WO2023120033A1 - 光電変換素子 - Google Patents

光電変換素子 Download PDF

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Publication number
WO2023120033A1
WO2023120033A1 PCT/JP2022/043594 JP2022043594W WO2023120033A1 WO 2023120033 A1 WO2023120033 A1 WO 2023120033A1 JP 2022043594 W JP2022043594 W JP 2022043594W WO 2023120033 A1 WO2023120033 A1 WO 2023120033A1
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layer
photoelectric conversion
polymer
conductive layer
supporting sheet
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French (fr)
Japanese (ja)
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良一 古宮
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Zeon Corp
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Zeon Corp
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Priority to KR1020247016430A priority Critical patent/KR20240127333A/ko
Priority to EP22910751.1A priority patent/EP4456694A4/en
Priority to CN202280082644.2A priority patent/CN118383096A/zh
Priority to JP2023569201A priority patent/JPWO2023120033A1/ja
Publication of WO2023120033A1 publication Critical patent/WO2023120033A1/ja
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • Y02E10/549—Organic PV 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 photoelectric conversion elements.
  • Solar cells are attracting attention as photoelectric conversion elements that convert light energy into electric power.
  • solar cells such as a perovskite solar cell using a perovskite compound as a power generation layer.
  • a photoelectric conversion layer provided between the first electrode and the second electrode and containing a material having a perovskite structure; and a carrier transport material provided between the photoelectric conversion layer and the second electrode.
  • a photoelectric conversion device has been proposed that includes a first layer containing
  • an object of the present invention is to provide a photoelectric conversion element having excellent structural stability.
  • the photoelectric conversion element of the present invention is a photoelectric conversion element obtained by integrating a laminate comprising a translucent substrate, a transparent conductive film, a first conductive layer, a power generation layer, and a second conductive layer in this order.
  • the second conductive layer is a porous layer containing at least carbon nanofibers, and a weight average molecular weight of 20,000 or more and 200,000 or less is present between the power generation layer and the second conductive layer
  • the polymer is preferably a hydrogenated polymer. With such a configuration, it is possible to further improve the structural stability of the photoelectric conversion element.
  • the polymer is preferably a polymer having a hydrogenated aromatic or diene skeleton in its main chain. With such a configuration, it is possible to further improve the structural stability of the photoelectric conversion element.
  • the polymer is a hydrogenated aromatic vinyl compound-conjugated diene block copolymer
  • the silicon of a hydrogenated aromatic vinyl compound-conjugated diene block copolymer It is preferably one or more selected from the group consisting of modified products with atom-containing polar groups.
  • the hydrogenated aromatic vinyl compound-conjugated diene block copolymer has both a non-aromatic carbon-carbon unsaturated bond and an aromatic carbon-carbon unsaturated bond. preferably have a hydrogenated structure. With such a configuration, it is possible to further improve the structural stability of the photoelectric conversion element.
  • the second conductive layer is made of a porous self-supporting sheet. According to such a configuration, it is possible to further improve the structural stability while facilitating the manufacture of the photoelectric conversion element.
  • porous self-supporting sheet refers to a sheet in which a plurality of pores are formed and which maintains its shape as a sheet without a support.
  • the porous self-supporting sheet used in the present invention is immersed in a predetermined solvent or solution, pulled out, and then attached to an object to be adhered. The shape of the sheet is maintained.
  • the porous self-supporting sheet used in the present invention can be handled, for example, by dripping chlorobenzene or the like, which is a poor solvent for the perovskite compound, onto the sheet, or by using a jig used for attaching the sheet. , there is no tearing or deformation of the sheet.
  • the porous self-supporting sheet used in the present invention preferably has a thickness of 1 ⁇ m to 200 ⁇ m and an area of 1 mm 2 to 100 cm 2 and maintains its shape as a sheet without a support.
  • the film thickness of the porous self-supporting sheet is 20 ⁇ m or more. According to such a configuration, manufacturing of the photoelectric conversion element is facilitated, and structural stability can be further improved.
  • the power generation layer preferably contains a perovskite compound. According to such a configuration, it is possible to reduce the manufacturing cost of the photoelectric conversion element and improve the ease of manufacturing the photoelectric conversion element.
  • the carbon nanofiber body has an average diameter (Av) and a standard deviation ( ⁇ ) of the diameter that satisfy the relational expression: 0.20 ⁇ (3 ⁇ /Av) ⁇ 0.60. preferably fulfilled. With such a configuration, it is possible to further improve the structural stability of the photoelectric conversion element.
  • the "average diameter (Av) of the carbon nanofibers” and the “standard deviation of the diameter of the carbon nanofibers ( ⁇ : standard deviation)” are the carbon nanofibers randomly selected using a transmission electron microscope. It can be obtained by measuring the diameter (outer diameter) of 100 fibrous bodies.
  • the average diameter (Av) and standard deviation ( ⁇ ) of the carbon nanofibers may be adjusted by changing the manufacturing method and manufacturing conditions of the carbon nanofibers, or the carbon nanofibers obtained by different manufacturing methods. It may be adjusted by combining a plurality of types of fibrous bodies.
  • the carbon nanofiber body preferably exhibits an upward convex shape in the t-plot obtained from the adsorption isotherm. With such a configuration, it is possible to further improve the structural stability of the photoelectric conversion element.
  • the photoelectric conversion device of the present invention after the polymer layer is laminated on the power generation layer, at least one joint surface between the porous self-supporting sheet that becomes the second conductive layer and the polymer layer retains a solvent. It is preferable to manufacture by a method including a step of laminating the porous self-supporting sheet to the polymer layer in a state of being folded. According to such a configuration, it is possible to easily manufacture a photoelectric conversion element that is easy to manufacture and has excellent structural stability.
  • the photoelectric conversion device of the present invention at least one joint surface of the porous self-supporting sheet serving as the second conductive layer and the power generation layer is coated with a solution in which a polymer for forming the polymer layer is dissolved. It is preferable to manufacture by a method including a step of laminating the porous self-supporting sheet to the power generation layer while holding it. According to such a configuration, it is possible to easily manufacture a photoelectric conversion element that is easy to manufacture and has excellent structural stability.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of a photoelectric conversion element according to one embodiment of the present invention
  • the photoelectric conversion device of the present invention is not particularly limited, and can be used, for example, as a perovskite solar cell.
  • One embodiment of the photoelectric conversion device of the present invention will be described in detail below with reference to FIG.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of a photoelectric conversion element 100 according to one embodiment of the present invention.
  • the photoelectric conversion element 100 includes a translucent substrate 1, a transparent conductive film 2, a first conductive layer 5 composed of an underlying layer 3 and a porous semiconductor layer 4, a power generation layer 6, and a second conductive layer 7. Laminates provided in order are integrated.
  • the second conductive layer 7 is composed of a porous self-supporting sheet as a porous layer containing at least carbon nanofibers. ,000 or less polymer layer 8 is provided. Each constituent member constituting the photoelectric conversion element 100 will be described in order below.
  • the translucent substrate 1 constitutes the base of the photoelectric conversion element 100 .
  • the translucent substrate 1 is not particularly limited, and examples thereof include a substrate made of glass or synthetic resin, a film made of synthetic resin, and the like.
  • Examples of the glass forming the translucent substrate 1 include inorganic glass such as soda glass.
  • Synthetic resins forming the translucent substrate 1 include, for example, polyacrylic resins, polycarbonate resins, polyester resins, polyimide resins, polystyrene resins, polyvinyl chloride resins, polyamide resins, and polycycloolefin resins.
  • polyacrylic resins polycarbonate resins, polyester resins, polyimide resins, polystyrene resins, polyvinyl chloride resins, polyamide resins, and polycycloolefin resins.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the thickness of the translucent substrate 1 is not particularly limited as long as it can maintain the shape of the substrate.
  • the thickness of the translucent substrate 1 can be, for example, 0.1 mm or more and 10 mm or less.
  • the transparent conductive film 2 is a film made of metal oxide formed on the surface of the translucent substrate 1 .
  • the surface of the translucent substrate 1 can be imparted with conductivity.
  • metal oxides forming the transparent conductive film 2 include fluorine-doped tin oxide (FTO), tin oxide (SnO), indium oxide ( In2O3 ), tin-doped indium oxide (ITO), and zinc oxide ( ZnO ). , indium oxide/zinc oxide (IZO), gallium oxide/zinc oxide (GZO), and the like.
  • FTO fluorine-doped tin oxide
  • SnO tin oxide
  • In2O3 indium oxide
  • ITO tin-doped indium oxide
  • ZnO zinc oxide
  • IZO indium oxide/zinc oxide
  • GZO gallium oxide/zinc oxide
  • each transparent conductive film may be made of the same metal oxide, or may be made of different metal oxides.
  • the thickness of the transparent conductive film 2 is not particularly limited as long as it can impart desired conductivity to the translucent substrate 1, and can be, for example, 1 nm or more and 1 ⁇ m or less.
  • the transparent conductive film 2 may be formed on the entire surface of the translucent substrate 1, or may be formed on a part of the surface of the translucent substrate 1 as shown in FIG.
  • the first conductive layer 5 is a layer that functions as a charge transport layer and is composed of an n-type semiconductor.
  • the first conductive layer 5 is composed of two layers, the base layer 3 and the porous semiconductor layer 4, but is not limited to this. It may be one layer composed of
  • the underlying layer 3 is an optional layer.
  • the transparent substrate 1 and the transparent conductive film 2 are prevented from coming into direct contact with the porous semiconductor layer 4 . This prevents the loss of electromotive force, so that the photoelectric conversion efficiency of the photoelectric conversion element 100 can be improved.
  • the underlayer 3 may be, for example, a porous film or a dense film as long as it is composed of an n-type semiconductor. From the viewpoint of sufficiently preventing contact with the semiconductor layer 4, the underlying layer 3 is preferably a non-porous dense film.
  • the thickness of the underlying layer 3 is not particularly limited, and can be, for example, 1 nm or more and 500 nm or less. Further, the underlying layer 3 may optionally contain an insulating material other than an n-type semiconductor in a proportion that does not impair the properties of the underlying layer 3 as an n-type semiconductor.
  • the porous semiconductor layer 4 is a porous layer. By including the porous semiconductor layer 4 in the first conductive layer 5, the photoelectric conversion efficiency of the photoelectric conversion element 100 can be further improved.
  • the thickness of the porous semiconductor layer 4 is not particularly limited, it is usually 5 nm or more, preferably 10 nm or more, and usually 500 nm or less, preferably 100 nm or less.
  • the porous semiconductor layer 4 may be formed from one layer, as shown in FIG. 1, or may be formed from a plurality of layers.
  • the power generation layer 6 is a layer made of a material that generates an electromotive force by absorbing light, preferably a layer containing a perovskite compound, more preferably a layer made of a perovskite compound (perovskite layer). be.
  • the perovskite compound that constitutes the power generation layer 6 is not limited to a lead-based or lead-free perovskite compound, and any compound that forms a perovskite structure and functions as a power generation layer may be used.
  • the thickness of the power generation layer 6 is not particularly limited, it is preferably 100 nm or more, more preferably 200 nm or more, and preferably 1 ⁇ m or less, more preferably 800 nm or less. By setting the thickness of the power generation layer 6 to 100 nm or more, the electromotive force of the power generation layer 6 can be increased.
  • the second conductive layer 7 is a porous layer containing at least carbon nanofibers.
  • the carbon nanofibers contained in the second conductive layer 7 are not particularly limited, but preferably contain carbon nanotubes (hereinafter, carbon nanotubes are also referred to as “CNT”).
  • the CNTs to be used preferably include single-walled CNTs. With such a configuration, the photoelectric conversion efficiency of the photoelectric conversion element 100 can be enhanced.
  • the second conductive layer 7 is preferably a layer made of a porous self-supporting sheet.
  • a porous self-supporting sheet which is a self-supporting film
  • the shape stability of the second conductive layer 7 can be improved, and the photoelectric conversion element 100 can be easily manufactured to have a large area due to the ease of production. can do.
  • a porous self-supporting sheet that is porous it is possible to easily dry the solvent or solution when wet processing is performed.
  • the porous self-supporting sheet must contain at least carbon nanofibers, preferably contains at least single-walled CNTs as carbon nanofibers, more preferably a sheet made of carbon nanofibers, more preferably a single CNT sheet.
  • the second conductive layer 7 is provided with an excellent function as a hole transport layer and a function as a collector electrode. be able to.
  • the carbon nanofibers contained in the second conductive layer 7 (more preferably the porous self-supporting sheet) contain carbon nanofibers (more preferably CNTs, more preferably single-walled CNTs) having the following properties: is preferred.
  • the carbon nanofiber body contained in the second conductive layer 7 has a ratio (3 ⁇ /Av) of the value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ ) of the diameter by 3 to the average diameter (Av) is more than 0.20. is preferably greater than 0.25, more preferably greater than 0.50, and preferably less than 0.60. If 3 ⁇ /Av is more than 0.20 and less than 0.60, even if the amount of carbon nanofibers contained in the second conductive layer 7 is small, the hole transport layer is sufficient for the second conductive layer 7 and a function as a collecting electrode.
  • the average diameter (Av) of the carbon nanofibers is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 15 nm or less, and more preferably 10 nm or less. If the average diameter (Av) of the carbon nanofibers is 0.5 nm or more, the aggregation of the carbon nanofibers can be suppressed, and the dispersibility of the carbon nanofibers in the second conductive layer 7 can be enhanced. . Moreover, when the average diameter (Av) of the carbon nanofibers is 15 nm or less, the second conductive layer 7 can sufficiently exhibit its function as a collector electrode.
  • the carbon nanofiber body preferably exhibits an upward convex shape in the t-plot obtained from the adsorption isotherm.
  • carbon nanofibers single-walled CNTs to which opening treatment has not been performed are more preferable.
  • a second conductive layer 7 having excellent strength can be obtained by using a carbon nanofiber material that exhibits an upward convex shape in the t-plot obtained from the adsorption isocurve.
  • the inflection point of the t-plot of the carbon nanofiber body is preferably in a range satisfying 0.2 ⁇ t (nm) ⁇ 1.5, and a range of 0.45 ⁇ t (nm) ⁇ 1.5. and more preferably in the range of 0.55 ⁇ t(nm) ⁇ 1.0.
  • Measurement of the adsorption isotherm of the carbon nanofibrous body, preparation of the t-plot, and analysis of the t-plot can be performed, for example, by a commercially available measurement device "BELSORP (registered trademark)-mini” (manufactured by Bell Japan Co., Ltd.). ).
  • Carbon nanofibers having the properties described above can be obtained, for example, by supplying a raw material compound and a carrier gas onto a base material having a catalyst layer for producing carbon nanofibers on the surface thereof, and performing chemical vapor deposition (CVD method). ) to dramatically improve the catalytic activity of the catalyst layer by allowing a small amount of oxidizing agent (catalyst activating substance) to exist in the system when synthesizing carbon nanofibers (super-growth method; international publication No. 2006/011655), the formation of the catalyst layer on the substrate surface by a wet process enables efficient production.
  • CVD method chemical vapor deposition
  • the second conductive layer 7 preferably contains the material (for example, perovskite compound) constituting the power generation layer 6 described above inside the second conductive layer 7 . More specifically, the second conductive layer 7 preferably contains a material (for example, a perovskite compound) that forms the power generation layer 6 inside the plurality of pores of the second conductive layer 7 .
  • the ratio of the carbon nanofibers contained in the second conductive layer 7 is not particularly limited, but is preferably 50% by mass or more, preferably 75% by mass or more.
  • Materials other than the carbon nanofibers that can optionally be contained in the second conductive layer 7 include, for example, organic materials and inorganic materials as p-type semiconductors.
  • the organic material that can be contained in the second conductive layer 7 includes, for example, 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamino)-9,9′- Spirobifluorene (spiro-MeOTAD), poly(3-hexylthiophene) (P3HT), polytriallylamine (PTAA), and the like.
  • spiro-MeOTAD 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamino)-9,9′- Spirobifluorene
  • P3HT poly(3-hexylthiophene)
  • PTAA polytriallylamine
  • Examples of inorganic materials that can be contained in the second conductive layer 7 include CuI, CuSCN, CuO, and Cu2O .
  • the thickness of the second conductive layer 7 is usually preferably 20 ⁇ m or more, preferably 30 ⁇ m or more, preferably 200 ⁇ m or less, and more preferably 80 ⁇ m or less.
  • the second conductive layer 7 can exhibit a better function as a collector electrode.
  • the method for producing the second conductive layer 7 is not particularly limited.
  • the solvent is removed from the carbon nanofiber dispersion liquid containing the carbon nanofibers, the dispersant, and the solvent to form the second conductive layer 7.
  • a method including a film forming step can be employed.
  • a coarse dispersion containing the carbon nanofibers, a dispersant, and a solvent is subjected to a dispersion treatment to disperse the carbon nanofibers.
  • a step of preparing a liquid may be included.
  • Dispersion preparation step In the dispersion preparation step, a coarse dispersion containing carbon nanofibers, a dispersant, and a solvent is subjected to, although not particularly limited to, a dispersion treatment capable of obtaining a cavitation effect or a pulverization effect, which will be described later in detail, to obtain carbon nanofibers. It is preferable to prepare a carbon nanofiber dispersion by dispersing the fibrous bodies. By carrying out the dispersing treatment that provides a cavitation effect or crushing effect in this manner, a carbon nanofiber dispersion in which the carbon nanofibers are well dispersed can be obtained.
  • the carbon nanofibers can be uniformly dispersed to improve electrical conductivity, thermal conductivity, and mechanical properties. It is possible to obtain the second conductive layer 7 having excellent properties such as properties.
  • the carbon nanofiber dispersion liquid used for manufacturing the second conductive layer 7 may be prepared by dispersing the carbon nanofibers in a solvent using a known dispersion treatment other than the above.
  • the carbon nanofibers used for preparing the carbon nanofiber dispersion preferably contain single-walled CNTs, and are mixtures of single-walled CNTs and carbon nanofibers other than single-walled CNTs (for example, multi-walled CNTs).
  • the content ratio of the single-walled CNT and the carbon nanofibers other than the single-walled CNT is, for example, a mass ratio (single-walled CNT/carbon nanofibers other than the single-walled CNT). It can be from 50/50 to 75/25.
  • dispersant The dispersing agent used for preparing the carbon nanofiber dispersion is not particularly limited as long as it can disperse the carbon nanofibers and dissolve in the solvent used for preparing the carbon nanofiber dispersion.
  • a dispersant for example, a surfactant, synthetic polymer or natural polymer can be used.
  • Surfactants include sodium dodecylsulfonate, sodium deoxycholate, sodium cholate, and sodium dodecylbenzenesulfonate.
  • Examples of synthetic polymers include polyether diol, polyester diol, polycarbonate diol, polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, and silanol group-modified polyvinyl alcohol.
  • Polyvinyl alcohol ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer resin, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylic resin, epoxy resin, modified epoxy resin, phenoxy resin, modified phenoxy resin Resins, phenoxy ether resins, phenoxy ester resins, fluorine resins, melamine resins, alkyd resins, phenol resins, polyacrylamides, polyacrylic acids, polystyrenesulfonic acids, polyethylene glycols, polyvinylpyrrolidone and the like.
  • natural polymers include, for example, polysaccharides such as starch, pullulan, dextran, dextrin, guar gum, xanthan gum, amylose, amylopectin, alginic acid, gum arabic, carrageenan, chondroitin sulfate, hyaluronic acid, curdlan, chitin, chitosan, Cellulose and its salts or derivatives are included.
  • Derivatives mean conventionally known compounds such as esters and ethers.
  • dispersants can be used singly or in combination of two or more.
  • surfactants are preferable as the dispersant, and sodium deoxycholate and the like are more preferable, because they are excellent in dispersibility of the carbon nanofibers.
  • solvent The solvent for the carbon nanofiber dispersion is not particularly limited, and examples include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, Alcohols such as octanol, nonanol, decanol, and amyl alcohol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, dioxane, and tetrahydrofuran, and N,N-dimethylformamide.
  • amide-based polar organic solvents such as N-methylpyrrolidone
  • aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ortho-dichlorobenzene, and para-dichlorobenzene. These may be used alone or in combination of two or more.
  • the dispersion liquid preparation step it is preferable to perform a dispersion treatment that provides, for example, the following cavitation effect or pulverization effect.
  • Dispersion treatment that provides a cavitation effect is a dispersion method that utilizes shock waves generated by the bursting of vacuum bubbles generated in water when high energy is applied to the liquid. By using this dispersing method, the carbon nanofibers can be well dispersed.
  • dispersion processing that can obtain a cavitation effect
  • dispersion processing by ultrasonic waves dispersion processing by a jet mill
  • dispersion processing by high-shear stirring Only one of these distributed processes may be performed, or a plurality of distributed processes may be combined. More specifically, for example, an ultrasonic homogenizer, a jet mill and a high-shear stirring device are preferably used. Conventionally known devices may be used for these devices.
  • the coarse dispersion may be irradiated with ultrasonic waves by the ultrasonic homogenizer.
  • the irradiation time may be appropriately set according to the amount of the carbon nanofibers, and is preferably 3 minutes or longer, more preferably 30 minutes or longer, and preferably 5 hours or shorter, and more preferably 2 hours or shorter.
  • the output is preferably 20 W or more and 500 W or less, more preferably 100 W or more and 500 W or less, and the temperature is preferably 15° C. or more and 50° C. or less.
  • the number of treatments may be appropriately set depending on the amount of the carbon nanofibers, etc. For example, it is preferably 2 times or more, more preferably 5 times or more, preferably 100 times or less, and 50 times or less. is more preferred. Further, for example, the pressure is preferably 20 MPa or more and 250 MPa or less, and the temperature is preferably 15° C. or more and 50° C. or less.
  • the coarse dispersion may be stirred and sheared by a high-shear stirring device.
  • the operating time time during which the machine is rotating
  • the peripheral speed is preferably 5 m/sec or more and 50 m/sec or less
  • the temperature is preferably 15° C. or more and 50° C. or less.
  • Dispersion processing that can obtain crushing effect
  • Dispersion treatment that provides a pulverization effect can, of course, uniformly disperse the carbon nanofibers in a solvent. This is more advantageous in that damage can be suppressed.
  • the back pressure applied to the coarse dispersion may be reduced to atmospheric pressure at once, but it is preferable to reduce the pressure in multiple stages.
  • the second conductive layer 7 is formed by removing the solvent from the above carbon nanofiber dispersion. Specifically, in the film formation step, the solvent is removed from the carbon nanofiber dispersion by using, for example, one of the methods (A) and (B) below, and the porous self-supporting layer that becomes the second conductive layer 7 is formed. Deposit a sheet.
  • A A method of applying a carbon nanofiber dispersion onto a film-forming substrate and then drying the applied carbon nanofiber dispersion.
  • B A method of filtering the carbon nanofiber dispersion liquid using a porous film-forming base material and drying the resulting filtrate.
  • the film-forming substrate is not particularly limited, and known substrates can be used.
  • examples of film-forming substrates to which the carbon nanofiber dispersion is applied in method (A) include resin substrates and glass substrates.
  • the resin base material polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polytetrafluoroethylene (PTFE), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, Substrates made of polymethyl methacrylate, alicyclic acrylic resins, cycloolefin resins, triacetyl cellulose and the like can be mentioned.
  • the glass substrate a substrate made of ordinary soda glass can be mentioned.
  • examples of film-forming substrates for filtering the carbon nanofiber dispersion in the above method (B) include filter paper and porous sheets made of cellulose, nitrocellulose, alumina, or the like.
  • the coating method includes a dipping method, a roll coating method, a gravure coating method, a knife coating method, an air knife coating method, a roll knife coating method, a die coating method, a screen printing method, a spray coating method, a gravure offset method, and the like. can be used.
  • a known filtration method can be employed as a method for filtering the carbon nanofiber dispersion liquid using the film-forming base material in the above method (B). Specifically, natural filtration, vacuum filtration, pressure filtration, centrifugal filtration, etc. can be used as the filtration method.
  • Drying As a method for drying the carbon nanofiber dispersion applied on the film-forming substrate in the above method (A) or the filtrate obtained in the above method (B), a known drying method can be employed. Drying methods include hot air drying, vacuum drying, hot roll drying, and infrared irradiation.
  • the drying temperature is not particularly limited, but usually room temperature to 200° C.
  • the drying time is not particularly limited, but is usually 0.1 to 150 minutes.
  • the porous self-supporting sheet formed as a film as described above usually contains the components contained in the carbon nanofiber dispersion, such as the carbon nanofibers and the dispersant, as the carbon nanofiber dispersion. It contains the same ratio. Therefore, in the method for manufacturing the second conductive layer 7, optionally, the porous self-supporting sheet deposited in the film-forming step may be washed to remove the dispersant from the porous self-supporting sheet. By removing the dispersant from the porous self-supporting sheet, the properties of the porous self-supporting sheet, such as electrical conductivity, can be further enhanced.
  • the washing of the porous self-supporting sheet can be performed by contacting the dispersing agent with a solvent capable of dissolving it, and eluting the dispersing agent in the porous self-supporting sheet into the solvent.
  • the solvent capable of dissolving the dispersant in the porous self-supporting sheet is not particularly limited. The same solvent can be used.
  • the contact between the porous self-supporting sheet and the solvent can be carried out by immersing the porous self-supporting sheet in the solvent or applying the solvent to the porous self-supporting sheet. Additionally, the porous self-supporting sheet after washing can be dried using known methods.
  • the porous self-supporting sheet formed in the film-forming process may optionally be press-processed to further increase the density, thereby adjusting the voids as necessary.
  • the press pressure during press working is preferably less than 3 MPa, and it is more preferable not to perform press working.
  • the polymer layer 8 provided between the power generation layer 6 and the second conductive layer 7 is a layer made of a polymer having a weight average molecular weight of 20,000 or more and 200,000 or less.
  • the polymer layer 8 preferably exists in contact with both the power generation layer 6 and the second conductive layer 7 at least partially.
  • the polymer constituting the polymer layer 8 is not particularly limited, and known polymers can be used. According to such a configuration, the polymer layer 8 can function as a buffer layer, and as a result, it is possible to stabilize the shape of the bonding surface while suppressing deterioration in the performance of the photoelectric conversion element 100 .
  • the polymer that constitutes the polymer layer 8 is not particularly limited as long as it can improve adhesion without inhibiting charge transport at the interface.
  • the polymer constituting the polymer layer 8 is preferably a hydrogenated polymer, more preferably a polymer having a hydrogenated aromatic or diene skeleton in its main chain, more preferably a hydrogenated aromatic It is one or more selected from the group consisting of a vinyl compound-conjugated diene block copolymer and a hydrogenated aromatic vinyl compound-conjugated diene block copolymer modified with a silicon atom-containing polar group.
  • the hydrogenated aromatic vinyl compound-conjugated diene block copolymer may have a structure in which both the non-aromatic carbon-carbon unsaturated bond and the aromatic carbon-carbon unsaturated bond are hydrogenated. preferable.
  • polymers constituting the polymer layer 8 include ethylene- ⁇ -olefin copolymers such as ethylene-propylene copolymers; ethylene- ⁇ -olefin-polyene copolymers; ethylene-methyl methacrylate and ethylene-butyl Copolymers of ethylene and unsaturated carboxylic acid esters such as acrylate copolymers; Copolymers of ethylene and vinyl fatty acids such as ethylene-vinyl acetate copolymers; Ethyl acrylate, butyl acrylate, acrylic acid Polymers of acrylic acid alkyl esters such as hexyl, 2-ethylhexyl acrylate, lauryl acrylate; polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene-(meth)acrylic acid alkyl ester copolymer Diene copolymers such as
  • a hydrogenated aromatic vinyl compound-conjugated diene block copolymer represents a hydride of an aromatic vinyl compound-conjugated diene block copolymer. That is, the hydrogenated aromatic vinyl compound-conjugated diene block copolymer has a non-aromatic carbon-carbon unsaturated bond and an aromatic carbon-carbon unsaturated bond of the aromatic vinyl compound-conjugated diene block copolymer. , or a polymer having a structure obtained by partially or wholly hydrogenating both of them.
  • the hydride is not limited by its production method.
  • the aromatic vinyl compound styrene and its derivatives; vinylnaphthalene and its derivatives; are preferred. It is particularly preferable to use styrene because of its industrial availability.
  • the conjugated diene is preferably a chain conjugated diene (linear conjugated diene, branched conjugated diene).
  • Preferred examples of conjugated dienes include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Among these, 1,3-butadiene and isoprene are particularly preferred because of their industrial availability.
  • w A be the mass fraction of all the aromatic vinyl monomer units in the aromatic vinyl compound-conjugated diene block copolymer, and all the conjugated diene monomer units are the aromatic vinyl compound-conjugated diene block copolymer.
  • w B is the mass fraction of the total coalescence
  • the ratio of w A to w B (w A /w B ) is preferably within a specific range. Specifically, the ratio (w A /w B ) is preferably 20/80 or more, more preferably 30/70 or more, and preferably 60/40 or less, more preferably 55/45 or less. .
  • the ratio w A /w B is equal to or higher than the lower limit of the range, the heat resistance of the polymer layer 8 can be improved. Moreover, when it is below an upper limit, the flexibility of the polymer layer 8 can be improved. Further, when the ratio (w A /w B ) is within the above range, the temperature range in which the polymer layer 8 has rubber elasticity can be widened, so the temperature range in which the photoelectric conversion element 100 has flexibility can be widened. be able to.
  • aromatic vinyl compound-conjugated diene block copolymers examples include styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, and mixtures thereof are preferred. More specific examples of these include JP-A-2-133406, JP-A-2-305814, JP-A-3-72512, JP-A-3-74409, and International Publication No. 2015/099079. and those described in technical literature such as.
  • the hydrogenation rate of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 90% or more, more preferably 97% or more, and particularly preferably 99% or more.
  • the hydrogenation rate of the hydride can be determined by 1H-NMR measurement.
  • the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds in the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 95% or more, more preferably 99% or more.
  • the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds is high, the light resistance and oxidation resistance of the polymer layer 8 can be further increased.
  • the hydrogenation rate of aromatic carbon-carbon unsaturated bonds in the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. be.
  • the degree of hydrogenation of the aromatic carbon-carbon unsaturated bond is high, the glass transition temperature of the hydride is high, so the heat resistance of the polymer layer 8 can be effectively improved. Furthermore, the photoelastic coefficient of the polymer layer 8 can be lowered to reduce the development of retardation.
  • the hydrogenated aromatic vinyl compound-conjugated diene block copolymer particularly preferably has a structure in which both non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds are hydrogenated. .
  • a particularly preferred block form of the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is that block [A] of hydrogenated aromatic vinyl polymer is bound to both ends of block [B] of hydrogenated conjugated diene polymer.
  • Triblock copolymer; a penta polymer block [B] bound to both ends of the polymer block [A], and a polymer block [A] bound to the other end of both polymer blocks [B] It is a block copolymer.
  • a triblock copolymer of [A]-[B]-[A] is particularly preferred because it is easy to produce and the physical properties as a thermoplastic elastomer can be within desired ranges.
  • the hydrogenated aromatic vinyl compound-conjugated diene block copolymer can be produced, for example, by the methods described in International Publication No. 2015/099079 and JP-A-2016-204217.
  • a polymer having a silicon atom-containing polar group may be used as the polymer.
  • Such polymers include, for example, modified products with silicon atom-containing polar groups of the polymers exemplified as polymers that can be used as thermoplastic elastomers. Adhesion between the organic sealing layer and other members can be improved when a polymer having a silicon-containing polar group is employed as the thermoplastic elastomer.
  • the polymer used in the reaction to obtain the modified product may be referred to as "pre-reaction polymer” as appropriate.
  • the modified product may have a structure obtained by graft polymerization of a pre-reaction polymer and a compound having a silicon atom-containing polar group as a monomer, for example.
  • the modified product is not limited by its production method.
  • An alkoxysilyl group is preferable as the silicon atom-containing polar group.
  • Examples of compounds having an alkoxysilyl group as a silicon atom-containing polar group include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltri methoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxysilane Ethylenically unsaturated silane compounds such as roxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,
  • a silicon atom-containing polar group By reacting the pre-reaction polymer with a compound having a silicon atom-containing polar group, a silicon atom-containing polar group can be introduced into the pre-reaction polymer to obtain a modified product having a silicon atom-containing polar group.
  • the amount of the alkoxysilyl group introduced is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, relative to 100 parts by weight of the pre-reaction polymer. , more preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 3 parts by weight or less.
  • the amount of alkoxysilyl groups to be introduced is within the above range, the degree of cross-linking between the alkoxysilyl groups decomposed by water can be prevented from becoming excessively high, so that high adhesiveness can be maintained.
  • substances having alkoxysilyl groups and modification methods used for introducing alkoxysilyl groups include those described in WO 2015/099079.
  • the amount of polar groups introduced can be measured by 1H-NMR spectrum.
  • the measurement can be performed by increasing the number of accumulations.
  • a hydrogenated aromatic vinyl compound-conjugated diene block copolymer and a hydrogenated aromatic vinyl compound-conjugated diene block copolymer One or more types selected from the group consisting of modified products with a silicon atom-containing polar group are preferred. Among them, a hydrogenated aromatic vinyl compound-conjugated diene block copolymer modified with a silicon atom-containing polar group is particularly preferred.
  • the modified product obtained by introducing an alkoxysilyl group as the silicon atom-containing polar group is preferable.
  • introducing an alkoxysilyl group as a polar group into a pre-reaction polymer such as a hydrogenated aromatic vinyl compound-conjugated diene block copolymer is sometimes referred to as silane modification.
  • silane modification an alkoxysilyl group may be directly bonded to the pre-reaction polymer, or may be bonded via a divalent organic group such as an alkylene group.
  • silane-modified product the polymer obtained by silane-modifying the pre-reaction polymer is also referred to as "silane-modified product".
  • a silane-modified hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferable.
  • silane-modified hydrogenated styrene-butadiene block copolymer silane-modified hydrogenated styrene-butadiene-styrene block copolymer, silane-modified hydrogenated styrene-isoprene block copolymer, and hydrogenated styrene
  • silane-modified products selected from the group consisting of silane-modified products of -isoprene-styrene block copolymers are particularly preferred.
  • the weight average molecular weight (Mw) of the polymer is not particularly limited, but is preferably 20,000 or more, more preferably 30,000 or more, still more preferably 35,000 or more, preferably 200,000 or less, and more preferably is 100,000 or less, more preferably 70,000 or less.
  • the weight average molecular weight of the thermoplastic elastomer can be measured in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the molecular weight distribution (Mw/Mn) of the thermoplastic elastomer is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and preferably 1 or more. When the weight-average molecular weight Mw and molecular weight distribution Mw/Mn of the thermoplastic elastomer are within the above ranges, the mechanical strength and heat resistance of the polymer layer 8 can be improved.
  • the glass transition temperature of the thermoplastic elastomer is not particularly limited, but is preferably 40° C. or higher, more preferably 70° C. or higher, preferably 200° C. or lower, more preferably 180° C. or lower, and still more preferably 160° C. or lower. . Further, when a thermoplastic elastomer containing a block copolymer is used, the adhesion and flexibility of the polymer layer 8 can be improved by adjusting the glass transition temperature by changing the weight ratio of each polymer block. You can balance your sexuality.
  • the glass transition temperature of the resin can be measured using a differential scanning calorimeter (DSC) by heating at a rate of 10°C/min.
  • DSC differential scanning calorimeter
  • the second conductive layer 7 may contain the material that constitutes the polymer layer 8 described above inside the second conductive layer 7 .
  • the power generation layer 6 may contain the material constituting the polymer layer 8 described above inside the power generation layer 6 .
  • the function of the hole transport layer and the function of the collector electrode can be achieved by the single second conductive layer 7 .
  • the photoelectric conversion element 100 includes the polymer layer 8 as a buffer layer between the power generation layer 6 and the second conductive layer 7, excellent structural stability and photoelectric conversion efficiency can be achieved. .
  • the photoelectric conversion element of the present invention is an integrated product of the laminate in which the order of the constituent members described above is maintained, the second conductive layer is a porous layer containing at least carbon nanofibers, and the power generation layer and the second conductive layer, as long as the photoelectric conversion element comprises a polymer layer composed of a polymer having a weight average molecular weight of 20,000 or more and 200,000 or less, other It may further comprise layers and the like.
  • the photoelectric conversion element of the present invention may include an extraction electrode made of one or more other conductive members in order to extract electricity collected by the second conductive layer to the outside of the photoelectric conversion element.
  • the method for manufacturing the photoelectric conversion element 100 of the above-described embodiment is not particularly limited.
  • a step of laminating a porous self-supporting sheet to the polymer layer 8 (hereinafter also referred to as step O) in a state in which at least one joint surface between the polymer layer 8 and the polymer layer 8 retains a solvent (hereinafter also referred to as solvent X). ).
  • At least one joint surface between the porous self-supporting sheet serving as the second conductive layer 7 and the power generation layer 6 is a solution in which a polymer for forming the polymer layer 8 is dissolved (hereinafter referred to as It may be manufactured by a method including a step of laminating a porous self-supporting sheet on the power generation layer 6 (hereinafter also referred to as a step P) while holding the solution Y). Any method may further include a step of drying the solvent X or the solution Y.
  • the above-mentioned "joint surface” means the surface of the side which the electric power generation layer 6 and the porous self-supporting sheet correspond.
  • the translucent substrate 1 is prepared.
  • the type of the translucent substrate those listed in the section "Photoelectric conversion element” can be used.
  • a transparent conductive film 2 is formed on the translucent substrate 1 .
  • the method for forming the transparent conductive film 2 is not particularly limited, and for example, known methods such as sputtering and vapor deposition can be employed. Note that the formation of the transparent conductive film 2 may be omitted by using a commercially available translucent substrate having a transparent conductive film formed on the surface thereof.
  • first conductive layer 5 is formed on the transparent conductive film 2 .
  • the first conductive layer 5 is obtained by forming the base layer 3 on the transparent conductive film 2 and then forming the porous semiconductor layer 4 .
  • the method of forming the underlayer 3 is not particularly limited, and for example, it can be formed by spraying a solution containing a material for forming an n-type semiconductor onto the transparent conductive film 2 and heating it if necessary.
  • examples of methods for spraying fine particles include a spray pyrolysis method, an aerosol deposition method, an electrostatic spray method, a cold spray method, and the like.
  • the method for forming the porous semiconductor layer 4 is not particularly limited.
  • the porous semiconductor layer 4 can be formed by applying a solution containing a precursor of an n-type semiconductor onto the underlying layer 3 by a spin coating method or the like and drying the solution. .
  • n-type semiconductor precursors include titanium alkoxides such as titanium tetrachloride (TiCl 4 ), peroxotitanic acid (PTA), titanium ethoxide, and titanium isopropoxide (TTIP); zinc alkoxides and alkoxysilanes; , zirconium alkoxide, titanium diisopropoxide bis(acetylacetonate) and other metal alkoxides;
  • the solvent used for the solution containing the n-type semiconductor precursor is not particularly limited, and for example, an alcohol solution such as ethanol can be used.
  • the temperature and time for drying the solution applied on the underlayer 3 are not particularly limited, and may be appropriately adjusted according to the type of n-type precursor and the type of solvent used.
  • a power generation layer 6 is formed on the first conductive layer 5 .
  • the method of forming the power generation layer 6 includes a vacuum deposition method, a coating method, and the like, but is not particularly limited. It can be formed by firing.
  • examples of precursors of perovskite compounds include lead iodide (PbI 2 ) and methylammonium iodide (CH 3 NH 3 I).
  • the solvent contained in the precursor-containing solution is not particularly limited, and for example, N,N-dimethylformamide, dimethylsulfoxide, or the like can be used. After applying these solutions, a poor solvent can be used to promote the precipitation of the perovskite compound.
  • the term “poor solvent” refers to a solvent in which the perovskite compound does not substantially change during the preparation process. In the manufacturing process, it can be said that the perovskite compound does not substantially change unless the appearance of the perovskite compound changes, such as turbidity of the film, by visual observation.
  • the concentration of the precursor of the perovskite compound in the precursor-containing solution may be set appropriately depending on the solubility of the material constituting the perovskite compound, for example, about 0.5M-1.5M. can be done.
  • the method of applying the precursor-containing solution onto the first conductive layer 5 is not particularly limited, and for example, known coating methods such as spin coating, spraying, and bar coating can be employed.
  • the block copolymer in the obtained solution (i) had a weight average molecular weight (Mw) of 44,900 and a molecular weight distribution (Mw/Mn) of 1.03 (gel permeation using tetrahydrofuran as a solvent). Measured in terms of polystyrene by chromatography (same below).
  • the solution (i) is transferred to a pressure-resistant reactor equipped with a stirrer, and a silica-alumina-supported nickel catalyst (E22U, 60% nickel supported; manufactured by Nikki Chemical Industry Co., Ltd.) is used as a hydrogenation catalyst in the solution (i). ) and 350 parts of dehydrated cyclohexane were added and mixed.
  • the inside of the reactor is replaced with hydrogen gas, hydrogen is supplied while stirring the solution, and a hydrogenation reaction is carried out at a temperature of 170° C. and a pressure of 4.5 MPa for 6 hours to hydrogenate the block copolymer and block A solution (iii) containing the copolymer hydride (ii) was obtained.
  • the weight average molecular weight (Mw) of hydride (ii) in solution (iii) was 45,100 and the molecular weight distribution (Mw/Mn) was 1.04.
  • the solution (iii) was filtered to remove the hydrogenation catalyst. Then, the filtered solution (iii) was added with a phosphorous antioxidant 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10- 0. Tetrakis-t-butyldibenzo[d,f][1.3.2]dioxaphosphepine (“Sumilyzer (registered trademark) GP” manufactured by Sumitomo Chemical Co., Ltd.; hereinafter referred to as “antioxidant A”); 1.0 part of a xylene solution in which 1 part was dissolved was added and dissolved to obtain a solution (iv).
  • Tetrakis-t-butyldibenzo[d,f][1.3.2]dioxaphosphepine (“
  • the solution (iv) is filtered through a Zeta Plus (registered trademark) filter 30H (Cuno, pore size 0.5 ⁇ m to 1 ⁇ m), and another metal fiber filter (pore size 0.4 ⁇ m, Nichidai Co., Ltd.). to remove minute solids.
  • a Zeta Plus (registered trademark) filter 30H Cross-linked polyethylene glycol
  • another metal fiber filter pore size 0.4 ⁇ m, Nichidai Co., Ltd.
  • the solid content is extruded in a molten state into strands, cooled, cut with a pelletizer, and pellets containing the block copolymer hydride and antioxidant A (v) 85 parts were obtained.
  • the weight average molecular weight (Mw) of the hydrogenated block copolymer (hydrogenated block copolymer) in the obtained pellet (v) was 45,000, and the molecular weight distribution (Mw/Mn) was 1.08. .
  • the hydrogenation rate measured by 1 H-NMR was 99.9%.
  • the method of forming the polymer layer 8 is not particularly limited.
  • the solution Y in which the polymer for forming the polymer layer 8 is dissolved is applied to the power generation layer 6, and dried as necessary. be able to.
  • the solvent for dissolving the polymer is not particularly limited, but examples include poor solvents such as chlorobenzene, toluene, and anisole.
  • the polymer those mentioned in the section of "polymer layer" can be used.
  • the concentration of the polymer in the solution Y can be appropriately selected according to the method, since the amount of the polymer carried varies depending on the coating amount and the coating method.
  • the method for applying the solution Y onto the power generation layer 6 is not particularly limited, and for example, known application methods such as spin coating, spraying, and bar coating can be employed.
  • Solvent X is not particularly limited, and examples thereof include poor solvents such as chlorobenzene, toluene, and anisole. By using these poor solvents, for example, when the power generation layer 6 is a perovskite layer made of a perovskite compound, even if the solvent X permeates the power generation layer 6 through the polymer layer 8, the performance of the power generation layer 6 can be maintained. be able to.
  • the method of holding the solvent X on at least one joint surface between the porous self-supporting sheet and the polymer layer 8 is not particularly limited. It may be applied to the molecular layer 8 , or the solvent X may be applied to both the porous self-supporting sheet and the polymer layer 8 .
  • the solvent X can be well retained on at least one joint surface between the porous self-supporting sheet and the polymer layer 8 .
  • the porous self-supporting sheet impregnated with the solvent X can be obtained, for example, by immersing the porous self-supporting sheet in the solvent X and then pulling it out. At that time, the immersion time is not particularly limited, and may be appropriately set according to the type of solvent used. In addition, a method of spraying or dropping the solvent X onto a porous self-supporting sheet placed on a sticking jig or the like can be appropriately selected according to the actual manufacturing process.
  • the solvent for the solution Y is not particularly limited, but examples thereof include poor solvents such as chlorobenzene, toluene, and anisole. By using these poor solvents, the performance of the power generation layer 6 can be maintained, for example, when the power generation layer 6 is a perovskite layer made of a perovskite compound.
  • the polymer in the solution Y those listed in the "polymer layer" section can be used.
  • the concentration of the polymer in the solution Y can be appropriately selected according to the method, since the amount of the polymer carried varies depending on the coating amount and the coating method.
  • the method of holding the solution Y on at least one joint surface of the porous self-supporting sheet and the power generation layer 6 is not particularly limited. 6 , or the solution Y may be applied to both the porous self-supporting sheet and the power generation layer 6 .
  • a specific method for applying the solution Y to the porous self-supporting sheet is not particularly limited, and examples thereof include dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, and die coating. coating method, screen printing method, spray coating method, gravure offset method and the like can be used.
  • the solution Y can be well retained on at least one joint surface between the porous self-supporting sheet and the power generation layer 6 .
  • the porous self-supporting sheet impregnated with the solution Y can be obtained, for example, by immersing the porous self-supporting sheet in the solution Y and then pulling it out.
  • the immersion time is not particularly limited, and may be appropriately set according to the type of solvent and polymer used.
  • a specific method for applying the solution Y to the power generation layer 6 is not particularly limited, and for example, a spin coating method, a spray method, a bar coating method, or the like can be used.
  • a drying step for drying the porous self-supporting sheet may be provided.
  • a known drying method can be employed. Examples of the drying method include hot air drying, vacuum drying, hot roll drying, infrared irradiation, and heat press.
  • the drying temperature and drying time can be appropriately selected depending on the solvent used for solvent X or solution Y, the amount of applied liquid, and the like.
  • the drying temperature is not particularly limited, but is preferably room temperature or higher, more preferably 80° C. or higher, preferably 200° C. or lower, and more preferably 120° C. or lower.
  • the drying time is not particularly limited, but is preferably 1 second or longer, more preferably 10 seconds or longer, preferably 10 minutes or shorter, and more preferably 1 minute or shorter.
  • the hot press method it is preferable to use the hot press method.
  • the hot pressing method the photoelectric conversion element 100 having excellent integrity can be obtained.
  • the pressure during hot pressing is not particularly limited as long as it does not affect the base material or the formed film, and can be, for example, 0.01 to 0.5 MPa.
  • the heating temperature and heating time during hot pressing can be appropriately selected depending on the solvent used for solvent X or solution Y, the amount of applied liquid, and the like.
  • a volatilization path for the solvent it is preferable to heat-press through a member having voids such as a thick wipe, porous rubber, porous metal, or porous ceramic.
  • the manufacturing method described above it is possible to easily manufacture the photoelectric conversion element 100 that is excellent in structural stability and photoelectric conversion efficiency.
  • the method for manufacturing the photoelectric conversion element 100 is not limited to the method described above, and may include steps other than the steps described above as long as the effects of the present invention are not impaired.
  • a perovskite solar cell as a photoelectric conversion element was manufactured by the following procedure.
  • Example 1 [Preparation of Translucent Substrate Formed with Transparent Conductive Film]
  • a conductive glass substrate manufactured by Sigma-Aldrich
  • FTO fluorine-doped tin
  • a translucent substrate with a transparent conductive film formed thereon hereinafter referred to as a “translucent substrate with a transparent conductive film”.
  • first conductive layer A solution obtained by dissolving titanium diisopropoxide bis(acetylacetonate) in isopropanol (manufactured by Sigma-Aldrich) was sprayed onto the surface of the FTO film of the translucent substrate with the transparent conductive film by a spray pyrolysis method. As a result, an underlying layer (thickness: 30 nm) made of titanium dioxide was formed on the FTO film. Next, a solution was prepared by diluting a titanium oxide paste (manufactured by Sigma-Aldrich) with ethanol, the resulting solution was applied to the surface of the underlayer by a spin coating method, and heat-treated at a temperature of 450° C. for 30 minutes. , a porous semiconductor layer (thickness: 120 nm) made of titanium dioxide (TiO 2 ) was formed to obtain a first conductive layer.
  • N,N-dimethylformamide containing lead iodide (PbI 2 ) at a concentration of 1.0 M and methylammonium iodide (CH 3 NH 3 I) at a concentration of 1.0 M as a solution (1) containing a perovskite compound precursor (DMF) solution was prepared.
  • the obtained solution (1) is applied to the surface of the first conductive layer by a spin coating method while dropping chlorobenzene, and then baked at a temperature of 100 ° C. for 10 minutes to form a perovskite layer (thickness 450 nm) was formed.
  • porous self-supporting sheet A porous self-supporting sheet containing single-walled CNTs was produced according to the following procedure.
  • Single-walled CNTs manufactured by Nippon Zeon Co., Ltd., product name “ZEONANO SG101”, average Diameter: 3.5 nm; G/D ratio: 2.1;
  • This coarse dispersion is filled into a high-pressure homogenizer (manufactured by Mitsuyu Co., Ltd., product name "BERYU SYSTEM PRO") having a multi-stage pressure control device (multi-stage pressure reducer) that applies back pressure during dispersion, and a pressure of 100 MPa is applied to the coarse dispersion. Dispersion processing of the dispersion liquid was performed.
  • a shearing force is applied to the coarse dispersion to disperse the fibrous carbon nanostructures containing single-walled CNTs, thereby obtaining a fibrous carbon nanostructures dispersion containing single-walled CNTs. Obtained.
  • the dispersion treatment was carried out for 10 minutes while returning the dispersion liquid discharged from the high-pressure homogenizer to the high-pressure homogenizer again.
  • the resulting carbon film (A) had a size equivalent to that of a membrane filter, had excellent film-forming properties, and maintained the state of the film even after it was peeled off from the filter, exhibiting excellent self-supporting properties. had.
  • the density was 0.85 g/cm 3 . From these results, it was found that the carbon membrane (A) was a porous self-supporting sheet (A).
  • the porous self-supporting sheet (A) was immersed in a solution of 10 mg of the polymer synthesized according to the above production example dissolved in 1 ml of chlorobenzene for 20 seconds, and then the porous self-supporting sheet was removed from the solution.
  • the sheet (A) is pulled up, the porous self-supporting sheet (1) is laminated on the pre-press laminate heated on a hot plate at a temperature of 80 ° C., and the resulting laminate is placed at zero from the porous self-supporting sheet (1) side.
  • a perovskite solar cell was fabricated according to Example 1, except that it was dried while being hot-pressed through a wipe at a pressure of 0.05 MPa.
  • Example 1 A perovskite solar cell was fabricated according to Example 1, except that the porous self-supporting sheet (A) was placed directly on the perovskite layer without forming a polymer layer.
  • Example 3 A perovskite solar cell was fabricated in the same manner as in Example 1, except that the formed perovskite layer was subjected to Li salt treatment as a surface treatment of the perovskite layer and then the polymer layer was formed.
  • Example 2 A perovskite solar cell was fabricated according to Example 2, except that the porous self-supporting sheet (A) was placed directly on the perovskite layer without forming a polymer layer.
  • Example 4 A perovskite solar cell was produced according to Example 1, except that a porous self-supporting sheet was produced without using a dispersant.
  • Example 3 A perovskite solar cell was fabricated according to Example 3, except that the porous self-supporting sheet (A) was placed directly on the perovskite layer without forming a polymer layer.
  • Example 5 A perovskite solar cell was fabricated according to Example 3, except that the perovskite layer thus formed was subjected to Li salt treatment as a surface treatment of the perovskite layer, and then the polymer layer was formed.
  • Example 4 A perovskite solar cell was fabricated according to Example 4, except that the porous self-supporting sheet (A) was placed directly on the perovskite layer without forming a polymer layer.
  • Tables 1 and 2 show the results of examining the presence or absence of peeling of the second conductive layer immediately after the production of the obtained perovskite solar cells and after a predetermined period of time.

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US4262161A (en) * 1980-01-16 1981-04-14 Shell Oil Company Covered solar cell assembly
WO2006011655A1 (ja) 2004-07-27 2006-02-02 National Institute Of Advanced Industrial Scienceand Technology 単層カーボンナノチューブおよび配向単層カーボンナノチューブ・バルク構造体ならびにそれらの製造方法・装置および用途
WO2015099079A1 (ja) 2013-12-26 2015-07-02 日本ゼオン株式会社 封止フィルム、有機エレクトロルミネッセンス表示装置及び有機半導体デバイス
JP2016204217A (ja) 2015-04-24 2016-12-08 日本ゼオン株式会社 複層ガラス
JP6339037B2 (ja) 2015-03-18 2018-06-06 株式会社東芝 光電変換素子およびその製造方法
WO2021153218A1 (ja) * 2020-01-31 2021-08-05 日本ゼオン株式会社 光電変換素子及びその製造方法
JP2021132108A (ja) * 2020-02-19 2021-09-09 シャープ株式会社 光電変換素子、及び光電変換素子の製造方法

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JPS6339037U (https=) 1986-08-30 1988-03-14
CN109599412B (zh) * 2017-09-30 2020-09-08 清华大学 一种光电自储能器件
KR102817168B1 (ko) * 2019-12-30 2025-06-05 엘지디스플레이 주식회사 페로브스카이트 광전자 소자 및 이의 제조방법

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US4262161A (en) * 1980-01-16 1981-04-14 Shell Oil Company Covered solar cell assembly
WO2006011655A1 (ja) 2004-07-27 2006-02-02 National Institute Of Advanced Industrial Scienceand Technology 単層カーボンナノチューブおよび配向単層カーボンナノチューブ・バルク構造体ならびにそれらの製造方法・装置および用途
WO2015099079A1 (ja) 2013-12-26 2015-07-02 日本ゼオン株式会社 封止フィルム、有機エレクトロルミネッセンス表示装置及び有機半導体デバイス
JP6339037B2 (ja) 2015-03-18 2018-06-06 株式会社東芝 光電変換素子およびその製造方法
JP2016204217A (ja) 2015-04-24 2016-12-08 日本ゼオン株式会社 複層ガラス
WO2021153218A1 (ja) * 2020-01-31 2021-08-05 日本ゼオン株式会社 光電変換素子及びその製造方法
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