyer furnace as a carrier gas and bringing it into contact with the surface of the glass substrate and thermally decomposing it.
- SE800 manufactured by IMEC
- it was glass / SiO 2 (40 nm) / ITO (40 nm) / FTO (13 nm).
- the result of measuring the sheet resistance value by the 4-terminal method is 96 ⁇ / ⁇ , and the crystal system on the surface of the FTO film was evaluated using a sample horizontal X-ray diffractometer for thin film evaluation (SmartLab manufactured by Rigaku Corporation). It was confirmed to be orthorhombic.
- high-purity titanium oxide powder having an average primary particle diameter of 20 nm was dispersed in ethyl cellulose to produce a first paste for screen printing.
- a high-purity titanium oxide powder having an average primary particle diameter of 20 nm and a high-purity titanium oxide powder having an average primary particle diameter of 400 nm were dispersed in ethyl cellulose to prepare a second paste for screen printing.
- the first paste was applied in a 1 cm ⁇ 3 cm square and dried. Was fired in air for 30 minutes to form a porous titanium oxide film having a thickness of 10 ⁇ m on the conductive glass substrate.
- a second paste is applied on the porous titanium oxide film, dried, and the obtained dried product is baked in air at 500 ° C. for 30 minutes to form a porous titanium oxide film having a thickness of 10 ⁇ m. Further, a titanium oxide film having a thickness of 4 ⁇ m was formed to obtain a semiconductor layer (light receiving area 3 cm 2 ). Next, the semiconductor layer was immersed in a solution containing a dye represented by [Ru (4,4′-dicarboxyl-2,2′-bipyridine) 2- (NCS) 2 ] and then taken out from the solution. The pigment was adsorbed to the semiconductor layer by allowing it to stand in the dark at room temperature for 24 hours.
- the solution was prepared by dissolving the dye in a mixed solvent obtained by mixing acetonitrile and t-butanol at a volume ratio of 50:50 so that the concentration becomes 3 ⁇ 10 ⁇ 4 mol / dm 3.
- a mixed solvent obtained by mixing acetonitrile and t-butanol at a volume ratio of 50:50 so that the concentration becomes 3 ⁇ 10 ⁇ 4 mol / dm 3.
- 5 mmol / dm 3 of a H 2 PtCl 6 solution solvent isopropyl alcohol
- heat treatment was performed at 450 ° C. for 15 minutes to prepare a counter electrode.
- a frame-shaped main seal material having a width of 1 mm and a thickness of 50 ⁇ m is disposed so as to surround the periphery of the titanium oxide film, and is 220 ° C. and 1.0 MPa. Under the conditions, heating and pressurization were simultaneously performed using a hot press machine.
- a thermoplastic synthetic resin DuPont “Binell”
- a gap having a width of 1 mm and a thickness of 50 ⁇ m was provided in the main sealing material. Since the electrolyte injection hole is formed by the gap, the cross-sectional area is 0.05 mm 2 .
- an electrolytic solution was injected from the electrolytic solution injection portion by a reduced pressure injection method. After the excess electrolytic solution adhering to the electrolytic solution injection portion was wiped off, the electrolytic solution injection portion was sealed with an end seal material to prepare a dye-sensitized solar cell.
- the electrolyte gamma-butyrolactone, methyltripropylammonium 0.5 mol / dm 3 , iodine 0.005 mol / dm 3 , lithium iodide 0.05 mol / dm 3 , N-methylbenzimidazole 0 .5 mol / dm 3 dissolved therein were used.
- a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the iodine concentration of the electrolytic solution was 0.05 mol / dm 3 .
- the SiO 2 film forming solution tetraethoxysilane (solution I)
- the ITO film forming solution indium acetylacetone containing 5 mol% of stannic chloride is 0.2 mol / L
- the laminated body was produced by the same method as Example 1 except having used each acetylacetone solution (solution II)).
- the obtained laminate was glass / SiO 2 (40 nm) / ITO (40 nm).
- one conveyor furnace heated to 500 ° C. was used, and the glass / SiO 2 / ITO laminate obtained in the first time was put into the conveyor furnace to prepare an FTO film forming solution (150 mol% fluorine).
- a laminate was prepared in the same manner as in Example 1 except that an ethanol solution (solution III) containing 0.5 mol / L of dibutyltin diacetate was used.
- solution III ethanol solution
- the film thickness was glass / SiO 2 (40 nm) / ITO (40 nm) / FTO (17 nm), the sheet resistance value was 143 ⁇ / ⁇ , and FTO
- the crystal system on the surface of the film was confirmed to be tetragonal.
- a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the conductive glass substrate (1.6 cm ⁇ 3.6 cm) provided with tetragonal FTO was used.
- Comparative Example 2 As the conductive glass substrate, the first film was formed by the same method as in Comparative Example 1, and the second film was formed by the same method except that the conveyance speed was slower than that in Comparative Example 1. A dye-sensitized solar cell was produced in the same manner as in Example 1 except that those were used. The obtained laminate was evaluated in the same manner as in Example 1. As a result, the film thickness was glass / SiO 2 (40 nm) / ITO (40 nm) / FTO (54 nm), and the sheet resistance value was 110 ⁇ / ⁇ . The crystal system of the surface of the FTO film was confirmed to be tetragonal.
- Example 3 Except for using a conductive glass substrate (surface resistance 200 ⁇ / ⁇ , thickness 0.7 mm, 1.6 cm ⁇ 3.6 cm) provided with an ITO film on a glass substrate, the same procedure as in Example 1 was carried out to increase the dye. A solar cell was prepared.
- the transparent conductive film provided in the dye-sensitized solar cell of the present invention has a heat resistance even when the film thickness is as thin as 5 to 20 nm because part or all of the surface of the FTO film has an orthorhombic crystal structure. An excellent, high-efficiency, high-output dye-sensitized solar cell can be obtained.
Abstract
Description
本願は、2008年6月24日に、日本に出願された特願2008-164418号に基づいて優先権を主張し、その内容をここに援用する。
(1)増感色素が担持された半導体層を一方の表面に有する電極と、前記半導体層に対して対向配置された対電極と、前記電極と前記対電極間に配置された電荷輸送層とを有する色素増感太陽電池において、前記電極が、ITO膜及びFTO膜を積層してなる透明導電膜であり、かつ、FTO膜の表面の結晶構造の一部又は全部が斜方晶であることを特徴とする色素増感太陽電池。
(2)透明導電膜のシート抵抗値が300Ω/□以下であることを特徴とする(1)記載の色素増感太陽電池。
(3)電荷輸送層に含まれるI3 -の濃度が、0mol/dm3を越え0.02mol/dm3以下であることを特徴とする(1)又は(2)記載の色素増感太陽電池。
基材6とその表面に形成された電極層7、又は、基材9とその表面上に形成された対電極層10の一方又は両方が透明に形成されて、半導体層8に光を入射させることが可能になっている。
本発明の透明導電膜は、電極層7と対電極層10の少なくとも一方に使用されるものであり、透明基材側にITO膜が設けられ、その上にFTO膜が積層されてなるものである。FTO膜の(半導体層8側の)表面の一部又は全部が斜方晶の結晶構造を有している。
本発明において、表面の一部が斜方晶とは、少なくとも、シート抵抗値の変化率が1.5倍以内となるために必要な量だけ斜方晶が含まれている状態をいう。ここで、「シート抵抗値の変化率」は、透明導電膜を350℃で1時間加熱を行った後のシート抵抗値を、加熱前のシート抵抗値で除して得ることができる。結晶構造の一部が斜方晶を有している場合、残りは正方晶又はその他の結晶系であり、通常、混晶状態となる。
斜方晶とは、結晶学の分野で一般に用いられている7つの結晶系(立方晶、六方晶、菱面体晶、正方晶、斜方晶、単斜晶、および三斜晶)のうち、軸長の関係がa≠b≠cであり、軸角の関係がα=β=γ=90°であるものをいう。結晶系の同定は、単結晶および粉末のX線回折、中性子線回折、電子線回折等により行われる。
斜方晶の結晶構造を生成させるためには、特にパイロゾル法により成膜する場合、後述するように、複数の成膜炉を連結した成膜炉内においてベルト上を移送される透明基材上にITO膜の成膜後に、連結した成膜炉内で引き続き連続的にFTO膜を成膜することが必要である。成膜炉でITO膜を成膜後、一旦成膜炉外に出した後、再度成膜炉でFTOを成膜すると、FTOの表面構造は正方晶になるとともに、シート抵抗値の変化率は1.5倍を超える。
FTO膜及びITO膜は各々、少なくとも1層からなり、前記膜厚を越えない限り、多層に積層できる。
本発明の透明導電膜は透明基材上に積層される。
透明基材は、具体的には、アルカリガラス、石英ガラス等のガラス、ポリカーボネート、ポリエチレンテレフタレート、ポリアリレート等のポリエステル、ポリエーテルスルホン系樹脂、アモルファスポリオレフィン、ポリスチレン、アクリル樹脂等が挙げられる。これらの材質は、最終的に用いる製品の用途に応じて最適なものが適宜選択される。
透明基材と透明導電膜との間には必要に応じて透明導電膜にアルカリ成分等が侵入するのを防止するために無機酸化物膜を形成することができる。無機酸化物膜として具体的には、ケイ素酸化物(SiO2)、アルミニウム酸化物(Al2O3)、チタン酸化物(TiO2)、ジルコニウム酸化物(ZrO2)、イットリウム酸化物(Y2O3)、イッテルビウム酸化物(Yb2O3)、マグネシウム酸化物(MgO)、タンタル酸化物(Ta2O5)、セリウム酸化物(CeO2)又はハフニウム酸化物(HfO2)、有機ポリシラン化合物から形成されるポリシラン膜、MgF2膜、CaF2膜、SiO2とTiO2の複合酸化物等からなる膜を例示することができる。
透明導電膜の製造方法としては、本発明の目的とする物性値を有する膜を成膜できる方法であればよく、具体的には、スパッター法、電子ビーム法、イオンプレーテイング法、スクリーン印刷法又は化学的気相成長法(CVD法)、スプレー熱分解法、パイロゾル法等を例示することができるが、特にパイロゾル法を好ましく例示することができる。
ITO膜形成溶液に含有されるインジウム化合物としては、熱分解して酸化インジウムになる物質が好ましく、具体的には、インジウムトリスアセチルアセトナート(In(CH3COCHCOCH3)3)、インジウムトリスベンゾイルメタネート(In(C6H5COCHCOC6H5)3)、三塩化インジウム(InCl3)、硝酸インジウム(In(NO3)3)、インジウムトリイソプロポキシド(In(OPr-i)3)等を例示することができる。
また、FTO膜形成溶液に含有されるフッ素化合物としては、フッ化水素、フッ化ナトリウム、トリフルオロ酢酸、ジフルオロエタン、ブロモトリフルオロメタンなどを挙げることができる。
予め400~750℃、好ましくは400~550℃に加熱したコンベア式成膜炉を複数基連結し、透明基材を炉内に投入する。第1基目の炉内でITO膜形成溶液を、第2基目の炉内でFTO膜形成溶液を、それぞれ超音波で霧滴状にして空気をキャリアガスとしてコンベアー炉の中に吹き込み、透明基材の表面に接触させて熱分解させることにより、膜を作製する。膜厚はコンベアの速度を変えることにより調整することができる。
成膜炉を3基以上連結することにより、ITO膜、FTO膜の少なくともいずれか一方を多層膜とすることもできる。また、第1基目でSiO2膜などの他の無機酸化物膜を成膜することもできる。
本発明の透明導電膜は、電極層7と対電極層10の少なくとも一方に使用されるものであり、これらのうち一方は不透明な電極で形成しても良い。この場合の電極は、金属そのもので形成するようにしてもよく、フィルム上に導電材層を積層して形成するようにしてもよい。好ましい導電材としては金属、例えば白金、金、銀、銅、アルミニウム、ロジウム、インジウム等、又は炭素、若しくは導電性の金属酸化物、例えばインジウム-錫複合酸化物、アンチモンをドープした酸化錫、フッ素をドープした酸化錫等、あるいは上記化合物の複合物、又はグラファイト、カーボンナノチューブ、白金を担持したカーボン等の炭素材料、若しくは上記化合物上に酸化シリコン、酸化スズ、酸化チタン、酸化ジルコニウム、酸化アルミニウムなどをコートした材料を挙げることができる。
この電極は、表面抵抗が低い程よいものであり、好ましい表面抵抗の範囲としては、200Ω/□以下であり、より好ましくは50Ω/□以下である。表面抵抗の下限は特に制限されないが、通常0.1Ω/□である。
半導体層8の膜厚は、0.1~100μmの範囲内であることが好ましい。この範囲内であれば、十分な光電変換効果が得られ、また、可視光及び近赤外光に対する透過性が悪化することもないからである。半導体層8の膜厚の一層好ましい範囲は1~50μmであり、特に好ましい範囲は5~30μmであり、最も好ましい範囲は10~20μmである。
半導体層8は、多孔質であり、各孔径は、1~100nm程度である。
そして半導体層8は、公知の方法で形成すればよく、例えば、半導体粒子とバインダーの混合溶液を、公知慣用の方法、例えば、ドクターブレードやバーコータなどを使う塗布方法、スプレー法、ディップコーティング法、スクリーン印刷法、スピンコート法などにより、電極層7の表面に塗布し、その後、基板6がガラス基板であれば500℃前後で加熱焼成し、基板6がフィルム基板であればプレス機で圧力を加えることによって、形成することができる。
半導体層8への増感色素の担持量としては、1×10-8~1×10-6mol/cm2の範囲にあることが好ましく、特に0.1×10-7~9.0×10-7mol/cm2の範囲であることがより好ましい。この範囲内であれば、経済的且つ十分に光電変換効率向上の効果を得ることができる。
これらの中でも、ヨウ素化合物-ヨウ素が好ましく、ヨウ素化合物としてはヨウ化リチウム、ヨウ化カリウムなどの金属ヨウ化物、テトラアルキルアンモニウムヨージド、ピリジニウムヨージドなどのヨウ化4級アンモニウム塩化合物、ヨウ化ジメチルプロピルイミダゾリウムなどのヨウ化イミダゾリウム化合物が特に好ましい。
電荷輸送層4に含まれるヨウ素(I3 -)濃度は、0mol/dm3を越え0.02mol/dm3以下であることが好ましい。ヨウ素(I3 -)濃度が当該範囲内である場合、ヨウ素ないしはI3 -が可視領域の光の一部を吸収するために生じる電解質の呈色と、当該呈色に起因する光吸収効率の低下および出力低下とを抑制することができる。特に、室内で使用される場合において出力特性のより優れた色素増感太陽電池を提供できる。
封止材5は、熱可塑性樹脂、例えば、オレフィン系樹脂などを含んで構成される。これらの中でも、特に、デュポン社製のバイネルが好ましく用いられる。
当該封止材5は、増感色素を担持させた半導体層8の周囲(平面視した場合の外周部)を囲むように、かつ、半導体層8と対電極層10との間に電荷輸送層4を形成するための隙間を設けて配置される。このとき、封止材5が、電極層7と対電極層10とに、図1に示されるように挟持される配置となることが好ましい。このように配置された封止材5は、例えば、ホットプレス法にて、基板2と3により挟持されるように固定される。当該ホットプレス法の条件は特に限定されないが、150~250℃、0.5~2MPaの条件で、加熱・加圧するのが好ましい。このように固定された封止材5の隙間に、電荷輸送層4を形成する電解質が、例えば、減圧注入法により注入され、封止材5によって封止され、電荷輸送層4が形成される。
次に、平均1次粒子径が20nmの高純度酸化チタン粉末をエチルセルロース中に分散させ、スクリーン印刷用の第1のペーストを作製した。一方、平均1次粒子径が20nmの高純度酸化チタン粉末と平均1次粒子径が400nmの高純度酸化チタン粉末とをエチルセルロース中に分散させ、スクリーン印刷用の第2のペーストを作製した。
そして上記斜方晶FTOが付与された導電性ガラス基板(1.6cm×3.6cm)上に、第1のペーストを1cm×3cm角に塗布し、乾燥し、得られた乾燥物を500℃で30分間、空気中で焼成して、導電性ガラス基板上に厚さ10μmの多孔質酸化チタン膜を形成した。次に、多孔質酸化チタン膜上に第2のペーストを塗布し、乾燥し、得られた乾燥物を500℃で30分間、空気中で焼成し、厚さ10μmの多孔質酸化チタン膜上にさらに厚さ4μmの酸化チタン膜を形成して、半導体層(受光面積3cm2)を得た。
次に、半導体層を、[Ru(4,4’-ジカルボキシル-2,2’-ビピリジン)2-(NCS)2]で表される色素を含む溶液に浸漬した後、上記溶液から取出し、室温で24時間暗所にて静置して、半導体層に色素を吸着させた。尚、溶液には、アセトニトリルとt-ブタノールとを容積比50:50で混合して得た混合溶媒に、上記色素を濃度が3×10-4mol/dm3となるように溶解したものを用いた。
一方で、上記斜方晶FTOが付与された導電性ガラス基板(1.6cm×3.6cm)に、5mmol/dm3のH2PtCl6溶液(溶媒イソプロピルアルコール)を5×10-6l/cm2塗布した後、450℃で15分間熱処理して、対電極を作製した。
酸化チタン膜を設けた電極と対電極との間に、上記酸化チタン膜の周囲を囲むように幅1mm、厚さ50μmの枠状のメインシール材を配設し、220℃、1.0MPaの条件でホットプレス機にて加熱と加圧を同時に行った。メインシール材としては、熱可塑性合成樹脂(デュポン製“バイネル”)を用いた。
なお、電解液注入部を形成するために、メインシール材には、幅1mm、厚さ50μmの隙間を設けた。電解液注入穴は、前記隙間により形成されるため、断面積は0.05mm2である。その後、この電解液注入部より電解液を減圧注入法で注液した。電解液注入部に付着した余分な電解液を拭き取った後、この電解液注入部をエンドシール材で封孔し、色素増感太陽電池を作製した。なお、電解液としては、ガンマブチロラクトンに、メチルトリプロピルアンモニウムを0.5mol/dm3、ヨウ素を0.005mol/dm3、ヨウ化リチウムを0.05mol/dm3、N-メチルベンゾイミダゾールを0.5mol/dm3をそれぞれ溶解したものを用いた。
実施例と同じ組成のITO膜をガラス基材に成膜後、一旦ガラス基材を取り出し、その後再度成膜炉にガラス基材を投入してITO膜の上にFTO膜を成膜して実施例とほぼ同じ膜厚の積層体を作製した。
1回目の成膜では、500℃に加熱したコンベアー炉を2基(炉(1)~(2))連結し、ソーダライムガラス基材(320×420×0.7mm)をコンベアー炉内に投入し、第1基においてはSiO2膜形成溶液(テトラエトキシシラン(溶液I))、第2基においてはITO膜形成溶液(塩化第2スズを5モル%含むインジウムアセチルアセトンを0.2モル/L含むアセチルアセトン溶液(溶液II))をそれぞれ用いた以外は実施例1と同じ方法で積層体を作製した。得られた積層体は、ガラス/SiO2(40nm)/ITO(40nm)であった。
2回目の成膜では500℃に過熱したコンベアー炉1基を使用し、1回目で得られたガラス/SiO2/ITO積層体をコンベアー炉に投入し、FTO膜形成溶液(フッ素を150モル%含むジブチルスズジアセテートを0.5モル/L含むエタノール溶液(溶液III))を用いた以外は実施例1と同じ方法で積層体を作製した。得られた積層体を実施例1と同様に評価した結果、膜厚はガラス/SiO2(40nm)/ITO(40nm)/FTO(17nm)であり、シート抵抗値は143Ω/□であり、FTO膜の表面の結晶系は、正方晶であることが確認された。
そして、この正方晶FTOが付与された導電性ガラス基板(1.6cm×3.6cm)を用いたこと以外はすべて実施例1と同様にして色素増感太陽電池を作製した。
導電性ガラス基板として、1回目の成膜は、比較例1と同じ方法で作製し、2回目の成膜は、搬送速度を比較例1よりも遅くした以外は同じ方法で積層体を作製したものを用いたこと以外はすべて実施例1と同様にして色素増感太陽電池を作製した。
なお、得られた積層体を実施例1と同様に評価した結果、膜厚はガラス/SiO2(40nm)/ITO(40nm)/FTO(54nm)であり、シート抵抗値は110Ω/□であり、FTO膜の表面の結晶系は、正方晶であることが確認された。
ガラス基材にITO膜が付与された導電性ガラス基板(表面抵抗200Ω/□、厚さ0.7mm、1.6cm×3.6cm)を用いた以外はすべて実施例1と同様にして色素増感太陽電池を作製した。
このようにして得られた色素増感太陽電池のうち実施例2および比較例1の特性については、擬似太陽光(1Sun)を光源として(色素増感太陽電池出力/光入射エネルギー)×100である変換効率により評価し、表1に示した。また、実施例1および実施例2と、比較例1および比較例2については、蛍光灯下200Lxの照度のもとでの電流―電圧曲線を測定し、最大出力点Pmax(W/cm2)の値についても評価し、表2に示した。
表1から、擬似太陽光(1Sun)においては、本発明を用いた実施例2は比較例1に対し高い変換効率を示すことがわかる。また、表2から、蛍光灯下200Lxの照度においては、本発明を用いた実施例1および2は、比較例1および2に比べて高いPmaxを示すことがわかる。
2,3 基板
6,9 基材
7 電極層
10 対電極層
5 封止材
4 電荷輸送層
8 色素担持半導体層
Claims (3)
- 増感色素が担持された半導体層を一方の表面に有する電極と、前記半導体層に対して対向配置された対電極と、前記電極と前記対電極間に配置された電荷輸送層とを有する色素増感太陽電池において、前記電極と前記対電極の少なくとも一方が、ITO膜及びFTO膜を積層してなる透明導電膜であり、かつ、FTO膜の表面の結晶構造の一部又は全部が斜方晶であることを特徴とする色素増感太陽電池。
- 前記透明導電膜のシート抵抗値が、300Ω/□以下であることを特徴とする請求項1記載の色素増感太陽電池。
- 前記電荷輸送層に含まれるI3 -の濃度が、0mol/dm3を越え0.02mol/dm3以下であることを特徴とする請求項1または2記載の色素増感太陽電池。
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CN200980123251.6A CN102067375B (zh) | 2008-06-24 | 2009-06-22 | 色素增感太阳能电池 |
US13/000,899 US8962982B2 (en) | 2008-06-24 | 2009-06-22 | Dye-sensitized solar cell |
JP2010517751A JP5275346B2 (ja) | 2008-06-24 | 2009-06-22 | 色素増感太陽電池 |
EP09769885A EP2296215A4 (en) | 2008-06-24 | 2009-06-22 | COLOR-SENSITIZED SOLAR CELL |
KR1020107028394A KR101246983B1 (ko) | 2008-06-24 | 2009-06-22 | 색소 증감 태양 전지 |
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US (1) | US8962982B2 (ja) |
EP (1) | EP2296215A4 (ja) |
JP (1) | JP5275346B2 (ja) |
KR (1) | KR101246983B1 (ja) |
CN (1) | CN102067375B (ja) |
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Cited By (4)
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US20130111974A1 (en) * | 2010-07-13 | 2013-05-09 | Universität Bremen | Gas sensor and method for producing the same |
JP2013200958A (ja) * | 2012-03-23 | 2013-10-03 | Nippon Steel & Sumikin Chemical Co Ltd | 太陽電池 |
JP2017011131A (ja) * | 2015-06-23 | 2017-01-12 | 積水化学工業株式会社 | 電解液、色素増感太陽電池およびその製造方法 |
US10566144B2 (en) | 2013-10-04 | 2020-02-18 | Asahi Kasei Kabushiki Kaisha | Solar cell, manufacturing method therefor, semiconductor device, and manufacturing method therefor |
Families Citing this family (7)
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JP5601686B2 (ja) * | 2008-06-24 | 2014-10-08 | 日本曹達株式会社 | Fto/ito積層体を有する透明導電膜 |
JP5634594B2 (ja) * | 2011-03-02 | 2014-12-03 | 株式会社フジクラ | 低照度用色素増感太陽電池 |
CN102867858A (zh) * | 2011-07-08 | 2013-01-09 | 亚树科技股份有限公司 | 具有良好雾度及导电度的导电基板 |
KR20150090022A (ko) * | 2012-11-27 | 2015-08-05 | 세키스이가가쿠 고교가부시키가이샤 | 태양 전지의 제조 방법 및 태양 전지 |
US20140246083A1 (en) * | 2013-03-01 | 2014-09-04 | First Solar, Inc. | Photovoltaic devices and method of making |
CN104112787B (zh) * | 2014-07-28 | 2016-04-13 | 武汉鑫神光电科技有限公司 | 一种硫化银/钙钛矿体异质结太阳能电池及其制备方法 |
KR102634852B1 (ko) * | 2021-10-27 | 2024-02-06 | 인천대학교 산학협력단 | 양면수광형 투명태양전지 및 그 제조방법 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01132004A (ja) * | 1987-11-17 | 1989-05-24 | Nippon Soda Co Ltd | 透光性導基板およびその製造方法 |
JP2003323818A (ja) * | 2002-02-26 | 2003-11-14 | Fujikura Ltd | 透明電極用基材 |
JP2005302695A (ja) * | 2004-03-18 | 2005-10-27 | Toyota Central Res & Dev Lab Inc | 光電極及びこれを備えた色素増感型太陽電池 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4485125A (en) * | 1982-03-19 | 1984-11-27 | Energy Conversion Devices, Inc. | Method for continuously producing tandem amorphous photovoltaic cells |
JPH07198648A (ja) * | 1993-12-29 | 1995-08-01 | Ricoh Co Ltd | ガス検知膜とその製法 |
WO1995018456A1 (fr) | 1993-12-29 | 1995-07-06 | Ecole Polytechnique Federale De Lausanne | Pile photo-electrochimique et electrolyte pour cette pile |
DE69534293T2 (de) | 1994-12-21 | 2006-05-18 | Centre National De La Recherche Scientifique (C.N.R.S.) | Flüssige, hydrophobe Salze, ihre Herstellung und ihre Verwendung in der Elektrochemie |
EP1628310A4 (en) * | 2003-05-26 | 2009-01-21 | Nippon Soda Co | TRANSLUCENT SUBSTRATE WITH TRANSPARENT ELECTRICALLY CONDUCTIVE FILM |
KR100857670B1 (ko) * | 2004-06-01 | 2008-09-08 | 도쿠리쓰교세이호징 가가쿠 기주쓰 신코 기코 | 광전변환소자 |
CN101133499B (zh) | 2005-03-04 | 2010-06-16 | 松下电工株式会社 | 多层有机太阳能电池 |
JP4591131B2 (ja) * | 2005-03-11 | 2010-12-01 | ソニー株式会社 | 色素増感光電変換素子およびその製造方法ならびに電子装置およびその製造方法ならびに電子機器 |
JP4982361B2 (ja) * | 2005-05-19 | 2012-07-25 | 日宝化学株式会社 | 電解質組成物 |
JP2007035893A (ja) | 2005-07-26 | 2007-02-08 | Matsushita Electric Works Ltd | 有機発電素子 |
US9208955B2 (en) * | 2007-05-17 | 2015-12-08 | Daido Metal Company Ltd. | Dye-sensitized solar cell fabricating kit, dye-sensitized solar cell and method of using the same |
-
2009
- 2009-06-22 JP JP2010517751A patent/JP5275346B2/ja not_active Expired - Fee Related
- 2009-06-22 KR KR1020107028394A patent/KR101246983B1/ko not_active IP Right Cessation
- 2009-06-22 WO PCT/JP2009/002840 patent/WO2009157175A1/ja active Application Filing
- 2009-06-22 US US13/000,899 patent/US8962982B2/en not_active Expired - Fee Related
- 2009-06-22 CN CN200980123251.6A patent/CN102067375B/zh not_active Expired - Fee Related
- 2009-06-22 EP EP09769885A patent/EP2296215A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01132004A (ja) * | 1987-11-17 | 1989-05-24 | Nippon Soda Co Ltd | 透光性導基板およびその製造方法 |
JP2003323818A (ja) * | 2002-02-26 | 2003-11-14 | Fujikura Ltd | 透明電極用基材 |
JP2005302695A (ja) * | 2004-03-18 | 2005-10-27 | Toyota Central Res & Dev Lab Inc | 光電極及びこれを備えた色素増感型太陽電池 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130111974A1 (en) * | 2010-07-13 | 2013-05-09 | Universität Bremen | Gas sensor and method for producing the same |
US9091669B2 (en) * | 2010-07-13 | 2015-07-28 | Eberghard Karls Universitat Tubingen | Gas sensor and method for producing the same |
JP2013200958A (ja) * | 2012-03-23 | 2013-10-03 | Nippon Steel & Sumikin Chemical Co Ltd | 太陽電池 |
US10566144B2 (en) | 2013-10-04 | 2020-02-18 | Asahi Kasei Kabushiki Kaisha | Solar cell, manufacturing method therefor, semiconductor device, and manufacturing method therefor |
JP2017011131A (ja) * | 2015-06-23 | 2017-01-12 | 積水化学工業株式会社 | 電解液、色素増感太陽電池およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2296215A1 (en) | 2011-03-16 |
US8962982B2 (en) | 2015-02-24 |
EP2296215A4 (en) | 2011-07-20 |
US20120090678A1 (en) | 2012-04-19 |
JP5275346B2 (ja) | 2013-08-28 |
CN102067375B (zh) | 2014-11-19 |
KR20110009710A (ko) | 2011-01-28 |
JPWO2009157175A1 (ja) | 2011-12-08 |
KR101246983B1 (ko) | 2013-03-25 |
CN102067375A (zh) | 2011-05-18 |
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