WO2011132287A1 - Method of forming a photocatalytic film on a transparent electrode - Google Patents

Method of forming a photocatalytic film on a transparent electrode Download PDF

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WO2011132287A1
WO2011132287A1 PCT/JP2010/057144 JP2010057144W WO2011132287A1 WO 2011132287 A1 WO2011132287 A1 WO 2011132287A1 JP 2010057144 W JP2010057144 W JP 2010057144W WO 2011132287 A1 WO2011132287 A1 WO 2011132287A1
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film
photocatalyst
transparent
transparent electrode
laser
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PCT/JP2010/057144
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French (fr)
Japanese (ja)
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剛 杉生
井上　鉄也
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日立造船株式会社
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Priority to KR1020127030240A priority Critical patent/KR20130092986A/en
Priority to CN2010800663372A priority patent/CN102859036A/en
Priority to PCT/JP2010/057144 priority patent/WO2011132287A1/en
Publication of WO2011132287A1 publication Critical patent/WO2011132287A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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 method for forming a photocatalytic film on the surface of a transparent electrode comprising a transparent substrate and a transparent conductive film thereon.
  • An electronic material formed by forming a photocatalytic film on a transparent electrode composed of a transparent substrate and a transparent conductive film thereon and dyeing it with a photosensitizing dye is suitable as an electrode of a photoelectric conversion element such as a dye-sensitized solar cell. Used for.
  • a photoelectric conversion element such as a dye-sensitized solar cell is formed by forming a transparent conductive film on a transparent substrate such as a glass plate and forming a photocatalytic film made of a metal oxide such as titanium oxide on the transparent conductive film.
  • An electrode obtained by dyeing a film with a photosensitizing dye such as a ruthenium complex and a counter electrode formed by forming a transparent conductive film on a counter electrode substrate are arranged opposite to each other, and an iodine electrolyte or the like is formed between the electrodes.
  • Patent Document 1 One having an electrolyte layer interposed is known (Patent Document 1).
  • Patent Documents 2 and 3 disclose a method for forming a photocatalytic film made of crystalline titanium oxide suitable for use in such a photoelectric conversion element.
  • JP 2002-93475 A Japanese Patent Laid-Open No. 11-310898 JP 2005-108807 A
  • Patent Document 3 a porous layer of titanium oxide is deposited on a substrate by an electrostatic electrodeposition method.
  • this method although it can be deposited on a substrate at a low temperature, the photocatalyst particles are bonded to each other inside the photocatalyst film.
  • the present invention makes it possible to use a material having low heat resistance for the transparent conductive film and the substrate by omitting the high-temperature treatment as described above, and to combine the photocatalyst particles inside the photocatalyst film and the photocatalyst film.
  • a method for forming a photocatalyst film that can strengthen the bond between photocatalyst particles and a transparent electrode.
  • the invention according to claim 1 is a photocatalyst obtained by electrostatically applying a metal oxide sol on a transparent conductive film in a transparent electrode comprising a transparent substrate and a transparent conductive film thereon, and firing the resulting coating film at a low temperature.
  • the invention according to claim 2 is a photocatalyst obtained by electrostatically applying a metal oxide sol on a transparent conductive film in a transparent electrode comprising a transparent substrate and a transparent conductive film thereon, and firing the resulting coating film at a low temperature.
  • the method of forming a photocatalyst film on a transparent electrode is characterized in that the additional operation consisting of:
  • a transparent electrode comprising a transparent substrate and a transparent conductive film thereon is coated with a metal oxide sol electrostatically on the transparent conductive film to form a photocatalytic film.
  • a transparent electrode composed of a transparent substrate and a transparent conductive film thereon is coated with a transparent electrode on the photocatalytic film while forming a photocatalytic film by electrostatically applying a metal oxide sol onto the transparent conductive film.
  • a photocatalyst film is bonded by irradiating a laser through the same electrode from the side, and an additional operation including the formation of the photocatalyst film on the photocatalyst film and the laser irradiation to the photocatalyst film is performed at least once.
  • a method of forming a photocatalytic film on a transparent electrode is performed at least once.
  • the invention according to claim 5 is characterized in that the coating film or the photocatalyst film is pressurized from the front side thereof either simultaneously with laser irradiation, before or after laser irradiation, or both.
  • This is a method for forming a photocatalytic film on a transparent electrode.
  • the invention according to claim 6 is the method for forming a photocatalyst film on a transparent electrode according to claim 5, wherein the coating film or the photocatalyst film is pressurized while the film is heated.
  • the bonds between the photocatalyst particles inside the photocatalyst film and the bond between the photocatalyst film and the transparent conductive film of the transparent electrode are both strong.
  • a photoelectric conversion element exhibiting sufficient efficiency can be manufactured.
  • FIG. 1 is a vertical longitudinal sectional view schematically showing a method of Example 1.
  • FIG. FIG. 6 is a vertical longitudinal sectional view schematically showing a method of Example 3.
  • 6 is a vertical longitudinal sectional view schematically showing a method of Example 4.
  • FIG. It is a vertical longitudinal cross-sectional view which shows the method of an Example roughly.
  • 10 is a vertical longitudinal sectional view schematically showing a method of Example 7.
  • FIG. 10 is a vertical longitudinal sectional view schematically showing the method of Example 8.
  • 5 is a vertical longitudinal sectional view showing a photoelectric conversion element of Reference Example 1.
  • a transparent electrode composed of a transparent substrate and a transparent conductive film thereon is electrostatically coated with a metal oxide sol on the transparent conductive film, and the resulting coating film is baked at a low temperature.
  • a method of forming a photocatalyst film on a transparent electrode comprising forming a photocatalyst film and irradiating the coating film or the photocatalyst film with laser before or after firing.
  • a transparent electrode composed of a transparent substrate and a transparent conductive film formed thereon will be described.
  • thermoplastic resin film such as a PEN (polyethylene naphthalate) film is preferable.
  • the synthetic resin may be polyethylene terephthalate, polyester, polycarbonate, polyolefin, or the like.
  • the thickness of the transparent substrate is preferably several tens of ⁇ m to 1 mm, and the thickness of the transparent conductive film is preferably several tens to several hundreds of nm.
  • the formation of the transparent conductive film on the transparent substrate is performed by a method in which a metal oxide sol is electrostatically coated on the transparent conductive film and baked at a low temperature.
  • the electrostatic coating apparatus is on the negative side and the transparent conductive film of the transparent electrode that is the object to be coated is on the positive side, a high voltage is applied between them to form an electrostatic field, and spray from the spray nozzle of the electrostatic coating apparatus The resulting metal oxide is charged to the negative side and applied to the surface of the transparent conductive film.
  • the electrostatic coating apparatus is not limited to the above configuration as long as it can apply the metal oxide sol onto the transparent conductive film.
  • metal compound used as a starting material for the metal oxide sol examples include metal alkoxides, metal acetylacetonates, metal carboxylates, and metal inorganic compounds such as metal nitrates, oxychlorides, and chlorides. Can be mentioned.
  • titanium oxide is preferable, and other examples include tin oxide, tungsten oxide, zinc oxide, and niobium oxide.
  • titanium oxide as metal alkoxide, titanium tetramethoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, etc.
  • metal acetylacetonate as titanium acetylacetonate
  • metal carboxylate Titanium carboxylate, titanium nitrate, titanium oxychloride, titanium tetrachloride and the like.
  • the above metal compounds include water, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, etc.
  • a solvent, acid or ammonia, and other additives sol-formation and gelation are performed.
  • the metal alkoxide when used, includes the metal oxide particles having a particle size of 20 to 60 nm, and optionally, metal oxide particles having a particle size of 100 to 400 ⁇ m as light scattering particles. Is preferred.
  • Drying is preferably performed at room temperature for about 5 to 15 minutes. Firing is preferably performed at a low temperature (120 to 150) ° C. for about 10 to 20 minutes.
  • the thickness of the photocatalyst film before laser irradiation formed by the above method is preferably 5 to 20 ⁇ m.
  • Laser irradiation is applied to the photocatalyst layer from the transparent electrode side and / or from the surface side of the photocatalyst layer, and the photocatalyst film is irradiated to strengthen the bond between the photocatalyst particles, and the photocatalyst film and the transparent conductive film of the transparent electrode By irradiating the interface, the bond between the transparent conductive film and the photocatalytic film is strengthened.
  • the laser that irradiates the photocatalyst film from the transparent electrode side is preferably a visible light region (380 nm to 800 nm), specifically, an Nd: YAG laser (1064 nm) infrared ray, and a green wavelength of 532 nm using a wavelength conversion element.
  • Light (SHG) or alexandrite laser (700-820nm) is applicable. Note that an optical system capable of forming a short focal point is assembled at the time of laser irradiation, and the coupling effect is further improved by focusing on the interface between the transparent conductive film and the photocatalytic film.
  • a laser oscillator that oscillates such a laser is equipped with a galvano scanner, and the laser irradiation position can be freely changed.
  • the laser that irradiates the photocatalyst film from the surface side is preferably visible light region to near infrared region (700 nm to 1100 nm), specifically Nd: YAG laser (1064 nm), Nd: YVO4 laser (1064 nm), or Tunable lasers such as TI: sapphire laser (650-1100 nm), Cr: LiSAF laser (780-1010 nm), alexandrite laser (700-820 nm), and CO2 laser are applicable.
  • Laser irradiation is performed either before or after firing.
  • a transparent electrode composed of a transparent substrate and a transparent conductive film thereon is coated with a metal oxide sol electrostatically on the transparent conductive film to form a photocatalytic film, while being transparent to the photocatalytic film.
  • the formation of the photocatalyst film and between the photocatalyst particles inside the photocatalyst film Bonding and bonding between the photocatalytic film and the transparent conductive film of the transparent electrode are performed.
  • Laser irradiation may be applied to the photocatalyst layer from the transparent electrode side and / or from the surface side of the photocatalyst layer.
  • the electrode for electrostatic coating and the stage on which the electrode is placed are made of a material that transmits the laser. Has been.
  • the laser that irradiates the photocatalyst film from the transparent electrode side and the laser that irradiates the photocatalyst film from the surface side thereof may each be the one described for the first invention.
  • first and second inventions after the photocatalyst film by electrostatic coating and the photocatalyst layer by laser irradiation thereafter are combined, another photocatalyst film is formed on the combined photocatalyst film and the photocatalyst film is formed. It is preferable to perform at least one additional operation consisting of the above laser irradiation.
  • the coating film or the photocatalyst film it is preferable to pressurize the coating film or the photocatalyst film at a pressure of 10 MPa to 100 MPa from the front side thereof either simultaneously with laser irradiation or before or after laser irradiation.
  • the pressurization of the photocatalyst film is performed using a flat plate press, a roll press, or the like.
  • a roll-shaped press device By using a roll-shaped press device, the photocatalytic film can be continuously pressurized.
  • a heating element may be provided inside the roll-shaped press device to heat it, or the roll-shaped press device may be made of a transparent material, and laser may be irradiated from the inside.
  • the pressurization of the coating film or the photocatalytic film is preferably performed while heating the photocatalytic film.
  • the photocatalyst film may be heated by a method in which an electric heater is installed inside the press apparatus or a high-temperature fluid is allowed to flow inside the press apparatus.
  • the heating temperature of the photocatalytic film is preferably 150 ° C.
  • the surface of the photocatalytic film is dyed.
  • This dyeing is performed, for example, by immersing the photocatalyst film formed on the transparent electrode in an immersion liquid containing a photosensitizing dye and adsorbing the dye on the surface of the photocatalyst film. After immersion, it is preferable to perform drying and further firing.
  • Photosensitizing dyes include, for example, ruthenium complexes and iron complexes having a ligand containing a bipyridine structure, a terpyridine structure, etc., porphyrin-based and phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and coumarin. It may be.
  • the dyeing photocatalyst film formed on the transparent electrode is suitably used as an electrode of a photoelectric conversion element such as a dye-sensitized solar cell.
  • the photoelectric conversion element is mainly composed of, for example, a transparent electrode provided with the dyeing photocatalyst film, a counter electrode facing the transparent electrode, and an electrolyte layer disposed between both electrodes.
  • an iodine-based electrolyte for example, an iodine-based electrolyte is used. Specifically, an electrolyte component such as iodine, iodide ion, or tertiary butyl pyridine is dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile. Is exemplified.
  • the electrolyte is not limited to an electrolyte and may be a solid electrolyte. Examples of the solid electrolyte include DMPImI (dimethylpropylimidazolium iodide).
  • metal iodides such as LiI, NaI, KI, CsI, and CaI2
  • quaternary ammonium compounds such as tetraalkylammonium iodide
  • iodide such as iodine salt and I2
  • bromide such as bromide
  • bromide of quaternary ammonium compound such as metal bromide such as LiBr, NaBr, KBr, CsBr and CaBr2
  • tetraalkylammonium bromide and Br2 can be used suitably.
  • the counter electrode may be one in which a transparent conductive film is formed on a transparent substrate for a counter electrode, or one in which a sheet of metal such as aluminum, copper, or tin is provided on the same substrate.
  • the counter electrode may be configured by holding a gel solid electrolyte on a mesh electrode made of metal (aluminum, copper, tin, etc.) or carbon, and conductive adhesion is performed on one side of the counter electrode substrate.
  • the counter electrode may be configured by forming an agent layer so as to cover the substrate and transferring a separately formed group of brush-like carbon nanotubes to the substrate via the adhesive layer.
  • the electrode provided with the dyeing photocatalyst film and the counter electrode are aligned to face each other, the gap between the electrodes is sealed with a heat-sealing film or a sealing material, and the counter electrode or the electrode is provided in advance.
  • Electrolyte is injected through the holes and gaps.
  • both electrodes are overlapped so that the photocatalyst film and the electrolyte layer are sandwiched therebetween, and the peripheral portions thereof are heat bonded.
  • Heating may be performed by a mold, or may be performed by irradiation with an energy beam such as plasma (having a long wavelength), microwave, visible light (600 nm or more), or infrared light.
  • a transparent conductive film for electrodes, a transparent conductive film for counter electrodes, a collector electrode, an electrolyte layer, and a photocatalyst film are arranged at a predetermined interval between a transparent electrode substrate and a transparent substrate for a counter electrode.
  • the connection between the electrode and the counter electrode at this time may be in series or in parallel.
  • the electrolyte layer and the photocatalyst film are separated from each other by the sealing material.
  • a gap is formed between adjacent transparent conductive films for electrodes, transparent conductive films for counter electrodes, and current collecting electrodes, and the transparent conductive films for electrodes adjacent to each other are conductors. Connected by.
  • the transparent conductive film for electrode, the transparent conductive film for counter electrode, and the current collecting electrode are formed such that there is no gap between adjacent ones.
  • Example 1 In FIG. 1 (a), titanium (IV) isopropoxide is applied to a transparent electrode (3) consisting of a transparent substrate (1) made of polyethylene naphthalate film and a transparent conductive film (2) made of ITO thereon.
  • TTIP transparent conductive film
  • the distance between the spray nozzle (7) and the transparent electrode (3) is 80 mm, and a voltage of 20 kv is applied between the nozzle (7) and the electrode (6) on the stage (5) to Electrostatic coating was performed until the thickness reached 10 ⁇ m.
  • the resulting coating film was then dried at room temperature and further baked at a low temperature of 150 ° C.
  • a photocatalytic film (4) was directly irradiated with an alexandrite laser (700-820nm) from the surface side. Irradiated.
  • an immersion liquid containing a photosensitizing dye (ruthenium complex (N719, molecular weight 1187.7 g./mol) was added to t-butanol: The dye was dissolved in acetonitrile (volume ratio 1: 1) and immersed in a dye concentration: 0.3 mM at a temperature of 40 ° C. for 40 minutes to adsorb the dye on the surface of the photocatalyst film.
  • Example 2 In Example 1, the photocatalytic film (4) was irradiated with an alexandrite laser (700-820 nm) from the transparent electrode (3) side while being irradiated with an alexandrite laser (700-820 nm) from the surface side through the same electrode.
  • an alexandrite laser 700-820 nm
  • Example 3 As shown in FIG. 2, a photocatalyst is formed using a laser oscillator (8) equipped with a galvano scanner while forming a photocatalyst film (4) on the transparent electrode (3) by electrostatic coating in the same manner as in Example 1.
  • the film (4) was also directly irradiated with alexandrite laser (700-820 nm) from the surface side.
  • Example 4 As shown in FIG. 3, a photocatalyst is formed using a laser oscillator (8) equipped with a galvano scanner while forming a photocatalyst film (4) on the transparent electrode (3) by electrostatic coating in the same manner as in Example 1.
  • the film (4) was irradiated with an alexandrite laser (700-820 nm) through a transparent stage (5) and a transparent electrode (6) thereon.
  • Example 5 As shown in FIG. 4 (a), after the first photocatalytic film (4) is bonded to the transparent electrode (3) in the same manner as in Example 1, the first photocatalyst film (4) is bonded as shown in FIG. 4 (b). On the photocatalyst film (4), electrostatic coating, drying and firing were carried out in the same manner as in Example 1 to form a second photocatalyst film (9). Next, using a laser oscillator (8) equipped with a galvano scanner, the second photocatalyst film (9) is directly irradiated with an alexandrite laser (700-820 nm) from the surface side to form the first photocatalyst film (4). A second photocatalyst film (9) was bonded on top.
  • a laser oscillator (8) equipped with a galvano scanner the second photocatalyst film (9) is directly irradiated with an alexandrite laser (700-820 nm) from the surface side to form the first photocata
  • the fourth photocatalyst film (11) is formed on the third photocatalyst film (10) by electrostatic coating, drying and firing by the same operation as described above. Formed. Subsequently, the fourth photocatalyst film (11) was bonded to the third photocatalyst film (10) by irradiating the fourth photocatalyst film (11) with laser from the surface side by the same operation as described above.
  • the fifth photocatalyst film (12) is formed on the fourth photocatalyst film (11) by electrostatic coating, drying and firing by the same operation as described above. Formed. Subsequently, the fourth photocatalyst film (12) was irradiated with laser from the surface side by the same operation as described above, and the fifth photocatalyst film (12) was bonded onto the fourth photocatalyst film (11).
  • Example 6 After the first photocatalyst film (4) having a thickness of 2 ⁇ m was bonded to the transparent electrode (3) in the same manner as in Example 3, four photocatalysts having a thickness of 2 ⁇ m were formed on the first photocatalyst film (4). A film was formed.
  • Example 7 In the laser irradiation step of Example 1, as shown in FIG. 5, before and after this firing, the photocatalyst film (4) was pressed from the surface side with a roll-shaped press device (13) at a pressure of 50 MPa for 30 seconds. Using a laser oscillator (8) equipped with a galvano scanner, the photocatalytic film (4) was irradiated with an alexandrite laser (700-820 nm) from the transparent electrode (3) side. By using the roll-shaped pressing device (13), it was possible to continuously pressurize the photocatalyst film (4).
  • Example 8 In Example 7, the photocatalyst film (4) was pressurized to the transparent electrode (3) using a flat plate pressing device (14) shown in FIG. 6 instead of the roll pressing device. Pressurization was carried out for 30 seconds at a pressure of 50 MPa and a press apparatus temperature of 150 ° C. using a flat press apparatus (15) provided with an electric heater wire (14) inside.
  • Example 9 laser irradiation to the photocatalyst film (4) is performed from the surface side of the photocatalyst film (4) through a transparent flat plate pressing device (14) and also from the transparent electrode (3) side, an alexandrite laser ( 700-820 nm).
  • FIG. 7 shows an example of a photoelectric conversion element constituted by using a transparent electrode provided with a photocatalytic film dyed with a photosensitizing dye.
  • the photoelectric conversion element is mainly composed of a transparent electrode provided with a dyeing photocatalyst film, a counter electrode facing the transparent electrode, and an electrolyte layer disposed between both electrodes.
  • (21) is a transparent substrate
  • (22) is a transparent conductive film formed on the transparent substrate (21)
  • (24) is a counter electrode substrate
  • (25) is provided on the substrate (24).
  • the counter electrode is made of platinum.
  • (26) is a plurality of sealing materials and separators provided between both electrodes, and a plurality of sections are formed between these electrodes.
  • (23) is a photocatalytic film formed on the transparent conductive film (22) in each section, which is dyed with a photosensitizing dye. An electrolyte is injected into each compartment.
  • (27) is a plurality of interelectrodes passed to both electrodes
  • (28) is a sealing material for interelectrode protection.
  • a dye-sensitized solar cell having a thickness of several ⁇ m and a square of 100 mm was prepared, and when the power conversion efficiency was measured by irradiation with a standard light source of AM 1.5 and 100 mW / cm 2, the dyed photocatalyst film obtained in Example 1 was provided.
  • conversion efficiency ⁇ 5 to 6%.
  • conversion efficiency ⁇ 6 to 7%. High efficiency was obtained.
  • Transparent substrate (2) Transparent conductive film (3) Transparent electrode (4) (9) (10) (11) (12) Photocatalytic membrane (5) Stage (6) Electrode (7) Spray nozzle (8) Laser oscillator (13) (15) Press left (14) Heater wire
  • the present invention relates to a method for forming a photocatalyst film on the surface of a transparent electrode, which enables the use of a material having low heat resistance for a transparent conductive film or a substrate, and the bonding of photocatalyst particles inside the photocatalyst film and the photocatalyst film. Since the bond between the photocatalyst particles and the transparent electrode can be strengthened, an electronic material formed by dyeing the photocatalyst film thus formed with a photosensitizing dye is used for photoelectric conversion such as dye-sensitized solar cells. It can contribute to being used suitably as an electrode of an element.

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Abstract

Disclosed is a method of forming a photocatalytic film capable of strengthening bonds between photocatalytic particles in the photocatalytic film, and between a transparent electrode and the photocatalytic particles of the photocatalytic film. A transparent electrode (3) comprises a transparent substrate (1) and a transparent conductive film (2) thereon. A metal oxide sol coating is applied electrostatically on the transparent conductive film (2), and a photocatalytic film is formed by low-temperature firing of the resulting coating. Before, after, or before and after the firing, the coating film or the photocatalytic film is irradiated with a laser.

Description

透明電極上における光触媒膜の形成方法Method for forming photocatalytic film on transparent electrode
　本発明は、透明基板とその上の透明導電膜とからなる透明電極の表面に光触媒膜を形成する方法に関する。透明基板とその上の透明導電膜とからなる透明電極に光触媒膜を形成し、これを光増感色素で染色して成る電子材料は、色素増感太陽電池などの光電変換素子の電極として好適に用いられる。 The present invention relates to a method for forming a photocatalytic film on the surface of a transparent electrode comprising a transparent substrate and a transparent conductive film thereon. An electronic material formed by forming a photocatalytic film on a transparent electrode composed of a transparent substrate and a transparent conductive film thereon and dyeing it with a photosensitizing dye is suitable as an electrode of a photoelectric conversion element such as a dye-sensitized solar cell. Used for.
　一般に、色素増感型太陽電池などの光電変換素子は、ガラス板などの透明基板上に透明導電膜を形成し、その上に酸化チタンのような金属酸化物からなる光触媒膜を形成し、同膜をルテニウム錯体などの光増感色素で染色してなる電極と、対極用基板上に透明導電膜を形成してなる対極とを対向状に配置し、両電極間にヨウ素系電解質などからなる電解質層を介在させたものが知られている（特許文献１）。 In general, a photoelectric conversion element such as a dye-sensitized solar cell is formed by forming a transparent conductive film on a transparent substrate such as a glass plate and forming a photocatalytic film made of a metal oxide such as titanium oxide on the transparent conductive film. An electrode obtained by dyeing a film with a photosensitizing dye such as a ruthenium complex and a counter electrode formed by forming a transparent conductive film on a counter electrode substrate are arranged opposite to each other, and an iodine electrolyte or the like is formed between the electrodes. One having an electrolyte layer interposed is known (Patent Document 1).
　また、特許文献２、３には、このような光電変換素子で使用するのに適した結晶性酸化チタンからなる光触媒膜を形成する方法が開示されている。 Patent Documents 2 and 3 disclose a method for forming a photocatalytic film made of crystalline titanium oxide suitable for use in such a photoelectric conversion element.
特開２００２－９３４７５号公報JP 2002-93475 A 特開平１１－３１０８９８号公報Japanese Patent Laid-Open No. 11-310898 特開２００５－１０８８０７号公報JP 2005-108807 A
　上記のような色素増感型太陽電池では、光触媒膜の内部における光触媒粒子同士の結合および光触媒膜の光触媒粒子と透明電極との結合を強固なものとすることが重要であり、そのために、特許文献１では、酸化チタン微粒子を有機バインダーと有機溶剤により分散させたペーストを、上記透明導電膜上に塗布した後、これを４５０℃の高温で処理することにより、酸化チタン微粒子を焼結させて酸化チタンの多孔質層を形成している。また、特許文献２では、電気泳動によって酸化チタン前駆体膜を形成した後、４００℃以上の温度で焼成することで酸化チタン膜を形成している。 In the dye-sensitized solar cell as described above, it is important to strengthen the bond between the photocatalyst particles inside the photocatalyst film and the bond between the photocatalyst particles of the photocatalyst film and the transparent electrode. In Document 1, a paste in which titanium oxide fine particles are dispersed with an organic binder and an organic solvent is applied on the transparent conductive film, and then treated at a high temperature of 450 ° C. to sinter the titanium oxide fine particles. A porous layer of titanium oxide is formed. Moreover, in patent document 2, after forming a titanium oxide precursor film | membrane by electrophoresis, the titanium oxide film | membrane is formed by baking at the temperature of 400 degreeC or more.
　しかしながら、４５０℃もの高温処理を行うと、透明導電膜の導電性が損なわれるため、このような高温でも導電性を失わない透明導電膜を得るには材料としてフッ素ドープ酸化スズ（ＦＴＯ）などを用いる必要があり、使用できる材料が限られる。また、上記透明導電膜を支持する基板も耐熱性を有するガラス基板などに限られるため、製品を低コスト化することおよび柔軟性を有するフレキシブルな太陽電池を作製することは困難であった。さらに、上記酸化チタン膜が高温下に晒されることにより活性低下し、電池性能の低下につながるという問題があった。 However, when the high temperature treatment at 450 ° C. is performed, the conductivity of the transparent conductive film is impaired. Therefore, in order to obtain a transparent conductive film that does not lose its conductivity even at such a high temperature, fluorine-doped tin oxide (FTO) or the like is used as a material. It is necessary to use, and the material which can be used is limited. Moreover, since the substrate supporting the transparent conductive film is also limited to a glass substrate having heat resistance, it has been difficult to reduce the cost of the product and to produce a flexible solar cell having flexibility. Furthermore, there has been a problem that the titanium oxide film is exposed to a high temperature to decrease its activity, leading to a decrease in battery performance.
　特許文献３では、酸化チタンの多孔質層を静電的電着法により基板に堆積させているが、この方法では、低温で基板に堆積はできるものの、光触媒膜の内部における光触媒粒子同士の結合および光触媒膜の光触媒粒子と透明電極との結合が十分でないという問題があった。 In Patent Document 3, a porous layer of titanium oxide is deposited on a substrate by an electrostatic electrodeposition method. In this method, although it can be deposited on a substrate at a low temperature, the photocatalyst particles are bonded to each other inside the photocatalyst film. In addition, there is a problem that the coupling between the photocatalyst particles of the photocatalyst film and the transparent electrode is not sufficient.
　そこで、本発明は、上記のような高温処理を省くことで、透明導電膜や基板に耐熱性の低い材料の使用を可能とし、かつ、光触媒膜の内部における光触媒粒子同士の結合および光触媒膜の光触媒粒子と透明電極との結合を強固なものとすることができる光触媒膜の形成方法を提供する。 Therefore, the present invention makes it possible to use a material having low heat resistance for the transparent conductive film and the substrate by omitting the high-temperature treatment as described above, and to combine the photocatalyst particles inside the photocatalyst film and the photocatalyst film. Provided is a method for forming a photocatalyst film that can strengthen the bond between photocatalyst particles and a transparent electrode.
　請求項１に係る発明は、透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、生じた塗膜を低温で焼成することにより光触媒膜を形成し、焼成の前後いずれか若しくは両方において塗膜または光触媒膜にレーザを照射することを特徴とする、透明電極上における光触媒膜の形成方法である。 The invention according to claim 1 is a photocatalyst obtained by electrostatically applying a metal oxide sol on a transparent conductive film in a transparent electrode comprising a transparent substrate and a transparent conductive film thereon, and firing the resulting coating film at a low temperature. A method for forming a photocatalyst film on a transparent electrode, comprising forming a film and irradiating the coating film or the photocatalyst film with a laser either before or after firing.
　請求項２に係る発明は、透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、生じた塗膜を低温で焼成することにより光触媒膜を形成し、焼成の前後いずれか若しくは両方において塗膜または光触媒膜にレーザを照射して光触媒膜を結合させ、さらにこの光触媒膜の上での光触媒膜の形成と同光触媒膜へのレーザ照射とからなる追加操作を少なくとも１回行うことを特徴とする、透明電極上における光触媒膜の形成方法である。 The invention according to claim 2 is a photocatalyst obtained by electrostatically applying a metal oxide sol on a transparent conductive film in a transparent electrode comprising a transparent substrate and a transparent conductive film thereon, and firing the resulting coating film at a low temperature. Form a film, irradiate the coating film or photocatalyst film with laser before or after firing, or combine the photocatalyst film, and then form the photocatalyst film on this photocatalyst film and irradiate the photocatalyst film with laser The method of forming a photocatalyst film on a transparent electrode is characterized in that the additional operation consisting of:
　請求項３に係る発明は、透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、光触媒膜を形成しながら、光触媒膜に透明電極側から同電極を経てレーザを照射することを特徴とする、透明電極上における光触媒膜の形成方法である。 According to a third aspect of the present invention, a transparent electrode comprising a transparent substrate and a transparent conductive film thereon is coated with a metal oxide sol electrostatically on the transparent conductive film to form a photocatalytic film. A method of forming a photocatalyst film on a transparent electrode, characterized in that a laser is irradiated from the side through the same electrode.
　請求項４に係る発明は、透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、光触媒膜を形成しながら、光触媒膜に透明電極側から同電極を経てレーザを照射して光触媒膜を結合させ、さらにこの光触媒膜の上への光触媒膜の形成と同光触媒膜へのレーザ照射とからなる追加操作を少なくとも１回行うことを特徴とする、透明電極上における光触媒膜の形成方法である。 According to a fourth aspect of the present invention, a transparent electrode composed of a transparent substrate and a transparent conductive film thereon is coated with a transparent electrode on the photocatalytic film while forming a photocatalytic film by electrostatically applying a metal oxide sol onto the transparent conductive film. A photocatalyst film is bonded by irradiating a laser through the same electrode from the side, and an additional operation including the formation of the photocatalyst film on the photocatalyst film and the laser irradiation to the photocatalyst film is performed at least once. And a method of forming a photocatalytic film on a transparent electrode.
　請求項５に係る発明は、レーザ照射と同時にまたはレーザ照射の前後いずれか若しくは両方において、塗膜または光触媒膜をその表側から加圧することを特徴とする、請求項１～４のいずれかに記載の透明電極上における光触媒膜の形成方法である。 The invention according to claim 5 is characterized in that the coating film or the photocatalyst film is pressurized from the front side thereof either simultaneously with laser irradiation, before or after laser irradiation, or both. This is a method for forming a photocatalytic film on a transparent electrode.
　請求項６に係る発明は、塗膜または光触媒膜の加圧を、同膜を加熱しながら行うことを特徴とする、請求項５記載の透明電極上における光触媒膜の形成方法である。 The invention according to claim 6 is the method for forming a photocatalyst film on a transparent electrode according to claim 5, wherein the coating film or the photocatalyst film is pressurized while the film is heated.
　本発明によれば、光触媒膜に透明電極側からレーザを照射することで、光触媒膜の内部における光触媒粒子同士の結合、および光触媒膜と透明電極の透明導電膜との結合をいずれも強固なものとすることができ、これにより、充分な効率を示す光電変換素子を製造することができる。 According to the present invention, by irradiating the photocatalyst film with a laser from the transparent electrode side, the bonds between the photocatalyst particles inside the photocatalyst film and the bond between the photocatalyst film and the transparent conductive film of the transparent electrode are both strong. Thus, a photoelectric conversion element exhibiting sufficient efficiency can be manufactured.
実施例１の方法を概略的に示す垂直縦断面図である。1 is a vertical longitudinal sectional view schematically showing a method of Example 1. FIG. 実施例３の方法を概略的に示す垂直縦断面図である。FIG. 6 is a vertical longitudinal sectional view schematically showing a method of Example 3. 実施例４の方法を概略的に示す垂直縦断面図である。6 is a vertical longitudinal sectional view schematically showing a method of Example 4. FIG. 実施例の方法を概略的に示す垂直縦断面図である。It is a vertical longitudinal cross-sectional view which shows the method of an Example roughly. 実施例７の方法を概略的に示す垂直縦断面図である。10 is a vertical longitudinal sectional view schematically showing a method of Example 7. FIG. 実施例８の方法を概略的に示す垂直縦断面図である。FIG. 10 is a vertical longitudinal sectional view schematically showing the method of Example 8. 参考例１の光電変換素子を示す垂直縦断面図である。5 is a vertical longitudinal sectional view showing a photoelectric conversion element of Reference Example 1. FIG.
　本発明の第１のものは、透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、生じた塗膜を低温で焼成することにより光触媒膜を形成し、焼成の前後いずれか若しくは両方において塗膜または光触媒膜にレーザを照射することを特徴とする、透明電極上における光触媒膜の形成方法である。 According to the first aspect of the present invention, a transparent electrode composed of a transparent substrate and a transparent conductive film thereon is electrostatically coated with a metal oxide sol on the transparent conductive film, and the resulting coating film is baked at a low temperature. A method of forming a photocatalyst film on a transparent electrode, comprising forming a photocatalyst film and irradiating the coating film or the photocatalyst film with laser before or after firing.
　まず、透明基板と、その上に形成された透明導電膜とからなる透明電極について、説明をする。 First, a transparent electrode composed of a transparent substrate and a transparent conductive film formed thereon will be described.
　透明基板としては、合成樹脂板、ガラス板などが適宜使用されるが、ＰＥＮ（ポリエチレン・ナフタレート）フィルムなどの熱可塑性樹脂フィルムが好ましい。合成樹脂は、ＰＥＮの他に、ポリエチレン・テレフタレート、ポリエステル、ポリカーボネート、ポリオレフィンなどであってもよい。 As the transparent substrate, a synthetic resin plate, a glass plate or the like is appropriately used, but a thermoplastic resin film such as a PEN (polyethylene naphthalate) film is preferable. In addition to PEN, the synthetic resin may be polyethylene terephthalate, polyester, polycarbonate, polyolefin, or the like.
　透明基板の厚さは好ましくは数十μm～1mm、透明導電膜の厚さは好ましくは数十～数百ｎｍである。 The thickness of the transparent substrate is preferably several tens of μm to 1 mm, and the thickness of the transparent conductive film is preferably several tens to several hundreds of nm.
　透明基板上への透明導電膜の形成は、透明導電膜上に金属酸化物ゾルを静電塗布し、低温で焼成する方法によって行われる。 The formation of the transparent conductive film on the transparent substrate is performed by a method in which a metal oxide sol is electrostatically coated on the transparent conductive film and baked at a low temperature.
　より詳しくは、静電塗布装置をマイナス側とし被塗物である透明電極の透明導電膜をプラス側として、この間に高電圧を加えて静電界を形成し、静電塗布装置のスプレーノズルから噴霧された金属酸化物をマイナス側に帯電させて透明導電膜表面に塗布する。静電塗布装置は金属酸化物ゾルを透明導電膜上に塗布できるものであれば良く、上記構成に限定されない。 More specifically, the electrostatic coating apparatus is on the negative side and the transparent conductive film of the transparent electrode that is the object to be coated is on the positive side, a high voltage is applied between them to form an electrostatic field, and spray from the spray nozzle of the electrostatic coating apparatus The resulting metal oxide is charged to the negative side and applied to the surface of the transparent conductive film. The electrostatic coating apparatus is not limited to the above configuration as long as it can apply the metal oxide sol onto the transparent conductive film.
　金属酸化物ゾルの出発原料となる金属化合物としては、金属有機化合物では、例えば金属アルコキシド、金属アセチルアセトネート、金属カルボキシレート、金属無機化合物では、例えば金属の硝酸塩、オキシ塩化物、塩化物などが挙げられる。 Examples of the metal compound used as a starting material for the metal oxide sol include metal alkoxides, metal acetylacetonates, metal carboxylates, and metal inorganic compounds such as metal nitrates, oxychlorides, and chlorides. Can be mentioned.
　上記金属酸化物としては、酸化チタンが好ましく、その他酸化スズ、酸化タングステン、酸化亜鉛、酸化ニオブなどが挙げられる。 As the metal oxide, titanium oxide is preferable, and other examples include tin oxide, tungsten oxide, zinc oxide, and niobium oxide.
　酸化チタンを用いた一例として、金属アルコキシドとしては、チタンテトラメトキシド、チタンエトキシド、チタンイソプロポキシド、チタンブタキシドなど、金属アセチルアセトネートとしては、チタンアセチルアセトネートなど、金属カルボキシレートとしては、チタンカルボキシレートなど、硝酸チタン、オキシ塩化チタン、四塩化チタンなどが挙げられる。 As an example using titanium oxide, as metal alkoxide, titanium tetramethoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, etc., as metal acetylacetonate, as titanium acetylacetonate, as metal carboxylate , Titanium carboxylate, titanium nitrate, titanium oxychloride, titanium tetrachloride and the like.
　さらに、上記金属化合物に、水、メタノール、エタノール、１－プロパノール、イソプロピルアルコール、１－ブタノール、２－ブタノール、イソブタノール、ｔ－ブタノール、１－ペンタノール、２－ペンタノール、３－ペンタノールなどの溶媒、酸またはアンモニア、その他添加物などを加えることでゾル化、ゲル化を行う。 Further, the above metal compounds include water, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, etc. By adding a solvent, acid or ammonia, and other additives, sol-formation and gelation are performed.
　上記、金属アルコキシドを用いる場合は、金属アルコキシドに、粒径20～60nmの上記金属酸化物の粒子、さらに必要に応じて光散乱用粒子として粒径100～400μmの金属酸化物の粒子を含んでなるものが好ましい。 When the metal alkoxide is used, the metal alkoxide includes the metal oxide particles having a particle size of 20 to 60 nm, and optionally, metal oxide particles having a particle size of 100 to 400 μm as light scattering particles. Is preferred.
　乾燥は、室温で、5～15分程度行うのが好ましい。焼成は、低温（１２０～１５０）℃で、10～20分程度行うのがこのましい。 Drying is preferably performed at room temperature for about 5 to 15 minutes. Firing is preferably performed at a low temperature (120 to 150) ° C. for about 10 to 20 minutes.
　上記方法により、より形成されたレーザ照射前の光触媒膜の厚みは、好ましくは5～20μmである。 The thickness of the photocatalyst film before laser irradiation formed by the above method is preferably 5 to 20 μm.
　次に、光触媒膜にレーザを照射する工程について、説明をする。 Next, the process of irradiating the photocatalyst film with laser will be described.
　レーザ照射は光触媒層に透明電極側から、および／または、光触媒層の表面側から照射され、光触媒膜に照射することにより光触媒粒子同士の結合を強固にし、光触媒膜と透明電極の透明導電膜との界面に照射することにより透明導電膜と光触媒膜との結合を強固にするものである。 Laser irradiation is applied to the photocatalyst layer from the transparent electrode side and / or from the surface side of the photocatalyst layer, and the photocatalyst film is irradiated to strengthen the bond between the photocatalyst particles, and the photocatalyst film and the transparent conductive film of the transparent electrode By irradiating the interface, the bond between the transparent conductive film and the photocatalytic film is strengthened.
　光触媒膜に透明電極側から照射するレーザとしては、好ましくは可視光域（380nm～800nm）、具体的にはNd:YAGレーザ（1064nm）の赤外線を、波長変換素子を用いて波長532nmの緑色の光（SHG）としたものや、アレキサンドライトレーザ（700-820nm）が適用可能である。なお、レーザ照射の際に、短焦点を形成できる光学系を組み、透明導電膜と光触媒膜との界面に焦点が合うようにすることで、結合効果がさらに向上する。 The laser that irradiates the photocatalyst film from the transparent electrode side is preferably a visible light region (380 nm to 800 nm), specifically, an Nd: YAG laser (1064 nm) infrared ray, and a green wavelength of 532 nm using a wavelength conversion element. Light (SHG) or alexandrite laser (700-820nm) is applicable. Note that an optical system capable of forming a short focal point is assembled at the time of laser irradiation, and the coupling effect is further improved by focusing on the interface between the transparent conductive film and the photocatalytic film.
　このようなレーザを発振するレーザ発振器はガルバノスキャナを備えており、自在にレーザ照射位置を変更することができる。 A laser oscillator that oscillates such a laser is equipped with a galvano scanner, and the laser irradiation position can be freely changed.
　同光触媒膜にその表面側から照射するレーザとしては、好ましくは可視光域～近赤外域（700nm～1100nm）、具体的にはNd:YAGレーザ（1064nm）やNd:YVO4レーザ（1064nm）、またはTI:サファイアレーザ（650-1100nm）、Cr:LiSAFレーザ（780-1010nm）、アレキサンドライトレーザ（700-820nm）、CO2レーザのような波長可変レーザが適用可能である。 The laser that irradiates the photocatalyst film from the surface side is preferably visible light region to near infrared region (700 nm to 1100 nm), specifically Nd: YAG laser (1064 nm), Nd: YVO4 laser (1064 nm), or Tunable lasers such as TI: sapphire laser (650-1100 nm), Cr: LiSAF laser (780-1010 nm), alexandrite laser (700-820 nm), and CO2 laser are applicable.
　レーザ照射は焼成の前後いずれか若しくは両方において行われる。 Laser irradiation is performed either before or after firing.
　本発明の第２のものは、透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、光触媒膜を形成しながら、光触媒膜に透明電極側から同電極を経てレーザを照射することを特徴とする、透明電極上における光触媒膜の形成方法である。 In the second aspect of the present invention, a transparent electrode composed of a transparent substrate and a transparent conductive film thereon is coated with a metal oxide sol electrostatically on the transparent conductive film to form a photocatalytic film, while being transparent to the photocatalytic film. A method of forming a photocatalyst film on a transparent electrode, wherein a laser is irradiated from the electrode side through the same electrode.
　第２発明の方法において、静電塗布しながら、レーザを照射することにより、静電塗布された塗膜の乾燥と低温焼成することによる、光触媒膜の形成および、光触媒膜内部における光触媒粒子同士の結合、および光触媒膜と透明電極の透明導電膜との結合を行うものである。 In the method of the second invention, by applying a laser while applying electrostatically, by drying and low-temperature baking of the electrostatically applied coating film, the formation of the photocatalyst film and between the photocatalyst particles inside the photocatalyst film Bonding and bonding between the photocatalytic film and the transparent conductive film of the transparent electrode are performed.
　レーザ照射は光触媒層に透明電極側から、および／または、光触媒層の表面側から照射してよいが、前者の場合、静電塗布用の電極およびこれを載せるステージはレーザを透過する材料で構成されている。 Laser irradiation may be applied to the photocatalyst layer from the transparent electrode side and / or from the surface side of the photocatalyst layer. In the former case, the electrode for electrostatic coating and the stage on which the electrode is placed are made of a material that transmits the laser. Has been.
　第２発明において、同光触媒膜に透明電極側から照射するレーザ、および、同光触媒膜にその表面側から照射するレーザは、それぞれ、第１発明について説明したものであってよい。 In the second invention, the laser that irradiates the photocatalyst film from the transparent electrode side and the laser that irradiates the photocatalyst film from the surface side thereof may each be the one described for the first invention.
　その他の構成は第１発明と同じであってよい。　
　第１発明および第２発明において、静電塗布による光触媒膜およびその後のレーザ照射による光触媒層の結合の後、さらにこの結合された光触媒膜の上への別の光触媒膜の形成と同光触媒膜へのレーザ照射とからなる追加操作を少なくとも１回行うことが好ましい。 Other configurations may be the same as those of the first invention.
In the first and second inventions, after the photocatalyst film by electrostatic coating and the photocatalyst layer by laser irradiation thereafter are combined, another photocatalyst film is formed on the combined photocatalyst film and the photocatalyst film is formed. It is preferable to perform at least one additional operation consisting of the above laser irradiation.
　第１発明および第２発明において、レーザ照射と同時にまたはレーザ照射の前後いずれか若しくは両方において、塗膜または光触媒膜をその表側から圧力10MPa～100MPaで加圧することが好ましい。 In the first and second inventions, it is preferable to pressurize the coating film or the photocatalyst film at a pressure of 10 MPa to 100 MPa from the front side thereof either simultaneously with laser irradiation or before or after laser irradiation.
　第１および第２発明において、光触媒膜の加圧は、平板状のプレス装置、ロール状のプレス装置等を用いて行われる。ロール状のプレス装置を用いて行いることにより、光触媒膜の加圧を連続的に行うことができる。ロール状のプレス装置の内部に加熱素子を設けてこれを加熱することや、ロール状のプレス装置を透明材料で構成して、その内部からレーザを照射してもよい。 In the first and second inventions, the pressurization of the photocatalyst film is performed using a flat plate press, a roll press, or the like. By using a roll-shaped press device, the photocatalytic film can be continuously pressurized. A heating element may be provided inside the roll-shaped press device to heat it, or the roll-shaped press device may be made of a transparent material, and laser may be irradiated from the inside.
　塗膜または光触媒膜の加圧は、光触媒膜を加熱しながら行うことが好ましい。光触媒膜の加熱は、プレス装置の内部に電気ヒータを設置したり、同内部に高熱流体を流す方法によってなされてよい。光触媒膜の加熱温度は、好ましくは150℃である。 The pressurization of the coating film or the photocatalytic film is preferably performed while heating the photocatalytic film. The photocatalyst film may be heated by a method in which an electric heater is installed inside the press apparatus or a high-temperature fluid is allowed to flow inside the press apparatus. The heating temperature of the photocatalytic film is preferably 150 ° C.
　本発明により光触媒膜が透明電極に強固に形成された後、光触媒膜の表面が染色される。この染色は、例えば、透明電極に形成した光触媒膜を、光増感色素を含む浸漬液に浸して光触媒膜の表面に同色素を吸着させることにより行われる。浸漬後、乾燥さらには焼成を行うことが好ましい。光増感色素は、例えばビピリジン構造、ターピリジン構造などを含む配位子を有するルテニウム錯体や鉄錯体、ポルフィリン系やフタロシアニン系の金属錯体、さらにはエオシン、ローダミン、メロシアニン、クマリンなどの有機色素などであってよい。 After the photocatalytic film is firmly formed on the transparent electrode according to the present invention, the surface of the photocatalytic film is dyed. This dyeing is performed, for example, by immersing the photocatalyst film formed on the transparent electrode in an immersion liquid containing a photosensitizing dye and adsorbing the dye on the surface of the photocatalyst film. After immersion, it is preferable to perform drying and further firing. Photosensitizing dyes include, for example, ruthenium complexes and iron complexes having a ligand containing a bipyridine structure, a terpyridine structure, etc., porphyrin-based and phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and coumarin. It may be.
　このようにして、透明電極に形成した染色光触媒膜は、色素増感太陽電池などの光電変換素子の電極として好適に用いられる。 Thus, the dyeing photocatalyst film formed on the transparent electrode is suitably used as an electrode of a photoelectric conversion element such as a dye-sensitized solar cell.
　光電変換素子は、例えば、上記染色光触媒膜を備えた透明電極と、これに対向する対極と、両極間に配された電解質層とから主として構成されている。 The photoelectric conversion element is mainly composed of, for example, a transparent electrode provided with the dyeing photocatalyst film, a counter electrode facing the transparent electrode, and an electrolyte layer disposed between both electrodes.
電解質としては、例えば、ヨウ素系電解液が使用され、具体的には、ヨウ素、ヨウ化物イオン、ターシャリーブチルピリジンなどの電解質成分が、エチレンカーボネートやメトキシアセトニトリルなどの有機溶媒に溶解されてなるものが例示される。電解質は、電解液からなるものに限定されず、固体電解質であってもよい。固体電解質としては、例えば、ＤＭＰＩｍＩ（ジメチルプロピルイミダゾリウムヨウ化物）が例示され、このほか、ＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＣａＩ２などの金属ヨウ化物、およびテトラアルキルアンモニウムヨーダイドなど４級アンモニウム化合物のヨウ素塩などのヨウ化物とＩ２とを組み合わせたもの；ＬｉＢｒ、ＮａＢｒ、ＫＢｒ、ＣｓＢｒ、ＣａＢｒ２などの金属臭化物、およびテトラアルキルアンモニウムブロマイドなど４級アンモニウム化合物の臭素塩などの臭化物とＢｒ２とを組み合わせたものなどを適宜使用することができる。 As the electrolyte, for example, an iodine-based electrolyte is used. Specifically, an electrolyte component such as iodine, iodide ion, or tertiary butyl pyridine is dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile. Is exemplified. The electrolyte is not limited to an electrolyte and may be a solid electrolyte. Examples of the solid electrolyte include DMPImI (dimethylpropylimidazolium iodide). In addition, metal iodides such as LiI, NaI, KI, CsI, and CaI2, and quaternary ammonium compounds such as tetraalkylammonium iodide are used. Combination of iodide such as iodine salt and I2; combination of bromide such as bromide such as bromide of quaternary ammonium compound such as metal bromide such as LiBr, NaBr, KBr, CsBr and CaBr2 and tetraalkylammonium bromide and Br2 A thing etc. can be used suitably.
　対極は、対極用透明基板上に透明導電膜が形成されたもの、あるいは同基板上にアルミニウム、銅、スズなどの金属のシートを設けたものであってよい。このほか、金属（アルミニウム、銅、スズなど）またはカーボン製などのメッシュ状電極にゲル状固体電解質を保持させることで対極を構成してもよく、また、対極用基板の片面上に導電性接着剤層を同基板を覆うように形成し、同接着剤層を介して、別途形成のブラシ状カーボンナノチューブ群を基板に転写することで、対極を構成してもよい。 The counter electrode may be one in which a transparent conductive film is formed on a transparent substrate for a counter electrode, or one in which a sheet of metal such as aluminum, copper, or tin is provided on the same substrate. In addition, the counter electrode may be configured by holding a gel solid electrolyte on a mesh electrode made of metal (aluminum, copper, tin, etc.) or carbon, and conductive adhesion is performed on one side of the counter electrode substrate. The counter electrode may be configured by forming an agent layer so as to cover the substrate and transferring a separately formed group of brush-like carbon nanotubes to the substrate via the adhesive layer.
　光電変換素子を組み立てるには、例えば、染色光触媒膜を備えた電極と対極とを対向状に位置合わせし、両極間を熱融着フィルムやシール材などで密封し、対極または電極などに予め設けておいた孔や隙間から電解質を注入する。また、固体電解質を用いる場合は、両極をこれらの間に光触媒膜および電解質層が挟まれるように重ね合わせ、その周縁部同士を加熱接着する。加熱は、金型によってもよく、プラズマ（波長の長いもの）、マイクロ波、可視光（６００ｎｍ以上）や赤外線などのエネルギービームを照射することによってもよい。 To assemble the photoelectric conversion element, for example, the electrode provided with the dyeing photocatalyst film and the counter electrode are aligned to face each other, the gap between the electrodes is sealed with a heat-sealing film or a sealing material, and the counter electrode or the electrode is provided in advance. Electrolyte is injected through the holes and gaps. When a solid electrolyte is used, both electrodes are overlapped so that the photocatalyst film and the electrolyte layer are sandwiched therebetween, and the peripheral portions thereof are heat bonded. Heating may be performed by a mold, or may be performed by irradiation with an energy beam such as plasma (having a long wavelength), microwave, visible light (600 nm or more), or infrared light.
　光電変換素子は、例えば、方形の電極用透明基板と方形の対極用透明基板との間に、電極用透明導電膜、対極用透明導電膜、集電電極、電解質層および光触媒膜が所定間隔で配置されることにより形成され、この際の電極と対極との接続は、直列とされることがあり、並列とされることもある。いずれの場合でも、電解質層および光触媒膜はシール材によって隣り合うもの同士の間が仕切られる。直列接続の場合、電極用透明導電膜、対極用透明導電膜および集電電極は、隣り合うもの同士の間に間隙が形成され、隣り合う電極用透明導電膜と対極用透明導電膜とが導体によって接続される。並列接続の場合、電極用透明導電膜、対極用透明導電膜および集電電極は、隣り合うもの同士の間に隙間がない形状とされる。 In the photoelectric conversion element, for example, a transparent conductive film for electrodes, a transparent conductive film for counter electrodes, a collector electrode, an electrolyte layer, and a photocatalyst film are arranged at a predetermined interval between a transparent electrode substrate and a transparent substrate for a counter electrode. The connection between the electrode and the counter electrode at this time may be in series or in parallel. In either case, the electrolyte layer and the photocatalyst film are separated from each other by the sealing material. In the case of series connection, a gap is formed between adjacent transparent conductive films for electrodes, transparent conductive films for counter electrodes, and current collecting electrodes, and the transparent conductive films for electrodes adjacent to each other are conductors. Connected by. In the case of parallel connection, the transparent conductive film for electrode, the transparent conductive film for counter electrode, and the current collecting electrode are formed such that there is no gap between adjacent ones.
　つぎに、本発明を具体的に説明するために、本発明の実施例をいくつか挙げる。 Next, in order to specifically explain the present invention, several examples of the present invention will be given.
実施例１
　図１(a)において、ポリエチレン・ナフタレートフィルムからなる透明基板(1)と、その上のITOからなる透明導電膜(2)とからなる透明電極(3)に、チタン（IV）イソプロポキシド（TTIP）60g、エタノール500ml、ジエタノールアミン20g、純水5gの混合液をスプレーノズル(7)を用いて透明電極(3)の透明導電膜(２)に静電塗布した。ここで、スプレーノズル(7)と透明電極(3)との距離は80mmとし、同ノズル(7)とステージ(5)上の電極(6)の間に20kvの電圧を印加し、塗膜の厚みが10μmになるまで静電塗布を行った。次いで、生じた塗膜を室温で乾燥させ、さらに温度150℃の低温で焼成した。この焼成の前後に、図１(b)に示すように、ガルバノスキャナを備えたレーザ発振器(8)を用いて、光触媒膜(4)にその表面側からも直接アレキサンドライトレーザ（700-820nm）を照射した。 Example 1
In FIG. 1 (a), titanium (IV) isopropoxide is applied to a transparent electrode (3) consisting of a transparent substrate (1) made of polyethylene naphthalate film and a transparent conductive film (2) made of ITO thereon. (TTIP) 60 g, 500 ml of ethanol, 20 g of diethanolamine, and 5 g of pure water were electrostatically applied to the transparent conductive film (2) of the transparent electrode (3) using a spray nozzle (7). Here, the distance between the spray nozzle (7) and the transparent electrode (3) is 80 mm, and a voltage of 20 kv is applied between the nozzle (7) and the electrode (6) on the stage (5) to Electrostatic coating was performed until the thickness reached 10 μm. The resulting coating film was then dried at room temperature and further baked at a low temperature of 150 ° C. Before and after this firing, as shown in Fig. 1 (b), using a laser oscillator (8) equipped with a galvano scanner, a photocatalytic film (4) was directly irradiated with an alexandrite laser (700-820nm) from the surface side. Irradiated.
　このようにして、光触媒膜(4)を透明電極(3)に強固に結合させた後、光増感色素を含む浸漬液（ルテニウム錯体(N719、分子量1187.7g./mol)をt-ブタノール：アセトニトリル（容量比１：１）に溶解させたもので、色素濃度：0.3mM）に温度４０℃で４０分間浸して光触媒膜の表面に同色素を吸着させた。 After the photocatalytic film (4) was firmly bonded to the transparent electrode (3) in this way, an immersion liquid containing a photosensitizing dye (ruthenium complex (N719, molecular weight 1187.7 g./mol) was added to t-butanol: The dye was dissolved in acetonitrile (volume ratio 1: 1) and immersed in a dye concentration: 0.3 mM at a temperature of 40 ° C. for 40 minutes to adsorb the dye on the surface of the photocatalyst film.
実施例２
　実施例１において、光触媒膜(4)にその表面側から同電極を経てアレキサンドライトレーザ（700-820nm）を照射しながら、透明電極(3)側からもアレキサンドライトレーザ（700-820nm）を照射した。 Example 2
In Example 1, the photocatalytic film (4) was irradiated with an alexandrite laser (700-820 nm) from the transparent electrode (3) side while being irradiated with an alexandrite laser (700-820 nm) from the surface side through the same electrode.
　その他の構成は実施例１のものと同じである。 Other configurations are the same as those in the first embodiment.
実施例３
　図２に示すように、実施例１と同様の操作で静電塗布によって透明電極(3)に光触媒膜(4)を形成しながら、ガルバノスキャナを備えたレーザ発振器(8)を用いて、光触媒膜(4)にその表面側からも直接アレキサンドライトレーザ（700-820nm）を照射した。 Example 3
As shown in FIG. 2, a photocatalyst is formed using a laser oscillator (8) equipped with a galvano scanner while forming a photocatalyst film (4) on the transparent electrode (3) by electrostatic coating in the same manner as in Example 1. The film (4) was also directly irradiated with alexandrite laser (700-820 nm) from the surface side.
　その他の構成は実施例１のものと同じである。ただし、焼成の前後出のレーザ照射は行わなかった。 Other configurations are the same as those in the first embodiment. However, laser irradiation before and after firing was not performed.
実施例４
　図３に示すように、実施例１と同様の操作で静電塗布によって透明電極(3)に光触媒膜(4)を形成しながら、ガルバノスキャナを備えたレーザ発振器(8)を用いて、光触媒膜(4)に透明のステージ(5)およびその上の透明の電極(6)を経てアレキサンドライトレーザ（700-820nm）を照射した。 Example 4
As shown in FIG. 3, a photocatalyst is formed using a laser oscillator (8) equipped with a galvano scanner while forming a photocatalyst film (4) on the transparent electrode (3) by electrostatic coating in the same manner as in Example 1. The film (4) was irradiated with an alexandrite laser (700-820 nm) through a transparent stage (5) and a transparent electrode (6) thereon.
　その他の構成は実施例１のものと同じである。ただし、焼成の前後出のレーザ照射は行わなかった。 Other configurations are the same as those in the first embodiment. However, laser irradiation before and after firing was not performed.
実施例５
　図４(a)に示すように、実施例１と同様にして透明電極(3)に第１の光触媒膜(4)を結合させた後、図４(b)に示すように、第１の光触媒膜(4)の上に、実施例１と同様の操作により静電塗布、乾燥、焼成を行って、第２の光触媒膜(9)を形成した。ついで、ガルバノスキャナを備えたレーザ発振器(8)を用いて、第２の光触媒膜(9)にその表面側から直接アレキサンドライトレーザ（700-820nm）を照射して第１の光触媒膜(4)の上に第２の光触媒膜(9)を結合させた。 Example 5
As shown in FIG. 4 (a), after the first photocatalytic film (4) is bonded to the transparent electrode (3) in the same manner as in Example 1, the first photocatalyst film (4) is bonded as shown in FIG. 4 (b). On the photocatalyst film (4), electrostatic coating, drying and firing were carried out in the same manner as in Example 1 to form a second photocatalyst film (9). Next, using a laser oscillator (8) equipped with a galvano scanner, the second photocatalyst film (9) is directly irradiated with an alexandrite laser (700-820 nm) from the surface side to form the first photocatalyst film (4). A second photocatalyst film (9) was bonded on top.
　その後、図４(c)に示すように、第２の光触媒膜(9)の上に、上記と同様の操作により静電塗布、乾燥、焼成を行って、第３の光触媒膜(10)を形成した。ついで、上記と同様の操作により第３の光触媒膜(10)にその表面側からレーザを照射して第２の光触媒膜(9)の上に第３の光触媒膜(10)を結合させた。 Thereafter, as shown in FIG. 4 (c), electrostatic coating, drying and firing are performed on the second photocatalyst film (9) by the same operation as described above, and the third photocatalyst film (10) is formed. Formed. Subsequently, the third photocatalyst film (10) was bonded onto the second photocatalyst film (9) by irradiating the third photocatalyst film (10) with laser from the surface side by the same operation as described above.
　その後、図４(ｄ)に示すように、第３の光触媒膜(10)の上に、上記と同様の操作により静電塗布、乾燥、焼成を行って、第４の光触媒膜(11)を形成した。ついで、上記と同様の操作により第４の光触媒膜(11)にその表面側からレーザを照射して第３の光触媒膜(10)の上に第４の光触媒膜(11)を結合させた。 Thereafter, as shown in FIG. 4 (d), the fourth photocatalyst film (11) is formed on the third photocatalyst film (10) by electrostatic coating, drying and firing by the same operation as described above. Formed. Subsequently, the fourth photocatalyst film (11) was bonded to the third photocatalyst film (10) by irradiating the fourth photocatalyst film (11) with laser from the surface side by the same operation as described above.
　その後、図４(e)に示すように、第４の光触媒膜(11)の上に、上記と同様の操作により静電塗布、乾燥、焼成を行って、第５の光触媒膜(12)を形成した。ついで、上記と同様の操作により第４の光触媒膜(12)にその表面側からレーザを照射して第４の光触媒膜(11)の上に第５の光触媒膜(12)を結合させた。 Thereafter, as shown in FIG. 4 (e), the fifth photocatalyst film (12) is formed on the fourth photocatalyst film (11) by electrostatic coating, drying and firing by the same operation as described above. Formed. Subsequently, the fourth photocatalyst film (12) was irradiated with laser from the surface side by the same operation as described above, and the fifth photocatalyst film (12) was bonded onto the fourth photocatalyst film (11).
　その他の構成は実施例１のものと同じである。 Other configurations are the same as those in the first embodiment.
　こうして厚さ２μｍの５層の光触媒膜を形成した。 Thus, five layers of a photocatalytic film having a thickness of 2 μm were formed.
実施例６
　実施例３と同様にして透明電極(3)に厚さ２μｍの第１の光触媒膜(4)を結合させた後、その上に、実施例５と同様にして厚さ２μｍの４層の光触媒膜を形成した。 Example 6
After the first photocatalyst film (4) having a thickness of 2 μm was bonded to the transparent electrode (3) in the same manner as in Example 3, four photocatalysts having a thickness of 2 μm were formed on the first photocatalyst film (4). A film was formed.
実施例７
　実施例１のレーザ照射工程において、図５に示すように、この焼成の前後に、光触媒膜(4)をその表面側からロール状のプレス装置(13)で圧力50MPaで、30秒間加圧しながら、ガルバノスキャナを備えたレーザ発振器(8)を用いて、光触媒膜(4)に透明電極(3)側からアレキサンドライトレーザ（700-820nm）を照射した。ロール状のプレス装置(13)を用いることにより、光触媒膜(4)の加圧を連続的に行うことができた。 Example 7
In the laser irradiation step of Example 1, as shown in FIG. 5, before and after this firing, the photocatalyst film (4) was pressed from the surface side with a roll-shaped press device (13) at a pressure of 50 MPa for 30 seconds. Using a laser oscillator (8) equipped with a galvano scanner, the photocatalytic film (4) was irradiated with an alexandrite laser (700-820 nm) from the transparent electrode (3) side. By using the roll-shaped pressing device (13), it was possible to continuously pressurize the photocatalyst film (4).
　その他の構成は実施例１のものと同じである。 Other configurations are the same as those in the first embodiment.
実施例８
　実施例７において、ロールのプレス装置の代わりに、図６に示す平板状のプレス装置(14)を用いて、透明電極(3)に光触媒膜(4)を加圧した。加圧は、内部に電熱ヒータ線(14)を設けた平板状のプレス装置(15)を用いて、圧力50MPaでプレス装置温度１５０℃で30秒間行った。 Example 8
In Example 7, the photocatalyst film (4) was pressurized to the transparent electrode (3) using a flat plate pressing device (14) shown in FIG. 6 instead of the roll pressing device. Pressurization was carried out for 30 seconds at a pressure of 50 MPa and a press apparatus temperature of 150 ° C. using a flat press apparatus (15) provided with an electric heater wire (14) inside.
　その他の構成は実施例７のものと同じである。 Other configurations are the same as those in the seventh embodiment.
実施例９
　実施例８において、光触媒膜(4)へのレーザ照射を、同光触媒膜(4)の表面側から透明の平板状プレス装置(14)を経て行うと共に透明電極(3)側からもアレキサンドライトレーザ（700-820nm）を用いて行った。 Example 9
In Example 8, laser irradiation to the photocatalyst film (4) is performed from the surface side of the photocatalyst film (4) through a transparent flat plate pressing device (14) and also from the transparent electrode (3) side, an alexandrite laser ( 700-820 nm).
　その他の構成は実施例８のものと同じである。 Other configurations are the same as those in the eighth embodiment.
参考例１
　図７に、光増感色素で染色された光触媒膜を備えた透明電極を用いて構成した光電変換素子の例を示す。光電変換素子は、染色光触媒膜を備えた透明電極と、これに対向する対極と、両極間に配される電解質層とから主として構成されている。 Reference example 1
FIG. 7 shows an example of a photoelectric conversion element constituted by using a transparent electrode provided with a photocatalytic film dyed with a photosensitizing dye. The photoelectric conversion element is mainly composed of a transparent electrode provided with a dyeing photocatalyst film, a counter electrode facing the transparent electrode, and an electrolyte layer disposed between both electrodes.
　同図において、(21)は透明基板、(22)は透明基板(21)上に形成された透明導電膜、(24)は対極用基板、(25)は同基板(24)に設けられた対極で、白金で構成されている。(26)は両極間に亘って設けられた複数のシール材兼セパレータで、これらによって両極間に複数の区画が形成されている。(23)は各区画において透明導電膜(22)上に形成された光触媒膜で、光増感色素で染色されている。各区画には電解液が注入されている。(27)は両極に渡された複数の極間電極、(28)は極間電極保護用シール材である。 In the figure, (21) is a transparent substrate, (22) is a transparent conductive film formed on the transparent substrate (21), (24) is a counter electrode substrate, and (25) is provided on the substrate (24). The counter electrode is made of platinum. (26) is a plurality of sealing materials and separators provided between both electrodes, and a plurality of sections are formed between these electrodes. (23) is a photocatalytic film formed on the transparent conductive film (22) in each section, which is dyed with a photosensitizing dye. An electrolyte is injected into each compartment. (27) is a plurality of interelectrodes passed to both electrodes, and (28) is a sealing material for interelectrode protection.
　膜厚数μｍ、１００ｍｍ角の色素増感太陽電池を作製し、ＡＭ１．５、１００ｍＷ／ｃｍ２の標準光源照射により電力変換効率を計測したところ、実施例１で得られた染色光触媒膜を備えた透明電極を用いた場合、変換効率η＝5～6％、実施例４または７で得られた染色光触媒膜を備えた透明電極を用いた場合、変換効率η=6～7％と、いずれも高効率が得られた。 A dye-sensitized solar cell having a thickness of several μm and a square of 100 mm was prepared, and when the power conversion efficiency was measured by irradiation with a standard light source of AM 1.5 and 100 mW / cm 2, the dyed photocatalyst film obtained in Example 1 was provided. When a transparent electrode is used, conversion efficiency η = 5 to 6%. When a transparent electrode provided with the dyed photocatalyst film obtained in Example 4 or 7 is used, conversion efficiency η = 6 to 7%. High efficiency was obtained.
(1)　透明基板
(2)　透明導電膜
(3)　透明電極
(4)(9)(10)(11)(12)　光触媒膜
(5)　ステージ
(6)　電極
(7)　スプレーノズル
(8)　レーザ発振器
(13)(15)　プレス放置
(14)　ヒータ線 (1) Transparent substrate
(2) Transparent conductive film
(3) Transparent electrode
(4) (9) (10) (11) (12) Photocatalytic membrane
(5) Stage
(6) Electrode
(7) Spray nozzle
(8) Laser oscillator
(13) (15) Press left
(14) Heater wire
　本発明は、透明電極の表面に光触媒膜を形成する方法に関し、透明導電膜や基板に耐熱性の低い材料の使用を可能とし、かつ、光触媒膜の内部における光触媒粒子同士の結合および光触媒膜の光触媒粒子と透明電極との結合を強固なものとすることができるので、このようにして形成された光触媒膜を光増感色素で染色して成る電子材料が色素増感太陽電池などの光電変換素子の電極として好適に用いられることに寄与できる。 The present invention relates to a method for forming a photocatalyst film on the surface of a transparent electrode, which enables the use of a material having low heat resistance for a transparent conductive film or a substrate, and the bonding of photocatalyst particles inside the photocatalyst film and the photocatalyst film. Since the bond between the photocatalyst particles and the transparent electrode can be strengthened, an electronic material formed by dyeing the photocatalyst film thus formed with a photosensitizing dye is used for photoelectric conversion such as dye-sensitized solar cells. It can contribute to being used suitably as an electrode of an element.

Claims (6)

  1. 　透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、生じた塗膜を低温で焼成することにより光触媒膜を形成し、焼成の前後いずれか若しくは両方において塗膜または光触媒膜にレーザを照射することを特徴とする、透明電極上における光触媒膜の形成方法。 In a transparent electrode composed of a transparent substrate and a transparent conductive film thereon, a metal oxide sol is electrostatically applied onto the transparent conductive film, and the resulting coating film is baked at low temperature to form a photocatalyst film. A method of forming a photocatalyst film on a transparent electrode, wherein the coating film or the photocatalyst film is irradiated with a laser in either or both.
  2. 　透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、生じた塗膜を低温で焼成することにより光触媒膜を形成し、焼成の前後いずれか若しくは両方において塗膜または光触媒膜にレーザを照射し、さらにこの光触媒膜の上での光触媒膜の形成と同光触媒膜へのレーザ照射とからなる追加操作を少なくとも１回行うことを特徴とする、透明電極上における光触媒膜の形成方法。 In a transparent electrode composed of a transparent substrate and a transparent conductive film thereon, a metal oxide sol is electrostatically applied onto the transparent conductive film, and the resulting coating film is baked at low temperature to form a photocatalyst film. The coating film or the photocatalyst film is irradiated with a laser in either or both, and an additional operation including the formation of the photocatalyst film on the photocatalyst film and the laser irradiation to the photocatalyst film is performed at least once. A method for forming a photocatalytic film on a transparent electrode.
  3. 　透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物ゾルを静電塗布し、光触媒膜を形成しながら、光触媒膜に透明電極側から同電極を経てレーザを照射することを特徴とする、透明電極上における光触媒膜の形成方法。 In a transparent electrode consisting of a transparent substrate and a transparent conductive film thereon, a metal oxide sol is electrostatically applied on the transparent conductive film to form a photocatalytic film, and a laser is applied to the photocatalytic film from the transparent electrode side through the same electrode. Irradiating, a method for forming a photocatalytic film on a transparent electrode.
  4. 　透明基板とその上の透明導電膜とからなる透明電極において透明導電膜上に金属酸化物を静電塗布し、光触媒膜を形成しながら、光触媒膜に透明電極側から同電極を経てレーザを照射し、さらにこの光触媒膜の上への光触媒膜の形成と同光触媒膜へのレーザ照射とからなる追加操作を少なくとも１回行うことを特徴とする、透明電極上における光触媒膜の形成方法。 In a transparent electrode consisting of a transparent substrate and a transparent conductive film thereon, a metal oxide is electrostatically applied on the transparent conductive film to form a photocatalyst film, and the photocatalyst film is irradiated with laser from the transparent electrode side through the same electrode. A method for forming a photocatalyst film on a transparent electrode, wherein an additional operation comprising the formation of the photocatalyst film on the photocatalyst film and laser irradiation of the photocatalyst film is performed at least once.
  5. 　レーザ照射と同時にまたはレーザ照射の前後いずれか若しくは両方において、塗膜または光触媒膜をその表側から加圧することを特徴とする、請求項１～４のいずれかに記載の透明電極上における光触媒膜の形成方法。 The photocatalyst film on the transparent electrode according to any one of claims 1 to 4, wherein the coating film or the photocatalyst film is pressurized from the front side thereof simultaneously with laser irradiation or before or after laser irradiation. Forming method.
  6. 　塗膜または光触媒膜の加圧を、同膜を加熱しながら行うことを特徴とする、請求項５記載の透明電極上における光触媒膜の形成方法。 6. The method for forming a photocatalytic film on a transparent electrode according to claim 5, wherein the coating film or the photocatalytic film is pressurized while the film is heated.
PCT/JP2010/057144 2010-04-22 2010-04-22 Method of forming a photocatalytic film on a transparent electrode WO2011132287A1 (en)

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