WO2012105581A1 - Procédé pour produire une couche d'oxyde semi-conducteur - Google Patents

Procédé pour produire une couche d'oxyde semi-conducteur Download PDF

Info

Publication number
WO2012105581A1
WO2012105581A1 PCT/JP2012/052196 JP2012052196W WO2012105581A1 WO 2012105581 A1 WO2012105581 A1 WO 2012105581A1 JP 2012052196 W JP2012052196 W JP 2012052196W WO 2012105581 A1 WO2012105581 A1 WO 2012105581A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide semiconductor
semiconductor layer
layer
fine particles
support
Prior art date
Application number
PCT/JP2012/052196
Other languages
English (en)
Japanese (ja)
Inventor
金子　直人
水野　幹久
亮介 岩田
武 両角
Original Assignee
ソニー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ソニー株式会社 filed Critical ソニー株式会社
Publication of WO2012105581A1 publication Critical patent/WO2012105581A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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 primary particle average particle diameter of the second granular fine particles 2B is larger than 100 nm and not larger than 10,000 nm.
  • the larger the average particle diameter of the second granular fine particles 2B, the more the ratio of the blending mass of the second granular fine particles 2B to the blending mass of the first granular fine particles 2A ( (the blending mass of the second granular fine particles 2B). ) / (Mixed mass of the first particulate fine particles 2A)) is larger, the cracks generated in the semiconductor electrode layer (metal oxide semiconductor porous layer) 21 are reduced.
  • FIG. 2 shows an example including two types of granular fine particles having different average particle sizes of primary particles, but it is obvious that a configuration including three or more types of granular fine particles having different average particle sizes may be used. is there.
  • the average primary particle diameter of the second granular fine particles 2B is more preferably 200 nm or more and 5000 nm or less. When the average particle diameter of the primary particles is smaller than 200 nm, the effect of suppressing the occurrence of cracks in the semiconductor electrode layer 21 is insufficient, and the performance of scattering incident light tends to be insufficient.
  • the ratio of the blending mass of the second granular fine particles 2B to the blending mass of the first granular fine particles 2A is preferably 0.06 or more and 6 or less. When it is less than 0.06, the effect of suppressing the occurrence of cracks in the semiconductor electrode layer 21 becomes insufficient, and the performance of scattering incident light tends to be insufficient.
  • the effect of suppressing the occurrence of cracks in the semiconductor electrode layer 21 is sufficient and the performance of scattering incident light is sufficient, but the actual surface area of the metal oxide semiconductor particles in the semiconductor electrode layer 21 is sufficient.
  • This may decrease the performance of an electrochemical device using the semiconductor electrode layer 21, for example, a dye-sensitized solar cell.
  • the larger the ratio ( (the blending mass of the second particulate microparticles 2B) / (the blending mass of the first particulate microparticles 2A)) to the blending mass of the first particulate microparticles 2A is, the larger the semiconductor electrode layer 1 is.
  • a light scattering function is imparted to the semiconductor electrode layer 21 so that the internal HAZE of the semiconductor electrode layer 21 increases and the total light transmittance decreases. Further, by adsorbing the photosensitizing dye to the semiconductor electrode layer 21, the total light transmittance is further lowered.
  • the dispersion method known methods such as stirring treatment, ultrasonic dispersion treatment, bead dispersion treatment, kneading treatment, and homogenizer treatment can be preferably used.
  • the solvent a solvent that can disperse the metal oxide semiconductor fine particles 2 and 3 and can dissolve the first compound and the second compound is appropriately selected and used. Specifically, for example, it is selected from alcohols, ketones, hydrocarbons, amides, sulfides and the like.
  • the compounding quantity of the metal oxide semiconductor fine particles 2 and 3 is 1 mass% or more and 50 mass% or less of the mass of the coating liquid formed by adding the 1st compound and 2nd compound which are mentioned later, for example, 20 mass %.
  • a 1st compound is a compound which hydrolyzes and produces
  • the second compound is a compound that is harder to hydrolyze than the first compound and that produces a second oxide having a higher hardness than the first oxide when hydrolyzed.
  • a metal element salt or alkoxide may be used as the first compound.
  • the metal element may be at least one element selected from the group consisting of titanium Ti, aluminum Al, silicon Si, vanadium V, zirconium Zr, niobium Nb, and tantalum Ta.
  • the ratio of the second compound that is hydrolyzed until the firing step is small, and most of the second compound is preferably hydrolyzed by moisture supplied from the air in the firing step.
  • the second oxide generated by hydrolysis of the second compound is mainly bound on the first oxide layer 4 to form the second oxide layer 5, and the metal oxide
  • the first oxide layer 4 bonded between the semiconductor fine particles 2 and 3 and between the metal oxide semiconductor fine particles 2 and 3 and the support 6 is strongly reinforced.
  • a semiconductor electrode layer (metal oxide semiconductor porous layer) 1 or 23 having excellent mechanical strength and high adhesion to the support 6 is obtained.
  • the second compound may be used, but the second compound alone tends to cause surface layer peeling or damage. This is because the second compound is less reactive with the surface of the metal oxide semiconductor fine particles 2 and 3 than the first compound, so that the number of necking between the fine particles 2 and 3 is reduced only with the second compound. This is because the strength tends to be insufficient. That is, in order to achieve both the mechanical strength of the semiconductor electrode layer 1 or 23 and the adhesion to the support 6, it is preferable to use both the first compound and the second compound.
  • Electromagnetic wave treatment After the firing treatment, the metal oxide semiconductor porous layer is heated by electromagnetic wave irradiation in order to promote necking.
  • the method of manufacturing a semiconductor electrode layer according to the first embodiment of the present disclosure includes a process-saving process for manufacturing a film-type dye-sensitized solar cell, a reduction in the firing temperature of the metal oxide semiconductor porous layer on the glass substrate, Contributes to shortening process time and improving photoelectric conversion efficiency of film-type dye-sensitized solar cells.
  • the metal oxide semiconductor is heated to a temperature at which the resin film substrate is altered and deformed (for example, the heat resistance temperature of the resin film substrate or higher). This is because the resin film substrate tends to be deformed and deteriorated by heating because it is necessary to perform the treatment on the porous layer.
  • the specific heating temperature range is typically 40 ° C. or higher and 1000 ° C. or lower, and preferably 200 ° C. or higher and 550 ° C. or lower.
  • the treatment time is not particularly limited, but is usually 1 second or more and 10 hours or less.
  • the specific cooling temperature range is typically 150 ° C. or lower, preferably 0 ° C. or lower.
  • the gap between the cooling member and the support 6 is small. It is possible to prevent the resin film base material from being altered and deformed by bringing the cooling member and the support 6 into contact with each other without any gaps and sufficiently dissipating heat.
  • an antifreeze liquid such as a liquid having a low freezing point such as ethanol or methanol
  • a cooling medium layer such as a gel-like coolant or an antifreeze sheet is provided to cool the support 6 and the cooling member.
  • the support 6 may be cooled in a state where there is no gap between the members.
  • a cooling member is not limited to a cooling plate and a cooling roll, What is necessary is just to have a cooling function which cools the support body 6 to appropriate temperature.
  • the atmosphere in which electromagnetic waves are irradiated is oxygen It is preferable that the atmosphere does not contain. This is because when ITO is treated at a high temperature (for example, about 250 ° C. or higher) in an atmosphere containing oxygen such as the air, oxygen deficiency disappears and carriers are reduced by taking in oxygen, resulting in an increase in resistance. This is because there is a problem.
  • examples of the atmosphere not containing oxygen include, but are not limited to, an inert gas atmosphere such as nitrogen, argon, and helium, a vacuum, a hydrogen atmosphere, and the like.
  • an inert gas atmosphere such as nitrogen, argon, and helium
  • a vacuum such as a vacuum
  • a hydrogen atmosphere such as a vacuum
  • a hydrogen atmosphere such as a hydrogen
  • metal salts such as titanium tetrachloride and titanium alkoxide, and metal alkoxides Necking processing may be performed using.
  • ⁇ Pressure treatment of metal oxide semiconductor porous layer> In addition to the electromagnetic wave irradiation treatment, a treatment for enhancing the physical contact between the fillers of the semiconductor fine particle layer (metal oxide semiconductor porous layer) such as a calendar treatment and a press treatment may be performed. Thereby, for example, the energy conversion efficiency of the dye-sensitized solar cell can be improved.
  • the pressure treatment of the semiconductor fine particle layer may be performed before or after irradiation heating by electromagnetic wave irradiation treatment, or before and after.
  • ⁇ Calendar treatment or press treatment promotes contact between the semiconductor fine particles, increases the transparency of the semiconductor fine particle layer, and reduces the thickness of the semiconductor fine particle layer.
  • the conversion efficiency is improved.
  • the temperature of the press roll is less than 150 ° C.
  • the temperature of the back roll is less than 150 ° C.
  • the linear pressure is more than 0 ° C. and 500 kg / cm or less.
  • the load is 15 t / 25 mm within the range below the temperature that the glass can withstand. 2 The following is preferred.
  • the pressurizing process such as the calendar process or the press process may be performed twice or more.
  • the semiconductor electrode layer and the method for manufacturing the semiconductor electrode layer will be described in more detail.
  • the thickness of the semiconductor electrode layer 1 or 23 is preferably 1 ⁇ m or more and 30 ⁇ m or less. When the thickness is less than 1 ⁇ m, sufficient photoelectric conversion efficiency cannot be obtained. As the thickness is increased, the photoelectric conversion efficiency is improved.
  • the thickness is preferably 30 ⁇ m or less.
  • the material of the metal oxide semiconductor fine particles 2 and 3 various metal oxide semiconductors, compounds having a perovskite structure, and the like can be used.
  • the material of the metal oxide semiconductor fine particles 2 and 3 is preferably an n-type semiconductor material in which conduction band electrons become carriers under photoexcitation to generate an anode current.
  • Such a semiconductor material is specifically exemplified by TiO. 2 , ZnO, WO 3 , Nb 2 O 5 , SrTiO 3 , And SnO 2 Among these, TiO 2 Is particularly preferred.
  • the material of the metal oxide semiconductor fine particles 2 and 3 is not limited to these. Also, two or more of these materials can be mixed and used.
  • the average particle diameter of the primary particles is preferably 1 to 100 nm in the granular metal oxide semiconductor fine particles 2 (in this case, however, the metal Cracks occur in the oxide semiconductor porous layer, the conductivity between the metal oxide semiconductor fine particles decreases, and the photoelectric conversion performance of the dye-sensitized solar cell using the metal oxide semiconductor porous layer decreases.
  • the metal oxide semiconductor fine particles 2 and 3 commercially available products may be used, or a predetermined value may be obtained by subjecting chloride or alkoxide to hydrolysis treatment or hydrothermal treatment by a known method such as a sol-gel method. You may produce the thing of a particle size.
  • the crystal type thereof may be one type selected from a rutile type, anatase type, and brookite type, or a mixture of two or more types.
  • the granular metal oxide semiconductor fine particles 2 and 3 for example, MZ-300 and MZ-500 (manufactured by Teika Co., Ltd.) Product name), FZO-50 (product name) manufactured by Ishihara Sangyo Co., Ltd., NanoTek Powder series (product name) manufactured by CI Kasei Co., Ltd., FINEX series (product name) manufactured by Sakai Chemical Industry Co., Ltd. F-1, F-2, F-3, Pazet CK, Pazet GK-40 (above, trade name) manufactured by Co., Ltd. can be used.
  • MZ-300 and MZ-500 manufactured by Teika Co., Ltd.
  • FZO-50 product name
  • NanoTek Powder series product name
  • FINEX series product name manufactured by Sakai Chemical Industry Co., Ltd.
  • F-1, F-2, F-3, Pazet CK, Pazet GK-40 above, trade name
  • the first compound may be a compound of at least one element such as Ti, Al, Si, V, Zr, Nb, and Ta.
  • the element is the same element as the metal element constituting the metal oxide semiconductor fine particle 2, and the first oxide generated from the first compound and the metal oxide semiconductor fine particle 2 are formed.
  • the constituent metal oxide is preferably the same kind of oxide. It can be expected that the adhesion between the metal oxide semiconductor fine particles 2 and the first oxide layer 4 will be the best. Further, as the first compound, it is preferable to use the first compound hydrolyzed at room temperature by the water usually contained in the metal oxide semiconductor fine particles 2 and / or the organic solvent.
  • the hydrolysis of the first compound starts in the coating liquid, and the metal oxide semiconductor fine particles 2 are connected by the generated first oxide.
  • a network is easily formed.
  • the salt it is possible to use nitrates, sulfates, acetates, oxalates, halides, etc. that are soluble in a solvent.
  • TiOSO 4 , Zr (CH 3 COO) 2 O, Zr (CH 3 COO) 4 , Al (NO 3 ) 3 , Al (CH 3 COO) 3 , Al 2 (SO 4 ) 3 TiCl 4 AlCl 3 , Ti (C 2 O 4 ) 2 , Zr (C 2 O 4 ) 2 And Al 2 (C 2 O 4 ) 3 Etc. can be used.
  • the alkoxide that can be used can be represented by the following general formula.
  • the alkoxide may be modified with ⁇ -diketones such as acetylacetone.
  • a part of the alkoxy group may be substituted with a hydroxy group.
  • the commercial product for example, the following can be used. That is, Nippon Soda Co., Ltd. A-1, B-1, TOT, TOG, T-50, T-60, A-10, B-2, B-4, B-7, B-10, TBSTA, DPSTA-25, S-151, S-152, S-181, TAT, and TLA-A-50 (above, trade names), TPT, TBT, DBT, TST, TEAT, TAA, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • the oxide forming the second oxide layer 5 is SiO. 2 , B 2 O 3 , Al 2 O 3 And ZrO 2 It is preferable that the oxide has high hardness.
  • titanium oxide is used as the material of the metal oxide semiconductor fine particles 2 and 3, as the second compound, for example, dimethyldimethoxysilane Si (CH 3 ) 2 (OCH 3 ) 2 , Dimethyldiethoxysilane Si (CH 3 ) 2 (OCH 2 CH 3 ) 2 , Methyltrimethoxysilane Si (CH 3 ) (OCH 3 ) 3 , Methyltriethoxysilane Si (CH 3 ) (OCH 2 CH 3 ) 3 , Tetramethoxysilane Si (OCH 3 ) 4 , Tetraethoxysilane Si (OCH 2 CH 3 ) 4 Tetrapropoxysilane Si (OCH 2 CH 2 CH 3 ) 4 Tetrabutoxysilane Si (OCH 2 CH 2 CH 2 CH 3 ) 4 , Ethoxysilane dimer, ethoxysilane oligomer, ethoxysilane polymer, trimethoxyborane B (OCH 3 ) 3
  • a solvent capable of dissolving the first compound and the second compound and dispersing the metal oxide semiconductor fine particles 2 and 3 is used.
  • a solvent capable of dissolving the first compound and the second compound and dispersing the metal oxide semiconductor fine particles 2 and 3 is used.
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • a high boiling point solvent can be added to control the evaporation rate of the solvent.
  • high-boiling solvents include butyl cellosolve, diacetone alcohol, butyl triglycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol Monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol isopropyl ether Tripropylene glycol isopropyl ether,
  • ⁇ Roll-to-roll process The semiconductor electrode layer manufacturing process described above may be performed in a roll-to-roll process.
  • a material having poor heat resistance such as a resin film substrate such as a lightweight, inexpensive and flexible plastic film can be used for the support 6.
  • a material having poor heat resistance such as a resin film substrate such as a lightweight, inexpensive and flexible plastic film can be used for the support 6.
  • the semiconductor fine particle layer applied on one main surface of the film substrate 16 is subjected to a baking process for drying and necking the coating liquid.
  • the firing temperature is preferably equal to or lower than the glass transition point of the material constituting the film substrate 16 and is typically 40 ° C. or higher and 200 ° C. or lower.
  • it is about 30 seconds or more and 10 hours or less.
  • necking is promoted, but is not sufficient because it is fired at a low temperature. Necking can be further promoted and characteristics can be improved by electromagnetic wave treatment described later.
  • the metal oxide semiconductor porous layer is calendered by the back roll 34 and the press roll 35, thereby promoting the contact between the semiconductor fine particles and increasing the transparency of the metal oxide semiconductor porous layer 33.
  • the thickness of 33 is reduced.
  • the photoelectric conversion efficiency of the dye-sensitized solar cell can be improved.
  • the temperature of the press roll 35 is, for example, less than 150 ° C.
  • the temperature of the back roll 34 is less than 150 ° C.
  • the linear pressure is more than 0 kg / cm and not more than 500 kg / cm.
  • an antifreeze liquid layer 47 such as ethanol is preferably provided on the surface of the cooling roll 36.
  • the atmosphere in which the electromagnetic wave treatment is performed is preferably an atmosphere containing no oxygen. Examples of the atmosphere not containing oxygen include an inert gas atmosphere, a vacuum, and a hydrogen atmosphere.
  • ITO tends to increase in resistance because electromagnetic wave treatment in an atmosphere containing oxygen such as in the air eliminates oxygen deficiency and reduces carriers by incorporating oxygen. Therefore, when processing a conductive layer that cannot be baked in an oxygen atmosphere such as ITO, it is necessary to create an atmosphere containing no oxygen.
  • the inert gas include nitrogen gas, argon gas, helium gas, and the like.
  • an inert gas may be filled in an atmosphere-controllable chamber 44 as shown in FIG. 4, and electromagnetic wave treatment may be performed in this chamber, and inert gas or the like is sprayed onto the film substrate 16. In this way, electromagnetic wave processing may be performed.
  • the dye-sensitized solar cell 60 mainly includes a transparent substrate 61, a transparent conductive layer (negative electrode current collector) 62, a semiconductor electrode layer (negative electrode) 63 holding a photosensitizing dye, an electrolyte layer 64, and a counter electrode (positive electrode). 65, a counter substrate 66, a sealing material 67, and the like.
  • the semiconductor electrode layer 63 is made of the above-described titanium oxide TiO. 2 Or the like, and a photosensitizing dye is held on the surfaces of the metal oxide semiconductor fine particles 2 and 3 and the like.
  • Excited electrons are taken out to the conduction band of the semiconductor electrode layer 63 through electrical coupling between the photosensitizing dye and the semiconductor electrode layer 63, and reach the transparent conductive layer 62 through the semiconductor electrode layer 63.
  • the photosensitizing dye that has lost the electrons is a reducing agent in the electrolyte layer 64, such as I. ⁇
  • the generated oxidant reaches the counter electrode 65 by diffusion, and the reverse reaction of the above reaction.
  • the semiconductor electrode layer 1 or 21 is formed on the transparent conductive layer 62 provided on the transparent substrate 61 by the method for manufacturing a semiconductor electrode layer described above.
  • the photosensitizing dye to be held in the semiconductor electrode layer 63 is not particularly limited as long as it exhibits a sensitizing action.
  • xanthene dyes such as rhodamine B, rose bengal, eosin, erythrosine, merocyanine, quinocyanine, Cyanine dyes such as cryptocyanine, basic dyes such as phenosafranine, cabry blue, thiocin and methylene blue, other azo dyes, porphyrin compounds such as chlorophyll, zinc porphyrin and magnesium porphyrin, phthalocyanine compounds, coumarin compounds, ruthenium Examples include Ru bipyridine complexes, terpyridine complexes, anthraquinone dyes, polycyclic quinone dyes, squarylium dyes, and the like.
  • iodine I 2 An electrolyte in which lithium iodide LiI, sodium iodide NaI, or quaternary ammonium compound such as imidazolium iodide is combined is preferable.
  • the concentration of the electrolyte salt in the electrolytic solution is preferably 0.05M or more and 5M or less, more preferably 0.1M or more and 3M or less.
  • Iodine I 2 Or bromine Br 2 The concentration of is preferably from 0.0005M to 1M, and more preferably from 0.005M to 0.5M.
  • additives such as 4-tert-butylpyridine and carboxylic acid can be added for the purpose of improving the open circuit voltage and the short circuit current.
  • the sealing method can also seal by sticking a glass plate or a plastic substrate with a sealing material.
  • the electrolyte is an electrolyte gelled using a polymer or the like, or an all-solid electrolyte
  • a polymer solution containing an electrolyte and a plasticizer is applied onto the semiconductor electrode layer 63 by a casting method or the like.
  • the plasticizer is volatilized and completely removed, and then sealed with a sealing material in the same manner as described above.
  • This sealing is preferably performed using a vacuum sealer or the like in an inert gas atmosphere or in a reduced pressure.
  • Second embodiment A method for manufacturing an oxide semiconductor layer according to the second embodiment of the present disclosure will be described.
  • the manufacturing method of the oxide semiconductor layer according to the second embodiment of the present disclosure is, for example, a manufacturing method of a transparent oxide semiconductor layer formed on a resin film substrate such as a plastic film.
  • a resin film substrate such as a plastic film.
  • Base film As the base film 86, triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester (TPEE), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), Polyacrylate, polyethersulfone, polysulfone, polypropylene (PP), diacetylcellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, urethane resin, melamine resin, and cycloolefin polymer resin (A resin film substrate such as a transparent plastic film made of a polymer material such as (COP) can be used.
  • TAC triacetyl cellulose
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • TPEE polyester
  • PA polyimide
  • PA polyamide
  • PE Polyacrylate
  • polyethersulfone polysulfone
  • PP polypropylene
  • PP
  • the transparent oxide semiconductor layer 81 is formed on one main surface of the base film 86 by, for example, a vapor phase such as a PVD (Physical Vapor Deposition) method or a CVD (Chemical Vapor Deposition) method. It can be formed by the method. Moreover, it can form by liquid phase methods, such as electroplating, electroless plating, the apply
  • a vapor phase such as a PVD (Physical Vapor Deposition) method or a CVD (Chemical Vapor Deposition) method. It can be formed by the method. Moreover, it can form by liquid phase methods, such as electroplating, electroless plating, the apply
  • Electromagnetic wave treatment After forming the transparent oxide semiconductor layer 81, electromagnetic wave treatment is performed to promote necking of the transparent oxide semiconductor particles, which are transparent conductive particles. Since a plastic material, which is a base material having a low softening point such as a film material, is used as the material of the base film 86, the base film 86 is damaged by being irradiated with electromagnetic waves while cooling the base film 86. It is possible to reduce resistance by promoting necking without giving. Electromagnetic waves include infrared rays, ultraviolet rays and visible rays. Other irradiation type treatments include microwave treatment, flame treatment, plasma treatment in air, plasma treatment in vacuum, corona treatment, induction heating treatment and the like, and these methods may be used.
  • the transparent oxide semiconductor layer 81 When heating the transparent oxide semiconductor layer 81 at a temperature higher than the temperature at which the film is altered or deformed, in order to suppress the temperature of the film from being higher than the temperature at which the film is altered or deformed by heating, support is provided. It is preferable to perform the treatment while cooling the body (film).
  • the cooling of the support may be performed by bringing a cooling plate such as a copper plate and a cooling member such as a cooling roll into close contact with the surface of the base film 86 where the transparent oxide semiconductor layer 81 is not formed.
  • a cooling plate it mounts on the cooling plate of the base film 86 in which the transparent oxide semiconductor layer 81 was formed.
  • the surface of the base film 86 where the transparent oxide semiconductor layer 81 is not formed is a surface that is in close contact with the cooling plate.
  • the base film 86 is cooled from the surface side of the side in which the semiconductor fine particle film of the base film 86 is not formed with a cooling plate.
  • the surface of the cooling roll 36 is brought into close contact with one main surface of the base film 86 where the transparent oxide semiconductor layer 81 is not formed. Cooling takes place.
  • a refrigerant composed of an antifreeze such as ethylene glycol is circulated in the cooling roll 36, and the temperature is, for example, 0 ° C. or less. It is preferable to provide an antifreeze layer 47 such as ethanol on the surface of the cooling roll 36.
  • an antifreeze layer 47 such as ethanol on the surface of the cooling roll 36.
  • Examples of the atmosphere not containing oxygen include an inert gas atmosphere, a vacuum, and a hydrogen atmosphere.
  • ITO that is used as the transparent oxide semiconductor layer 81 has an increased resistance because an oxygen deficiency disappears and carriers are reduced by incorporating oxygen in an electromagnetic wave treatment in an atmosphere containing oxygen such as in the air. There is a tendency. Therefore, when ITO is used as the transparent oxide semiconductor layer 81, it is necessary to create an atmosphere that does not contain oxygen when heating by electromagnetic wave treatment is performed.
  • Examples of the inert gas include nitrogen gas, argon gas, helium gas, and the like.
  • Example 1 With reference to non-patent literature (Adv. Mater. 2003, 15, 2101), a dye-sensitized solar cell (opposing cell) was produced as follows. ⁇ Preparation of coating liquid> As the granular metal oxide semiconductor fine particles 2, the first granular titanium oxide fine particles 2A were used. As the first granular titanium oxide fine particles 2A, P25 (trade name; manufactured by Degussa, a mixture of anatase type crystal (80%) and rutile type crystal (20%), average particle size of primary particles is about 21 nm) was used.
  • P25 trade name; manufactured by Degussa, a mixture of anatase type crystal (80%) and rutile type crystal (20%), average particle size of primary particles is about 21 nm
  • This fine particle powder is mixed with ethanol so that the titanium oxide content is 30% by mass, and is subjected to a bead dispersion treatment with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm to form a granular metal oxide.
  • a dispersion of semiconductor fine particles 2 was prepared.
  • a predetermined amount of the first compound is added to the dispersion, stirred and mixed uniformly, a solvent is added to adjust the concentration, and the first titanium oxide fine particles 2A and the first compound are contained.
  • a coating solution was prepared. At this time, it was observed that the viscosity of the dispersion increased by the addition of the first compound.
  • butoxy titanium dimer Mitsubishi Gas Chemical Co., Ltd.
  • the blending amount in the coating liquid was kept constant at 2.5% by mass.
  • ethanol was used in all examples.
  • a PET film with an ITO layer manufactured by Oike Industry Co., Ltd.
  • the coating solution was applied to the support by a bar coating method using a coil bar (# 44) and then dried at room temperature.
  • the semiconductor fine particles The layer was calendered. Specifically, both the back roll 34 and the press roll 35 nipped the ITO / PET film with a semiconductor fine particle layer at a linear pressure of 1000 N / 15 mm. Thus, the semiconductor fine particle layer was continuously calendered. The number of calendar processes was one. Thereby, the adhesiveness of a support body (ITO / PET film) and a semiconductor fine particle layer improves, The clearance gap between fine particles is filled, and the effect that contact resistance falls is acquired.
  • the semiconductor fine particle layer was cut at the edge of the glass plate to a size of 5 mm ⁇ 5 mm, and then fired at 150 ° C. for 30 minutes to obtain a metal oxide semiconductor porous layer.
  • IR treatment Infrared treatment
  • the metal oxide semiconductor porous layer formed on one main surface of the ITO / PET film is irradiated with infrared rays using an infrared radiation heater (product name IR298, manufactured by Thermo Riko Co., Ltd.). Current output value 20A, treatment time 1 second) was performed and heated, and the other main surface of the ITO / PET film was brought into close contact with the cooling copper plate to cool the ITO / PET film.
  • D358 dye solution is a solution prepared by dissolving D358 dye (trade name; manufactured by Mitsubishi Paper Industries Co., Ltd.) in a mixed solvent in which acetonitrile and tert-butyl alcohol are mixed at a volume ratio of 1: 1 at a concentration of 0.5 mM. It is.
  • this semiconductor electrode metal oxide semiconductor porous layer
  • the acetonitrile was naturally evaporated and the semiconductor electrode was dried.
  • the counter electrode used was a carbon counter electrode formed on a SUS316 substrate.
  • ⁇ Assembly> Next, the two substrates were placed so that the semiconductor electrode layer and the counter electrode face each other, and bonded together via a silicon rubber sheet having a thickness of 30 ⁇ m. Next, an electrolyte solution was introduced between the electrodes using a capillary phenomenon to produce a dye-sensitized solar cell.
  • an electrolytic solution a solution in which 0.6 M iodide (1-propyl-3-methylimidazolium) and 0.1 M iodine were dissolved in 3-methoxypropionitrile was used.
  • This fine particle powder is mixed with ethanol so that the titanium oxide content is 14% by mass, and is subjected to bead dispersion treatment with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm, and the first granular oxidation.
  • a dispersion of titanium fine particles 2A was prepared.
  • TA-300 (trade name: manufactured by Fuji Titanium Industry Co., Ltd., anatase type crystal, average particle size of primary particles of about 390 nm) was used as the second granular fine particles 2B.
  • This fine particle powder was mixed with ethanol so that the titanium oxide content was 3.5% by mass, and was subjected to bead dispersion treatment with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm.
  • a dispersion of granular titanium oxide fine particles 2B was prepared.
  • each fine particle dispersion was mixed in a predetermined ratio.
  • a predetermined amount of the first compound is added to the dispersion, stirred and mixed uniformly, a solvent is added to adjust the concentration, and the titanium oxide fine particles 2A and 2B and the first compound are contained.
  • a coating solution was prepared. At this time, it was observed that the viscosity of the dispersion increased by the addition of the first compound.
  • butoxy titanium dimer Mitsubishi Gas Chemical Co., Ltd.
  • the blending amount in the coating liquid was kept constant at 2.5% by mass.
  • ethanol was used in all examples.
  • the first granular fine particles 2A and the second granular fine particles 2B which are the granular metal oxide semiconductor fine particles 2, two types of titanium oxide TiO 2 fine particles having a spherical shape and different sizes were used.
  • P25 trade name; manufactured by Degussa, a mixture of anatase type crystal (80%) and rutile type crystal (20%), average particle size of primary particles is about 21 nm
  • P25 trade name; manufactured by Degussa, a mixture of anatase type crystal (80%) and rutile type crystal (20%), average particle size of primary particles is about 21 nm
  • This fine particle powder was mixed with ethanol so that the titanium oxide content was 10.5% by mass, and the beads were dispersed with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm.
  • a dispersion of granular titanium oxide fine particles 2A was prepared.
  • TA-300 (trade name: manufactured by Fuji Titanium Industry Co., Ltd., anatase type crystal, average particle size of primary particles of about 390 nm) was used as the second granular fine particles 2B.
  • This fine particle powder was mixed with ethanol so that the titanium oxide content was 5.25% by mass, and was subjected to bead dispersion treatment with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm.
  • a dispersion of granular titanium oxide fine particles 2B was prepared.
  • acicular titanium oxide TiO 2 fine particles were used as the acicular metal oxide semiconductor fine particles 3.
  • FTL-300 trade name; manufactured by Ishihara Sangyo Co., Ltd., rutile type crystal, average primary particle diameter of about 0.27 ⁇ m, average length of about 5.15 ⁇ m
  • This fine particle powder is mixed with ethanol so that the titanium oxide content is 1.75% by mass, and the beads are dispersed with a zirconia bead having a diameter of 0.65 mm for 24 hours using a paint shaker.
  • a dispersion of the metal oxide semiconductor fine particles 3 was prepared.
  • each fine particle dispersion was mixed in a predetermined ratio.
  • a predetermined amount of the first compound is added to the dispersion, stirred and mixed uniformly, a solvent is added to adjust the concentration, and the titanium oxide fine particles 2A, 2B and 3 and the first compound are added.
  • a coating liquid containing was prepared. At this time, it was observed that the viscosity of the dispersion increased by the addition of the first compound.
  • butoxy titanium dimer Mitsubishi Gas Chemical Co., Ltd.
  • the blending amount in the coating liquid was kept constant at 2.5% by mass.
  • ethanol was used in all examples.
  • a PET film with an ITO layer having a surface resistance of 12 to 15 ⁇ / ⁇ manufactured by Oike Industry Co., Ltd.
  • a first coating liquid was applied on the support 6 by a bar coating method using a coil bar (# 30), and then dried at room temperature, thereby forming a first semiconductor fine particle layer on the support.
  • a second coating liquid is applied by a bar coating method using a coil bar (# 14) on the first semiconductor fine particle layer formed on the support, and then dried at room temperature, whereby the second A semiconductor fine particle layer was formed.
  • Example 3 ⁇ Preparation of coating liquid>
  • the first granular fine particles 2A and the second granular fine particles 2B which are the granular metal oxide semiconductor fine particles 2
  • two types of titanium oxide TiO 2 fine particles having a spherical shape and different sizes were used.
  • the first granular fine particles 2A P25 (trade name; manufactured by Degussa, a mixture of anatase type crystal (80%) and rutile type crystal (20%), average particle size of primary particles is about 21 nm) was used.
  • This fine particle powder is mixed with ethanol so that the titanium oxide content is 14% by mass, and is subjected to bead dispersion treatment with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm, and the first granular oxidation.
  • a dispersion of titanium fine particles 2A was prepared.
  • TA-300 (trade name: manufactured by Fuji Titanium Industry Co., Ltd., anatase type crystal, average particle size of primary particles of about 390 nm) was used as the second granular fine particles 2B.
  • This fine particle powder was mixed with ethanol so that the titanium oxide content was 3.5% by mass, and was subjected to bead dispersion treatment with an agitator for 24 hours using zirconia beads having a diameter of 0.65 mm.
  • a dispersion of granular titanium oxide fine particles 2B was prepared.
  • each fine particle dispersion was mixed in a predetermined ratio.
  • a predetermined amount of the first compound is added to the dispersion, stirred and mixed uniformly, a solvent is added to adjust the concentration, and the titanium oxide fine particles 2A and 2B and the first compound are contained.
  • a coating solution was prepared. At this time, it was observed that the viscosity of the dispersion increased by the addition of the first compound.
  • butoxy titanium dimer Mitsubishi Gas Chemical Co., Ltd.
  • the blending amount in the coating liquid was kept constant at 2.5% by mass.
  • ethanol was used in all examples.
  • the adhesiveness of a base material and a semiconductor fine particle layer improves, The clearance gap between fine particles is filled, and the effect that contact resistance falls is acquired.
  • the semiconductor fine particle layer was shaved with an edge of a glass plate to a size of 5 mm ⁇ 5 mm, and then fired at 150 ° C. for 30 minutes to obtain a metal oxide semiconductor porous layer.
  • ⁇ Infrared treatment> the semiconductor fine particle layer formed on one main surface of the glass substrate with an FTO layer is irradiated with infrared rays in the atmosphere using an infrared radiation heater (product name IR298, manufactured by Thermo Riko Co., Ltd.).
  • FIG. 1 shows the open-circuit voltage (VOC), short-circuit current (JSC), fill factor (FF), photoelectric conversion efficiency ( ⁇ ), and series resistance value of Examples 1 to 3 and Comparative Examples 1 to 3 ( Rs).
  • FIG. 8 is an IV curve when measuring the light conversion efficiency.
  • ⁇ is the IV curve of the counter cell of Example 1 prepared by performing the electromagnetic wave irradiation treatment
  • ⁇ is the IV curve of the counter cell of Comparative Example 1 manufactured without performing the electromagnetic wave irradiation treatment.
  • the current density is shifted upward as compared with the result of not performing the electromagnetic wave irradiation process. That is, it is considered that the application of electromagnetic wave irradiation improves the bonding between the semiconductor fine particles and decreases the resistance, resulting in an increase in current density.
  • the performance of the counter cell subjected to the electromagnetic wave irradiation treatment is superior to the performance of the counter cell not subjected to the electromagnetic wave irradiation treatment (Comparative Examples 1 to 3). Can be confirmed. 3.
  • Other Embodiments The present disclosure is not limited to the above-described embodiments of the present disclosure, and various modifications and applications are possible without departing from the gist of the present disclosure.
  • the numerical values, structures, shapes, materials, raw materials, processes, and the like given in the above-described embodiments and examples are merely examples, and numerical values, structures, shapes, materials, raw materials, processes that are different from these as necessary. Etc. may be used.
  • Transparent substrate 62 Transparent conductive layer 63 .
  • Semiconductor electrode layer 64 Electrolyte layer 65 .
  • Opposite Electrode 66 Counter substrate 67 .
  • Sealing material 81 Transparent acid Things semiconductor layer 86 ... substrate film

Abstract

La présente invention concerne un procédé pour produire une couche d'oxyde semi-conducteur qui est capable d'effectuer un traitement thermique dans une région à haute température, à laquelle des substrats de film de résine sont modifiés et se déforment, par rapport à une couche d'oxyde semi-conducteur formée sur un corps de support, même si un corps de support contenant un substrat de film de résine est utilisé. Un substrat de film se déplaçant est séquentiellement soumis à une enduction par un revêtement de film, traitement de séchage/cuisson, traitement de calandrage, et traitement par onde électromagnétique. Dans le traitement par onde électromagnétique dans une unité d'irradiation d'onde électromagnétique, une couche poreuse d'oxyde de métal semi-conducteur formée sur le substrat de film est chauffée au moyen de l'irradiation d'onde électromagnétique, et le substrat de film est refroidi par un rouleau refroidisseur.
PCT/JP2012/052196 2011-02-02 2012-01-25 Procédé pour produire une couche d'oxyde semi-conducteur WO2012105581A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011020529A JP2012160394A (ja) 2011-02-02 2011-02-02 酸化物半導体層の製造方法
JP2011-020529 2011-09-09

Publications (1)

Publication Number Publication Date
WO2012105581A1 true WO2012105581A1 (fr) 2012-08-09

Family

ID=46602788

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/052196 WO2012105581A1 (fr) 2011-02-02 2012-01-25 Procédé pour produire une couche d'oxyde semi-conducteur

Country Status (2)

Country Link
JP (1) JP2012160394A (fr)
WO (1) WO2012105581A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018221693A1 (fr) * 2017-05-31 2018-12-06 国立大学法人北海道大学 Structure fonctionnelle et procédé de production de structure fonctionnelle
US11161101B2 (en) 2017-05-31 2021-11-02 Furukawa Electric Co., Ltd. Catalyst structure and method for producing the catalyst structure
US11547987B2 (en) 2017-05-31 2023-01-10 Furukawa Electric Co., Ltd. Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method
US11648543B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648542B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648538B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11654422B2 (en) 2017-05-31 2023-05-23 Furukawa Electric Co., Ltd. Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization
US11666894B2 (en) 2017-05-31 2023-06-06 Furukawa Electric Co., Ltd. Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water
US11680211B2 (en) 2017-05-31 2023-06-20 Furukawa Electric Co., Ltd. Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization
US11684909B2 (en) 2017-05-31 2023-06-27 Furukawa Electric Co., Ltd. Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112853266B (zh) * 2021-01-05 2023-02-28 西京学院 一种柔性透明太阳能水解光电极及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002121683A (ja) * 2000-10-12 2002-04-26 Seiko Epson Corp 酸化チタン膜の製造方法、酸化チタン膜および太陽電池
JP2004196644A (ja) * 2002-10-22 2004-07-15 Kansai Paint Co Ltd 半導体膜、半導体膜の形成方法、及び光電極
JP2004342319A (ja) * 2003-03-19 2004-12-02 Kansai Paint Co Ltd 高分子フィルム表面に半導体微粒子分散液を焼結する方法、及び光電池
JP2005139498A (ja) * 2003-11-05 2005-06-02 Bridgestone Corp 薄膜の処理方法、結晶性薄膜、結晶性酸化チタンフィルム、光触媒フィルム、色素増感型太陽電池用半導体電極、及び薄膜の処理装置
JP2009155704A (ja) * 2007-12-27 2009-07-16 Fujifilm Corp 熱処理方法、成膜装置およびバリアフィルム
JP2009174002A (ja) * 2008-01-24 2009-08-06 Fujifilm Corp 熱処理方法、およびバリアフィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002121683A (ja) * 2000-10-12 2002-04-26 Seiko Epson Corp 酸化チタン膜の製造方法、酸化チタン膜および太陽電池
JP2004196644A (ja) * 2002-10-22 2004-07-15 Kansai Paint Co Ltd 半導体膜、半導体膜の形成方法、及び光電極
JP2004342319A (ja) * 2003-03-19 2004-12-02 Kansai Paint Co Ltd 高分子フィルム表面に半導体微粒子分散液を焼結する方法、及び光電池
JP2005139498A (ja) * 2003-11-05 2005-06-02 Bridgestone Corp 薄膜の処理方法、結晶性薄膜、結晶性酸化チタンフィルム、光触媒フィルム、色素増感型太陽電池用半導体電極、及び薄膜の処理装置
JP2009155704A (ja) * 2007-12-27 2009-07-16 Fujifilm Corp 熱処理方法、成膜装置およびバリアフィルム
JP2009174002A (ja) * 2008-01-24 2009-08-06 Fujifilm Corp 熱処理方法、およびバリアフィルム

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018221693A1 (fr) * 2017-05-31 2018-12-06 国立大学法人北海道大学 Structure fonctionnelle et procédé de production de structure fonctionnelle
AU2018277967B2 (en) * 2017-05-31 2021-05-27 Furukawa Electric Co., Ltd. Functional structure and production method for functional structure
US11161101B2 (en) 2017-05-31 2021-11-02 Furukawa Electric Co., Ltd. Catalyst structure and method for producing the catalyst structure
US11547987B2 (en) 2017-05-31 2023-01-10 Furukawa Electric Co., Ltd. Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method
US11648543B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648542B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648538B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11655157B2 (en) 2017-05-31 2023-05-23 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11654422B2 (en) 2017-05-31 2023-05-23 Furukawa Electric Co., Ltd. Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization
US11666894B2 (en) 2017-05-31 2023-06-06 Furukawa Electric Co., Ltd. Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water
US11680211B2 (en) 2017-05-31 2023-06-20 Furukawa Electric Co., Ltd. Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization
US11684909B2 (en) 2017-05-31 2023-06-27 Furukawa Electric Co., Ltd. Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon
US11904306B2 (en) 2017-05-31 2024-02-20 Furukawa Electric Co., Ltd. Catalyst structure and method for producing the catalyst structure

Also Published As

Publication number Publication date
JP2012160394A (ja) 2012-08-23

Similar Documents

Publication Publication Date Title
WO2012105581A1 (fr) Procédé pour produire une couche d'oxyde semi-conducteur
TW516242B (en) Photoelectric conversion element
Mohan et al. Poly (acrylonitrile)/activated carbon composite polymer gel electrolyte for high efficiency dye sensitized solar cells
US20070175510A1 (en) Photoelectric conversion apparatus and gelling agent
KR20100038077A (ko) 색소 증감 광전 변환 소자 및 그의 제조 방법 및 전자 기기 및 반도체 전극 및 그의 제조 방법
JP5358790B2 (ja) 色素増感型光電変換素子用光電極及びその製造方法
JP2011165469A (ja) 半導体電極層及びその製造方法、並びに電気化学装置
JP4925605B2 (ja) 光電変換装置およびそれを用いた光発電装置
JP2003163360A (ja) 光電変換素子
JP2011154988A (ja) 半導体電極層及びその製造方法、並びに電気化学装置
JPH11219734A (ja) 光電変換材料用半導体及びこの半導体を用いた積層体並びにこれらの製造方法及び光電池
WO2011083688A1 (fr) Procédé de fabrication de cellules solaires sensibilisées par colorant
JP5292549B2 (ja) 色素増感型太陽電池モジュールおよびその製造方法
JP2003234486A (ja) 光電変換素子
Lv et al. Dye-sensitized solar cells with enhanced efficiency using hierarchical TiO 2 spheres as a scattering layer
JP5725438B2 (ja) 色素増感型太陽電池モジュールおよびその製造方法
JP2003234485A (ja) 光電変換素子
JP2013191273A (ja) 光電極、その製造方法、およびそれを用いた色素増感太陽電池
Lupitskyy et al. Toward high‐efficiency dye‐sensitized solar cells with a photoanode fabricated via a simple water‐based formulation
JP2011165615A (ja) 光電変換素子およびその製造方法
JP2015028857A (ja) 色素増感型光電変換素子およびそれを用いた色素増感型太陽電池の製造方法
JP2012043724A (ja) 半導体電極層及びその製造方法、並びに電気化学装置
JP2012226830A (ja) 色素増感太陽電池および色素増感太陽電池の製造方法
JP2012156070A (ja) 色素増感太陽電池における光触媒膜の形成方法および色素増感太陽電池
Hočevar et al. Dye-sensitized solar cells

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12741792

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12741792

Country of ref document: EP

Kind code of ref document: A1