WO2012173110A1 - Cellule solaire à colorant et procédé de préparation de cellule solaire à colorant - Google Patents

Cellule solaire à colorant et procédé de préparation de cellule solaire à colorant Download PDF

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Publication number
WO2012173110A1
WO2012173110A1 PCT/JP2012/065004 JP2012065004W WO2012173110A1 WO 2012173110 A1 WO2012173110 A1 WO 2012173110A1 JP 2012065004 W JP2012065004 W JP 2012065004W WO 2012173110 A1 WO2012173110 A1 WO 2012173110A1
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layer
dye
solar cell
sensitized solar
metal wiring
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PCT/JP2012/065004
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English (en)
Japanese (ja)
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直之 柴山
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凸版印刷株式会社
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    • 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
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • 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. More specifically, the present invention relates to a dye-sensitized solar cell that generates power by irradiating light through a counter electrode (positive electrode) provided to face a negative electrode.
  • the dye-sensitized solar cell has a structure in which a positive electrode 11 is provided on a negative electrode 7 via an electrolyte layer 8 as shown in FIG. Further, as shown in FIG. 1, the negative electrode 7 includes an electrode substrate 1 in which a transparent conductive film 1b (for example, an ITO film) is provided on a transparent substrate 1a such as transparent glass or a transparent resin film, A porous layer 3 formed of a metal semiconductor such as titanium dioxide provided on the transparent conductive film 1b of the electrode substrate 1 and having a sensitizer (for example, Ru dye) 5 adsorbed on the surface thereof; Yes.
  • a transparent conductive film 1b for example, an ITO film
  • a porous layer 3 formed of a metal semiconductor such as titanium dioxide provided on the transparent conductive film 1b of the electrode substrate 1 and having a sensitizer (for example, Ru dye) 5 adsorbed on the surface thereof; Yes.
  • the sensitizer (photoelectric conversion material) 5 when visible light is irradiated from the negative electrode 7 side, the sensitizer (photoelectric conversion material) 5 is excited and transitions from the ground state to the excited state.
  • the excited electrons contained in the photoelectric conversion material 5 are injected into the conduction band of the porous layer 3 formed of a semiconductor, and move to the positive electrode 11 through the external circuit 12. Furthermore, the electrons that have moved to the positive electrode 11 are carried to the photoelectric conversion material 5 by ions in the electrolytic solution and return to the original state. Electrical energy is extracted by repeating the above process.
  • the power generation mechanism of the above-described dye-sensitized solar cell is a mechanism very similar to the photoelectric conversion process of plants because light capture and electronic conduction are performed in different places unlike a pn junction photoelectric conversion element. .
  • Patent Document 1 discloses a dye-sensitized solar cell that generates power by irradiating light through a counter electrode (positive electrode) of a negative electrode.
  • the solar cell having this structure since light is not irradiated through the electrode substrate provided on the negative electrode side, the semiconductor porous layer carrying the dye can be directly provided on the low-resistance metal substrate. Therefore, by using the solar cell having this structure, it is possible to effectively avoid an increase in internal resistance due to an increase in cell size and a decrease in conversion efficiency.
  • the present invention has been made in view of the above circumstances, and generates power by irradiating light through a counter electrode, and prevents a decrease in conversion efficiency due to an increase in the internal resistance of the counter electrode due to an increase in the size of the cell. It is an object of the present invention to provide a dye-sensitized solar cell that is capable of maintaining high conversion durability and stable conversion efficiency over a long period of time.
  • the insulating resin preferably includes fluorine-based leveling.
  • the insulating resin preferably includes leveling containing silicone leveling.
  • the insulating resin preferably includes leveling containing acrylic leveling.
  • the total light transmittance of a portion where the transparent base material, the transparent conductive layer, and the catalyst layer are laminated is 60%. It is preferable that it is in the range of 95% or less.
  • the ratio of the area of the counter electrode in which the transparent conductive layer is covered with the metal wiring layer and the protective layer in the counter electrode is 2 It is preferably 5% or more and 30% or less.
  • the surface resistance value of the transparent conductive layer is preferably within a range of 0.1 ⁇ / ⁇ to 1000 ⁇ / ⁇ .
  • the metal wiring layer is preferably formed of a metal or alloy having a specific resistance of 5 ⁇ 10 ⁇ 3 ⁇ ⁇ m or less.
  • the metal wiring layer is preferably formed of aluminum, copper, titanium, or silver.
  • the insulating protective layer preferably contains inorganic particles.
  • the inorganic particles preferably have a primary particle diameter in the range of 1 nm to 5 ⁇ m.
  • the catalyst layer is preferably platinum, a compound containing a platinum compound, a compound containing carbon, or a compound containing a conductive polymer. .
  • the negative electrode substrate according to the second aspect of the present invention a photoelectric conversion layer carrying a sensitizer formed on the negative electrode substrate, an electrolyte layer formed on the photoelectric conversion layer, and the electrolyte layer
  • the manufacturing method of the counter electrode in the dye-sensitized solar cell including the counter electrode formed thereon is formed by forming a transparent conductive layer on a transparent substrate and forming a predetermined pattern shape on the transparent conductive layer. Forming a metal wiring layer, applying a coating solution containing a protective layer material containing an insulating resin so as to cover the metal wiring having the predetermined pattern shape, curing the protective layer material, and forming a protective layer And forming a catalyst layer so as to cover the transparent conductive layer and the protective layer.
  • the dye-sensitized solar cell and the method for producing the dye-sensitized solar cell of the present invention it is possible to reduce the electric resistance of the transparent electrode layer used for the counter electrode and improve the total light transmittance and the aperture ratio.
  • the photoelectric conversion efficiency can be improved.
  • the manufacturing method of the dye-sensitized solar cell of this invention the yield of a manufacturing process can be improved.
  • the internal resistance in the counter electrode increases due to the increase in the size of the cell, thereby reducing the photoelectric conversion efficiency.
  • the total light transmittance of the counter electrode is lowered, and the photoelectric conversion efficiency is lowered.
  • the metal wiring layer is in direct contact with the electrolyte layer, and therefore deteriorates. As a result, the photoelectric conversion efficiency decreases.
  • the dye-sensitized solar cell of the present invention covering the metal wiring layer with a protective layer ensures excellent durability and stable conversion efficiency over a long period of time.
  • the protective layer is formed using an insulating resin. Since the protective layer is insulative, electrons can be prevented from moving from the metal wiring to the electrolyte layer, and a decrease in photoelectric conversion efficiency can be prevented.
  • the dye-sensitized solar cell shown in FIG. 2 includes an electrode substrate 10, a photoelectric conversion layer 20 having a sensitizer 25 formed on the electrode substrate 10, and an electrolyte layer 30 formed on the photoelectric conversion layer 20.
  • the counter electrode 40 formed on the electrolyte layer 30 is laminated. Furthermore, the counter electrode 40 is insulated from the transparent base material 41, the transparent conductive layer 42 formed on the transparent base material 41, the metal wiring layer 43 disposed on the transparent conductive layer 42 and having a predetermined pattern shape.
  • the protective layer 45 that covers the metal wiring layer 43 and the catalyst layer 47 that covers the transparent conductive layer 42 and the protective layer 45 are formed.
  • the thickness of the metal substrate in the present invention is preferably 10 ⁇ m or more and 2000 ⁇ m or less, more preferably 10 ⁇ m or more and 1000 ⁇ m or less, and particularly preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • ⁇ / ⁇ used for the unit of surface resistance represents the resistance per unit area, and can be replaced with “ ⁇ / sq.” Or “ ⁇ / cm 2 ”.
  • the photoelectric conversion layer 20 is formed by supporting the sensitizer 25 on the oxide semiconductor porous film 21.
  • the oxide semiconductor porous membrane preferably contains at least two kinds of semiconductor particles having different average particle diameters.
  • the photoelectric conversion layer 20 is formed by forming a coating film of a paste containing a specific group of semiconductor particles and sintering the coating film. As described above, a large number of nanopores can be formed in the oxide semiconductor porous film by forming semiconductor particles having different average particle diameters by sintering. Therefore, the ratio of the surface area of the semiconductor particles per unit area of the electrode substrate 10 can be extremely increased. Thereby, a sufficient amount of sensitizer can be carried, and as a result, high light absorption efficiency can be obtained.
  • the oxide semiconductor porous film contains two or more kinds of semiconductor particles having different average particle diameters, for example, nano-sized semiconductor particles having an average particle diameter of about 20 nm that tend to transmit long wavelength light;
  • the semiconductor particles having a large particle diameter of about 100 nm are mixed, light is scattered, the optical path length in the oxide semiconductor porous film is increased, and a so-called light confinement effect can be sufficiently obtained.
  • the thickness of the porous oxide semiconductor film is preferably 2 ⁇ m or more and 20 ⁇ m or less.
  • the oxide semiconductor porous film has a thickness of 5 ⁇ m or more and 20 ⁇ m or less.
  • the film thickness is less than 5 ⁇ m, the amount of dye adsorbed is small, so that the photoelectric conversion efficiency decreases.
  • the film thickness exceeds 20 ⁇ m, the adhesion between the oxide semiconductor porous film and the electrode substrate 10 is reduced, and is weak against external factors such as impact, so that there is a problem that durability is lowered.
  • the oxide semiconductor porous film exceeds 20 ⁇ m, the internal resistance of the oxide semiconductor porous film increases, and the voltage decreases.
  • the semiconductor particles are composed of a semiconductor that exhibits an electron transfer action. Specifically, for example, TiO 2 , SnO, ZnO, WO 3 , Nb 2 O 5 , In 2 O 3 , ZrO 2 , Ta 2 O 5 , Or an oxide semiconductor such as TiSrO 3 ; a sulfide semiconductor such as CdS, ZnS, In 2 S, PbS, Mo 2 S, WS 2 , Sb 2 S 3 , Bi 2 S 3 , ZnCdS 2 , or CuS 2 ; Metal chalcogenides such as In 2 Se 2 , WSe 2 , PbSe, or CdTe; elemental semiconductors such as GaAs, Si, Se, or InP can be used.
  • a composite of SnO and ZnO, TiO 2 and Nb 2 O 5 It is also possible to use a composite comprising two or more of these, such as a composite of Moreover, the kind of semiconductor is not limited to these, Two or more kinds can also be mixed and used.
  • the semiconductor constituting the semiconductor particles Ti, Zn, Sn, or Nb oxide is preferable among the above, and TiO 2 is particularly preferable.
  • titania particles formed of TiO 2 include anatase crystal type particles and rutile crystal type particles. Both of the above-mentioned particles can be used. In particular, when anatase crystal-type titania particles are used, the expected performance can be reliably obtained in a dye-sensitized solar cell.
  • the semiconductor particles having a small average particle size preferably have an average particle size of 3 to 40 nm, and more preferably 15 ⁇ 25 nm.
  • a semiconductor particle having a large average particle size among semiconductor particles constituting a specific semiconductor particle group (hereinafter, also referred to as “semiconductor large particle”) has light scattering ability, and the average particle size is preferably It is 50 nm or more, more preferably 80 to 400 nm, particularly preferably 90 to 120 nm.
  • the sensitizer supported on the semiconductor particles in the photoelectric conversion layer 20 is not particularly limited as long as it is a material exhibiting a sensitizing action.
  • an N3 complex an N719 complex (N719 dye), a Ru terpyridine complex (black dye).
  • a Ru complex such as a Ru diketonate complex; an organic dye such as a coumarin dye, a merocyanine dye, or a polyene dye; a metal porphyrin dye; or a phthalocyanine dye.
  • an N719 dye and a black dye it is preferable to use an N719 dye and a black dye.
  • the N719 dye is a compound represented by (RuL 2 (NCS) 2 ⁇ 2TBA), and the Blackdye dye is a compound represented by (RuL ′ 1 (NCS) 3 ⁇ 2TBA).
  • L is 4,4′-dicarboxy-2,2′-bipyridine
  • L ′ is 4,4 ′, 4 ′′ -tetra-carboxy-2,2 ′, 2 ′′ -terpyridine
  • TBA is Tetrabutylammonium chaotin.
  • the supported amount of the sensitizer in the photoelectric conversion layer 20 is such that the amount per unit surface area of the oxide semiconductor porous film is 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 7 mol / cm 2 , preferably 3 ⁇ 10 6. It is preferably ⁇ 8 to 7 ⁇ 10 ⁇ 8 mol / cm 2 .
  • the carrying amount of the sensitizing dye is within this range, the sensitizing dye is carried as a monomolecular layer on the surface of the semiconductor particles. Therefore, sufficient light absorption efficiency can be obtained without causing an energy loss caused by electrons excited in the sensitizing dye reducing the electrolyte in the electrolyte portion.
  • the electrolyte layer 30 may be in a liquid state, a solid state, a solidified body state, or a room temperature molten salt state.
  • the electrolyte layer 30 is, for example, in the form of a solution, the electrolyte layer 30 is preferably composed of an electrolyte, a solvent, and an additive.
  • the electrolyte includes a combination of a metal iodide such as lithium iodide, sodium iodide, potassium iodide, or cesium iodide and iodine, a quaternary compound such as tetraalkylammonium iodide, pyridinium iodide, or imidazolium iodide.
  • a metal iodide such as lithium iodide, sodium iodide, potassium iodide, or cesium iodide and iodine
  • a quaternary compound such as tetraalkylammonium iodide, pyridinium iodide, or imidazolium iodide.
  • a combination of an iodine salt of an ammonium compound and iodine, or a combination of a bromine compound and bromine is used instead of the iodine or iod
  • the electrolyte may be a gel electrolyte, a polymer electrolyte, or a solid electrolyte, and an organic charge transport material may be used instead of the electrolyte.
  • the solvent when the electrolyte layer 30 is in the form of a solution include nitrile solvents such as acetonitrile, methoxyacetonitrile, or propionitrile, carbonate solvents such as ethylene carbonate, ether solvents, or alcohol solvents. It is done.
  • the transparent substrate 41 is made of a transparent resin.
  • the transparent substrate 41 is preferably a material having a high total light transmittance.
  • a transparent film formed of, for example, the materials listed below can be used besides polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • PEN Polyethylene naphthalate
  • PC polycarbonate
  • PES polyethersulfone
  • low density polyethylene high density polyethylene
  • polypropylene poly 1-butene
  • poly 4-methyl-1-pentene polyethylene
  • propylene Polyolefin resins such as random or block copolymers of ⁇ -olefins such as 1-butene and 4-methyl-1-pentene.
  • An ethylene-vinyl compound copolymer resin such as an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, or an ethylene-vinyl chloride copolymer.
  • Styrenic resins such as polystyrene, acrylonitrile-styrene copolymer, ABS, ⁇ -methylstyrene-styrene copolymer.
  • Vinyl resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polyacrylic acid, polymethacrylic acid, polymethyl acrylate, or polymethyl methacrylate.
  • Polyamide resin such as nylon 6, nylon 6-6, nylon 6-10, nylon 11 or nylon 12.
  • Polyphenylene oxide such as Cellulose derivatives such as carboxymethylcellulose or hydroxyethylcellulose.
  • Starch such as oxidized starch, etherified starch, or dextrin; (9) A resin formed from a mixture of the materials described in (1) to (8) above.
  • the transparent substrate 41 for example, a substrate having a thickness of 80 to 200 ⁇ m and a total light transmittance of 75% or more is preferably used. Since sunlight is incident on the dye-sensitized solar cell through the transparent base material 41, the total light transmittance of the transparent base material 41 is preferably as high as possible.
  • the transparent conductive layer 42 is formed on the transparent substrate 41 by a technique such as sputtering, vapor deposition, SPD, or CVD.
  • the transparent conductive layer 42 is made of a conductive metal oxide such as tin-added indium oxide (ITO), tin oxide (SnO 2 ), or fluorine-added tin oxide (FTO). Since the transparent conductive layer 42 is required to have a certain light transmittance and conductivity, the film thickness is preferably about 5 nm to 10 ⁇ m. Further, the film thickness is more preferably 20 nm to 300 nm. Further, the surface resistance value of the transparent conductive layer at this time is preferably 1000 ⁇ / ⁇ or less. Further, the surface resistance value of the transparent conductive layer is preferably 0.1 ⁇ / ⁇ or more. Furthermore, the surface resistance value of the transparent conductive layer is more preferably 5 ⁇ / ⁇ or more and 300 ⁇ / ⁇ or less.
  • the metal wiring layer 43 is formed of a metal such as gold, silver, copper, platinum, aluminum, nickel, or titanium.
  • the metal wiring layer 43 has a predetermined pattern shape such as a lattice shape, a stripe shape, or a comb shape.
  • the metal wiring layer is preferably formed of aluminum, copper, titanium, or silver in terms of low resistance.
  • the surface 43a in contact with the transparent conductive layer 42 and the surface 43b of the metal wiring layer 43 opposite to the surface 43a are formed substantially in parallel. Yes. Furthermore, in this cross section, the length of the surface 43a is formed to be longer than the length of the surface 43b. More specifically, in this cross section, when a reference line S passing through the center of the surface 43a and orthogonal to the surface 43a is defined, one end of the surface 43a with respect to the reference line S is the above-described reference line S of the surface 43b. It is arrange
  • the end of the surface 13a opposite to the first end with respect to the reference line S is farther from the reference line S than the end of the surface 13b opposite to the first end with respect to the reference line S. Placed in position. That is, the shape of the metal wiring layer 43 in this cross section is similar to an isosceles trapezoid.
  • each metal wiring layer 43 is preferably 3,000 ⁇ m or less.
  • the thickness (height) of the metal wiring layer 43 is not particularly limited, but is preferably 0.1 to 30 ⁇ m.
  • the metal wiring layer 43 is formed of conductive particles and a binder (binder matrix) such as resin fine particles. Examples of the conductive particles forming the metal wiring layer 43 include metal particles such as gold, silver, copper, platinum, aluminum, nickel, or titanium.
  • resin the material containing a polyester resin, an epoxy resin, an acrylic resin, and a urethane resin can be mentioned. These resins may be removed by baking.
  • the metal wiring layer forming material is made into a paste form, and this is coated by screen printing or the like so that the metal wiring layer 43 has a predetermined pattern shape. It is formed by heat curing (curing, baking) or UV curing. Further, the metal wiring layer forming material is more preferably a thermosetting material in order to remove the resin and to increase the number of bonding points of conductive particles.
  • a temperature lower than a temperature 10 ° C. higher than the melting point of the transparent substrate 41 is preferable to use a temperature lower than a temperature 10 ° C. higher than the melting point of the transparent substrate 41 as the above-mentioned curing reference temperature. Collection, Shosodo, Oct. 4, 1982, p. 438-439. In the table of the upper limit temperature of use of the organic material (thermosetting resin), the value described in the column (No. 2) When a value is not described in the column, it is more preferable to use a temperature lower than the value described in the column 1).
  • the melting point of the transparent substrate 41 is about 260 ° C., and the value described in Part 2 of the above document is 125 ° C. Therefore, in this case, it is preferable to use a temperature lower than about 270 ° C., more preferably a temperature lower than 125 ° C., as the curing reference temperature of the transparent substrate 41.
  • the transparent base material 41 is cured at a temperature higher than the melting point of the transparent base material 11 by 10 ° C. or more, the transparent base material 41 is deformed due to thermal deterioration, or the adhesion between the transparent base material 41 and the transparent conductive layer 42. This causes a problem of lowering.
  • thermosetting When thermosetting is performed at a curing reference temperature of 60 ° C. or less, the bonding and melting of the metal fine particles contained in the material of the metal wiring layer 43 are difficult to proceed, so that there is a problem that the conductivity is significantly lowered. In this case, since the removal of the binder matrix contained in the material of the metal wiring layer 43 does not proceed, the conductivity of the metal wiring layer 43 is reduced.
  • the leveling property can be enhanced when the metal wiring layer 43 is formed. Therefore, by adding the leveling agent, the surface of the metal wiring layer 43 on the electrode substrate 10 side (the side away from the interface between the metal wiring layer 43 and the transparent conductive layer 42) in the cross section perpendicular to the axis C1 of the wiring 13 is added. There is an effect that it is easy to form 43b so as to protrude in a direction away from the transparent conductive layer 42 from both end portions toward the intermediate portion.
  • the metal wiring layer 43 may have a volume resistance of 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less. More preferably, the volume resistance is 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
  • the metal wiring layer 43 has a shape similar to an isosceles trapezoidal shape as shown in FIG. 3, and as shown in FIG. 8, in the cross section perpendicular to the axis C ⁇ b> 1 of the metal wiring layer 43
  • the surface 43b of the metal wiring layer 43 closer to the metal electrode 10 (the side away from the transparent conductive layer 42) is formed so as to protrude in a direction away from the transparent conductive layer 42 from both end portions toward the intermediate portion. May be.
  • the protective layer 45 covers the metal wiring 43 with a substantially uniform thickness along the shape of the metal wiring layer 43.
  • the surface 45a on the metal electrode 10 side is separated from the transparent conductive layer 42 from both ends toward the intermediate portion 45b in the cross section orthogonal to the axis of the metal wiring layer 43 with respect to the shape of the protective layer 45 more efficiently. It can be formed so as to protrude in the direction.
  • the metal wiring layer forming material is allowed to stand and be leveled before being cured by heat or light irradiation. Can be achieved. Further, by setting the metal wiring layer forming material to a predetermined viscosity, leveling is likely to occur, and the cross-sectional shape is naturally adjusted.
  • the metal wiring layer 43 may be formed by a plating method after a part of the transparent conductive layer 42 is protected with a resist in addition to the above screen printing method, a transfer type screen printing method, or an ink jet which is direct drawing. It may be formed by a method or the like. If direct drawing is performed by the ink jet method, the surface 43b of the metal wiring layer 43 is transparently conductive from both ends toward the middle in the cross section perpendicular to the axis C1 of the metal wiring layer 43 without leveling. It can be formed so as to protrude in a direction away from the layer 42.
  • the metal wiring layer 43 is formed by a known method such as an etching method for forming a printed wiring on the transparent substrate 41, and the transparent substrate is formed on the metal wiring layer 43.
  • a method of forming the transparent conductive layer 42 on the entire 41 can be used.
  • a predetermined pattern is formed on the metal wiring layer as shown in FIG.
  • the metal wiring layer 43 is formed on the transparent conductive layer 42 of the transparent substrate 41 so as to have a lattice shape, but the pattern shape of the metal wiring layer is not limited to this.
  • the protective layer 45 is formed with substantially the same thickness on each of the two surfaces of the metal wiring layer 43 orthogonal to the width direction and the surface on the metal electrode 10 side.
  • FIG. 4 shows a top view of the metal wiring layer 43 and the protective layer 45 in the dye-sensitized solar cell of the present invention.
  • the surface 15a of the protective layer 45 on the metal electrode 10 side is from the transparent conductive layer 42 toward both ends to the intermediate portion 45b. It is formed so as to protrude in the separating direction.
  • the protective layer 45 is formed of a transparent resin having insulating properties.
  • Examples of the material for forming the protective layer 45 include epoxy resins, acrylic resins, urethane resins, silicone resins, phosphase resins, melamine resins, polyimide resins, polyamide resins, isobutylene resins, or fluorine resins. It is done.
  • the protective layer 45 may be formed of any resin as long as it has insulating properties, and the color may not be transparent.
  • the protective layer 45 is formed by thermally curing the above materials or UV curing.
  • the material for forming the protective layer 45 is preferably curable at a temperature lower than the melting point of the transparent substrate 41 by 10 ° C. or more, and more preferably an ionizing radiation curable material.
  • a leveling material can be added to the protective layer.
  • the ionizing radiation curable material that can be used for forming the protective layer 45 of the present invention include acrylic resins, urethane resins, and epoxy resins.
  • an acrylic resin or an epoxy resin is particularly preferable.
  • a fluorine leveling material, a silicone leveling material, or an acrylic leveling material can be used.
  • acrylic leveling material examples include BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-380, manufactured by BYK Japan.
  • examples include BYK-392 or BYK-394.
  • Specific examples of the fluorine leveling material include Footent 222F (manufactured by Neos), F470 (manufactured by DIC), F489 (manufactured by DIC), or RS-75 (manufactured by DIC). .
  • silicone leveling material examples include BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-322, BYK-323, BYK- manufactured by BYK Japan. 325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYKUV3570, BYK-Silclean3700, or BYK-Silclean3720 can be used.
  • silicone leveling materials include TSF410, TSF411, TSF4700, TSF4701, XF42-B0970, TSF4730, YF3965, TSF4421, XF42-334, XF42-B3629, XF42-A3161, TSF4440, manufactured by Momentive.
  • TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, or TSF4460 can be used.
  • examples of the silicone leveling material include Polyflow KL400X, Polyflow KL400HL, Polyflow KL401, Polyflow KL402, Polyflow KL403, and Polyflow KL404 manufactured by Kyoeisha Chemical Co., Ltd.
  • the leveling material can prevent elimination of the leveling material from the resin, an —OH group (hydroxy group) or a double bond is introduced into the leveling material, and a material that can react with the resin is selected. Is desirable.
  • the level ring material having an —OH group include BYK-394, BYK-370, BYK-375, and BYK-377.
  • the level ring material having a double bond include BYK-UV3500, BYK-UV3570, and RS-75.
  • the water-repellent groups are arranged on the surface of the protective layer 45 in a self-organizing manner. Therefore, when the protective layer 45 is cured, the water repellency of the protective layer can be increased.
  • the leveling material preferably has an ionizing radiation curable reactive group. When the leveling material has an ionizing radiation curable reactive group, the durability of the protective layer can be enhanced when the leveling material is incorporated into the protective layer. By increasing the water repellency of the protective layer, the electrolyte contained in the photoelectric conversion layer can be prevented from attacking the protective layer. In addition, adsorption of the sensitizer detached from the photoelectric conversion layer can be prevented, and a reduction in efficiency can be prevented.
  • the contact angle of the surface of the protective layer 45 with respect to water is preferably 70 ° or more and less than 130 °. If the contact angle is less than 70 °, contact between the protective film and the electrolyte tends to occur, and durability is lowered. Further, when the contact angle is 130 ° or more, the compatibility with the metal wiring layer 43 or the transparent conductive layer 42 as a base is poor when the protective layer 45 is applied, and therefore, there is a problem that uneven coating and pinholes are likely to occur. .
  • the contact angle was measured by using a contact angle meter (Kyowa Interface Science Co., Ltd., CA-X type) to form a droplet with a diameter of 1.8 mm at the needle tip in a dry state (20 ° C.-65% RH). The measurement was performed by bringing the droplet into contact with the surface of the protective layer.
  • the contact angle is an angle formed between a solid surface and a tangent to the liquid surface at a point where a solid having a horizontal plane and a liquid (droplet) dropped on the horizontal plane come into contact, and is defined as an angle on the side including the liquid. did.
  • distilled water was used as the liquid.
  • the pure water contact angle was measured according to JIS-R3257.
  • the protective layer 45 may contain inorganic fine particles. Since the inorganic fine particles have high solvent resistance and chemical resistance, it is possible to compensate for a decrease in solvent resistance caused by the protective layer 45 being a resin. That is, when the protective layer 45 contains inorganic fine particles, the electrolyte layer can be prevented from attacking the protective layer 45 in the manufacturing process of the dye-sensitized solar cell. Further, the protective layer 45 can be given light scattering properties, and the photoelectric conversion efficiency can be improved.
  • Examples of the inorganic fine particles that can be added to the protective layer 45 include silica, talc, and titanium oxide fine particles. Further, the shape of the inorganic fine particles is not particularly limited.
  • the primary particle diameter of the inorganic fine particles is preferably 1 nm or more and 5 ⁇ m or less, more preferably 10 nm or more and 3 ⁇ m or less when measured by a light scattering method. When the primary particle size is smaller than the above range, it is difficult to use practically at this stage. When the primary particle diameter is larger than the above range, the primary particle size may fall off from the protective layer 15, and the patterning accuracy of the protective layer 15 is likely to decrease.
  • the amount of inorganic fine particles added is mass% in the protective layer 45, preferably 0.5% by mass or more for imparting scattering properties, and 5% by mass or more for imparting solvent resistance. It is preferable. There is no particular upper limit on the amount of inorganic fine particles added, but the limit at which the protective layer 45 can be formed is about 80% by mass. Note that the fine particles to be added may be resin fine particles only for the purpose of imparting light scattering properties. Since the light scattering property of the protective layer 45 is enhanced, the light passing through the protective layer 45 can be guided not to the direction of the metal wiring layer 43 but to the photoelectric conversion layer. can do.
  • the catalyst layer 47 is formed so as to cover the transparent conductive layer 42 and the protective layer 45.
  • a material for forming the catalyst layer 47 platinum, a platinum compound, carbon, or a conductive polymer can be used.
  • platinum or a conductive polymer it is particularly preferable to use platinum or a conductive polymer from the viewpoint of excellent transparency.
  • platinum it is most preferable to use platinum as the above-mentioned material from the viewpoint of excellent catalytic ability.
  • the thickness of the thin film layer formed of platinum is preferably 0.5 nm or more and 100 nm or less.
  • the thickness of the thin film formed of platinum is 0.5 nm or less, the catalytic function is insufficient and a sufficient current cannot be obtained. Moreover, since the total light transmittance falls that the thickness of the thin film formed with platinum is 100 nm or more, photoelectric conversion efficiency falls. In the case where a conductive polymer is used, the thickness of the thin film is preferably 5 nm to 100 nm. Moreover, PEDOT * PSS and polyaniline can be used suitably as a conductive polymer.
  • Transparent conductive layer forming step First, as shown in FIG. 5, a transparent conductive layer 42 made of tin-added indium oxide is formed on a film-like substrate 41 made of, for example, transparent polyethylene naphthalate by sputtering. Thereafter, in order to improve the adhesion of the metal wiring layer 43 to the transparent conductive layer 42, a surface treatment such as UV-ozone treatment may be performed.
  • the metal wiring layer 43 is formed by arranging the metal wiring layer 43 on the transparent conductive layer 42 in a grid pattern by a screen printing method. At this time, after the metal wiring layer forming material is applied on the transparent conductive layer 42, the metal wiring layer 43 is cured by baking for 1 hour or less at a curing reference temperature or less of the transparent base material 41. Thereafter, in order to improve the adhesion between the transparent conductive layer 42 and the metal wiring layer 43, a surface treatment such as UV-ozone treatment may be performed.
  • a protective layer forming material 45 c that is an epoxy resin is applied by screen printing or the like so as to cover the metal wiring layer 43.
  • the protective layer forming material 45c for example, a material in which an epoxy resin is dissolved in a solvent, and an insulating material is used.
  • the central portion of the surface away from the interface between the metal wiring layer 43 and the protective layer forming material 45c is formed flat.
  • the protective layer forming material 45c is baked for 1 hour or less and cured at a temperature lower than the curing reference temperature of the transparent substrate 41 to form the protective layer 45 as shown in FIG.
  • the protective layer forming material 45c has a property of rounding corners that protrude when it is cured.
  • the reason for this is that the protective layer forming material 45c is paste-like and has fluidity, so that it is leveled along the metal wiring layer 43 by being left standing for a certain period of time after being applied to the metal wiring layer 43. it is conceivable that.
  • the tendency of the corners to be rounded increases due to the reflow effect during heating.
  • leveling of a protective layer can be supplemented by addition of a leveling agent or adjustment of a viscosity.
  • the cross-sectional shape of the protective layer in the dye-sensitized solar cell of the present invention has a rounded shape (R shape) that does not have corners and curves from both ends toward the middle. ) Is preferable.
  • R shape rounded shape
  • the contact area between the protective layer and the electrolyte layer can be reduced, and the resulting dye-sensitized solar cell can be made less likely to break when stress is applied from the outside. .
  • the above-mentioned flat surface of the protective layer forming material 45c also has a roundness.
  • the leveling time is preferably 10 seconds or more, When it is 10 Pa ⁇ s or more and less than 100 Pa ⁇ s, the leveling time is preferably 30 seconds or more, and when it is 100 Pa ⁇ s or more and less than 2000 Pa ⁇ s, the leveling time is preferably 1 minute or more.
  • the leveling temperature is preferably 20 ° C. or higher and 150 ° C. or lower, more preferably 40 ° C. or higher and 120 ° C. or lower. About the temperature which performs leveling, it is good to set so that the protective layer formation material 45c may become a predetermined viscosity range.
  • the protective layer forming material 45c so as to have a predetermined pattern shape, according to direct drawing such as an ink jet method, the cross-sectional shape is formed from the beginning of the arrangement. Therefore, the effort of leveling is not required and a mask is not required.
  • the surface 45a on the side away from the transparent conductive layer 42 is separated from the transparent conductive layer 42 from both ends toward the intermediate portion 45b. It is formed so as to protrude in the direction.
  • Catalyst layer forming step As a catalyst layer forming method, when the catalyst layer is platinum, a sputtering method or a CVD method can be optimally used, but other methods may be used.
  • the platinum layer can be formed by a magnetron sputtering method using a sputtering apparatus.
  • a platinum layer can be formed as a catalyst layer by setting the transparent base material formed up to the protective layer by the above method in the chamber and performing sputtering. Moreover, the thickness of the formed platinum layer can be confirmed by measuring using a fine shape measuring machine.
  • the catalyst layer can be formed by coating using a coating solution containing the conductive polymer or carbon.
  • the coating method is not particularly limited, and a method capable of uniform coating using a roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, or a dip coater can be used. Further, as another coating method, an inkjet method or a screen method can be used. A conductive polymer or carbon formed by any of the above methods was used as the catalyst layer. Moreover, the film thickness of a catalyst layer can be calculated
  • the total light transmittance of the portion where the transparent base material 41, the transparent conductive layer 42, and the catalyst layer 47 are laminated contributes to the photoelectric conversion efficiency.
  • the laminated portion is defined as a window portion, and the total light transmittance of the window portion in the counter electrode 40 is preferably 60% or more and 95% or less. When the total light transmittance is improved, the photoelectric conversion efficiency is improved. Therefore, the total light transmittance of the window portion is more preferably 70% or more and 95% or less.
  • aqueous paste containing at least two semiconductor particles having different average particle diameters is applied on the metal substrate 10 to form the coating film 20a. Moreover, the paste used for this manufacturing method contains the semiconductor particle, and can select a binder or a solvent timely.
  • the method for preparing a paste containing a specific group of semiconductor particles constituting the photoelectric conversion layer 20 is not particularly limited.
  • a basic method in which alkoxide is hydrolyzed with a quaternary ammonium salt is preferably used.
  • alkoxide for obtaining small semiconductor particles is obtained by hydrolysis with a quaternary ammonium salt, and alkoxide for obtaining large semiconductor particles in the same manner is quaternary. It is obtained by hydrolysis with an ammonium salt, and a paste containing a specific group of semiconductor particles can be prepared by mixing them.
  • the average particle size of the obtained semiconductor particles can be controlled by adjusting the amount of quaternary ammonium salt to be subjected to hydrolysis. The larger the amount of quaternary ammonium salt added, the larger the average particle size. Small semiconductor particles can be obtained.
  • TMAH tetramethylammonium hydroxide
  • the methyl group is not limited and examples thereof include materials having an alkyl group having 1 to 4 carbon atoms. it can.
  • the metal alkoxide constituting the above-described semiconductor particles can be used.
  • the semiconductor particles are titania particles
  • Ti (OC 3 H 5 ) 4 can be used as the alkoxide of the semiconductor particles
  • TMAH can be used as the quaternary ammonium salt.
  • the method for applying the paste onto the electrode substrate 10 is not particularly limited, and can be performed according to various known methods such as a doctor blade method, a spray method, or a screen printing method.
  • the region where the paste is applied on the metal substrate 10 functions as a working electrode, and the area of the working electrode region can be appropriately selected depending on the application.
  • the applied paste is heated in order to bring the semiconductor particles into electronic contact with each other and to improve the strength of the coating film and the adhesion to the metal electrode 10. It is preferable to process.
  • the range of preferable heating temperature is 40 ° C. or higher and 700 ° C. or lower, and more preferably 100 ° C. or higher and 600 ° C. or lower.
  • the heating time is preferably about 10 minutes to 10 hours.
  • the method for forming the photoelectric conversion layer 20 by supporting the sensitizing dye on the oxide semiconductor porous film 20b is not particularly limited.
  • the sensitizing dye may be alcohols, nitriles, nitromethane, halogenated hydrocarbons, ethers.
  • a photoelectric conversion layer by using a dipping method, a spray coating method, a printing coating method, or the like in which the oxide semiconductor porous film 20b is immersed in a mixed solvent in which two or more types are mixed. It is done.
  • an electrolyte layer 30 is formed on the photoelectric conversion layer 20, and the electrolyte layer 30 is sandwiched between the photoelectric conversion layer 20 and the counter electrode 40 on the electrolytic layer 30.
  • the dye-sensitized solar cell is completed by disposing the counter electrode 40 on the surface.
  • the metal wiring layer 43 is disposed on the transparent conductive layer 42. For this reason, the electrical resistance of the transparent conductive layer 12 can be lowered by the metal wiring layer 14. Further, the metal wiring layer 43 and the electrolyte layer 30 are separated by covering the metal wiring layer 43 with the protective layer 45. For this reason, in general, the electrolyte forming the electrolyte layer 30 penetrates into the metal wiring layer 43 and causes corrosion. However, the electrolyte layer 30 and the metal wiring layer 43 are separated by the protective layer 45, so that the electrolyte The corrosion of the metal wiring 43 by the layer 30 can be prevented and the durability can be improved.
  • the protective layer 45 is formed so that the surface 45a protrudes in a direction away from the transparent conductive layer 42 from both end portions toward the intermediate portion 45b. Therefore, the contact area between the protective layer 45 and the electrolyte layer 30 can be reduced as compared with the case where it does not protrude. Therefore, the protective layer 45 is not easily affected by the electrolyte.
  • the light incident on the transparent base material 41 enters the photoelectric conversion layer 20 through the transparent base material 41, the transparent conductive layer 42, and the electrolyte layer 30. Further, the photoelectric conversion layer 20 absorbs light incident on the sensitizer, thereby generating electrons. Light that has not been absorbed by the sensitizer is scattered and reflected by the photoelectric conversion layer 20 and the metal substrate 10 while changing the traveling direction, passes through the electrolyte layer 30 again, and reenters the counter electrode 40. At this time, when the protective layer 45 contains a substance that is easily scattered, light can be reflected again toward the photoelectric conversion layer.
  • the protective layer 45 is formed of a transparent resin
  • the light incident on the protective layer 45 via the transparent base material 41 and the transparent conductive layer 42 also passes through the protective layer 45 and passes through the electrolyte layer 30. Therefore, since it can enter into the photoelectric converting layer 20, it can utilize effectively for electric power generation. For this reason, the photoelectric conversion efficiency of incident light can be further improved.
  • the surface of the metal substrate 10 is a metal and reflects light well, the light that has been transmitted without being absorbed by the photoelectric conversion layer 20 can be reflected toward the photoelectric conversion layer 20. Therefore, the photoelectric conversion efficiency of the photoelectric conversion layer 20 can be further increased.
  • the counter electrode 40 becomes difficult to break by using resin for the transparent substrate 41, and the oxide semiconductor porous film 20 is formed on the metal electrode. Therefore, a dye-sensitized solar cell that is flexible and does not break can be produced.
  • Example 1 [Preparation of semiconductor porous layer] A titanium plate (JIS-1 type, thickness 0.3 mm) was washed with acetone, and a titanium oxide paste (Dyesol) mixed with 18NR-T and 18NR-A0 at a weight ratio of 10: 1 on one side of the titanium plate. was applied uniformly using a screen printer so as to be 5 cm ⁇ 10 cm. Then, in order to form a semiconductor porous layer, the titanium oxide paste was heat-treated at 450 ° C. for 5 hours. The film thickness of the semiconductor porous layer formed at this time is 5 ⁇ m. Moreover, it confirmed that the semiconductor porous layer formed by the X-ray structural analysis was anatase type titanium oxide.
  • an ITO / PEN (polyethylene naphthalate) substrate manufactured by Oji Tobi, PEN film thickness 200 ⁇ m
  • a metal wiring 43 as shown in FIG. 10 was formed on the transparent substrate 41 and the transparent conductive film 42.
  • a silver paste for printing (specific resistivity after sintering is 3.5 ⁇ 10 ⁇ 5 ⁇ ) was screen-printed and leveled for 10 minutes. Thereafter, it was dried in a hot air circulating furnace at 135 ° C. for 60 minutes to form a metal wiring layer 43 composed of a silver circuit.
  • the circuit width of the metal wiring layer 43 was 500 ⁇ m, and the film thickness was 5 ⁇ m at the maximum. Moreover, the metal wiring layer 43 and the current collecting terminal were connected by forming the metal wiring layer 43 in a lattice shape. Further, 31X-101 (manufactured by ThreeBond Co., Ltd.) is printed as a protective layer material by screen printing while aligning using a CCD camera so that the metal wiring layer 43 and the protective layer overlap each other. Formed.
  • the width of the protective layer 45 is about 100 ⁇ m per side on both sides in the width direction of the metal wiring layer 12, and the height from the surface of the transparent conductive film is 10 ⁇ m at a maximum. did.
  • the thickness of the protective layer 45 laminated on the metal wiring layer 43 is about 5 ⁇ m at the maximum.
  • the catalyst layer was formed by vapor-depositing platinum on it.
  • platinum was deposited by 10 nm by using a sputtering apparatus.
  • the film thickness of this catalyst layer was determined by using XRF.
  • the total light transmittance of the window portion was 70%.
  • the total light transmittance was measured using a image clarity measuring device (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • positioned at the counter electrode was 15%.
  • 31X-101 was applied, and 31X-101 was cured by irradiating light with 3000 J / ⁇ again using a xenon lamp.
  • a dye-sensitized solar cell was formed.
  • an electrolyte layer forming material an acetonitrile solution in which iodine, lithium iodide, 1,2-dimethyl-3-propylimidazolium iodide, and t-butylpyridine were dissolved was used. These solutions were prepared by dissolving in acetonitrile under a nitrogen atmosphere to be 0.05M, 0.1M, 0.6M, and 0.5M, respectively. It should be noted that “J / ⁇ ” used for the above-mentioned unit of irradiation dose can be replaced with “J / cm 2 ”.
  • Example 2 Dye-sensitized solar cell using the same method as in Example 1 except that 31X-101 and RS-75 were mixed at a weight ratio of 99.95 to 0.05, and a protective layer material was used. was made.
  • Example 3 A dye-sensitized solar cell using the same method as in Example 1 except that 31X-101 and BYK-UV3500 were mixed at a weight ratio of 99.95 to 0.05, and a protective layer material was used. Was made.
  • Example 4 A dye-sensitized solar cell using the same method as in Example 1 except that a protective layer material in which BYK-350 was mixed with 31X-101 at a weight ratio of 99.95 to 0.05 was used. Was made.
  • Example 1 A dye-sensitized solar cell was produced using the same method as in Example 1 except for the step of producing the counter electrode.
  • an ITO / PEN (polyethylene naphthalate) substrate (PEN film thickness 200 ⁇ m manufactured by Oji Tobi) having a sheet resistance of 5 cm ⁇ 10 cm and 13 ⁇ / ⁇ was used.
  • a metal wiring 43 as shown in FIG. 10 was formed on the transparent substrate 41 and the transparent conductive film 42.
  • a silver paste for printing (specific resistivity after sintering is 3.5 ⁇ 10 ⁇ 5 ⁇ ) is screen-printed, leveled for 10 minutes, dried in a hot air circulating oven at 135 ° C. for 60 minutes, and composed of a silver circuit A metal wiring layer 43 to be formed was formed.
  • the circuit width of the metal wiring layer 43 was 500 ⁇ m, and the film thickness was 5 ⁇ m at the maximum.
  • the metal wiring layer 43 and the current collecting terminal were connected by forming the metal wiring layer 43 in a lattice shape.
  • a catalyst layer was formed thereon by depositing platinum.
  • a sputtering apparatus was used to deposit 10 nm of platinum. The film thickness of this catalyst layer was determined by using XRF.
  • a metal wiring layer was formed by vapor-depositing platinum as shown in FIG. 10 on a 200 ⁇ m thick PEN (manufactured by Teijin DuPont). The film thickness of platinum at this time is 1 ⁇ m. On this, the ITO layer was vapor-deposited so that sheet resistance might be 13 ohms / square using the sputtering device. Further, a catalyst layer was formed thereon by depositing platinum. For the formation of the catalyst layer, a sputtering apparatus was used to deposit 10 nm of platinum. The film thickness of this catalyst layer was determined by using XRF.
  • a catalyst layer was formed by depositing platinum on PEN (manufactured by Teijin DuPont) having a thickness of 200 ⁇ m.
  • PEN manufactured by Teijin DuPont
  • a sputtering apparatus was used to deposit 10 nm of platinum.
  • the film thickness of this catalyst layer was determined by using XRF.
  • the dye-sensitized solar cell of the present invention produced by the process shown in Example 1 can be obtained from Table 1 and can obtain high conversion efficiency and does not deteriorate. Moreover, in the dye-sensitized solar cell produced at the process shown by the comparative example 1 to the comparative example 3, internal resistance rises and battery performance improves because the metal wiring layer provided in the counter electrode deteriorates by the electrolyte layer. Declined. Further, in Comparative Example 4, since the metal wiring layer was not provided on the counter electrode, the internal resistance was high from the initial stage, and desired battery performance could not be obtained.
  • Electrode substrate 20 Photoelectric conversion layer 25 Sensitizer 30 Electrolyte layer 40 Counter electrode 41 Transparent base material 42 Transparent electroconductive layer 43 Metal wiring layer 45 Protective layer 47 Catalyst layer

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Abstract

La présente invention concerne une cellule solaire à colorant, la cellule solaire comprenant un substrat d'électrode négative, une couche de conversion photoélectrique formée sur le substrat d'électrode négative et adaptée à transporter un sensibilisateur, une couche électrolyte formée sur la couche de conversion photoélectrique et une électrode opposée formée sur la couche électrolyte. L'électrode opposée comprend : un substrat transparent, une couche conductrice transparente formée sur le substrat transparent ; une couche de câblage métallique ayant un motif prédéterminé et disposée sur la couche conductrice transparente ; une couche protectrice formée d'une matière contenant une résine isolante et agencée pour couvrir la couche de câblage métallique ayant le motif prédéterminé ; et une couche catalytique pour couvrir la couche conductrice transparente et la couche protectrice.
PCT/JP2012/065004 2011-06-16 2012-06-12 Cellule solaire à colorant et procédé de préparation de cellule solaire à colorant WO2012173110A1 (fr)

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JP2014110169A (ja) * 2012-12-03 2014-06-12 Toppan Printing Co Ltd 電極および色素増感太陽電池
JP2014165049A (ja) * 2013-02-26 2014-09-08 Rohm Co Ltd 色素増感太陽電池およびその製造方法、および電子機器
WO2018092739A1 (fr) * 2016-11-15 2018-05-24 株式会社フジクラ Élément de conversion photoélectrique

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KR101709689B1 (ko) 2013-12-19 2017-02-23 주식회사 엘지화학 다이싱 필름 점착층 형성용 조성물 및 다이싱 필름

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JP2006134827A (ja) * 2004-11-09 2006-05-25 Nippon Oil Corp 電極および色素増感型太陽電池
JP2006252957A (ja) * 2005-03-10 2006-09-21 Nippon Oil Corp 色素増感型太陽電池
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JP2010041040A (ja) * 2008-07-10 2010-02-18 Semiconductor Energy Lab Co Ltd 光電変換装置および光電変換装置の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014110169A (ja) * 2012-12-03 2014-06-12 Toppan Printing Co Ltd 電極および色素増感太陽電池
JP2014165049A (ja) * 2013-02-26 2014-09-08 Rohm Co Ltd 色素増感太陽電池およびその製造方法、および電子機器
WO2018092739A1 (fr) * 2016-11-15 2018-05-24 株式会社フジクラ Élément de conversion photoélectrique

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