WO2014083884A1 - 多孔質酸化チタン積層体の製造方法 - Google Patents
多孔質酸化チタン積層体の製造方法 Download PDFInfo
- Publication number
- WO2014083884A1 WO2014083884A1 PCT/JP2013/069158 JP2013069158W WO2014083884A1 WO 2014083884 A1 WO2014083884 A1 WO 2014083884A1 JP 2013069158 W JP2013069158 W JP 2013069158W WO 2014083884 A1 WO2014083884 A1 WO 2014083884A1
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- WIPO (PCT)
- Prior art keywords
- titanium oxide
- porous titanium
- dye
- porous
- producing
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 172
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/62—Surface treatment of fibres or filaments made from glass, minerals or slags by application of electric or wave energy; by particle radiation or ion implantation
- C03C25/6206—Electromagnetic waves
- C03C25/6226—Ultraviolet
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/256—Coating containing TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/002—Thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 producing a porous titanium oxide laminate capable of producing a porous titanium oxide layer having a high porosity and low impurities even at low temperature firing, and a dye using the porous titanium oxide laminate It relates to a sensitized solar cell.
- This titanium oxide layer is 1) adsorption of sensitizing dye, 2) acceptance of electron injection from excited sensitizing dye, 3) electron transport to conductive layer, 4) electron transfer from iodide ion to dye (reduction) It is one of the most important factors that determine the performance of the solar cell because it has a role of providing a reaction field, and 5) light scattering and light confinement.
- the titanium oxide layer is required to be porous, and it is required to increase its surface area as much as possible and to reduce impurities as much as possible.
- a paste containing titanium oxide particles and an organic binder is printed on a substrate, the solvent is volatilized, and then a high-temperature baking treatment is performed. A method of eliminating the organic binder is used. Thereby, a porous film in which many fine voids exist in the layer can be obtained while the titanium oxide particles are sintered.
- ethyl cellulose is generally used from the viewpoint of printability such as dispersion retention of the titanium oxide particles and viscosity of the paste.
- a high-temperature baking treatment exceeding 500 ° C. is required, and there is a problem that a resin base material that has been in increasing demand for further cost reduction in recent years cannot be used. there were.
- the organic binder residue remains on the surface of the titanium oxide particles, so that the sensitizing dye cannot be adsorbed and the photoelectric conversion efficiency is remarkably lowered.
- Patent Document 1 discloses performing a baking process at a low temperature using a paste in which the content of the organic binder is reduced.
- the paste described in Patent Document 1 has a low viscosity and it is difficult to maintain the shape during printing. The film thickness is not uniform and the end shape is collapsed. There was a problem that the coalescence occurred.
- ethyl cellulose when using ethyl cellulose as the organic binder, a lower alcohol or a mixed solvent of a lower alcohol and a high viscosity solvent such as terpineol is used as a solvent. Since external force such as strong shear is received from a device such as a squeegee, the dispersion medium volatilizes before printing and the viscosity increases, so the printability may change, and there is a new problem that stable production is difficult. Had occurred. On the other hand, in a dye-sensitized solar cell, it is preferable to carry as much sensitizing dye as possible in order to improve photoelectric conversion efficiency. However, when a paste containing a conventional organic binder is used, a sufficient amount is used. There has been a problem that a sensitizing dye cannot be supported or a long time is required for supporting a sensitizing dye.
- the present invention relates to a method for producing a porous titanium oxide laminate capable of producing a porous titanium oxide layer having a high porosity and low impurities even at low temperature firing, and a dye using the porous titanium oxide laminate
- An object is to provide a sensitized solar cell.
- the present invention includes a step of printing a titanium oxide paste containing titanium oxide fine particles, a (meth) acrylic resin, and an organic solvent on a base material to form a titanium oxide paste layer on the base material;
- a method for producing a porous titanium oxide laminate comprising a step of firing a titanium paste layer and a step of irradiating the titanium oxide paste layer after firing with ultraviolet rays, wherein the titanium oxide fine particles have an average particle size of 5
- the present invention is described in detail below.
- the present inventors have baked the titanium oxide paste layer in a method for producing a porous titanium oxide laminate using a titanium oxide paste containing titanium oxide fine particles, a (meth) acrylic resin, and an organic solvent. Then, by performing the process of irradiating with ultraviolet rays, it becomes possible to produce a porous titanium oxide layer having a high porosity and low impurities even at low temperature firing. For example, it is used as a material for a dye-sensitized solar cell. And found that high photoelectric conversion efficiency can be realized. Further, it has also been found that a dye-sensitized solar cell obtained using such a porous titanium oxide laminate can sufficiently adsorb a sensitizing dye in a short time, and the present invention has been completed. It was.
- the manufacturing method of the porous titanium oxide laminated body of this invention has a process of printing a titanium oxide paste on a base material, and forming a titanium oxide paste layer on this base material.
- a method for printing the titanium oxide paste on the substrate is not particularly limited, but a screen printing method is preferably used.
- a base material has a softness
- the base material is coated on the transparent conductive layer of the transparent substrate on which the transparent conductive layer is formed. By doing it.
- the transparent substrate if it is a transparent substrate, Glass substrates, such as silicate glass, etc. are mentioned.
- the glass substrate may be chemically and thermally strengthened.
- various plastic substrates or the like may be used as long as light transmittance can be secured.
- the thickness of the transparent substrate is preferably from 0.1 to 10 mm, more preferably from 0.3 to 5 mm.
- the transparent conductive layer examples include a layer made of a conductive metal oxide such as In 2 O 3 or SnO 2 and a layer made of a conductive material such as a metal.
- a conductive metal oxide such as In 2 O 3 or SnO 2
- a conductive material such as a metal.
- the conductive metal oxide include In 2 O 3 : Sn (ITO), SnO 2 : Sb, SnO 2 : F, ZnO: Al, ZnO: F, and CdSnO 4 .
- the titanium oxide paste contains titanium oxide fine particles. Titanium oxide can be suitably used because it has a wide band gap and a relatively large amount of resources.
- titanium oxide fine particles for example, rutile type titanium oxide fine particles, anatase type titanium oxide fine particles, brookite type titanium oxide fine particles, and titanium oxide fine particles modified with these crystalline titanium oxides can be used.
- the average particle diameter of the titanium oxide fine particles has a lower limit of 5 nm and an upper limit of 50 nm, a preferable lower limit of 10 nm, and a preferable upper limit of 25 nm. By setting it within the above range, the obtained porous titanium oxide layer has a sufficient specific surface area. In addition, recombination of electrons and holes can be prevented. Two or more kinds of fine particles having different particle size distributions may be mixed.
- a preferable lower limit of the addition amount of the titanium oxide fine particles is 5% by weight with respect to the titanium oxide paste, and a preferable upper limit is 75% by weight.
- a preferable upper limit is 75% by weight.
- a more preferred lower limit is 10% by weight, and a more preferred upper limit is 50% by weight.
- a more preferred lower limit is 20% by weight, and a more preferred upper limit is 35% by weight.
- the titanium oxide paste contains a (meth) acrylic resin. Since the (meth) acrylic resin is excellent in low-temperature decomposability, a titanium oxide paste with a small amount of organic residue can be obtained even when low-temperature baking is performed. In addition, since the (meth) acrylic resin has low viscosity characteristics, even if solvent volatilization occurs in the working environment, the change in viscosity characteristics can be greatly suppressed, and thus stable printing can be performed.
- the (meth) acrylic resin is not particularly limited as long as it decomposes at a low temperature of about 300 ° C., for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) ) Acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate
- a polymer composed of at least one selected from the group consisting of (meth) acrylic monomers having a polyoxyalkylene structure is suitably used.
- (meth) acrylate means acrylate or methacrylate.
- polyisobutyl methacrylate isobutyl methacrylate polymer which is a polymer of methyl methacrylate having a high glass transition temperature (Tg) and excellent low-temperature degreasing property is obtained. Is preferred.
- the minimum with a preferable weight average molecular weight by polystyrene conversion of the said (meth) acrylic resin is 5000, and a preferable upper limit is 500,000.
- a preferable upper limit is 500,000.
- the weight average molecular weight is less than 5,000, sufficient viscosity cannot be expressed, so that it may not be suitable for printing applications.
- the weight average molecular weight exceeds 500,000, the adhesive strength of the titanium oxide paste increases, May occur, and printability may deteriorate.
- a more preferable upper limit of the weight average molecular weight is 100,000, and a more preferable upper limit is 50,000.
- the measurement of the weight average molecular weight in terms of polystyrene can be obtained by performing GPC measurement using, for example, a column LF-804 (manufactured by SHOKO) as a column.
- a preferable minimum is 10 weight% and a preferable upper limit is 50 weight%.
- the (meth) acrylic resin preferably has a smaller content than the titanium oxide fine particles. If the (meth) acrylic resin is larger than the titanium oxide fine particles, the (meth) acrylic resin residual amount after heating may increase.
- the titanium oxide paste may be added with a small amount of other binder resin within a range in which no impurities remain even at low temperature firing.
- the binder resin include polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyethylene glycol, polystyrene, polylactic acid, and the like.
- the titanium oxide paste contains an organic solvent.
- organic solvent those having excellent (meth) acrylic resin solubility and high polarity are preferable.
- terpene solvents such as ⁇ -terpineol and ⁇ -terpineol
- alcohol solvents such as ethanol and isopropyl alcohol
- diols terpene solvents
- polyhydric alcohol solvents such as triol, mixed solvents such as the above alcohol solvents / hydrocarbons, and hetero compounds such as dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran.
- terpene solvents are preferred.
- the organic solvent preferably has a boiling point of 100 to 300 ° C.
- the boiling point of the organic solvent is less than 100 ° C.
- the resulting titanium oxide paste is easily dried during printing, and may cause problems when used for continuous printing for a long time.
- the boiling point exceeds 300 ° C.
- the resulting titanium oxide paste has reduced drying properties in the drying step after printing.
- the said boiling point means the boiling point in a normal pressure.
- the minimum with preferable content of the said organic solvent is 55 weight%, and a preferable upper limit is 74 weight%. If the content of the organic solvent is less than 55% by weight, the resulting titanium oxide paste may have a high viscosity and poor printability. If the content of the organic solvent exceeds 74% by weight, the viscosity of the resulting titanium oxide paste may be too low, resulting in poor printability. A more preferred lower limit is 60% by weight, and a more preferred upper limit is 70% by weight.
- the titanium oxide paste preferably contains a photoacid generator.
- a photoacid generator in addition to the oxidative decomposition by ultraviolet rays described later, two actions of organic matter decomposition by acid from the photoacid generator occur, so that the residue decomposition can be more effectively performed. .
- the photoacid generator is not particularly limited as long as it generates an acid when irradiated with light.
- the photoacid generator include compounds in which an acid compound and a light absorbing compound are ester-bonded.
- Specific examples of the photoacid generator include trade names “TPS-105” (CAS No. 66003-78-9) and “TPS-109” (CAS No. 144317-44-2) manufactured by Midori Chemical Co., Ltd. "MDS-105" (CAS No. 116808-67-4), “MDS-205" (CAS No. 81416-37-7), “DTS-105" (CAS No. 111281-12-2), "NDS -105 "(CAS No. 195057-83-1), sulfonium salt compounds such as” NDS-165 "(CAS No.
- DPI-105 (CAS No. 66003-76-7) , “DPI-106” (CAS No. 214534-44-8), “DPI-109” (CAS No. 194999-82-1), “DPI -201 "(CAS No. 6293-66-9),” BI-105 “(CAS No. 154557-16-1),” MPI-105 “(CAS No. 115298-63-0),” MPI-106 “ (CAS No. 260061-46-9), “MPI-109” (CAS No. 260061-47-0), “BBI-105” (CAS No. 84563-54-2), “BBI-106” (CAS No. 185195-30-6), “BBI-109” (CAS No.
- a photo-acid generator may be used independently and 2 or more types may be used together. Especially, it is preferable to use the photo-acid generator which has a structure shown to following formula (1).
- a preferable minimum is 0.0025 weight% and a preferable upper limit is 2.5 weight%. If the content of the photoacid generator is less than 0.0025% by weight, the effect of decomposing organic matter by adding the photoacid generator may be insufficient. If the content exceeds 2.5% by weight, for example, The ratio of the above light-absorbing compound is also increased, which may have an adverse effect. A more preferred lower limit is 0.025% by weight, and a more preferred upper limit is 1.25% by weight.
- the titanium oxide paste has a preferable lower limit of viscosity of 15 Pa ⁇ s and a preferable upper limit of 50 Pa ⁇ s. If the viscosity is less than 15 Pa ⁇ s, it may be difficult to maintain the shape during printing. When the viscosity exceeds 50 Pa ⁇ s, the resulting titanium oxide paste may be inferior in coatability. A more preferable lower limit of the viscosity is 17.5 Pa ⁇ s, and a more preferable upper limit is 45 Pa ⁇ s. In addition, the said viscosity measured kinematic viscosity at the time of 25 degreeC and 10 rpm shear using an E-type viscosity meter.
- the preferable lower limit of the thixo ratio is 2.
- the more preferable lower limit of the thixo ratio is 2.25, and the preferable upper limit is 5.
- the thixo ratio can be determined by dividing the kinematic viscosity at 25 rpm and 0.5 rpm shear by the kinematic viscosity at 5 rpm shear using an E-type viscometer.
- the titanium oxide paste preferably has a viscosity change rate of 105% or less when the squeegee operation is repeated 25 times at room temperature and in an air atmosphere.
- the rate of change in viscosity is the ratio of the viscosity before and after the operation of placing the titanium oxide paste on the glass, extending the titanium oxide paste thinly on the glass surface using a rubber squeegee, and rubbing it 25 times.
- the viscosity is a kinematic viscosity measured at 25 ° C. and 10 rpm shear using an E-type viscometer.
- the titanium oxide paste preferably has a content of (meth) acrylic resin and organic solvent of 1% by weight or less after heating at a rate of temperature increase of 10 ° C./min from 25 ° C. to 300 ° C. in an air atmosphere. . Since the titanium oxide paste has few surface impurities after heating, bonding between fine particles (necking) is likely to occur, and as a result, resistance between particles can be reduced. When used as a material, high photoelectric conversion efficiency can be realized. If the content exceeds 1% by weight, impurities remain on the surface of the titanium oxide fine particles, so that the sensitizing dye cannot be adsorbed. In addition, the said content is content with respect to a titanium oxide microparticle.
- the titanium oxide paste not only has excellent printability, but also makes it possible to suitably produce a porous titanium oxide layer that has a high porosity and low impurities even at low temperature firing.
- the titanium oxide paste is excellent in compatibility with organic solvents generally used for cleaning screen plates and can be sufficiently washed and removed after use, thereby reducing clogging of screen plates. And screen printing can be performed stably for a long period of time.
- the sensitizing dye can be sufficiently adsorbed in a short time, and the resulting dye-sensitized solar cell has high photoelectric conversion efficiency. Can be realized.
- a method for producing the titanium oxide paste a method having a mixing step of mixing titanium oxide fine particles, a (meth) acrylic resin, and an organic solvent can be used.
- the mixing means include, for example, a method of mixing using a two-roll mill, a three-roll mill, a bead mill, a ball mill, a disper, a planetary mixer, a rotation / revolution stirrer, a kneader, an extruder, a mix rotor, a stirrer, etc. Is mentioned.
- the manufacturing method of the porous titanium oxide laminated body of this invention has the process of baking the said titanium oxide paste layer.
- the temperature, time, atmosphere, and the like can be appropriately adjusted depending on the type of substrate to be coated. For example, it is preferably performed in the range of about 50 to 800 ° C. for about 10 seconds to 12 hours in the air or in an inert gas atmosphere.
- the drying and firing may be performed once at a single temperature or twice or more by changing the temperature.
- the method for producing a porous titanium oxide laminate of the present invention includes a step of irradiating ultraviolet rays onto the fired titanium oxide paste layer.
- a trace amount of organic residue in the titanium oxide paste layer can be oxidatively decomposed due to the catalytic activity effect of titanium oxide.
- the effect of such an ultraviolet irradiation process is particularly prominent when a (meth) acrylic resin is used as the organic binder.
- the contact area with the organic binder can be increased by using titanium oxide particles having a small average particle diameter. As a result, the catalytic activity effect of titanium oxide can be further enhanced.
- the cumulative amount of ultraviolet irradiation is 100 J / cm 2 or more.
- the organic residue cannot be sufficiently removed.
- a preferred lower limit of the cumulative light quantity is 150 J / cm 2, preferable upper limit is 10000 J / cm 2.
- the integrated light quantity can be simply calculated by irradiation intensity (mW / cm 2 ) ⁇ irradiation time (seconds).
- the irradiation intensity of the ultraviolet rays is preferably 0.5 to 1000 mW / cm 2 .
- the irradiation time of ultraviolet rays is preferably 1 second to 300 minutes, more preferably 1 second to 60 minutes. If the irradiation intensity is too low or the irradiation time is too short, the removal of the organic residue will only partially proceed, so a sufficient effect cannot be obtained and the irradiation intensity is too high or the irradiation time is too long. , It may cause ultraviolet deterioration and thermal deterioration of the transparent substrate.
- the method of irradiating the ultraviolet rays is not particularly limited, and examples thereof include a method using a low-pressure mercury lamp, a high-pressure mercury lamp, a mercury-xenon lamp, or the like.
- the step of irradiating with ultraviolet rays it is preferable to irradiate ultraviolet rays from both the front side (the side opposite to the base material) and the back side (base material side) of the titanium oxide paste layer after firing. Thereby, it is possible to sufficiently irradiate the inside of the titanium oxide paste layer with ultraviolet rays. As a result, it is possible to sufficiently obtain the effect of ultraviolet irradiation even with a small amount of integrated light, leading to a reduction in the time of the entire manufacturing process. Note that the irradiation from the front side and the irradiation from the back side may be performed simultaneously, or may be performed sequentially in a plurality of times.
- the present invention it is preferable to perform a step of irradiating pulsed white light having a smaller pulse width after performing the step of irradiating the ultraviolet rays. Irradiation with the pulsed white light causes densification due to melting of the surface between the titanium oxide particles in the titanium oxide paste layer, and as a result, the surface resistance can be reduced.
- the pulse light preferably has a pulse width of 0.1 to 10 ms. Thereby, powerful light energy can be irradiated instantaneously.
- the integrated light quantity of the pulsed light is not particularly limited, but is preferably 4 J / cm 2 or more. Thereby, sufficient energy can be applied for fusion between particles. More preferably, it is 15 to 40 J / cm 2 . Further, the number of irradiations is desirably 1 to 5 times.
- Examples of the means for irradiating the pulsed light include a halogen flash lamp, a xenon flash lamp, and an LED flash lamp, and it is particularly preferable to use a xenon flash lamp.
- a porous titanium oxide laminate in which a porous titanium oxide layer is formed on the substrate is obtained by performing the above-described steps.
- the step of adsorbing the sensitizing dye to the porous titanium oxide laminate thus obtained is performed so as to be opposed to the counter electrode, and an electrolyte layer is formed between these electrodes, thereby sensitizing the dye.
- a solar battery cell can be manufactured.
- the dye-sensitized solar cell thus obtained can achieve high photoelectric conversion efficiency.
- Examples of the method for adsorbing the sensitizing dye include a method of immersing the porous titanium oxide laminate in an alcohol solution containing the sensitizing dye and then removing the alcohol by drying.
- sensitizing dye examples include ruthenium-tris and ruthenium-bis type ruthenium dyes, and organic dyes such as phthalocyanine, porphyrin, cyanidin dye, merocyanine dye, rhodamine dye, xanthene dye, and triphenylmethane dye.
- the manufacturing method of the porous titanium oxide laminated body which can manufacture the porous titanium oxide layer with a high porosity and few impurities also by low-temperature baking, and this porous titanium oxide laminated body are used.
- a dye-sensitized solar cell can be provided.
- Example 1 (Production of titanium oxide paste) Titanium oxide fine particles having an average particle diameter of 20 nm, isobutyl methacrylate polymer (weight average molecular weight 50000) as an organic binder, ⁇ -terpineol (boiling point 219 ° C.) as an organic solvent, and a bead mill so as to have the composition shown in Table 1.
- a titanium oxide paste was prepared by mixing uniformly.
- the obtained titanium oxide paste was printed on a 25 mm square FTO transparent electrode-formed glass substrate in a 5 mm square shape and baked at 300 ° C. for 1 hour. Then, using a high-pressure mercury lamp (HLR100T-2, manufactured by Sen Special Light Source Co., Ltd.), porous titanium oxide was irradiated by irradiating ultraviolet rays from the side opposite to the glass substrate (front side) at an irradiation intensity of 100 mW / cm 2 for 30 minutes. A layer was obtained. The printing conditions were finely adjusted so that the obtained porous titanium oxide layer had a thickness of 10 ⁇ m.
- HLR100T-2 high-pressure mercury lamp
- Example 2 In Example 1, as shown in Table 1, the porous titanium oxide layer and the dye were the same as in Example 1 except that the amount of organic binder, organic solvent, baking temperature, ultraviolet irradiation time, and integrated light amount were changed. A sensitized solar cell was obtained.
- As the organic solvent ⁇ -terpineol (boiling point 219 ° C.) and 2,4-diethyl-1,5-pentanediol (PD-9, boiling point 264 ° C.) were used.
- Example 9 In (formation of a porous titanium oxide layer), using a high-pressure mercury lamp (HLR100T-2, manufactured by Sen Special Light Source Co., Ltd.), ultraviolet rays are irradiated from the side opposite to the glass substrate (front side) at an irradiation intensity of 100 mW / cm 2 for 15 minutes. After irradiation, a porous titanium oxide layer and a dye-sensitized solar cell were obtained in the same manner as in Example 7, except that irradiation was further performed for 15 minutes at an irradiation intensity of 100 mW / cm 2 from the glass substrate side (back side).
- HLR100T-2 high-pressure mercury lamp
- Example 10 In (formation of a porous titanium oxide layer), using a high-pressure mercury lamp (HLR100T-2, manufactured by Sen Special Light Source Co., Ltd.), ultraviolet rays are irradiated from the side opposite to the glass substrate (front side) at an irradiation intensity of 100 mW / cm 2 for 30 minutes. After irradiation, a porous titanium oxide layer and a dye-sensitized solar cell were obtained in the same manner as in Example 7, except that irradiation was further performed at an irradiation intensity of 100 mW / cm 2 for 30 minutes from the glass substrate side (back side).
- HLR100T-2 high-pressure mercury lamp
- Example 11 and 12 In (Preparation of titanium oxide paste), a porous titanium oxide layer and a dye-sensitized solar cell were obtained in the same manner as in Example 7 except that titanium oxide fine particles having an average particle diameter shown in Table 1 were used.
- Example 13 and 14 In (Production of titanium oxide paste), a porous titanium oxide layer and a dye-sensitized solar cell were obtained in the same manner as in Example 8, except that titanium oxide fine particles having an average particle diameter shown in Table 1 were used.
- Example 15 to 20 In Example 1, as shown in Table 1, except that the organic binder, the amount of the organic solvent, the amount of the photoacid generator, the firing temperature, the ultraviolet irradiation time, and the integrated light amount were changed, the same as in Example 7, A porous titanium oxide layer and a dye-sensitized solar cell were obtained. In addition, as a photo-acid generator, what has the structure shown to said Formula (1) was used.
- Example 21 to 29 In (formation of a porous titanium oxide layer), ultraviolet rays were irradiated for 30 minutes at an irradiation intensity of 100 mW / cm 2 from the side opposite to the glass substrate (front side) using a high-pressure mercury lamp, and then a xenon flash lamp (Altec). Sinteron 2000), a porous titanium oxide layer and a dye-sensitized sun in the same manner as in Example 7 except that pulsed light was irradiated under the conditions of light quantity, irradiation time, and number of irradiations shown in Table 1. A battery was obtained.
- Example 3 (Comparative Examples 1 to 3)
- ethyl cellulose manufactured by Wako Pure Chemical Industries, 45% ethoxy, 10 cP
- Table 2 the firing temperature, the ultraviolet irradiation time, and the integrated light amount were set. Except for the change, a porous titanium oxide layer and a dye-sensitized solar cell were obtained in the same manner as in Example 1.
- Example 1 As shown in Table 2, the porous titanium oxide layer and the dye were the same as in Example 1 except that the amount of the organic binder, the organic solvent, the firing temperature, the ultraviolet irradiation time, and the integrated light amount were changed. A sensitized solar cell was obtained.
- the manufacturing method of the porous titanium oxide laminated body which can manufacture the porous titanium oxide layer with a high porosity and few impurities also by low-temperature baking, and this porous titanium oxide laminated body are used.
- a dye-sensitized solar cell can be provided.
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Abstract
Description
従来、実用化されてきたのは、単結晶Si、多結晶Si、アモルファスSi等に代表されるシリコン系太陽電池であるが、高価であることや原料Siの不足問題等が表面化するにつれて、次世代太陽電池への要求が高まりつつある。
一方、色素増感太陽電池では、光電変換効率の向上のため、可能な限り多くの増感色素を担持させることが好ましいが、従来の有機バインダを含有するペーストを用いた場合、充分な量の増感色素を担持できなかったり、増感色素の担持に長期間を要したりするという問題があった。
以下に本発明を詳述する。
また、このような多孔質酸化チタン積層体を用いて得られる色素増感太陽電池は、短時間で増感色素を充分に吸着させることが可能となることも見出し、本発明を完成させるに至った。
上記酸化チタンペーストを基材上に印刷する方法としては特に限定されないが、スクリーン印刷法を用いることが好ましい。
また、基材が柔軟性を有する場合はロールトゥロール方式による連続印刷工程を用いることで量産性及び生産コストの観点で大きな利点となる。
上記透明基板の厚さは、0.1~10mmが好ましく、0.3~5mmがより好ましい。
なお、上記(メタ)アクリル樹脂は、上記酸化チタン微粒子よりも少ない含有量であることが好ましい。上記(メタ)アクリル樹脂が、上記酸化チタン微粒子よりも多くなると、加熱後の(メタ)アクリル樹脂残留量が多くなることがある。
なかでも、下記式(1)に示す構造を有する光酸発生剤を用いることが好ましい。
なお、上記粘度は、E型粘度計を用いて25℃、10rpmせん断時における動粘度を測定したものである。
なお、上記粘度変化率は、酸化チタンペーストをガラス上に乗せ、ゴム製スキージを用いてガラス表面に酸化チタンペーストを薄く延ばし、また擦り取るという操作を25回繰り返した前後の粘度の比率であり、粘度は、E型粘度計を用いて25℃、10rpmせん断時における動粘度を測定したものである。
上記酸化チタンペーストは、加熱後の表面不純物が少ないことから、微粒子間の結合(ネッキング)が起こりやすく、その結果、粒子間抵抗を低減することが可能となることから、色素増感太陽電池の材料として用いた場合に、高い光電変換効率を実現することができる。
上記含有量が1重量%を超えると、酸化チタン微粒子表面に不純物が残ってしまうため増感色素を吸着することが出来ない。なお、上記含有量は、酸化チタン微粒子に対する含有量である。
また、上記酸化チタンペーストは、スクリーン版の洗浄に一般的に使用される有機溶剤との相溶性に優れ、使用後に充分に洗浄除去することができることから、スクリーン版の目詰まりを低減することができ、スクリーン印刷を安定して長期間行うことが可能となる。
更に、上記酸化チタンペーストは、色素増感太陽電池の材料として用いた場合、短時間で増感色素を充分に吸着させることが可能となり、得られる色素増感太陽電池は、高い光電変換効率を実現することができる。
例えば、大気下又は不活性ガス雰囲気下、50~800℃程度の範囲内で、10秒~12時間程度行うことが好ましい。
また、乾燥及び焼成は、単一の温度で1回又は温度を変化させて2回以上行ってもよい。
なお、積算光量は照射強度(mW/cm2)×照射時間(秒)にて簡易的に算出することが出来る。
更に、紫外線の照射時間は1秒~300分間であることが好ましく、より好ましくは1秒~60分間照射である。照射強度が小さすぎたり、照射時間が短すぎたりすると、有機残渣の除去が部分的にしか進行しないため充分な効果を得ることが出来ず照射強度が大きすぎたり、照射時間が長すぎたりすると、透明基板の紫外線劣化や熱的劣化を及ぼすことがある。
このようにして得られた多孔質酸化チタン積層体に増感色素を吸着させる工程を行い、対向電極と対向させて設置し、これらの電極の間に電解質層を形成することで、色素増感太陽電池セルを製造することができる。このようにして得られた色素増感太陽電池は、高い光電変換効率を達成することができる。上記増感色素を吸着する方法としては、例えば、増感色素を含むアルコール溶液に、上記多孔質酸化チタン積層体を浸漬した後、アルコールを乾燥除去する方法等が挙げられる。
(酸化チタンペーストの作製)
平均粒子径が20nmの酸化チタン微粒子、有機バインダとしてイソブチルメタクリレート重合体(重量平均分子量50000)、有機溶媒としてα-テルピネオール(沸点219℃)を用い、表1の組成となるようにビーズミルを用いて均一に混合することにより酸化チタンペーストを作製した。
得られた酸化チタンペーストを、25mm角のFTO透明電極形成済みガラス基板上に、5mm角の正方形状に印刷し、300℃で1時間焼成した。
その後、更に高圧水銀ランプ(セン特殊光源社製、HLR100T-2)を用いて、紫外線をガラス基板とは逆側(表側)から照射強度100mW/cm2で30分間照射することにより多孔質酸化チタン層を得た。なお、得られた多孔質酸化チタン層の厚みが10μmとなるよう、印刷条件の微調整を行った。
得られた多孔質酸化チタン層付き基板を、Ru錯体色素(N719)のアセトニトリル:t-ブタノール=1:1溶液(濃度0.3mM)中に1日浸漬することにより、多孔質酸化チタン層表面に増感色素を吸着させた。
次に、この基板上に、一方向を除いて多孔質酸化チタン層を取り囲むように厚さ30μmのハイミラン社製フィルムを載せ、更にその上から白金電極を蒸着したガラス基板を乗せ、その隙間にヨウ化リチウム及びヨウ素のアセトニトリル溶液を注入、封止することで色素増感太陽電池を得た。
実施例1において、表1に示すように、有機バインダ、有機溶媒の量、焼成温度、紫外線照射時間、積算光量を変更した以外は、実施例1と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
なお、有機溶媒としては、α-テルピネオール(沸点219℃)のほか、2,4-ジエチル-1,5-ペンタンジオール(PD-9、沸点264℃)を用いた。
(多孔質酸化チタン層の形成)において、高圧水銀ランプ(セン特殊光源社製、HLR100T-2)を用いて、紫外線をガラス基板とは逆側(表側)から照射強度100mW/cm2で15分間照射した後、更にガラス基板側(裏側)から照射強度100mW/cm2で15分間照射した以外は、実施例7と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
(多孔質酸化チタン層の形成)において、高圧水銀ランプ(セン特殊光源社製、HLR100T-2)を用いて、紫外線をガラス基板とは逆側(表側)から照射強度100mW/cm2で30分間照射した後、更にガラス基板側(裏側)から照射強度100mW/cm2で30分間照射した以外は、実施例7と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
(酸化チタンペーストの作製)において、表1に示す平均粒子径を有する酸化チタン微粒子を用いた以外は、実施例7と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
(酸化チタンペーストの作製)において、表1に示す平均粒子径を有する酸化チタン微粒子を用いた以外は、実施例8と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
実施例1において、表1に示すように、有機バインダ、有機溶媒の量、光酸発生剤の量、焼成温度、紫外線照射時間、積算光量を変更した以外は、実施例7と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。なお、光酸発生剤としては、上記式(1)に示す構造を有するものを用いた。
(多孔質酸化チタン層の形成)において、高圧水銀ランプを用いて、紫外線をガラス基板とは逆側(表側)から照射強度100mW/cm2で30分間照射を行った後、キセノンフラッシュランプ(アルテック社製、Sinteron2000)を用いて、表1に示す光量、照射時間、照射回数の条件で、パルス光を照射した以外は、実施例7と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
実施例1において、有機バインダとしてイソブチルメタクリレート重合体に代えて、エチルセルロース(和光純薬工業社製、45%エトキシ、10cP)を用い、表2に示すように焼成温度、紫外線照射時間、積算光量を変更した以外は、実施例1と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
実施例1において、表2に示すように、有機バインダ、有機溶媒の量、焼成温度、紫外線照射時間、積算光量を変更した以外は、実施例1と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
(多孔質酸化チタン層の形成)において、高圧水銀ランプ(セン特殊光源社製、HLR100T-2)を用いて、紫外線をガラス基板とは逆側(表側)から照射強度100mW/cm2で7.5分間照射した後、更にガラス基板側(裏側)から照射強度100mW/cm2で7.5分間照射した以外は、実施例1と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
(酸化チタンペーストの作製)において、表2に示す平均粒子径を有する酸化チタン微粒子を用いた以外は、実施例7と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
(酸化チタンペーストの作製)において、表2に示す平均粒子径を有する酸化チタン微粒子を用いた以外は、実施例8と同様にして、多孔質酸化チタン層、色素増感太陽電池を得た。
実施例及び比較例で得られた多孔質酸化チタン層、色素増感太陽電池について以下の評価を行った。結果を表3に示した。
得られた多孔質酸化チタン層について、X線光電子分法装置(アルバックファイ社製、PHI5000)を用いて、表面から100nmをスパッタリングし表面汚染層を除去した後、薄膜表面の炭素ピークを測定した。得られた測定値と紫外線照射前の測定値とを比較することにより、膜中に残留する有機残渣量の相対評価を行った。
紫外線照射前の炭素ピークのピーク強度に対して、ピーク強度が100%以下で50%を超える場合を「×」、50%以下で25%を超える場合を「△」、25%以下で10%を超える場合を「○」、10%以下である場合を「◎」とした。
(色素増感太陽電池の作製)において、得られた増感色素を吸着させた多孔質酸化チタン層を、水酸化カリウム溶液中に浸漬することで増感色素を脱着させ、その脱着液の吸光スペクトルを分光光度計(U-3000、日立製作所社製)を用いて測定することで、色素吸着量を測定した。なお、酸化チタンペースト及び焼成条件が同じである場合における[(紫外線を照射した場合の色素吸着量/紫外線を照射しなかった場合の色素吸着量)×100]を相対変化率として算出した。
各実施例及び比較例と同様の形成方法により10cm角の多孔質酸化チタン層を形成し、鉛筆硬度試験(JIS K 5600)を行うことで酸化チタン微粒子同士の焼結度合いを測定した。
得られた色素増感太陽電池の電極間に、電源(236モデル、KEYTHLEY社製)を接続し、100mW/cm2の強度のソーラーシミュレータ(山下電装社製)を用いて、色素増感太陽電池の光電変換効率を測定した。酸化チタンペースト及び焼成条件が同じである場合における[(紫外線を照射した場合の光電変換効率/紫外線を照射しなかった場合の光電変換効率)×100]を相対変化率として算出した。
Claims (4)
- 酸化チタン微粒子と、(メタ)アクリル樹脂と、有機溶媒とを含有する酸化チタンペーストを基材上に印刷し、該基材上に酸化チタンペースト層を形成する工程と、前記酸化チタンペースト層を焼成する工程と、前記焼成後の酸化チタンペースト層に紫外線を照射する工程とを有する多孔質酸化チタン積層体の製造方法であって、前記酸化チタン微粒子は、平均粒子径が5~50nmであり、前記焼成後の酸化チタンペースト層に紫外線を照射する工程において、紫外線照射の積算光量を100J/cm2以上とすることを特徴とする多孔質酸化チタン積層体の製造方法。
- (メタ)アクリル樹脂は、ポリイソブチルメタクリレートであることを特徴とする請求項1記載の多孔質酸化チタン積層体の製造方法。
- 有機溶媒は、沸点が100~300℃であることを特徴とする請求項1又は2記載の多孔質酸化チタン積層体の製造方法。
- 請求項1、2又は3記載の多孔質酸化チタン積層体の製造方法を用いて製造された多孔質酸化チタン積層体を用いてなることを特徴とする色素増感太陽電池。
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