WO2016136950A1 - 半導体膜の製造方法、及び色素増感太陽電池 - Google Patents
半導体膜の製造方法、及び色素増感太陽電池 Download PDFInfo
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- WO2016136950A1 WO2016136950A1 PCT/JP2016/055845 JP2016055845W WO2016136950A1 WO 2016136950 A1 WO2016136950 A1 WO 2016136950A1 JP 2016055845 W JP2016055845 W JP 2016055845W WO 2016136950 A1 WO2016136950 A1 WO 2016136950A1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/08—Flame spraying
- B05D1/10—Applying particulate materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/12—Applying particulate materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a semiconductor film manufacturing method and a dye-sensitized solar cell. This application claims priority based on Japanese Patent Application No. 2015-037233 for which it applied to Japan on February 26, 2015, and uses the content here.
- a porous film made of a semiconductor adsorbed with a photosensitizing dye is used.
- various film-forming methods using a powder spraying method have been studied. Examples include an aerosol deposition method (AD method), a spray method, a cold spray method, an electrostatic spray method, and a thermal spray method.
- AD method aerosol deposition method
- spray method a spray method
- cold spray method a cold spray method
- electrostatic spray method electrostatic spray method
- thermal spray method a thermal spray method.
- Patent Document 1 discloses a porous membrane in which small-diameter particles that are not subjected to brittle deformation are joined by forming a film by mixing two or more kinds of large and small different-diameter particles in the AD method.
- a film forming method is disclosed. According to this film-forming method, a powder in which large particles having a large particle mass are added to small particles is sprayed on a substrate, collision energy is generated by striking the large particles, and the small particles are joined together.
- a membrane can be formed.
- Patent Document 2 discloses a porous structure in which small-sized particles are sintered by firing in a compacted state in which small-sized particles and a binder are mixed, and physically pulverizing the obtained fired body in a mortar or the like.
- a method is disclosed in which a large-diameter particle is obtained, and a powder of the porous large-diameter particle is sprayed onto a substrate to form a porous film.
- the porous film thus formed has a relatively dense porosity inside the large-diameter particles and a relatively sparse porosity in the voids between the large-diameter particles, so that the uniformity of the membrane structure is achieved. There is a problem that the specific surface area and film strength are reduced as a result.
- the present invention has been made in view of the above circumstances, and provides a method for manufacturing a semiconductor film, in which preparation of a powder to be sprayed is simple, and a porous film in which semiconductor particles are bonded to each other can be easily obtained. It is an object of the present invention to provide a dye-sensitized solar cell provided with a formed semiconductor film as a photoelectrode.
- a method for producing a semiconductor film comprising obtaining aggregated particles in which the semiconductor particles are aggregated and spraying the aggregated particles on a substrate to form a semiconductor film on the substrate.
- the method for producing a semiconductor film according to [1] wherein the semiconductor particles are dried by evaporating the alcohol in a state where the semiconductor particles are precipitated in the alcohol.
- [4] The method for producing a semiconductor film according to any one of [1] to [3], wherein the semiconductor particles are metal oxide semiconductor particles.
- [5] The method for producing a semiconductor film according to any one of [1] to [4], wherein the semiconductor film is a porous film.
- [6] A dye-sensitized solar comprising a photoelectrode obtained by adsorbing a sensitizing dye to a semiconductor film obtained by the method for producing a semiconductor film according to any one of [1] to [5] battery.
- the method for producing a semiconductor film of the present invention it is not necessary to sinter or pulverize the raw material particles in order to prepare the agglomerated particles to be sprayed.
- the specific surface area is large by spraying on the substrate in the same manner as in the conventional AD method, the porosity and light transmittance of the entire film are uniform, and the structural A porous semiconductor film having excellent strength can be easily obtained.
- the dye-sensitized solar cell of the present invention includes a photoelectrode in which a sensitizing dye is adsorbed on the porous structure of the semiconductor film having the above-described excellent characteristics, the photoelectric conversion efficiency, IV characteristics, etc. Excellent performance.
- FIG. 2 is a particle size distribution of aggregated particles prepared in Example 1.
- FIG. 2 is the SEM image which observed the aggregated particle prepared in Example 1 with the electron microscope.
- 2 is an SEM image obtained by observing a cross section of a porous film formed in Example 1 with an electron microscope.
- It is the SEM image which observed the raw material particle prepared by the comparative example 1 with the electron microscope.
- 3 is a graph showing VI characteristics of simple cells produced in Example 1 and Comparative Example 1. Schematic diagram showing a state in which raw material powder in which large particles and small particles are mixed is sprayed by the AD method and a state in which large particles are mixed in the formed porous film by the method of Patent Document 1. It is.
- ⁇ Semiconductor Film Manufacturing Method In the method for producing a semiconductor film according to the first embodiment of the present invention, after obtaining a dispersion in which semiconductor particles having an average particle diameter of 1 nm or more and less than 100 nm are dispersed in alcohol, the alcohol is added from the dispersion. A method of forming a semiconductor film on the substrate by obtaining the aggregated particles in which the semiconductor particles are aggregated by evaporating and drying the semiconductor particles and spraying the aggregated particles on the substrate. .
- the kind of the semiconductor particles is not particularly limited, and semiconductor particles constituting a photoelectrode of a known dye-sensitized solar cell can be applied.
- the semiconductor that constitutes the semiconductor particles is preferably a semiconductor in which a transition between band gaps occurs.
- TiO 2 , TiSrO 3 , BaTiO 3 , Nb 2 O 5 , MgO, ZnO, WO 3 , Bi 2 O 3 Examples thereof include CdS, CdSe, CdTe, In 2 O 3 , and SnO 2 .
- These semiconductors are preferable because they have good dye adsorption and function well as a photoelectrode carrying a sensitizing dye.
- a metal oxide semiconductor such as titanium oxide, zinc oxide, strontium titanate, and stannic oxide is preferable from the viewpoint of improving the photoelectric conversion efficiency and from the viewpoint of easily forming the aggregated particles described later.
- the secondary bonding force of the hydroxyl group, polar group or polar site on the particle surface contributes to suitable cohesion.
- the said semiconductor particle may be used individually by 1 type, and may use 2 or more types together.
- semiconductor particles having an average particle diameter in the range of 1 nm or more and less than 100 nm are used as the semiconductor particles.
- semiconductor particles in the above range aggregated particles having a size and strength suitable for forming a porous membrane can be obtained.
- the average particle size of the semiconductor particles is preferably 5 nm or more and less than 70 nm, more preferably 10 nm or more and less than 50 nm, and even more preferably 15 nm or more and less than 30 nm.
- the strength of the agglomerated particles suitable for the formation of the porous film refers to the strength of the individual semiconductor particles before the individual semiconductor particles constituting the agglomerated particles applied to the base material in an aggregated state are brittlely deformed.
- the strength is such that a new surface is formed and joined at a location where the semiconductor particles are in contact with each other while the aggregation of the particles is partially solved.
- agglomerated particles having moderate strength that is neither too hard nor too soft it is considered that the gap between the individual semiconductor particles plays a role as an appropriate cushion when colliding with the base material.
- the method of preparing the agglomerated particles for spraying includes the first step of obtaining a dispersion in which semiconductor particles having an average particle diameter of 1 nm or more and less than 100 nm are dispersed in alcohol; A second step of obtaining aggregated particles in which the semiconductor particles are aggregated by evaporating alcohol and drying the semiconductor particles.
- the semiconductor material of the semiconductor particles used in the first stage may be one kind or plural kinds, preferably 1 to 3 kinds, more preferably 1 or 2 kinds, and further preferably 1 kind. . This is because it is easy to control the dispersion and aggregation of the semiconductor particles, and it is easy to obtain aggregated particles having an appropriate size and strength.
- the average particle size of the semiconductor particles used in the first stage is in the range of 1 nm or more and less than 100 nm.
- the average particle diameter of the semiconductor particles may be 4 or more types, preferably 1 to 3 types, more preferably 1 or 2 types, and even more preferably 1 type.
- semiconductor particles having an average particle diameter of 20 nm, semiconductor particles having an average particle diameter of 50 nm, and semiconductor particles having an average particle diameter of 80 nm in an arbitrary ratio It can be said that semiconductor particles having three kinds of average particle diameters are used.
- the fewer kinds of semiconductor particles used in the first stage the easier it is to control the dispersion and aggregation of the semiconductor particles, and it is easier to obtain aggregated particles having an appropriate size and strength.
- the semiconductor particles used in the first stage are preferably not mixed with semiconductor particles having an average particle diameter outside the range of 1 nm or more and less than 100 nm. That is, it is preferable to prepare a dispersion liquid in which only semiconductor particles contained in an average particle diameter of 1 nm or more and less than 100 nm are dispersed in alcohol. This is because, for example, when semiconductor particles having a mean particle size of 20 nm (small particles) and semiconductor particles having a mean particle size of 200 nm are mixed and used, in the second stage of aggregation process, This is because large particles are aggregated non-uniformly.
- agglomeration states there are at least three types of agglomeration states: aggregation between small-diameter particles, aggregation between small-diameter particles and large-diameter particles, and aggregation between large-diameter particles, and further differences in the mixing ratio of each particle and the type of semiconductor material, etc. This is because it is difficult to control the aggregation process, and it is difficult to obtain target aggregated particles having an appropriate size and strength.
- the above-mentioned small diameter particles (average particle diameter 20 nm) and the above large diameter particles (average particle diameter 200 nm) are mixed without using a dispersion medium, and the dried powder is subjected to an electron microscope.
- the SEM photograph observed in FIG. 10 is shown in FIG. It is observed that the heterogeneous lump in which the small diameter particles are aggregated is unevenly distributed in a plurality of local areas of the aggregates of the large diameter particles.
- a nominal value of the average particle diameter is given if it is a commercially available powder.
- two kinds of powders having different nominal values can be mixed and used.
- the particle size distribution (horizontal axis: particle diameter, vertical axis: number of particles (frequency)) of the mixed powder in a dispersed state is measured and two peaks are observed in the above range, each peak corresponds to each peak.
- semiconductor particles having two types of average particle sizes are used. Therefore, when using a powder of semiconductor particles having one type of average particle size, one peak is usually observed when the particle size distribution of the powder is measured (unimodal), The mode diameter of the particle size distribution corresponds to the average particle diameter.
- the number of observed peaks is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. This is because the degree of aggregation between the semiconductor particles can be easily controlled, and aggregated particles having an appropriate size and strength can be easily obtained.
- the method for dispersing the semiconductor particles having an average particle size of 1 nm or more and less than 100 nm in the alcohol is not particularly limited, and the alcohol is stirred while gradually adding the semiconductor particle powder into the container in which the alcohol has been previously added.
- the method is preferred.
- the powder may become balls and be difficult to be dispersed.
- the series and valence of the alcohol used for dispersion are not particularly limited, and may be any series of primary, secondary, tertiary, and any of monovalent, divalent, trivalent or higher polyvalent. It may be a valence.
- the monovalent alcohol molecule used in the first stage has one hydroxyl group and a hydrocarbon group, and the hydrocarbon group may be linear, branched or cyclic, and saturated hydrocarbon. Either a group or an unsaturated hydrocarbon group may be used.
- the number of carbon atoms of the hydrocarbon group is not particularly limited. For example, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 or 3.
- suitable alcohols used in the first step include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, and cyclohexanol.
- methanol, ethanol, 1-pentanol, n-propanol, isopropanol are preferred from the viewpoints of excellent dispersibility of semiconductor particles, easy drying, and easy aggregation particles having an appropriate size and strength after drying. Is preferred, and ethanol is more preferred.
- the temperature of the alcohol in which the semiconductor particles are dispersed in the first stage is not particularly limited and can be, for example, in the range of 4 to 55 ° C. At any temperature, it is preferable to sufficiently stir the alcohol into which the semiconductor particles are charged so that the individual semiconductor particles are dispersed.
- the temperature is 55 ° C. or lower, the cohesiveness of the particles does not become too high, and it becomes easy to make the aggregated particle diameter uniform.
- it is 40 degrees C or less.
- the temperature is 4 ° C. or higher, the dispersibility of the particles is increased, and there is no possibility that the aggregated particle diameter becomes extremely large.
- it is 20 degreeC or more.
- a dispersion liquid in which only semiconductor particles having an average particle diameter of 1 nm or more and less than 100 nm are dispersed in alcohol.
- the method for evaporating the alcohol after the dispersion of the semiconductor particles is not particularly limited, and for example, a known method such as heat treatment or reduced pressure treatment can be applied.
- the alcohol dispersion may be evaporated with stirring, but if it is vigorously stirred, the target aggregated particles may be crushed or the particle size distribution may be widened. For this reason, it is preferable to stand still or to evaporate and dry with gentle stirring.
- the resulting dispersion is allowed to stand for 30 minutes to 48 hours, whereby the alcohol is evaporated and dried in a state where most of the semiconductor particles are precipitated in the alcohol. preferable. By gently drying in this manner, aggregated particles having an appropriate size and strength in which the semiconductor particles are aggregated can be easily obtained.
- the temperature at which the semiconductor particles are dried by evaporating the alcohol is not particularly limited.
- aggregated particles having an appropriate size and strength can be easily obtained. .
- it is less than 30 degreeC.
- the evaporation / drying time is preferably 1 to 72 hours, more preferably 2 to 48 hours, and even more preferably 5 to 48 hours.
- the shape of the aggregated particles obtained in the second stage is not particularly limited, but is preferably a lump having a shape suitable for spraying.
- the average particle diameter of the aggregated particles obtained in the second stage is not particularly limited as long as it can be formed by spraying on the substrate.
- the average particle diameter of the aggregated particles is, for example, preferably 0.2 ⁇ m or more and less than 100 ⁇ m, more preferably 0.5 ⁇ m or more and less than 50 ⁇ m, further preferably 0.8 ⁇ m or more and less than 10 ⁇ m. It is particularly preferably from 0.0 ⁇ m to less than 5.0 ⁇ m.
- the average particle size is in the above preferred range, a porous film excellent in strength, electrical conductivity, light transmission, and sensitizing dye adsorption can be easily formed with a desired thickness by the AD method. it can.
- the number of observed peaks is preferably one or two, and more preferably one.
- the mode diameter in the particle size distribution is not particularly limited, but is preferably 0.2 ⁇ m or more and less than 100 ⁇ m, more preferably 0.5 ⁇ m or more and less than 50 ⁇ m, further preferably 0.8 ⁇ m or more and less than 10 ⁇ m, 1.0 ⁇ m or more and 5.0 ⁇ m or less. Less than is particularly preferred.
- the mode diameter of the particle size distribution is a particle diameter corresponding to the maximum value of the frequency distribution. By being within the preferable range, a porous film excellent in strength, electrical conductivity, light transmittance, and sensitizing dye adsorptivity can be easily formed with a desired thickness by the AD method.
- the 10% particle diameter (d10) in the particle size distribution is not particularly limited, and is preferably 0.1 ⁇ m or more and less than 5.0 ⁇ m, more preferably 0.2 ⁇ m or more and less than 3.0 ⁇ m, and more preferably 0.3 ⁇ m or more and less than 1.0 ⁇ m. Is more preferable.
- the 10% particle diameter (d10) of the particle size distribution is the particle diameter at the point where the integrated value 10% of the integrated distribution curve intersects the horizontal axis.
- a porous film excellent in strength, electrical conductivity, light transmittance, and sensitizing dye adsorptivity can be easily formed with a desired thickness by the AD method.
- the 50% particle size (d50) in the particle size distribution is not particularly limited, and is preferably 0.1 ⁇ m or more and less than 10 ⁇ m, more preferably 0.5 ⁇ m or more and less than 5.0 ⁇ m, and further preferably 1.0 ⁇ m or more and less than 3.0 ⁇ m. preferable.
- the 50% particle diameter (d50) of the particle size distribution is a particle diameter at a point where the integrated value 50% of the integrated distribution curve intersects the horizontal axis, and is a so-called median diameter.
- a porous film excellent in strength, electrical conductivity, light transmittance, and sensitizing dye adsorptivity can be easily formed with a desired thickness by the AD method.
- the 90% particle size (d90) in the particle size distribution is not particularly limited, and is preferably 1.0 ⁇ m or more and less than 100 ⁇ m, more preferably 2.0 ⁇ m or more and less than 20 ⁇ m, and further preferably 3.0 ⁇ m or more and less than 10 ⁇ m.
- the 90% particle size (d90) of the particle size distribution is the particle size at the point where the integrated value 90% of the integrated distribution curve intersects the horizontal axis.
- a porous film excellent in strength, electrical conductivity, light transmittance, and sensitizing dye adsorptivity can be easily formed with a desired thickness by the AD method.
- aggregated particles in which semiconductor particles having an average particle diameter of 1 nm or more and less than 100 nm are aggregated can be obtained.
- the agglomerated particles of the present embodiment can obtain sufficient acceleration and collision energy against the base material by spraying by the conventional AD method, so that either a porous film or a dense film can be formed on the base material. .
- the agglomerated particles of the present embodiment are composed only of semiconductor particles having a relatively small average particle diameter in the above range, so that large particles having a large particle size exceeding the above range are mixed in the formed semiconductor film. It is impossible. Therefore, the formed film has a uniform film structure.
- ⁇ Measurement of average particle diameter> As a method for obtaining the average particle diameter of the semiconductor particles and the aggregated particles, a method of determining the peak value of the volume average diameter distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus can be employed.
- the average particle diameter of the semiconductor particles (primary particles) is measured “wet” by a laser diffraction particle size distribution analyzer.
- the average particle diameter of the agglomerated particles is measured “dry” by a laser diffraction particle size distribution analyzer.
- the film forming step in the present embodiment is a step of forming a semiconductor film on the base material by spraying the aggregated particles on the base material.
- an aerosol deposition method in which an aerosol mixed with a carrier gas and the aggregated particles is sprayed, an electrostatic fine particle coating method for accelerating the aggregated particles by electrostatic attraction, The cold spray method etc. are mentioned.
- the AD method capable of easily forming a porous film suitable for the photoelectrode is preferable.
- a film forming method by the AD method for example, a method disclosed in International Publication No. WO2012 / 161161A1 can be applied.
- application of the AD method will be specifically described.
- the film forming apparatus used for the film forming method of the present embodiment is not particularly limited, and examples thereof include a film forming apparatus 60 shown in FIG.
- the film forming apparatus 60 includes a gas cylinder 55, a transfer pipe 56, a nozzle 52, a base 63, and a film forming chamber 51.
- the gas cylinder 55 is filled with a gas (carrier gas) for accelerating the agglomerated particles 54 and spraying them on the base material 53.
- One end of a transfer pipe 56 is connected to the gas cylinder 55.
- the carrier gas supplied from the gas cylinder 55 is supplied to the carrier pipe 56.
- the transport pipe 56 is provided with a mass flow controller 57, an aerosol generator 58, a disintegrator 59 and a classifier 61 that can appropriately adjust the dispersion state of the aggregated particles 54 in the transport gas in order from the front side. .
- the crusher 59 By the crusher 59, the state where the aggregated particles 54 adhere to each other due to moisture or the like can be solved. Even if there are aggregated particles that have passed through the crusher 59 in a state of being attached to each other, such excessively large particles can be removed by the classifier 61. Note that if there is a possibility that the aggregated particles 54 may be crushed into individual semiconductor particles by the crusher 59, the crusher 59 may not be used.
- the mass flow controller 57 can adjust the flow rate of the carrier gas supplied from the gas cylinder 55 to the carrier pipe 56.
- the aerosol generator 58 is loaded with agglomerated particles 54.
- the agglomerated particles 54 are dispersed in the carrier gas supplied from the mass flow controller 57 and conveyed to the crusher 59 and the classifier 61.
- the nozzle 52 is arranged so that an opening (not shown) faces the base material 53 on the base 63.
- the other end of the transport pipe 56 is connected to the nozzle 52.
- the carrier gas containing the agglomerated particles 54 is injected from the opening of the nozzle 52 onto the base material 53.
- the base material 53 is placed on the upper surface 72 of the base 63 so that one surface 73 of the base material 53 comes into contact therewith. Further, the other surface 71 (film forming surface) of the substrate 53 faces the opening of the nozzle 52. Aggregated particles 54 injected together with the carrier gas from the nozzle 52 collide with the film forming surface, and a porous film made of semiconductor particles constituting the aggregated particles 54 is formed.
- the base material 53 is preferably made of a material that allows the sprayed aggregated particles 54 to be joined without penetrating the film forming surface 71.
- a substrate include a glass substrate, a resin substrate, a resin film, a resin sheet, and a metal substrate.
- a transparent conductive film such as ITO is formed in advance on the surface of the non-conductive substrate. Since the porous film formed on the substrate has sufficient structural strength and conductivity suitable for the use of the photoelectrode, it does not need to be separately fired. For this reason, a resin base material with low heat resistance can be used.
- the thickness of the substrate is not particularly limited, and preferably has a thickness that prevents the sprayed aggregated particles from penetrating. More specific selection of the base material 53 is appropriately performed according to the material of the aggregated particles 54, the film forming conditions such as the spraying speed, and the use of the formed film.
- the film forming chamber 51 is provided for film formation in a reduced pressure atmosphere.
- a vacuum pump 62 is connected to the film forming chamber 51, and the inside of the film forming chamber 51 is depressurized as necessary.
- the vacuum pump 62 is operated to depressurize the film forming chamber 51.
- the pressure in the film forming chamber 51 is not particularly limited, but is preferably set to 5 to 1000 Pa. By reducing the pressure to this extent, convection in the film forming chamber 51 is suppressed, and it becomes easy to spray the aggregated particles 54 to a predetermined position on the film forming surface 71.
- the carrier gas is supplied from the gas cylinder 55 to the carrier pipe 56, and the flow rate and flow rate of the carrier gas are adjusted by the mass flow controller 57.
- the carrier gas for example, O 2 , N 2 , Ar, He, air, or the like can be used.
- the flow rate and flow rate of the carrier gas can be appropriately set according to the material, average particle size, flow rate and flow rate of the agglomerated particles 54 sprayed from the nozzle 52.
- the agglomerated particles 54 are loaded into the aerosol generator 58, and the agglomerated particles 54 are dispersed in the carrier gas flowing in the carrier pipe 56 and accelerated. Aggregated particles 54 are ejected from the opening of the nozzle 52 at a subsonic to supersonic speed, and are laminated on the film forming surface 71 of the substrate 53. At this time, the spraying speed of the aggregated particles 54 onto the film forming surface 71 can be set to 10 to 1000 m / s, for example. The spraying speed is not particularly limited, and can be appropriately set according to the material of the base material 53, the type and size of the aggregated particles 54, and the like.
- the structure of the semiconductor film composed of the semiconductor particles constituting the aggregated particles 54 can be made into a dense film or a porous film. Furthermore, the porosity of the porous membrane can be controlled. Usually, the higher the speed at which the agglomerated particles 54 are sprayed, the more the structure of the film to be formed tends to become dense (porosity tends to decrease). In addition, when a film is formed at an extremely slow spraying speed, a semiconductor film having sufficient strength may not be obtained and a green compact may be obtained. In order to form a porous film having a sufficient structural strength, it is preferable to form a film at a spraying speed that is approximately between the speed at which a dense film is obtained and the speed at which a green compact is obtained.
- the agglomerated particles 54 collide with the semiconductor particles bonded to the film forming surface 71 of the base material 53 one after another, and the semiconductor particles constituting the agglomerated particles 54 collide with each other.
- a new surface is formed on the surface of the semiconductor particles, and the semiconductor particles are bonded to each other on the new surface.
- agglomeration between the individual semiconductor particles is partially solved, and a new surface is formed and joined at a location where the semiconductor particles are in contact with each other.
- the spraying of the agglomerated particles 54 is stopped.
- a porous film having a predetermined film thickness made of semiconductor particles constituting the aggregated particles 54 can be formed on the film forming surface 71 of the substrate 53.
- the film structure of the semiconductor film formed on the substrate by the semiconductor film manufacturing method of the first embodiment may be a dense film (non-porous film) or a porous film.
- the film thickness is not particularly limited, and examples thereof include a thickness of about 1 ⁇ m to 500 ⁇ m.
- the film forming method of the first embodiment since it is possible to form a film by applying a conventional spraying method using aggregated particles consisting only of semiconductor particles having a relatively small average particle size, the inside of the semiconductor film A large number of large-sized particles greatly exceeding the average particle diameter cannot be mixed. Accordingly, since the semiconductor film has a uniform film structure, a semiconductor film having excellent strength, electrical conductivity, and light transmittance can be obtained. Even when the semiconductor film is a porous film, the film strength is sufficient and uniform, and the semiconductor film is sufficiently adhered to a flexible substrate such as a film, and peeling and cracking are unlikely to occur. Such characteristics are suitable as a porous film used for a photoelectrode of a flexible dye-sensitized solar cell.
- the application of the semiconductor film is not limited to the photoelectrode, and can be widely applied to applications that can make use of the physical characteristics or chemical characteristics of the semiconductor film.
- Photoelectrode It can be used as a photoelectrode by adsorbing a sensitizing dye to a semiconductor film formed on a substrate by the method for producing a semiconductor film of the first embodiment.
- the semiconductor film may be a dense film, but is preferably a porous film from the viewpoint of adsorbing more sensitizing dye.
- the type of sensitizing dye is not particularly limited, and known sensitizing dyes can be applied.
- the semiconductor film is preferably formed on a substrate on which a known transparent conductive film is formed.
- the method for adsorbing the sensitizing dye to the semiconductor film is not particularly limited, and examples thereof include a method of immersing the semiconductor film in a dye solution.
- the photoelectrode can be manufactured by a conventional method except that the semiconductor film obtained by the film forming method of the first embodiment is used.
- the porous film is formed on the conductive surface of the ITO glass substrate, a photoelectrode having a sensitizing dye adsorbed on the porous film is formed, and if necessary, the conductive surface near the porous film is formed on the conductive surface.
- a photoelectrode substrate can be manufactured by connecting the lead wiring.
- the semiconductor film is a porous film
- its porosity (sometimes referred to as porosity, porosity, or porosity) is preferably 50% or more, more preferably 50 to 85%, and more preferably 50 to 85%. 75% is more preferable, and 50 to 65% is particularly preferable.
- porosity sometimes referred to as porosity, porosity, or porosity
- strength of a porous membrane can be strengthened more as it is below the upper limit of the said range.
- the porosity can be measured by a known gas adsorption test or mercury intrusion test.
- the thickness of the porous film is preferably 1 ⁇ m to 200 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, and even more preferably 5 ⁇ m to 50 ⁇ m.
- the probability that the sensitizing dye supported on the porous film absorbs light energy can be further increased, and the photoelectric conversion efficiency in the dye-sensitized solar cell can be further improved.
- the amount is not more than the upper limit of the above range, the exchange between the bulk electrolyte (electrolyte in the solar battery cell) and the electrolyte in the porous film is more efficiently performed by diffusion, and the photoelectric conversion efficiency can be further improved.
- the dye-sensitized solar cell according to the second embodiment of the present invention includes a photoelectrode obtained by adsorbing a sensitizing dye to a semiconductor film obtained by the method for manufacturing a semiconductor film according to the first embodiment, a counter electrode, and an electrolytic solution. Or an electrolyte layer.
- the electrolytic solution is preferably sealed with a sealing material between the photoelectrode and the counter electrode.
- a resin film or a resin sheet having a transparent conductive film formed on the surface can be used as the substrate on which the semiconductor film constituting the photoelectrode is formed.
- the resin those having visible light permeability are preferable, and examples thereof include polyacryl, polycarbonate, polyester, polyimide, polystyrene, polyvinyl chloride, and polyamide.
- polyester especially polyethylene terephthalate is suitable as a transparent heat-resistant film, and a thin and light flexible dye-sensitized solar cell can be produced.
- the said electrolyte solution is not specifically limited, For example, the electrolyte solution of a well-known dye-sensitized solar cell is applicable.
- a redox couple electrolyte
- electrolytic solution a redox couple (electrolyte) is dissolved and may contain other additives such as a filler and a thickener.
- electrolyte solution a well-known solid electrolyte instead of electrolyte solution.
- the solid electrolyte is in a gel state or a solid state. By using the gel or solid electrolyte layer, there is no possibility of the electrolyte solution leaking from the dye-sensitized solar cell.
- the type of the sealing material is not particularly limited, and a sealing resin used in a known dye-sensitized solar cell can be applied.
- a sealing resin used in a known dye-sensitized solar cell can be applied.
- an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, etc. are mentioned.
- the thickness of the sealing material is not particularly limited, and is appropriately adjusted so that the photoelectrode and the counter electrode film are separated from each other with a predetermined interval, and the electrolytic solution or the electrolyte layer has a predetermined thickness.
- the dye-sensitized solar cell of the second embodiment can be manufactured by a conventional method except that the photoelectrode is used.
- the electrolytic solution or the electrolyte is disposed between the photoelectrode and the counter electrode and sealed, and if necessary, the lead-out wiring is electrically connected to the photoelectrode and / or the counter electrode. be able to.
- Example 1 As the substrate, an ITO-PEN substrate in which ITO (tin-doped indium oxide) was previously formed on a PEN (polyethylene naphthalate) substrate was used.
- ITO indium oxide
- PEN polyethylene naphthalate
- Preparation of aggregated particles As the inorganic oxide semiconductor particles, anatase TiO 2 particles having an average particle diameter of about 21 nm were used. The titania particles were dispersed in ethanol at 30 wt%, and a dispersion obtained by sufficiently dispersing the titania particles was allowed to stand to allow the titania particles to settle on the bottom of the container. While maintaining this stationary state, ethanol was evaporated under reduced pressure below 30 ° C. to dry the titania particles.
- the aggregated particles are lumps having a shape that can be approximated to a sphere, and the semiconductor particles constituting the aggregated particles are closely aggregated. Due to such a dense aggregate state, it was confirmed that the aggregated particles could collide with the substrate as aggregated particles without being crushed before the aggregated particles reached the substrate when sprayed.
- the aggregated particles were sprayed from the nozzle 52 having a rectangular opening of 10 mm ⁇ 0.5 mm to the ITO-PEN substrate in the film forming chamber 51.
- the carrier gas N 2 was supplied from the cylinder 55 to the carrier pipe 56, and the flow rate was adjusted by the mass flow controller 57.
- Aggregated particles for spraying were loaded into an aerosol generator 58, dispersed in a carrier gas, conveyed to a pulverizer 59 and a classifier 61, and jetted from a nozzle 52 onto a substrate 53.
- a vacuum pump 62 is connected to the film forming chamber 51, and the film forming chamber is set to a negative pressure.
- FIG. 4 shows an SEM image obtained by observing a cross section of the porous film with an electron microscope. From this SEM image, it was confirmed that a uniform film structure in which the titania particles were sufficiently joined was formed.
- Example 1 ⁇ Preparation of raw material particles> The titania particles used in Example 1 were not dispersed in ethanol but dried to obtain raw material particles. The raw material particles were observed with an electron microscope to obtain an SEM image shown in FIG. From this SEM image, a plurality of aggregated lumps were observed in the raw material particles. However, these agglomerates have a non-uniform particle size and small particles compared to the agglomerated particles of Example 1. Moreover, since many shadows were observed deeply on the surface of the agglomerate, it was confirmed that the degree of aggregation was weak and the aggregation state was relatively sparse.
- Example 2 Using the raw material particles, spraying was performed in the same manner as in Example 1 to form a porous film. As a result, a porous film having a predetermined thickness was barely obtained. However, compared with Example 1, the spraying time required for film formation was long, and a large amount of particles to be sprayed was required.
- the porous film of Example 1 did not peel off even when the substrate was deformed, and the titania particles constituting the porous film did not fall off. From this result, it was confirmed that the bonding between the particles and the bonding between the particles and the substrate are both excellent.
- the porous film of Comparative Example 1 was peeled off immediately after deformation of the substrate.
- the porous film of Comparative Example 1 was considered to be in a state close to a green compact (only a lump of powder was placed on the substrate). This conclusion was supported by the fact that the amount of dye adsorption was small and the power generation characteristics were inferior.
- Example 2 Aggregated particles were prepared in the same manner as in Example 1 except that methanol was used in place of ethanol to form a porous film made of titania particles. When an SEM image of the obtained porous membrane was observed, it was confirmed that it had a uniform membrane structure in which titania particles were sufficiently joined. A simple cell equipped with this porous membrane was produced in the same manner as in Example 1, and good power generation characteristics were obtained.
- Example 3 Aggregated particles were prepared in the same manner as in Example 1 except that 1-pentanol was used in place of ethanol to form a porous film made of titania particles. When an SEM image of the obtained porous membrane was observed, it was confirmed that it had a uniform membrane structure in which titania particles were sufficiently joined. A simple cell equipped with this porous membrane was produced in the same manner as in Example 1, and good power generation characteristics were obtained.
- Example 4 Aggregated particles were prepared in the same manner as in Example 1 except that isopropanol, which is a secondary alcohol, was used in place of ethanol, and a porous film made of titania particles was formed. When an SEM image of the obtained porous membrane was observed, it was confirmed that it had a uniform membrane structure in which titania particles were sufficiently joined. A simple cell equipped with this porous membrane was produced in the same manner as in Example 1, and good power generation characteristics were obtained.
- Example 5 Aggregated particles were prepared in the same manner as in Example 1 except that t-butanol, which is a tertiary alcohol, was used instead of ethanol, to form a porous film made of titania particles.
- t-butanol which is a tertiary alcohol
- the method for producing a semiconductor film according to the present invention is widely applicable in the field of solar cells.
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Abstract
Description
本願は、2015年2月26日に、日本に出願された特願2015-037233号に基づき優先権を主張し、その内容をここに援用する。
また、粉砕して得た大径粒子の粒度分布が広く(図9)、粒径400μm超の大径粒子が混入するため、ブラスト効果が生じてしまい、製膜体が破壊される又は製膜体の一部が削られて製膜速度が低下する、という課題がある。このため、吹き付ける前に巨大な大径粒子を分級して除く手間が生じ、吹き付け可能な大径粒子の収率(原料使用率)が大幅に低下する、という問題がある。
さらに、製膜した多孔質膜には、大径粒子内部の比較的密な多孔度と、大径粒子間の空隙における比較的疎な多孔度と、が併存するため、膜構造の均一性が欠けており、結果として比表面積や膜強度が低下する、という問題がある。
[2]前記半導体粒子が前記アルコール中に沈降した状態で、前記アルコールを蒸発させて前記半導体粒子を乾燥する、前記[1]に記載の半導体膜の製造方法。
[3]50℃未満で前記アルコールを蒸発させる、前記[1]又は[2]に記載の半導体膜の製造方法。
[4]前記半導体粒子が金属酸化物半導体の粒子である、前記[1]~[3]の何れか一項に記載の半導体膜の製造方法。
[5]前記半導体膜が多孔質膜である、前記[1]~[4]の何れか一項に記載の半導体膜の製造方法。
[6]前記[1]~[5]の何れか一項に記載の半導体膜の製造方法によって得られた半導体膜に、増感色素を吸着させてなる光電極を備えた、色素増感太陽電池。
本発明の第一実施形態の半導体膜の製造方法は、平均粒子径が1nm以上100nm未満の範囲である半導体粒子をアルコール中に分散させた分散液を得た後、前記分散液から前記アルコールを蒸発させて前記半導体粒子を乾燥することにより、前記半導体粒子同士が凝集した凝集粒子を得て、前記凝集粒子を基材に吹き付けることにより、前記基材上に半導体膜を製膜する方法である。
前記半導体粒子を構成する半導体の種類は、バンドギャップ間の遷移が生じる半導体が好ましく、例えば、TiO2,TiSrO3,BaTiO3,Nb2O5,MgO,ZnO,WO3,Bi2O3,CdS,CdSe,CdTe,In2O3,SnO2などが挙げられる。これらの半導体は、色素吸着が良好であり、増感色素を担持した光電極として良好に機能するため好ましい。光電変換効率を向上させる観点及び後述する凝集粒子を容易に形成できる観点から、酸化チタン、酸化亜鉛、チタン酸ストロンチウム、酸化第二錫などの金属酸化物半導体が好適である。これらの金属酸化物半導体からなる粒子が好適であるメカニズムとして、粒子表面の水酸基、極性基又は極性部位の2次結合力が好適な凝集性に寄与していると推測される。
前記半導体粒子は、1種を単独で使用してもよいし、2種以上を併用してもよい。
上記範囲の半導体粒子を使用することにより、多孔質膜の製膜に適した大きさと強度を有する凝集粒子が得られる。
上記好適な範囲の半導体粒子を使用することにより、多孔質膜の製膜に適した大きさと強度を有する凝集粒子がより容易に得られる。
一方、特許文献2に記載されているような、個々の半導体粒子が焼成によって予め接合された状態の大径粒子においては、個々の半導体粒子の接合が過度に硬いため、基材に衝突する際に解れ難く、個々の半導体粒子同士の間隙が上記の様なクッションとして機能することは困難である。
本実施形態において吹き付け用の凝集粒子を調製する方法は、平均粒子径が1nm以上100nm未満の範囲である半導体粒子をアルコール中に分散させた分散液を得る第一段階と、前記分散液から前記アルコールを蒸発させて前記半導体粒子を乾燥することにより、前記半導体粒子同士が凝集した凝集粒子を得る第二段階と、を有する。
第一段階において使用する半導体粒子の半導体材料は、1種類であってもよいし複数種類であってもよいが、1~3種類が好ましく、1又は2種類がより好ましく、1種類がさらに好ましい。半導体粒子同士の分散と凝集を制御し易いため、適度な大きさと強度を有する凝集粒子が得られ易いからである。
55℃以下であると、粒子の凝集性が高くなり過ぎず、凝集粒子径を均一にすることが容易となる。好ましくは40℃以下である。4℃以上であると粒子の分散性が高まり、凝集粒子径が極度に大きくなる恐れがなくなる。好ましくは20℃以上である。
後述する半導体粒子同士の接合を高めるために、上記揮発性溶媒以外に、残留する恐れがある物質を含まないことが好ましい。よって、平均粒子径が1nm以上100nm未満の範囲である半導体粒子のみをアルコール中に分散させた分散液を調製することが好ましい。
半導体粒子の分散後にアルコールを蒸発させる方法は特に限定されず、例えば、加熱処理、減圧処理等の公知方法を適用することができる。当該アルコール分散液を撹拌しながら蒸発させてもよいが、激しく撹拌すると目的の凝集粒子が解砕したり、粒度分布が広くなったりする可能性がある。このため、静置するか又は穏やかに撹拌しながら蒸発及び乾燥させることが好ましい。例えば、分散液の調整後、得られた分散液を30分~48時間の間静置することにより、半導体粒子の大部分をアルコール中に沈降させた状態でアルコールを蒸発させて乾燥させることが好ましい。このように穏やかに乾燥させることにより、前記半導体粒子同士が凝集した、適度な大きさ及び強度を有する凝集粒子を容易に得ることができる。
上記の好適な範囲の平均粒子径であると、AD法によって、強度、電気伝導性、光透過性、増感色素吸着性に優れた多孔質膜を所望の厚みで容易に製膜することができる。
上記好適な範囲であることにより、AD法によって、強度、電気伝導性、光透過性、増感色素吸着性に優れた多孔質膜を所望の厚みで容易に製膜することができる。
上記好適な範囲であることにより、AD法によって、強度、電気伝導性、光透過性、増感色素吸着性に優れた多孔質膜を所望の厚みで容易に製膜することができる。
上記好適な範囲であることにより、AD法によって、強度、電気伝導性、光透過性、増感色素吸着性に優れた多孔質膜を所望の厚みで容易に製膜することができる。
上記好適な範囲であることにより、AD法によって、強度、電気伝導性、光透過性、増感色素吸着性に優れた多孔質膜を所望の厚みで容易に製膜することができる。
前記半導体粒子及び前記凝集粒子の平均粒子径を求める方法としては、レーザー回折式粒度分布測定装置の測定により得られた体積平均径の分布のピーク値として決定する方法を採用できる。
前記半導体粒子(1次粒子)の平均粒子径はレーザー回折式粒度分布測定装置によって「湿式で」測定する。
前記凝集粒子の平均粒子径はレーザー回折式粒度分布測定装置によって「乾式で」測定する。
本実施形態における製膜工程は、前記凝集粒子を基材に吹き付けることにより、前記基材上に半導体膜を製膜する工程である。
以下、図1を参照して製膜方法の一例を説明する。なお、説明で用いる図面は模式的なものであり、長さ、幅、及び厚みの比率等は実際のものと同一とは限らず、適宜変更できる。本実施形態の製膜方法に用いる製膜装置は特に限定されず、例えば、図1に示す製膜装置60が挙げられる。
製膜装置60は、ガスボンベ55と、搬送管56と、ノズル52と、基台63と、製膜室51と、を備えている。ガスボンベ55には、凝集粒子54を加速させて基材53に吹き付けるためのガス(搬送ガス)が充填されている。ガスボンベ55には、搬送管56の一端が接続されている。ガスボンベ55から供給される搬送ガスは搬送管56に供給される。
以下、凝集粒子54の吹き付け方法の一例を説明する。
まず、真空ポンプ62を稼動させて製膜室51内を減圧する。製膜室51内の圧力は特に制限されないが、5~1000Paに設定することが好ましい。この程度に減圧することにより、製膜室51内の対流を抑制し、凝集粒子54を製膜面71の所定の位置に吹き付けることが容易になる。
以上の工程により、基材53の製膜面71の上に凝集粒子54を構成する半導体粒子からなる所定の膜厚の多孔質膜を製膜することができる。
第一実施形態の半導体膜の製造方法により基材上に形成された半導体膜の膜構造は緻密膜(非多孔質膜)であってもよいし、多孔質膜であってもよい。その膜厚は特に限定されず、例えば1μm~500μm程度の厚みが挙げられる。
第一実施形態の半導体膜の製造方法により基材上に形成された半導体膜に増感色素を吸着させることによって、光電極として使用することができる。半導体膜は緻密膜であってもよいが、より多くの増感色素を吸着させる観点から、多孔質膜であることが好ましい。
増感色素の種類は特に制限されず、公知の増感色素が適用できる。光電極の用途において、前記半導体膜は公知の透明導電膜が形成された基材上に製膜されていることが好ましい。前記半導体膜に増感色素を吸着させる方法は特に限定されず、例えば、半導体膜を色素溶液中に浸漬させる方法が挙げられる。
上記範囲の下限値以上であると、増感色素をより多く担持することができる。上記範囲の上限値以下であると多孔質膜の強度をより強固にすることができる。
空隙率の測定は、公知のガス吸着試験又は水銀圧入試験によって行うことができる。
上記範囲の下限値以上であると、多孔質膜に担持させた増感色素が光エネルギーを吸収する確率を一層高めることができ、色素増感太陽電池における光電変換効率を一層向上できる。また、上記範囲の上限値以下であると、バルクの電解質(太陽電池セル内の電解質)と多孔質膜内の電解質との交換が、拡散によって一層効率よく行われ、光電変換効率を一層向上できる。
本発明の第二実施形態の色素増感太陽電池は、第一実施形態の半導体膜の製造方法によって得られた半導体膜に増感色素を吸着させてなる光電極と、対向電極と、電解液又は電解質層とを備えている。電解液は、光電極と対向電極の間において封止材によって封止されていることが好ましい。
前記樹脂としては、可視光の透過性を有するものが好ましく、例えばポリアクリル、ポリカーボネート、ポリエステル、ポリイミド、ポリスチレン、ポリ塩化ビニル、ポリアミド等が挙げられる。これらのうち、ポリエステル、特にポリエチレンテレフタレートが、透明耐熱フィルムとして好適であり、薄くて軽いフレキシブルな色素増感太陽電池を製造することができる。
前記固体電解質は、ゲル状又は固体状の何れかの状態である。ゲル状又は固体状の電解質層を用いることにより、色素増感太陽電池から電解液が漏出する虞がなくなる。
基材として、あらかじめITO(スズドープ酸化インジウム)がPEN(ポリエチレンナフタレート)基板に製膜されたITO-PEN基板を用いた。
<凝集粒子の調製>
無機酸化物半導体粒子として、平均粒子径が約21nmのアナターゼ型TiO2粒子を使用した。このチタニア粒子をエタノール中に30wt%で分散させ、充分に分散して得られた分散液を静置して、容器の底にチタニア粒子を沈降させた。この静置状態を保ったまま、30℃未満の減圧下でエタノールを蒸発させて、チタニア粒子を乾燥させた。
乾燥して得られた凝集粒子の粒度分布をレーザー回折式粒度分布計で測定し、図2に示す様に、粒径分布が0.1μm~10μmであり、単峰性のピークを有する凝集粒子であることを確認した。図2の粒度分布グラフから、調製した凝集粒子は、d10=約0.4μm、d50=約1.5μm、モード径=約1.8μm、d90=約4.0μmというパラメータを有することが分かる。
さらに、凝集粒子を電子顕微鏡で観察し、図3に示すSEM像を得た。このSEM像から、凝集粒子は球体に近似し易い形状の塊であり、凝集粒子を構成する各半導体粒子が互いに密に凝集していることが確認された。このような密な凝集状態であるため、凝集粒子の吹き付け時に、凝集粒子が基材に到達する前に解砕することなく、凝集粒子として基材に衝突し得ることが確認された。
図1に示す製膜装置60を使用して、製膜室51内において、10mm×0.5mmの長方形の開口部を持つノズル52からITO-PEN基板に対して前記凝集粒子を吹き付けた。この際、搬送ガスであるN2をボンベ55から搬送管56へ供給し、その流速をマスフロー制御器57で調整した。吹き付け用の凝集粒子をエアロゾル発生器58に装填し、搬送ガスに分散させて、解砕器59および分級器61へ搬送し、ノズル52から基材53へ噴射した。製膜室51には真空ポンプ62が接続されており、製膜室内を陰圧にした。ノズル52における搬送速度は5mm/secとした。
前記凝集粒子を前記基材に吹き付けることにより、凝集粒子を構成するチタニア粒子同士が互いに接合してなる多孔質膜を製膜することができた。この多孔質膜の断面を電子顕微鏡で観察したSEM像を図4に示す。このSEM像から、チタニア粒子が充分に接合した均一な膜構造が形成されていることが確認できた。
<原料粒子の準備>
実施例1で使用したチタニア粒子をエタノール中に分散せず、乾燥して、原料粒子とした。
この原料粒子を電子顕微鏡で観察し、図5に示すSEM像を得た。このSEM像から、原料粒子の中には凝集した塊が複数観察された。しかし、これらの凝集塊は、実施例1の凝集粒子と比べると粒子径が不均一かつ小粒である。また、凝集塊の表面に多数の影が濃く観察されることから、凝集の程度が弱く、比較的疎な凝集状態であることが確認された。このような疎な凝集状態であるため、原料粒子の吹き付け時に、凝集粒子が基材に到達する前に解砕し、凝集塊として基材に衝突することが比較的難しく、仮に凝集塊として衝突したとしても、基材表面で解砕し易く、製膜(粒子同士の接合)に必要なエネルギーが得られ難いと考えられた。
前記原料粒子を使用して、実施例1と同様に吹き付けを行い、多孔質膜を製膜した。
その結果、所定厚みの多孔質膜は辛うじて得られたが、実施例1に比べて、製膜に要する吹き付け時間が長く、吹き付ける粒子量が多く必要であった。
実施例1及び比較例1の多孔質膜を備えた各基板を、0.3mMのRu錯体色素(N719、ソラロニクス社製)のアルコール溶液中に、室温で18時間浸漬させて、当該多孔質膜に色素を吸着させることにより、光電極基板を得た。
光電極基板と、白金コーティング付きガラス基板からなる対極基板とを対向配置し、この間にスペーサーとして厚み30μmの樹脂フィルム(ハイミラン、三井・デュポン ポリケミカル社製)を挟んで、ダブルクリップで留めて圧着した。さらに、対極基板に予め空けておいた注入孔から、両基板の間に、電解液(Iodolyte50、ソラロニクス社製)を注入した後、注入孔をガラス板で塞ぐことにより、色素増感太陽電池の簡易セルを作製した。受光する有効面積は0.16cm2であった。
得られた各試験例の簡易セルの光電変換効率等の性能を、ソーラーシミュレーター(AM1.5、100mW/cm2)を用いて評価した。その結果を表1に示す。また、各簡易セルのV-I特性を比較した結果を図6に示す。
比較例1の多孔質膜は基板の変形において直ぐに剥離した。比較例1の多孔質膜は圧粉体(粉の塊が基板上に載っているだけ)に近い状態であると考えられた。この結論は、色素吸着量が少なく、発電特性が劣ることからも支持された。
エタノールに替えてメタノールを使用した以外は、実施例1と同様の方法で、凝集粒子を調製し、チタニア粒子からなる多孔質膜を製膜した。得られた多孔質膜のSEM像を観察したところ、チタニア粒子が充分に接合した均一な膜構造を有することが確認できた。この多孔質膜を備えた簡易セルを実施例1と同様に作製し、良好な発電特性が得られた。
エタノールに替えて1-ペンタノールを使用した以外は、実施例1と同様の方法で、凝集粒子を調製し、チタニア粒子からなる多孔質膜を製膜した。得られた多孔質膜のSEM像を観察したところ、チタニア粒子が充分に接合した均一な膜構造を有することが確認できた。この多孔質膜を備えた簡易セルを実施例1と同様に作製し、良好な発電特性が得られた。
エタノールに替えて2級アルコールであるイソプロパノールを使用した以外は、実施例1と同様の方法で、凝集粒子を調製し、チタニア粒子からなる多孔質膜を製膜した。得られた多孔質膜のSEM像を観察したところ、チタニア粒子が充分に接合した均一な膜構造を有することが確認できた。この多孔質膜を備えた簡易セルを実施例1と同様に作製し、良好な発電特性が得られた。
エタノールに替えて3級アルコールであるt-ブタノールを使用した以外は、実施例1と同様の方法で、凝集粒子を調製し、チタニア粒子からなる多孔質膜を製膜した。得られた多孔質膜のSEM像を観察したところ、チタニア粒子が充分に接合した均一な膜構造を有することが確認できた。この多孔質膜を備えた簡易セルを実施例1と同様に作製し、良好な発電特性が得られた。
52 ノズル
53 基材
54 半導体粒子
55 ボンベ
56 搬送管
57 マスフロー制御器
58 エアロゾル発生器
59 解砕器
60 製膜装置
61 分級器
62 真空ポンプ
63 基台
71 製膜面
72 基台の載置面(上面)
73 製膜面の反対側の面
Claims (6)
- 平均粒子径が1nm以上100nm未満の範囲である半導体粒子をアルコール中に分散させた分散液を得た後、前記分散液から前記アルコールを蒸発させて前記半導体粒子を乾燥することにより、前記半導体粒子同士が凝集した凝集粒子を得て、
前記凝集粒子を基材に吹き付けることにより、前記基材上に半導体膜を製膜する、半導体膜の製造方法。 - 前記半導体粒子が前記アルコール中に沈降した状態で、前記アルコールを蒸発させて前記半導体粒子を乾燥する、請求項1に記載の半導体膜の製造方法。
- 50℃未満の温度で前記アルコールを蒸発させる、請求項1又は2に記載の半導体膜の製造方法。
- 前記半導体粒子が金属酸化物半導体の粒子である、請求項1~3の何れか一項に記載の半導体膜の製造方法。
- 前記半導体膜が多孔質膜である、請求項1~4の何れか一項に記載の半導体膜の製造方法。
- 請求項1~5の何れか一項に記載の半導体膜の製造方法によって得られた半導体膜に、増感色素を吸着させてなる光電極を備えた、色素増感太陽電池。
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2016
- 2016-02-25 TW TW105105616A patent/TWI684297B/zh active
- 2016-02-26 CN CN201680005016.9A patent/CN107109662B/zh active Active
- 2016-02-26 WO PCT/JP2016/055845 patent/WO2016136950A1/ja active Application Filing
- 2016-02-26 KR KR1020177018290A patent/KR20170125800A/ko unknown
- 2016-02-26 JP JP2017502512A patent/JPWO2016136950A1/ja not_active Withdrawn
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WO2012161161A1 (ja) * | 2011-05-20 | 2012-11-29 | 独立行政法人産業技術総合研究所 | 製膜方法、製膜体、及び色素増感太陽電池 |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2020262115A1 (ja) * | 2019-06-27 | 2020-12-30 | Dowaエレクトロニクス株式会社 | 銀粉およびその製造方法 |
JP2021006661A (ja) * | 2019-06-27 | 2021-01-21 | Dowaエレクトロニクス株式会社 | 銀粉およびその製造方法 |
CN114008724A (zh) * | 2019-06-27 | 2022-02-01 | 同和电子科技有限公司 | 银粉及其制造方法 |
JP7093812B2 (ja) | 2019-06-27 | 2022-06-30 | Dowaエレクトロニクス株式会社 | 銀粉およびその製造方法 |
Also Published As
Publication number | Publication date |
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TWI684297B (zh) | 2020-02-01 |
CN107109662A (zh) | 2017-08-29 |
JPWO2016136950A1 (ja) | 2017-12-21 |
KR20170125800A (ko) | 2017-11-15 |
CN107109662B (zh) | 2019-07-12 |
TW201703304A (zh) | 2017-01-16 |
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