WO2023234136A1 - Procédé de production de couche fonctionnelle d'élément de conversion photoélectrique et procédé de production d'élément de conversion photoélectrique - Google Patents

Procédé de production de couche fonctionnelle d'élément de conversion photoélectrique et procédé de production d'élément de conversion photoélectrique Download PDF

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WO2023234136A1
WO2023234136A1 PCT/JP2023/019307 JP2023019307W WO2023234136A1 WO 2023234136 A1 WO2023234136 A1 WO 2023234136A1 JP 2023019307 W JP2023019307 W JP 2023019307W WO 2023234136 A1 WO2023234136 A1 WO 2023234136A1
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mist
liquid
specific component
manufacturing
substrate
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PCT/JP2023/019307
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English (en)
Japanese (ja)
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桂也 ▲徳▼田
哲雄 奥山
啓介 松尾
奈織美 瀧本
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東洋紡株式会社
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    • 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
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • 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
    • H10K71/10—Deposition of organic active material

Definitions

  • the present invention relates to a method for manufacturing a functional layer of a photoelectric conversion element selected from an active layer, an electron transport layer, and a hole transport layer, and a method for manufacturing a photoelectric conversion element.
  • Patent Documents 1 and 2 disclose methods for manufacturing functional layers that constitute photoelectric conversion elements such as active layers, electron transport layers, and hole transport layers.
  • Patent Documents 1 and 2 disclose methods for manufacturing functional layers that constitute photoelectric conversion elements such as active layers, electron transport layers, and hole transport layers.
  • Patent Documents 1 and 2 disclose methods for manufacturing functional layers that constitute photoelectric conversion elements such as active layers, electron transport layers, and hole transport layers.
  • Patent Documents 1 and 2 disclose methods for manufacturing functional layers that constitute photoelectric conversion elements such as active layers, electron transport layers, and hole transport layers.
  • Patent Document 3 discloses a method of forming an active layer by turning a solution forming the active layer into a mist and spraying it onto a substrate.
  • the present invention includes the following method for manufacturing a functional layer of a photoelectric conversion element and method for manufacturing a photoelectric conversion element.
  • a method for manufacturing a functional layer of a photoelectric conversion element selected from an active layer, an electron transport layer and a hole transport layer comprising: generating a first mist from a first liquid containing a specific component forming the functional layer and a first organic solvent; generating a second mist from a second liquid containing a second organic solvent; a conveying step of introducing the first mist and the second mist into a chamber in which a substrate is placed and depositing the specific component on the substrate;
  • a method for manufacturing a functional layer of a photoelectric conversion element comprising a heating step of heating the substrate to which the specific component is attached to form the functional layer.
  • the specific component is deposited on the cooled substrate.
  • the functional layer is an electron transport layer or a hole transport layer, and the first liquid contains a metal compound or a conductive organic compound as the specific component. Manufacturing method described.
  • the functional layer is an active layer, and the first liquid contains at least one of a p-type semiconductor compound and an n-type semiconductor compound as the specific component. Manufacturing method described.
  • a method for manufacturing a photoelectric conversion element comprising the step of forming a functional layer by the method according to any one of [1] to [11].
  • the manufacturing method according to [12], wherein the photoelectric conversion element is an organic thin film solar cell.
  • the manufacturing method of the present invention by introducing a first mist containing a specific component forming a functional layer of a photoelectric conversion element into a chamber, the specific component is deposited on a substrate placed in the chamber, A functional layer precursor can be deposited on a substrate, and by heating it, a functional layer can be formed on the substrate.
  • the first mist is Volatization of the solvent from the mist can be suppressed. Therefore, a functional layer precursor containing a specific component can be efficiently formed on the substrate.
  • the surface properties of the functional layer precursor formed on the substrate are improved, and it becomes possible to easily obtain a functional layer having a smooth surface.
  • FIG. 1 shows a configuration example of a manufacturing system used in the manufacturing method of the present invention.
  • the present invention relates to a method for manufacturing a functional layer of a photoelectric conversion element.
  • a photoelectric conversion element is an element that converts light energy and electrical energy.
  • an organic EL device that emits light by the action of excitons formed by the recombination of electrons and holes, and a device that converts light into electricity.
  • FIG. 1 shows an example of the configuration of an organic thin film solar cell, which is a type of photoelectric conversion element.
  • a photoelectric conversion element (organic thin film solar cell) 1 has a structure in which an active layer 4 is disposed between a cathode 2 and an anode 6. It is preferable that the photoelectric conversion element 1 further includes an electron transport layer 3 and a hole transport layer 5, in which the electron transport layer 3 is arranged between the cathode 2 and the active layer 4, and the hole transport layer 5 is arranged between the anode 6 and the active layer. It is placed between 4. That is, the photoelectric conversion element 1 preferably has a structure in which the cathode 2, the electron transport layer 3, the active layer 4, the hole transport layer 5, and the anode 6 are arranged in this order.
  • the photoelectric conversion element 1 has a base material 7, and the cathode 2 or the anode 6 may be arranged on the base material 7. In FIG. 1, the cathode 2 is placed on the base material 7.
  • the active layer, the electron transport layer, and the hole transport layer are referred to as functional layers.
  • the active layer is a layer where photoelectric conversion is performed, and contains a p-type semiconductor compound and an n-type semiconductor compound.
  • the photoelectric conversion element receives light, the light is absorbed by the active layer, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is taken out from the cathode and the anode.
  • p-type semiconductor compound can be used as the p-type semiconductor compound and the n-type semiconductor compound.
  • p-type semiconductor compounds include conjugated copolymer semiconductor compounds such as polythiophene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyacetylene, and polyaniline; copolymer semiconductor compounds such as oligothiophene substituted with an alkyl group or other substituents; etc.
  • a copolymer semiconductor compound obtained by copolymerizing two or more types of monomer units may also be used.
  • n-type semiconductor compounds include fullerene and its derivatives, octaazaporphyrin, and perfluorinated compounds in which the hydrogen atoms of p-type semiconductor compounds are replaced with fluorine atoms (for example, perfluoropentacene and perfluorophthalocyanine).
  • polymer compounds containing aromatic carboxylic anhydrides such as naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic anhydride, perylenetetracarboxylic acid diimide, or imidized products thereof as a skeleton can be used. You can also do it.
  • Examples of the layer structure of the active layer include a thin film laminated structure in which a p-type semiconductor compound and an n-type semiconductor compound are laminated, and a bulk heterojunction structure having a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed.
  • the bulk heterojunction structure has a layer (i-layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed.
  • the i-layer has a structure in which a p-type semiconductor compound and an n-type semiconductor compound are phase-separated, carrier separation occurs at the phase interface, and the generated carriers (holes and electrons) are transported to the electrode.
  • the mass ratio of the p-type semiconductor compound to the n-type semiconductor compound (p-type semiconductor compound/n-type semiconductor compound) in the i-layer is set to 0 from the viewpoint of improving photoelectric conversion efficiency by obtaining a good phase separation structure. .5 or more is preferable, more preferably 1 or more, 4 or less is preferable, 3 or less is more preferable, and 2 or less is even more preferable.
  • the active layer may contain additives in addition to the p-type semiconductor compound and the n-type semiconductor compound.
  • the phase separation structure of the p-type semiconductor compound and the n-type semiconductor compound in the bulk heterojunction active layer affects light absorption, exciton generation/diffusion, exciton dissociation (carrier separation), carrier transport, etc. It is expected that good photoelectric conversion efficiency will be achieved by optimizing the phase separation structure.
  • the active layer contains an additive having high affinity with the p-type semiconductor compound or the n-type semiconductor compound, an active layer having a preferable phase separation structure can be obtained, and photoelectric conversion efficiency can be improved.
  • additives include aliphatic hydrocarbon compounds having 8 to 20 carbon atoms and aromatic compounds having 8 to 20 carbon atoms. These aliphatic hydrocarbon compounds and aromatic compounds may have a substituent. Examples of substituents that the aliphatic hydrocarbon compound may have include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, amino groups, carbamoyl groups, carbonyloxy groups, carboxyl groups, carbonyl groups, aromatic groups, etc. It will be done.
  • substituents that aromatic compounds may have include halogen atoms, hydroxyl groups, cyano groups, amino groups, amide groups, carbonyloxy groups, carboxyl groups, carbonyl groups, oxycarbonyl groups, silyl groups, alkenyl groups, and alkynyl groups. group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aromatic group, and the like.
  • Preferred specific examples of the additive include benzene which may have a substituent, naphthalene which may have a substituent, and octane which may have a substituent.
  • a halogen atom is particularly preferable.
  • the thickness of the active layer is preferably 70 nm or more, more preferably 90 nm or more, even more preferably 100 nm or more, and preferably 1000 nm or less, more preferably 750 nm or less, and even more preferably 500 nm or less.
  • the electron transport layer is a layer that extracts electrons from the active layer to the cathode.
  • the constituent material of the electron transport layer is preferably an electron transport material that improves the efficiency of electron extraction, and may be an organic compound or an inorganic compound, but an inorganic compound is preferable.
  • the inorganic compound constituting the electron transport layer is preferably a metal compound, and examples include salts of alkali metals such as lithium, sodium, potassium, and cesium, and metal oxides.
  • alkali metals such as lithium, sodium, potassium, and cesium
  • fluoride salts such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride are preferable as alkali metal salts, and as metal oxides, titanium oxide (TiOx) and zinc oxide (ZnOx) are preferable.
  • Metal oxides having n-type semiconductor properties such as ) are preferred.
  • Examples of the organic compound constituting the electron transport layer include conductive organic compounds, such as polyethyleneimine ethoxylate.
  • the thickness of the electron transport layer is preferably 0.1 nm or more, more preferably 0.5 nm or more, even more preferably 1.0 nm or more, and preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less.
  • the hole transport layer is a layer that extracts holes from the active layer to the anode.
  • the constituent material of the hole transport layer is not particularly limited as long as it is a hole transporting material that can improve the efficiency of hole extraction, and examples thereof include conductive organic compounds and metal compounds.
  • Examples of the conductive organic compound constituting the hole transport layer include conductive polymers in which polythiophene, polypyrrole, polyacetylene, triphenylene diamine, polyaniline, etc. are doped with sulfonic acid and/or iodine, etc., and conductive polymers having sulfonyl groups as substituents. Examples include polythiophene derivatives and arylamines. Examples of the metal compound constituting the hole transport layer include metal oxides having p-type semiconductor characteristics such as molybdenum trioxide, vanadium pentoxide, and nickel oxide, and metals such as gold, indium, silver, and palladium. Alternatively, the hole transport layer may be formed from a p-type semiconductor compound.
  • a conductive polymer doped with sulfonic acid is preferable as a constituent material of the hole transport layer, and poly(3,4-ethylenedioxythiophene) poly(styrene sulfonic acid) is a polythiophene derivative doped with polystyrene sulfonic acid.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrene sulfonic acid) is a polythiophene derivative doped with polystyrene sulfonic acid.
  • metal oxides such as molybdenum oxide and vanadium oxide are preferred.
  • the thickness of the hole transport layer is preferably 0.2 nm or more, more preferably 0.5 nm or more, even more preferably 1.0 nm or more, and preferably 400 nm or less, more preferably 200 nm or less, even more preferably 100 nm or less, and 70 nm or less. The following are even more preferred.
  • the cathode and anode are composed of conductive materials. At least one of the cathode and the anode is preferably translucent, that is, it is preferably a transparent electrode. This allows light to pass through the transparent electrode and reach the active layer.
  • the cathode is composed of a conductive material that has a smaller work function than the anode.
  • the cathode has a function of taking out electrons generated in the active layer.
  • Examples of cathode constituent materials include conductive metal oxides such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, and zinc oxide; gold, platinum, etc. , silver, chromium, cobalt, and their alloys.
  • a conductive metal oxide with translucency such as ITO, zinc oxide, or tin oxide, and it is particularly preferable to use ITO.
  • the anode is composed of a conductive material that has a larger work function than the cathode.
  • the anode has a function of taking out holes generated in the active layer.
  • the constituent materials of the anode include, for example, metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, magnesium, and their alloys; lithium fluoride and inorganic salts such as cesium fluoride; and metal oxides such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide.
  • a conductive n-type semiconductor compound such as zinc oxide
  • a material having a small work function such as ITO may be used as the anode material.
  • the thickness of the cathode and anode is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 50 nm or more, and preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 500 nm or less.
  • the constituent material of the base material is not particularly limited, and is appropriately set depending on the use of the photoelectric conversion element.
  • the base material include inorganic materials such as quartz, glass, sapphire, and titania; polyester (e.g., polyethylene terephthalate, polyethylene naphthalate), polyether sulfone, polyimide, polyamide (e.g., nylon), polystyrene, and polyvinyl.
  • Organic materials such as alcohol, ethylene vinyl alcohol copolymer, fluororesin, vinyl chloride, polyolefin (e.g.
  • Material Polyethylene, polypropylene), cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, epoxy resin, etc.
  • Material Paper material: Composite materials made of metals such as stainless steel, titanium, and aluminum coated with resin.
  • Examples of the shape of the base material include a plate shape, a film shape, and a sheet shape.
  • the thickness of the base material is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and preferably 20 mm or less, and more preferably 10 mm or less.
  • the method for manufacturing a functional layer of a photoelectric conversion element of the present invention includes producing a first mist from a first liquid containing a specific component forming a functional layer and an organic solvent (hereinafter referred to as "first organic solvent”).
  • first organic solvent an organic solvent
  • second organic solvent a second organic solvent
  • second mist generation step a conveyance step in which the first mist and the second mist are introduced into a chamber in which the substrate is placed, and a specific component is deposited on the substrate; and a heating step of heating the attached substrate to form a functional layer.
  • the manufacturing method of the present invention by introducing the first mist containing the specific component forming the functional layer into the chamber, the specific component is deposited on the substrate placed in the chamber, and the functional layer precursor is formed. can be formed into a film on a substrate, and by heating this, a functional layer can be formed on the substrate.
  • the first mist to accompany the second mist containing the second organic solvent, it is possible to prevent the solvent from volatilizing from the first mist before the first mist is transported to the substrate. For example, precipitation of specific components can be suppressed. Therefore, it becomes possible to efficiently form a functional layer precursor containing a specific component on the substrate.
  • the surface properties of the functional layer precursor formed on the substrate will be improved, and that it will be possible to form a functional layer with a smoother surface.
  • a first mist is generated from a first liquid containing a specific component forming a functional layer and a first organic solvent.
  • the first liquid contains a component that forms the functional layer, and in the present invention, the component that forms the functional layer is referred to as a "specific component.”
  • the specific component can be set as appropriate depending on the type of functional layer to be formed.
  • the functional layer is an electron transport layer or a hole transport layer
  • the first liquid may contain a metal compound or a conductive material as the specific component.
  • the organic compound contains a natural organic compound.
  • the first liquid preferably contains at least one of a p-type semiconductor compound and an n-type semiconductor compound as a specific component.
  • the first liquid may contain both a p-type semiconductor compound and an n-type semiconductor compound as specific components.
  • the first liquid may further contain an additive as a specific component in addition to at least one of a p-type semiconductor compound and an n-type semiconductor compound.
  • an additive as a specific component in addition to at least one of a p-type semiconductor compound and an n-type semiconductor compound.
  • the first liquid contains a first organic solvent along with specific components.
  • the first organic solvent is not particularly limited as long as it can dissolve or disperse a specific component, and examples include aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, and decane; toluene, xylene, mesitylene, Aromatic hydrocarbons such as cyclohexylbenzene, naphthalene, methylnaphthalene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin, decalin; chloroform, methylene chloride, dichloroethane, trichloroethane, Halogenated hydrocarbons such as trichloroethylene, chlorobenzene, orthodichlorobenzene, and chlor
  • ketones such as ethyl acetate, isopropyl acetate, butyl acetate, methyl lactate; ethers such as ethyl ether, tetrahydrofuran, cyclopentyl methyl ether, dibutyl ether, diphenyl ether, dioxane; dimethylformamide, N-methylpyrrolidone (NMP) , 1,3-dimethyl-2-imidazolidinone (DMI), and amides such as dimethylacetamide.
  • NMP N-methylpyrrolidone
  • DMI 1,3-dimethyl-2-imidazolidinone
  • amides such as dimethylacetamide.
  • the first liquid may be a solution in which a specific component is dissolved, or a dispersion in which a specific component is dispersed. It is preferable that the specific component is uniformly dissolved or dispersed in the first liquid.
  • the specific component is a metal oxide
  • the first liquid can be a dispersion.
  • the specific component is preferably dispersed in the solvent as fine particles.
  • the concentration of the specific component in the first liquid (the content of the specific component in 100 g of the first liquid) is not particularly limited.
  • the concentration of the specific component in the first liquid is determined so that the mist state is maintained during the first mist being transported into the chamber in the transport process until it is deposited on the substrate, and the concentration of the specific component is determined on the substrate.
  • the concentration may be appropriately set so as to obtain a desired film formation rate.
  • the concentration of the specific component in the first liquid is, for example, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and preferably 20% by mass or less, More preferably, it is 10% by mass or less.
  • the concentration of the specific component in the first liquid may be adjusted depending on the thickness of the functional layer to be formed. For example, if the thickness of the functional layer is less than 100 nm, the concentration of the specific component in the first liquid is 0. 0.05% by mass or more is preferred, 0.1% by mass or more is more preferred, 0.5% by mass or more is even more preferred, and 10% by mass or less is preferred, more preferably 5% by mass or less, and even more preferably 3% by mass or less. . When the thickness of the functional layer is 100 nm or more, the specific component concentration of the first liquid is preferably 1% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and 20% by mass. The content is preferably at most 10% by mass, more preferably at most 10% by mass.
  • the method of turning the first liquid into a mist is not particularly limited.
  • Methods of making the first liquid into a mist include a method of spraying the first liquid from a nozzle to make it a mist, a method of applying ultrasonic waves to the first liquid to make it a mist, and a method of bubbling the first liquid. Examples include a method of turning it into a mist. Further, other known misting methods may be employed. Among these, it is preferable to apply ultrasonic waves to the first liquid to form it into a mist, which makes it easier to generate the first mist more uniformly.
  • the frequency of the ultrasonic waves when applying ultrasonic waves to the first liquid to form a mist is not particularly limited.
  • the larger the frequency, the smaller the particle size of the first mist, so the frequency may be set appropriately depending on the thickness of the functional layer desired to be formed on the substrate and the surface properties of the functional layer.
  • the frequency of the ultrasonic wave when generating a mist with an average particle size of 10 ⁇ m or more, is preferably 10 kHz or more and less than 0.7 MHz.
  • the frequency of the ultrasonic wave is preferably 0.7 MHz or more and 5 MHz or less, more preferably 1.5 MHz or more and 3.5 MHz or less.
  • the first mist is generated from the first liquid in a first mist generating section that has a space inside to generate the first mist. It is preferable that the first misting section has an inlet and an outlet, and is configured such that the carrier gas can be introduced from the inlet and the carrier gas can be discharged from the outlet. Thereby, the first mist generated in the first mist forming section can be transported to the outside of the first misting section together with the carrier gas.
  • the first liquid is stored in a first storage tank, and by applying ultrasonic waves to the first liquid stored in the first storage tank, the first mist is generated from the first liquid. It is preferable to generate the first mist.
  • the first storage tank is preferably installed in the internal space of the first misting section.
  • the ultrasonic transducer may be installed on the inner surface (wall surface or bottom surface) of the first storage tank that is in contact with the first liquid, or may be installed in the first liquid instead of on the inner surface of the first storage tank.
  • a second mist is generated from a second liquid containing a second organic solvent.
  • the second organic solvent is preferably one that can dissolve or disperse the specific component, and is preferably one that is compatible with the first organic solvent.
  • the organic solvents exemplified as the first organic solvent can be used.
  • the second organic solvent is preferably an organic solvent in the same category as the first organic solvent.
  • the first organic solvent and the second organic solvent are both alcohols or aromatic hydrocarbons.
  • the second organic solvent is the same solvent as the first organic solvent.
  • hexane is used as the first organic solvent
  • hexane is also used as the second organic solvent. The same applies when other substances are used as the first organic solvent. This makes it easier to prevent the solvent from volatilizing from the first mist and precipitation of specific components before the first mist is transported to the substrate.
  • the second liquid does not substantially contain the specific component.
  • concentration of the specific component in the second liquid (the content of the specific component in 100 g of the second liquid) is smaller than the concentration of the specific component in the first liquid.
  • concentration of the specific component in the second liquid is, for example, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and even more preferably 0.01% by mass or less. preferable.
  • the concentration of the specific component in the second liquid is preferably 1/50 or less, more preferably 1/100 or less, of the concentration of the specific component in the first liquid.
  • the second liquid basically consists of only the second organic solvent.
  • the solute concentration of the second liquid is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and even more preferably 0.05% by mass or less. Particularly preferred is .01% by mass or less.
  • the solute concentration of the second liquid is preferably 1/20 or less, more preferably 1/50 or less, and even more preferably 1/100 or less of the concentration of the specific component in the first liquid.
  • solute concentration described here is preferably the concentration of the solute and solid content combined.
  • the second liquid may also be substantially free of water.
  • concentration of the second organic solvent in the second liquid is preferably 99% by mass or more, more preferably 99.5% by mass or more, and even more preferably 99.9% by mass or more.
  • the method of turning the second liquid into a mist is not particularly limited.
  • the method of making a mist of the second liquid refer to the above explanation of making a mist of the first liquid, and preferably, applying ultrasonic waves to the second liquid to generate the second mist. This makes it easy to generate the second mist having the same particle size as the first mist. Therefore, when the first mist and the second mist are transported by the carrier gas in the subsequent transport step, it becomes easy to control the amount of transport of the first mist and the second mist.
  • the second mist is generated from the second liquid in a second mist generating section that has a space inside to generate the second mist.
  • the second misting section has an inlet and an outlet, and is configured such that the carrier gas can be introduced from the inlet and the carrier gas can be discharged from the outlet. Thereby, the second mist generated in the second mist forming section can be transported to the outside of the second misting section together with the carrier gas.
  • the second liquid is stored in a second storage tank, and by applying ultrasonic waves to the second liquid stored in the second storage tank, the second mist is generated from the second liquid. It is preferable to generate a second mist.
  • the second storage tank is preferably installed in the internal space of the second misting section.
  • the ultrasonic transducer may be installed on the inner surface (wall surface or bottom surface) of the second storage tank that is in contact with the second liquid, or may be installed in the second liquid instead of on the inner surface of the second storage tank.
  • the first mist and the second mist are introduced into the chamber in which the substrate is placed.
  • the chamber has an interior space, and a base is disposed in the interior space.
  • the first mist and the second mist adhere to the substrate, forming a functional layer precursor containing a specific component on the substrate. can do.
  • the volatilization rate of the organic solvent within the chamber can be adjusted.
  • the volatilization rate of the organic solvent on the substrate can be adjusted, and the rate of volatilization of the organic solvent on the substrate can be adjusted. It is also expected that surface properties can be improved.
  • the first mist and the second mist are introduced into the chamber while being transported by a carrier gas.
  • the chamber has an inlet for a first mist and a second mist.
  • the chamber may be provided with an outlet.
  • the first mist and the second mist can be circulated within the chamber, and the internal space of the chamber can be replaced with the first mist and the second mist. can.
  • the first mist and the second mist may be introduced into the chamber separately, or the first mist and the second mist may be combined before being introduced into the chamber.
  • a flow path connecting the outlet of the first misting section and the chamber and a flow path connecting the outlet of the second misting section and the chamber are provided separately.
  • the chamber is separately provided with a first mist inlet and a second mist inlet.
  • the flow path extending from the outlet of the second misting section may be connected in the middle of the channel connecting the outlet of the first misting section and the chamber, or the outlet of the second misting section and the chamber may be connected.
  • a flow path extending from the outlet of the first misting section may be connected in the middle of the flow path connecting the two.
  • the chamber is provided with an inlet through which the first mist and the second mist are combined and introduced.
  • the first mist generated in the first mist forming section and the second mist generated in the second mist forming section are transported by different carrier gases.
  • the flow path extending from the outlet of the first mist forming section is connected to the inlet of the second misting section, and the second mist forming section is connected to the inlet of the second mist forming section.
  • a channel extending from the outlet of the second misting section may be connected to the chamber, a channel extending from the outlet of the second misting section may be connected to an inlet of the first misting section, and a channel extending from the outlet of the first misting section may be connected to the chamber. It may also be connected to a chamber. In these cases, the first mist generated in the first mist forming section and the second mist generated in the second mist forming section are transported by a common carrier gas.
  • the type of carrier gas is not particularly limited as long as it is inert to the specific component and the organic solvent contained in the first mist and second mist.
  • the carrier gas include inert gases such as nitrogen and argon, air, oxygen, and hydrogen.
  • the flow rate of the carrier gas may be appropriately set depending on the amount of first mist generated, the amount of second mist generated, the size of the chamber, the size of the substrate installed in the chamber, and the like.
  • the conveyance step it is preferable to introduce the first mist and the second mist into the chamber after merging the first mist and the second mist.
  • the substrate is placed in the chamber in advance.
  • the substrate placed in the chamber is appropriately set depending on the type of functional layer to be formed.
  • the substrate is placed in the chamber so that a surface to which the specific component adheres and a surface to which the specific component does not adhere are formed.
  • the substrate When forming an electron transport layer as a functional layer, the substrate may be placed in the chamber as follows.
  • the substrate has at least a cathode, and the substrate is installed in the chamber so that the cathode serves as an attachment surface for the specific component, or the substrate has at least an active layer, and the active layer serves as an attachment surface for the specific component. All you have to do is place the base inside the chamber.
  • the substrate with the active layer may further include an anode or an anode and a hole transport layer.
  • the base further has a base material on the side of the cathode opposite to the surface on which the specific component is attached, a base material on the side of the anode opposite to the surface on which the active layer is disposed, or a base material on the side of the anode opposite to the surface on which the active layer is disposed, or a hole in the anode.
  • a base material may be provided on the opposite side of the surface on which the transport layer is arranged.
  • the substrate When forming a hole transport layer as a functional layer, the substrate may be placed in the chamber as follows.
  • the base has at least an anode, and the base is installed in the chamber so that the anode serves as an attachment surface for the specific component, or the base has at least an active layer, and the active layer serves as an attachment surface for the specific component. All you have to do is place the base inside the chamber.
  • the substrate with the active layer may further have a cathode or a cathode and an electron transport layer.
  • the base further has a base material on the anode opposite to the surface on which the specific component is attached, a base material on the cathode opposite to the surface on which the active layer is disposed, or A base material may be provided on the opposite side of the surface on which the transport layer is arranged.
  • the substrate When forming an active layer as a functional layer, the substrate may be placed in the chamber as follows.
  • the substrate has at least a cathode, and the substrate is installed in the chamber so that the cathode serves as an attachment surface for the specific component, or the substrate has at least an electron transport layer and a cathode, and the electron transport layer serves as an attachment surface for the specific component.
  • the substrate is installed in the chamber such that the substrate has at least an anode, and the anode is the attachment surface for the specific component, or the substrate has at least a hole transport layer.
  • a substrate may be installed in the chamber so that the substrate has an anode and the hole transport layer serves as the surface to which the specific component is attached.
  • the base further has a base material on the side of the cathode opposite to the surface on which the specific component is attached, a base material on the cathode opposite to the surface on which the electron transport layer is disposed, and a base material on the side of the cathode opposite to the surface on which the electron transport layer is disposed,
  • the anode may have a base material on the side opposite to the surface to which the hole transport layer is disposed, or the anode may have a base material on the side opposite to the surface on which the hole transport layer is disposed.
  • the base is arranged so as to be in contact with the internal space of the chamber, and the first mist and the second mist are introduced into the internal space of the chamber, so that the first mist and the second mist adhere to the base.
  • specific components are deposited on the substrate.
  • the functional layer precursor can be formed on the substrate.
  • the temperature of the substrate is preferably maintained at 80°C or lower, more preferably 60°C or lower, and even more preferably 40°C or lower.
  • the amount of the first mist introduced into the chamber is appropriately set depending on the amount of the specific component to be deposited on the substrate, that is, the film thickness of the functional layer precursor.
  • the amount of the second mist introduced into the chamber is appropriately set depending on the surface properties of the functional layer precursor formed on the substrate. As mentioned above, by introducing the second mist into the chamber together with the first mist, the surface properties of the functional layer precursor formed on the substrate are improved, and by heating in the subsequent heating step, it is smoothed. It is possible to form a functional layer having a surface of
  • the chamber may be set at a positive pressure, ie, the pressure within the chamber may be higher than the pressure outside the chamber. This can prevent contamination within the chamber.
  • the mounting table of the substrate has a temperature adjustment means, and the substrate can be cooled by placing the substrate on such a mounting table and cooling the mounting table with the temperature adjustment means.
  • the cooling temperature of the substrate is preferably set within a range of 5° C. to 20° C., for example.
  • the temperature adjustment means of the mounting table may include both cooling and heating means.
  • the first mist generation step it is preferable to generate the first mist from the cooled first liquid. That is, in the first mist generation step, it is preferable to cool the first liquid and generate the first mist from the cooled first liquid. As a result, the volatilization of the organic solvent from the first mist is suppressed until the first mist is transported to the substrate, making it possible to deposit more organic solvent along with the specific component onto the substrate. Become.
  • the cooling temperature of the first liquid may be set, for example, in a range of 5°C to 20°C.
  • the second mist may be generated from the cooled second liquid. That is, in the second mist generation step, the second liquid may be cooled and the second mist may be generated from the cooled second liquid. Thereby, when the second mist merges with the first mist, the first mist is cooled, and it becomes possible to deposit a larger amount of the organic solvent together with the specific component on the substrate.
  • the cooling temperature of the second liquid may be set, for example, in the range of 5°C to 20°C.
  • the substrate to which the specific component has been attached is heated, that is, the functional layer precursor on the substrate is heated to form a functional layer on the substrate.
  • the heating temperature in the heating step is within a range that can volatilize the first organic solvent and second organic solvent attached to the substrate, is below the boiling point or decomposition point of the specific component, and is within a range that does not adversely affect the substrate. You can set it as appropriate.
  • the lower limit of the heating temperature may be, for example, 40°C or higher, 80°C or higher, 100°C or higher, 120°C or higher, or 150°C or higher.
  • the upper limit of the heating temperature may be, for example, 350°C or less, 300°C or less, 250°C or less, or 200°C or less.
  • the substrate to which the specific component is attached may be heated while it is placed in the chamber, or the substrate to which the specific component is attached may be taken out of the chamber or heated while the chamber is removed.
  • the heating step it is preferable to heat the substrate to which the specific component is attached without introducing the first mist and the second mist into the chamber.
  • the heating means in the heating step is not particularly limited, and for example, heating may be performed using a heater or heating may be performed using hot air.
  • the mounting table for the substrate may include a temperature adjustment means, and the substrate to which the specific component is attached may be heated by heating the mounting table with the temperature adjustment means.
  • Heating in the heating step may be performed under atmospheric pressure, under increased pressure, or under reduced pressure. Heating may be performed, for example, under an air atmosphere or an inert gas atmosphere.
  • FIG. 2 shows an example of a system configuration used in the manufacturing method of the present invention. Note that the manufacturing system used in the manufacturing method of the present invention is not limited to the embodiment shown in the drawings.
  • the manufacturing system shown in FIG. 2 includes a first misting section 11, a second misting section 21, and a chamber 31.
  • the first misting section 11 , the second misting section 21 , and the chamber 31 are connected to each other through a first flow path 41 and a second flow path 42 .
  • a mounting table 32 is installed in the chamber 31, and a base 33 is placed on the mounting table 32.
  • the first misting section 11 has an internal space, a first storage tank 12 is installed in the internal space, and an ultrasonic vibrator 13 is installed on the inner surface (bottom surface) of the first storage tank 12.
  • a first liquid 14 is stored in a first storage tank 12 , and a first mist 15 is generated from the first liquid 14 by applying ultrasonic waves to the first liquid 14 using an ultrasonic transducer 13 .
  • the first liquid 14 stored in the first storage tank 12 is preferably cooled by any cooling means.
  • the second misting section 21 has an internal space, a second storage tank 22 is installed in the internal space, and an ultrasonic vibrator 23 is installed on the inner surface (bottom surface) of the second storage tank 22.
  • a second liquid 24 is stored in the second storage tank 22 , and a second mist 25 is generated from the second liquid 24 by applying ultrasonic waves to the second liquid 24 by the ultrasonic vibrator 23 .
  • a carrier gas introduction path 16 is connected to the first misting section 11 . It is preferable that the introduction path 16 is provided with a valve 17 and a flow meter 18 .
  • a first flow path 41 is further connected to the first mist forming section 11, and the first flow path 41 is provided so as to connect the first mist forming section 11 and the chamber 31.
  • the carrier gas is supplied from the introduction path 16 to the internal space of the first misting section 11 , and flows from the internal space of the first misting section 11 into the chamber 31 through the first flow path 41 .
  • the first mist 15 generated in the first mist-forming section 11 is transported by the carrier gas and introduced into the chamber 31 through the first flow path 41 .
  • a carrier gas introduction path 26 is connected to the second misting section 21 . It is preferable that the introduction path 26 is provided with a valve 27 and a flow meter 28 .
  • a second flow path 42 is further connected to the second mist forming section 21, and the second flow path 42 is provided so as to connect the second mist forming section 21 and the first flow path 41.
  • the carrier gas is supplied from the introduction path 26 to the internal space of the second misting section 21, and flows from the internal space of the second misting section 21 into the chamber 31 through the second flow path 42 and the first flow path 41. do.
  • the second mist 25 generated in the second mist forming section 21 is transported by the carrier gas and introduced into the chamber 31 through the second flow path 42 and the first flow path 41.
  • the manufacturing system shown in FIG. 2 is operated, for example, as follows. First, the internal space of the first misting section 11, the second misting section 21, the first flow path 41, the second flow path 42, and the chamber 31 are replaced with carrier gas in advance. The first mist 15 is generated in the first mist forming section 11, the second mist 25 is generated in the second mist forming section 21, and then the valve 17 of the introduction path 16 and the valve 27 of the introduction path 26 are opened, The first mist 15 and the second mist 25 are transported by carrier gas and introduced into the chamber 31 . When a predetermined amount of the specific component adheres to the substrate 33, the valve 17 of the introduction path 16 and the valve 27 of the introduction path 26 are closed. The substrate 33 is taken out from the chamber 31, and the substrate 33 to which the specific component is attached is heated to form a functional layer. The substrate 33 to which the specific component has been attached may be heated within the chamber 31 to form a functional layer.
  • a functional layer of a photoelectric conversion element selected from an active layer, an electron transport layer, and a hole transport layer can be manufactured as described above.
  • a polymer compound as the specific component, which makes it easier to dissolve the specific component in the first solvent at a high concentration, or to obtain a functional layer with higher performance. It becomes easier.
  • Examples of the polymer compound that forms the active layer and functions as a p-type semiconductor compound include the following compounds.
  • Examples of the polymer compound that forms the active layer and functions as an n-type semiconductor compound include the following compounds.
  • Examples of the polymer compound forming the electron transport layer include the following compounds.
  • Examples of the polymer compound forming the hole transport layer include the following compounds.
  • the method for producing a functional layer of a photoelectric conversion element of the present invention can be suitably applied to the production of a photoelectric conversion element, and in particular, can be suitably applied to the production of an organic thin film solar cell, which is a type of photoelectric conversion element. can. Therefore, the present invention also provides a method for manufacturing a photoelectric conversion element and a method for manufacturing an organic thin film solar cell, which includes a step of forming a functional layer of the photoelectric conversion element by the above manufacturing method.
  • the method for manufacturing a photoelectric conversion element and the method for manufacturing an organic thin film solar cell of the present invention at least one of the functional layers constituting the photoelectric conversion element is manufactured by the method described above. That is, at least one selected from the active layer, electron transport layer, and hole transport layer may be manufactured by the above method. It is preferable that the organic thin film solar cell has a layer structure as shown in FIG. If at least one selected from the active layer, electron transport layer, and hole transport layer is manufactured by a method other than the above, the active layer, electron transport layer, or hole transport layer may be manufactured by a known method, such as spinning. These layers can be formed by a wet coating method such as a coating method, an inkjet method, or a gravure coat, or by a vacuum deposition method when a sublimable material is used.
  • the active layer contains a polymer compound having a benzobistiazole structural unit.
  • a polymer compound having a benzobisthiazole structural unit represented by (1) (hereinafter referred to as "polymer compound P") is preferred.
  • T 1 and T 2 are each independently a thiophene ring, a hydrocarbon group, or an organosilyl group which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group.
  • B 1 and B 2 represent a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group, or an ethynylene group.
  • an organosilyl group means a monovalent group in which an Si atom is substituted with one or more hydrocarbon groups, and the number of hydrocarbon groups substituted with an Si atom may be 2 or more and 3 or less. The number is preferably three, and more preferably three.
  • the polymer compound P is a type of p-type semiconductor compound, and by having the benzobistiazole structural unit represented by formula (1), it can deepen the HOMO level and narrow the band gap, resulting in photoelectric conversion efficiency. can be increased.
  • T 1 and T 2 may be the same or different from each other, but are preferably the same from the viewpoint of easy production.
  • B 1 and B 2 may be the same or different, but are preferably the same for ease of manufacture.
  • T 1 and T 2 are preferably groups represented by the following formulas (t1) to (t5), respectively.
  • the alkoxy group of T 1 and T 2 is preferably a group represented by the following formula (t1)
  • the thioalkoxy group is preferably a group represented by the following formula (t2)
  • the hydrocarbon is preferably a group represented by the following formula (t3)
  • the thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t3).
  • the group represented by t4) is preferable, and the phenyl group optionally substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is the following formula (t5)
  • a group represented by is preferable.
  • T 1 and T 2 are groups represented by the following formulas (t1) to (t5), it is possible to absorb short wavelength light and have high planarity, so that efficient ⁇ - ⁇ stacking can be achieved. is formed, so the photoelectric conversion efficiency can be increased.
  • the groups represented by formulas (t1) to (t3) exhibit electron-donating properties
  • the groups represented by formulas (t4) to (t5) exhibit electron-withdrawing properties.
  • R 13 to R 14 each independently represent a hydrocarbon group having 6 to 30 carbon atoms.
  • R 15 to R 16 each independently represent a hydrocarbon group having 6 to 30 carbon atoms or a group represented by *-Si(R 18 ) 3 .
  • R 15' represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by *-Si(R 18 ) 3 .
  • R 17 represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, *-O-R 19 , *-SR 20 , *-Si(R 18 ) 3 or *-CF 3 .
  • R 18 each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R 18s may be the same or different.
  • R 19 to R 20 represent a hydrocarbon group having 6 to 30 carbon atoms. * represents a bond bonded to the thiazole ring of benzobistiazole.
  • the hydrocarbon group having 6 to 30 carbon atoms in R 13 to R 17 , R 19 to R 20 , and R 15' is preferably a hydrocarbon group having a branch. , more preferably a branched saturated hydrocarbon group.
  • the hydrocarbon groups of R 13 to R 17 , R 19 to R 20 , and R 15' can increase solubility in organic solvents by having branches.
  • the number of carbon atoms in the hydrocarbon group of R 13 to R 17 , R 19 to R 20 , and R 15' is preferably 8 to 25, more preferably 8 to 20, and still more preferably 8 to 16.
  • the number of carbon atoms of the aliphatic hydrocarbon group of R 18 is preferably is from 1 to 18, more preferably from 1 to 8.
  • the number of carbon atoms in the aromatic hydrocarbon group of R 18 is preferably 6 to 8, more preferably 6 to 7, and still more preferably 6.
  • Examples of the aromatic hydrocarbon group for R 18 include a phenyl group.
  • R 18 is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and even more preferably an isopropyl group.
  • R18's may be the same or different, but are preferably the same.
  • R 15 to R 17 and R 15' are groups represented by *-Si(R 18 ) 3
  • the group represented by *-Si(R 18 ) 3 is preferably an alkylsilyl group, more preferably a trimethylsilyl group or a triisopropylsilyl group.
  • R 17 when R 17 is a halogen atom, any of fluorine, chlorine, bromine, and iodine can be used.
  • R 17 is preferably a halogen atom or *-CF 3 .
  • R 15' is a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms exemplified as R 15 , or a group similar to the group represented by *-Si(R 18 ) 3 , and is a hydrogen atom. It is preferable.
  • T 1 and T 2 groups represented by formulas (t1), (t3), and (t5) are more preferable because the structural unit represented by formula (1) has excellent planarity as a whole; A group represented by (t3) is more preferred.
  • B 1 and B 2 are preferably groups each represented by one of the following formulas (b1) to (b3).
  • the polymer compound P has good planarity and can enhance photoelectric conversion efficiency.
  • R 21 , R 22 , and R 21' represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms.
  • * represents a bond, particularly the left * represents a bond bonded to the benzene ring of the benzobistiazole compound.
  • hydrocarbon groups having 6 to 30 carbon atoms for R 21 , R 22 , and R 21' include the hydrocarbon groups having 6 to 30 carbon atoms for R 13 to R 17 , R 19 to R 20 , and R 15' . groups can be preferably used. It is preferable that R 21 , R 22 , and R 21' be hydrocarbon groups having 6 to 30 carbon atoms, since this may further increase the photoelectric conversion efficiency. On the other hand, when R 21 , R 22 , and R 21' are hydrogen atoms, it becomes easy to form a donor-acceptor type semiconductor polymer.
  • B 1 and B 2 groups represented by formulas (b1) and (b2) are more preferable.
  • B 1 and B 2 are groups represented by formulas (b1) and (b2), interaction between S atoms and N atoms occurs in the benzobistiazole structural unit, and the planarity is further improved. As a result, the planarity of the resulting polymer compound P can be improved.
  • the polymer compound P is preferably a donor-acceptor type semiconductor polymer. Therefore, the polymer compound P has a benzobistiazole structural unit represented by formula (1) and also has a donor unit or an acceptor unit. It is preferable to have the specific structural unit given below.
  • the donor unit means an electron-donating structural unit
  • the acceptor unit means an electron-accepting structural unit.
  • the donor-acceptor type semiconductor polymer preferably has donor units and acceptor units arranged alternately. Therefore, the donor-acceptor type semiconductor polymer has benzobisthiazole structural units represented by formula (1) and , and specific structural units are preferably arranged alternately.
  • the polymer compound P having such a structure can be suitably used as a p-type semiconductor compound.
  • specific structural units a conventionally known structural unit that provides a donor unit or an acceptor unit can be used.
  • specific structural units include the following structural units, among which formulas (c1), (c3) to (c5), (c7), (c9), (c12), and (c21) , (c27), (c37), and (c42) are preferable, and structures represented by formulas (c1), (c5), (c9), (c21), (c37), and (c42) are preferable. Units are more preferred.
  • R 30 to R 73 and R 75 to R 76 each independently represent a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms
  • R 74 represents a hydrogen atom or Represents a hydrocarbon group having 4 to 30 carbon atoms.
  • a 30 and A 31 each independently represent the same groups as T 1 and T 2
  • j represents an integer of 1 to 4. * represents a bond bonded to B 1 or B 2 of the structural unit represented by formula (1).
  • the groups represented by formulas (c1) to (c30) above are groups that act as acceptor units, and the groups represented by formulas (c32) to (c43) are groups that act as donor units. .
  • the group represented by formula (c31) may act as an acceptor unit or a donor unit depending on the types of A 30 and A 31 .
  • the repeating ratio of the benzobistiazole structural unit represented by formula (1) in the polymer compound P is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, and even more preferably 30 mol%. % or more, and usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and still more preferably 70 mol% or less.
  • the repeating ratio of specific structural units in the polymer compound P is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, even more preferably 30 mol% or more, and usually 99 mol% or less. , preferably 95 mol% or less, more preferably 85 mol% or less, even more preferably 70 mol% or less.
  • the arrangement of the benzobisthiazole structural unit represented by formula (1) and the specific structural unit may be alternate, block, or random. That is, the polymer compound P may be any of an alternating copolymer, a block copolymer, and a random copolymer. Preferably, the benzobistiazole structural units represented by formula (1) and the specific structural units are arranged alternately.
  • the weight average molecular weight and number average molecular weight of the polymer compound P are preferably 2,000 or more and 500,000 or less, more preferably 3,000 or more and 200,000 or less.
  • the weight average molecular weight and number average molecular weight of the polymer compound P can be calculated using gel permeation chromatography based on a calibration curve prepared using polystyrene as a standard sample.
  • Photoelectric conversion element organic thin film solar cell
  • Cathode 3 Electron transport layer 4: Active layer 5: Hole transport layer 6: Anode 7: Base material 11: First misting section 12: First storage tank 13: Ultrasonic vibrator 14: First liquid 15 : First mist 21: Second mist forming section 22: Second storage tank 23: Ultrasonic vibrator 24: Second liquid 25: Second mist 31: Chamber 32: Mounting table 33: Base

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Abstract

L'invention concerne un procédé de production d'une couche fonctionnelle d'un élément de conversion photoélectrique qui est choisi parmi une couche active, une couche de transport d'électrons et une couche de transport de trous, ledit procédé comprenant : une étape de génération d'un premier brouillard (15) à partir d'un premier liquide (14) qui contient un premier solvant organique et un composant spécifique pour former la couche fonctionnelle ; une étape de génération d'un second brouillard (25) à partir d'un second liquide (24) qui contient un second solvant organique ; une étape de transport pour introduire le premier brouillard (15) et le second brouillard (25) dans une chambre (31) dans laquelle un substrat (33) a été disposé et pour faire adhérer le composant spécifique sur le substrat (33) ; et une étape de chauffage pour chauffer le substrat (33) sur lequel est collé le composant spécifique pour former la couche fonctionnelle.
PCT/JP2023/019307 2022-06-03 2023-05-24 Procédé de production de couche fonctionnelle d'élément de conversion photoélectrique et procédé de production d'élément de conversion photoélectrique WO2023234136A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002172355A (ja) * 2000-12-05 2002-06-18 Auto Network Gijutsu Kenkyusho:Kk 薄膜形成方法及び薄膜形成装置
US20120060924A1 (en) * 2010-09-09 2012-03-15 Alion, Inc. Methods and systems for forming functionally graded films by spray pyrolysis
JP2013129867A (ja) * 2011-12-20 2013-07-04 Sharp Corp 薄膜成膜装置、薄膜成膜方法および薄膜太陽電池の製造方法
WO2015177899A1 (fr) * 2014-05-22 2015-11-26 東芝三菱電機産業システム株式会社 Procédé de formation en film de couche tampon et couche tampon
WO2016203594A1 (fr) * 2015-06-18 2016-12-22 東芝三菱電機産業システム株式会社 Procédé de formation d'un film d'oxyde métallique
WO2018163338A1 (fr) * 2017-03-08 2018-09-13 堺ディスプレイプロダクト株式会社 Procédé de fabrication d'un dispositif el organique et appareil de formation de film
WO2019043947A1 (fr) * 2017-09-04 2019-03-07 シャープ株式会社 Dispositif de gravure, et procédé de fabrication de dispositif d'affichage

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002172355A (ja) * 2000-12-05 2002-06-18 Auto Network Gijutsu Kenkyusho:Kk 薄膜形成方法及び薄膜形成装置
US20120060924A1 (en) * 2010-09-09 2012-03-15 Alion, Inc. Methods and systems for forming functionally graded films by spray pyrolysis
JP2013129867A (ja) * 2011-12-20 2013-07-04 Sharp Corp 薄膜成膜装置、薄膜成膜方法および薄膜太陽電池の製造方法
WO2015177899A1 (fr) * 2014-05-22 2015-11-26 東芝三菱電機産業システム株式会社 Procédé de formation en film de couche tampon et couche tampon
WO2016203594A1 (fr) * 2015-06-18 2016-12-22 東芝三菱電機産業システム株式会社 Procédé de formation d'un film d'oxyde métallique
WO2018163338A1 (fr) * 2017-03-08 2018-09-13 堺ディスプレイプロダクト株式会社 Procédé de fabrication d'un dispositif el organique et appareil de formation de film
WO2019043947A1 (fr) * 2017-09-04 2019-03-07 シャープ株式会社 Dispositif de gravure, et procédé de fabrication de dispositif d'affichage

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