WO2023234137A1 - Procédé de fabrication d'élément de conversion photoélectrique - Google Patents

Procédé de fabrication d'élément de conversion photoélectrique Download PDF

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WO2023234137A1
WO2023234137A1 PCT/JP2023/019308 JP2023019308W WO2023234137A1 WO 2023234137 A1 WO2023234137 A1 WO 2023234137A1 JP 2023019308 W JP2023019308 W JP 2023019308W WO 2023234137 A1 WO2023234137 A1 WO 2023234137A1
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mist
type semiconductor
semiconductor compound
solution
chamber
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PCT/JP2023/019308
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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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • 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 a method for manufacturing a photoelectric conversion element having an active layer.
  • Patent Document 1 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 layer structure of the active layer As the layer structure of the active layer, 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 in which a p-type semiconductor compound and an n-type semiconductor compound are mixed are known. There is.
  • the active layer it is desirable to be able to form these structures arbitrarily, and it is expected that this will result in a photoelectric conversion element having high photoelectric conversion efficiency. In particular, it is desirable to be able to easily form various bulk heterojunction structures.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing a photoelectric conversion element that can easily form an active layer with an arbitrary structure.
  • the present invention includes the following method for manufacturing a photoelectric conversion element.
  • a method for manufacturing a photoelectric conversion element having an active layer comprising: generating a first mist from a first solution containing a p-type semiconductor compound; generating a second mist from a second solution containing an n-type semiconductor compound; A transporting step of introducing the first mist and the second mist into a chamber in which a substrate is placed, and depositing the p-type semiconductor compound and the n-type semiconductor compound on the substrate;
  • a method for manufacturing a photoelectric conversion element comprising a heating step of heating the substrate to which the p-type semiconductor compound and the n-type semiconductor compound are attached to form an active layer.
  • step of generating the first mist in the step of generating the first mist from the cooled first solution, and/or in the step of generating the second mist, the step of generating the first mist from the cooled first solution.
  • the first solution contains a first solvent
  • the second solution contains a second solvent different from the first solvent.
  • Production method [6] The method according to any one of [1] to [5], wherein in the conveying step, the ratio between the amount of the first mist and the amount of the second mist introduced into the chamber is changed over time. Production method.
  • the ratio of the amount of the first mist introduced into the chamber to the amount of the second mist continues to increase or decrease over time [1] to [ 6].
  • the active layer has a ratio of the n-type semiconductor compound to the p-type semiconductor compound on one side in the thickness direction is larger than the ratio on the other side.
  • the manufacturing method described in. [9] The first solution contains the p-type semiconductor compound which is a polymer compound, and/or the second solution contains the n-type semiconductor compound which is a polymer compound [1 ] to [8].
  • a first mist generated from a first solution containing a p-type semiconductor compound and a second mist generated from a second solution containing an n-type semiconductor compound are produced.
  • a p-type semiconductor compound and an n-type semiconductor compound can be deposited on the substrate placed in the chamber, and an active layer precursor can be formed on the substrate.
  • An active layer can be formed on the substrate.
  • active layers having not only a thin film stacked structure but also various bulk heterojunction structures can be easily formed.
  • 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 photoelectric conversion element having an active layer.
  • 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 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 active layer among the layers constituting the photoelectric conversion element is manufactured by a specific method.
  • the method for manufacturing a photoelectric conversion element of the present invention includes a step of generating a first mist from a first solution containing a p-type semiconductor compound (hereinafter referred to as "first mist generation step"), and a step of generating a first mist from a first solution containing a p-type semiconductor compound.
  • first mist generation step a step of generating a first mist from a first solution containing a p-type semiconductor compound
  • second mist generation step A step of generating a second mist from a second solution containing
  • the method includes a transport step of depositing a p-type semiconductor compound and an n-type semiconductor compound on the substrate, and a heating step of heating the substrate to which the p-type semiconductor compound and the n-type semiconductor compound are attached to form an active layer.
  • an active layer precursor can be formed on a substrate by depositing a p-type semiconductor compound and an n-type semiconductor compound, and by heating this, an active layer can be formed on the substrate.
  • an active layer can be formed on the substrate.
  • the p-type semiconductor By adjusting the amount of the first mist containing a p-type semiconductor compound and the second mist containing an n-type semiconductor compound introduced into the chamber, the p-type semiconductor It is possible to form a layer containing many compounds, a layer containing many n-type semiconductor compounds, or a layer containing a mixture of p-type semiconductor compounds and n-type semiconductor compounds. Further, it becomes easy to arbitrarily adjust the thickness of each of these regions. Therefore, according to the present invention, active layers having various bulk heterojunction structures can be easily formed. Each step will be explained in detail below.
  • a first mist is generated from a first solution containing a p-type semiconductor compound.
  • a p-type semiconductor compound is dissolved in a solvent, and the solvent contained in the first solution is referred to as a "first solvent.”
  • the first solution may further contain the additives described above.
  • a second mist is generated from a second solution containing an n-type semiconductor compound.
  • an n-type semiconductor compound is dissolved in a solvent, and the solvent contained in the second solution is referred to as a "second solvent.”
  • the second solution may further contain the additives described above.
  • the first solvent is not particularly limited as long as it can dissolve the p-type semiconductor compound.
  • the second solvent is not particularly limited as long as it can dissolve the n-type semiconductor compound.
  • the first solvent and the second solvent are preferably organic solvents, such as aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, and decane; toluene, xylene, mesitylene, cyclohexylbenzene, and naphthalene.
  • aromatic hydrocarbons such as methylnaphthalene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin, decalin; chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, Halogenated hydrocarbons such as orthodichlorobenzene and chloronaphthalene; Alcohols such as methanol, ethanol, propanol, and anisole; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone, and propiophenone; Esters such as ethyl acetate, isopropyl acetate, butyl acetate, methyl lactate; Ethers
  • the first solvent and the second solvent may be the same or different, it is preferable that the first solvent and the second solvent are different from each other.
  • the solvent used when forming an active layer, a solution containing both a p-type semiconductor compound and an n-type semiconductor compound was used, so the solvent used must be one that can dissolve both the p-type semiconductor compound and the n-type semiconductor compound. I had to choose appropriately. Therefore, the solvents that can be used are limited, and halogenated hydrocarbons are usually used as the solvent.
  • the p-type semiconductor compound and the n-type semiconductor compound are handled as separate mist, the first mist containing the n-type semiconductor compound and the second mist containing the n-type semiconductor compound are separated.
  • halogenated hydrocarbons as a solvent, it becomes easy to dissolve the p-type semiconductor compound in the first solvent and increase the concentration of the p-type semiconductor compound in the first solution. It becomes easy to dissolve the n-type semiconductor compound in the solvent and increase the concentration of the n-type semiconductor compound in the second solution.
  • a solvent other than halogenated hydrocarbons it is possible to use an environmentally friendly production method, and by appropriately setting the types of the first solvent and the second solvent, various bulk heterogeneous products can be produced. It also becomes possible to form a bonded structure.
  • the concentration of the p-type semiconductor compound in the first solution is not particularly limited.
  • the concentration of the p-type semiconductor compound in the first solution is set such that the first mist is transported into the chamber in the transport process and is maintained in a mist state until it is deposited on the substrate, and is activated on the substrate.
  • the concentration may be appropriately set so as to obtain a desired film formation rate of the layer precursor.
  • the concentration of the p-type semiconductor compound in the first solution 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 20% by mass or less. It is preferably 10% by mass or less, and more preferably 10% by mass or less.
  • the concentration of the p-type semiconductor compound in the first solution may be adjusted depending on the thickness of the active layer to be formed. For example, when the thickness of the active layer is less than 100 nm, the concentration of the p-type semiconductor compound in the first solution The concentration is 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 10% by mass or less, more preferably 5% by mass or less, and 3% by mass. The following are more preferred. When the thickness of the active layer is 100 nm or more, the p-type semiconductor compound concentration in the first solution 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 or more. It is preferably at most 10% by mass, more preferably at most 10% by mass. Note that the first solution preferably does not contain an n-type semiconductor compound.
  • the concentration of the n-type semiconductor compound in the second solution is not particularly limited.
  • the concentration of the n-type semiconductor compound in the second solution is set such that the second mist is transported into the chamber in the transport process and is maintained in a mist state until it is deposited on the substrate, and is activated on the substrate.
  • the concentration may be appropriately set so as to obtain a desired film formation rate of the layer precursor.
  • the concentration of the n-type semiconductor compound in the second solution 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 20% by mass or less. It is preferably 10% by mass or less, and more preferably 10% by mass or less.
  • the concentration of the n-type semiconductor compound in the second solution may be adjusted depending on the thickness of the active layer to be formed. For example, when the thickness of the active layer is less than 100 nm, the concentration of the n-type semiconductor compound in the second solution The concentration is 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 10% by mass or less, more preferably 5% by mass or less, and 3% by mass. The following are more preferred. When the thickness of the active layer is 100 nm or more, the n-type semiconductor compound concentration in the second solution 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 or more. It is preferably at most 10% by mass, more preferably at most 10% by mass. Note that the second solution preferably does not contain a p-type semiconductor compound.
  • the method of turning the first solution into a mist is not particularly limited.
  • Methods of making the first solution into a mist include a method of spraying the first solution from a nozzle to make it a mist, a method of applying ultrasonic waves to the first solution and making it a mist, and a method of bubbling the first solution. 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 solution 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 solution 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 and structure of the active layer desired to be formed on the substrate.
  • 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 method of turning the second solution into a mist is not particularly limited.
  • the method of making a mist from the second solution refer to the above description of making a mist from the first solution, and preferably, applying ultrasonic waves to the second solution to generate the second mist. This makes it easier to generate the second mist more uniformly.
  • the frequency of the ultrasonic waves when applying ultrasonic waves to the second solution to form a mist is not particularly limited. The larger the frequency, the smaller the particle size of the second mist, so the frequency may be set appropriately depending on the thickness and structure of the active layer desired to be formed on the substrate.
  • the frequency at which ultrasonic waves are applied to the second solution the above description of the frequency at which ultrasonic waves are applied to the first solution is referred to.
  • the first mist is generated from the first solution in a first misting 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.
  • a first solution is stored in a first storage tank, and by applying ultrasound to the first solution stored in the first storage tank, mist is generated from the first solution. 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 in contact with the first solution, or may be installed in the first solution instead of on the inner surface of the first storage tank.
  • the second mist is generated from the second solution in a second misting 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 solution is stored in a second storage tank, and by applying ultrasound to the second solution stored in the second storage tank, the second mist is removed from the second solution. 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 in contact with the second solution, or may be installed in the second solution instead of on the inner surface of the second storage tank.
  • the first mist generation step it is preferable to generate the first mist from the cooled first solution. That is, in the first mist generation step, it is preferable to cool the first solution and generate the first mist from the cooled first solution. This suppresses volatilization of the first solvent from the first mist until the first mist is transported into the chamber and attached to the substrate, making it easier to maintain the mist state.
  • the cooling temperature of the first solution may be set, for example, in the range of 5°C to 20°C.
  • the second mist generation step it is preferable to generate the second mist from the cooled second solution. That is, in the second mist generation step, it is preferable to cool the second solution and generate the second mist from the cooled second solution. As a result, volatilization of the second solvent from the second mist is suppressed until the second mist is transported into the chamber and attached to the substrate, and the mist state is easily maintained.
  • the cooling temperature of the second solution may be set, for example, in the range of 5°C to 20°C.
  • 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 and contain a p-type semiconductor compound and an n-type semiconductor compound on the substrate.
  • An active layer precursor can be formed.
  • 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 is replaced with the first mist and/or the second mist. be able to.
  • it becomes easy to adjust the concentration of the first mist and the second mist in the internal space of the chamber and it becomes easy to adjust the amounts of the p-type semiconductor compound and the n-type semiconductor compound to be attached to the substrate. .
  • 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 may be any gas that is inert to the p-type semiconductor compound and first solvent contained in the first mist and the n-type semiconductor compound and second solvent contained in the second mist. Not particularly limited.
  • 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 first mist and the second mist are mixed before being transported to the chamber, and the layer structure of the active layer precursor to be formed on the substrate is formed into the desired layer structure. It becomes easy to adjust.
  • the substrate is placed in the chamber in advance.
  • the substrate is placed in the chamber so that a surface to which a p-type semiconductor compound and an n-type semiconductor compound are attached and a surface to which a p-type semiconductor compound is not attached are formed.
  • the substrate placed in the chamber is appropriately set according to the layer structure of the photoelectric conversion element, and the substrate may be placed in the chamber as follows.
  • the substrate has at least a cathode, and the substrate is placed in the chamber such that the cathode serves as an attachment surface for the p-type semiconductor compound and the n-type semiconductor compound, or the substrate has at least an electron transport layer and a cathode, and the substrate has at least an electron transport layer and A substrate is placed in the chamber such that the layer serves as an attachment surface for a p-type semiconductor compound and an n-type semiconductor compound, or the substrate has at least an anode, and the anode serves as an attachment surface for a p-type semiconductor compound and an n-type semiconductor compound.
  • the substrate is placed in a chamber so that It may be installed in
  • the substrate further has a base material on the side of the cathode opposite to the surface on which the p-type semiconductor compound and the n-type semiconductor compound are attached, or has a base material on the side of the cathode opposite to the surface on which the electron transport layer is disposed. or has a base material on the side of the anode opposite to the surface on which the p-type semiconductor compound and n-type semiconductor compound are attached, or has a base material on the side of the anode opposite to the surface on which the hole transport layer is disposed. It's okay.
  • 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.
  • a p-type semiconductor compound and an n-type semiconductor compound are deposited on the substrate.
  • the active 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 amounts of the first mist and the second mist introduced into the chamber are determined as appropriate depending on the amount of p-type semiconductor compound and n-type semiconductor compound to be deposited on the substrate and the film thickness of the active layer precursor. Just set it.
  • the p-type semiconductor compound and the n-type semiconductor compound may be deposited on the substrate by keeping the ratio of the amount of the first mist and the amount of the second mist introduced into the chamber constant. The ratio of the amount of the first mist and the amount of the second mist introduced into the container may be changed over time.
  • the first mist and the second mist are introduced into the chamber as in the former case, it is possible to form an active layer having a layer structure similar to that of an active layer formed by, for example, a spin coating method. Become.
  • a layer containing many p-type semiconductor compounds is formed in the thickness direction of the active layer precursor; It becomes easy to form a layer in which a large amount of a type semiconductor compound exists, or a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed. It was difficult to adjust the layer structure of the active layer as desired using conventional wet coating methods, but according to the present invention, it is possible to adjust the layer structure of the active layer as desired. Become.
  • the ratio of the amount of the first mist introduced into the chamber to the amount of the second mist may continue to increase or decrease over time.
  • the content ratio of the p-type semiconductor compound and the n-type semiconductor compound can be adjusted toward one side or the other side in the thickness direction of the active layer. It becomes possible to form an active layer in which the gradient changes.
  • the active layer formed in this manner is expected to have advantageous photoelectric conversion efficiency.
  • the ratio of the amount of the first mist to the amount of the second mist changes over time. There may be a fixed time period.
  • the ratio of the n-type semiconductor compound to the p-type semiconductor compound on one side in the thickness direction is larger than the ratio on the other side. Therefore, in the conveyance step, the amount of the first mist deposited on the substrate is adjusted such that the ratio of the n-type semiconductor compound to the p-type semiconductor compound on one side in the thickness direction of the active layer is larger than the ratio on the other side. It is preferable to change the ratio of the second mist to the amount over time.
  • 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 first mist and the second mist are deposited on the cooled substrate, and the p-type semiconductor compound and the n-type semiconductor compound are deposited on the substrate.
  • 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 photoelectric conversion element of the present invention is manufactured from the viewpoint of suppressing the volatilization of the solvent as much as possible between the first mist and the second mist being transported into the chamber and adhering to the substrate, and making it easier to maintain the mist state.
  • the method may include the step of generating a third mist from a third solution containing a solvent, and in the conveying step, the third mist may be conveyed with a carrier gas and introduced into the chamber. good.
  • the third mist may be introduced into the chamber separately from the first mist and the second mist, or may be combined with the first mist or the second mist before being introduced into the chamber. It's okay.
  • For the method of turning the third solution into a mist refer to the explanation of the method of turning the first or second solution into a mist.
  • the solvents exemplified as the first solvent and the second solvent can be used. It is preferable that the third solution basically consists of only a solvent. Therefore, the solute concentration of the third solution is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.
  • the substrate to which the p-type semiconductor compound and the n-type semiconductor compound are attached is heated, that is, the active layer precursor on the substrate is heated to form an active layer on the substrate.
  • the heating temperature in the heating step is within a range that can volatilize the solvent contained in the first mist and the second mist, and is below the boiling point or decomposition point of the p-type semiconductor compound and the n-type semiconductor compound, so as not to adversely affect the substrate. It may be set as appropriate within a range that does not affect.
  • 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 p-type semiconductor compound and the n-type semiconductor compound are attached may be heated while being placed in the chamber, and the substrate to which the p-type semiconductor compound and the n-type semiconductor compound are attached is taken out from the chamber. Alternatively, heating may be performed with the chamber removed. In the former case, in the heating step, it is preferable to heat the substrate to which the p-type semiconductor compound and the n-type semiconductor compound are 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 by heating the mounting table with the temperature adjustment means, the substrate to which the p-type semiconductor compound and the n-type semiconductor compound are attached may be heated.
  • 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 solution 14 containing a p-type semiconductor compound is stored in a first storage tank 12, and by applying ultrasonic waves to the first solution 14 with an ultrasonic transducer 13, the first solution 14 is A mist 15 is generated.
  • the first solution 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 solution 24 containing an n-type semiconductor compound is stored in a second storage tank 22, and by applying ultrasonic waves to the second solution 24 with an ultrasonic transducer 23, a second solution 24 is extracted from the second solution 24.
  • a mist 25 is generated.
  • 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 p-type semiconductor compound and the n-type semiconductor compound are deposited on 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 p-type semiconductor compound and the n-type semiconductor compound are attached is heated to form an active layer.
  • the substrate 33 to which the p-type semiconductor compound and the n-type semiconductor compound are attached may be heated in the chamber 31 to form an active layer.
  • the active layer of a photoelectric conversion element can be manufactured as described above.
  • the photoelectric conversion element further has an electron transport layer or a hole transport layer
  • the electron transport layer and the hole transport layer can be coated by a known method, for example, a wet coating method such as a spin coating method, an inkjet method, a gravure coating, or a sublimation method.
  • a wet coating method such as a spin coating method, an inkjet method, a gravure coating, or a sublimation method.
  • it can be formed by a vacuum evaporation method or the like.
  • the electron transport layer or hole transport layer may be formed by generating a mist from a liquid containing the components forming the electron transport layer or hole transport layer and a solvent, and depositing the mist on the substrate as described above. good.
  • the method for manufacturing a photoelectric conversion element of the present invention can be suitably applied to manufacturing an organic thin film solar cell. Therefore, it is preferable that the photoelectric conversion element is an organic thin film solar cell. It is preferable that the organic thin film solar cell has a layer structure as shown in FIG.
  • the active layer may contain a p-type semiconductor compound of a polymer compound and/or an n-type semiconductor compound of a polymer compound.
  • the first solution contains a p-type semiconductor compound that is a high-molecular compound
  • the second solution contains an n-type semiconductor compound that is a high-molecular compound.
  • Examples of the polymer compound that functions as a p-type semiconductor compound include the following compounds.
  • Examples of the polymer compound that functions as an n-type semiconductor compound include the following compounds.
  • the active layer contains a polymer compound having a benzobisthiazole structural unit, and specifically, a polymer having a benzobisthiazole structural unit represented by the following formula (1). It is preferable to contain a compound (hereinafter referred to as "polymer compound P").
  • 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 preferred.
  • 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 solution 15 : First mist 21: Second mist forming section 22: Second storage tank 23: Ultrasonic vibrator 24: Second solution 25: Second mist 31: Chamber 32: Mounting table 33: Base

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Abstract

L'invention concerne un procédé de fabrication d'un élément de conversion photoélectrique ayant une couche active, le procédé comprenant : une étape de génération d'un premier brouillard (15) à partir d'une première solution (14) contenant un composé semi-conducteur de type p ; une étape de génération d'un second brouillard (25) à partir d'une seconde solution (24) contenant un composé semi-conducteur de type n ; une étape de transport pour introduire le premier brouillard (15) et le second brouillard (25) dans une chambre (31) dans laquelle un substrat (33) est placé et déposer le composé semi-conducteur de type p et le composé semi-conducteur de type n sur le substrat (33) ; et une étape de chauffage pour former une couche active par chauffage du substrat (33) ayant le composé semi-conducteur de type p et le composé semi-conducteur de type n déposés sur celui-ci.
PCT/JP2023/019308 2022-06-03 2023-05-24 Procédé de fabrication d'élément de conversion photoélectrique WO2023234137A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004165474A (ja) * 2002-11-14 2004-06-10 Matsushita Electric Ind Co Ltd 光電変換素子及びその製造方法
JP2008078113A (ja) * 2006-08-25 2008-04-03 Fujikura Ltd 透明導電性基板の製造装置
US20120060924A1 (en) * 2010-09-09 2012-03-15 Alion, Inc. Methods and systems for forming functionally graded films by spray pyrolysis
JP2012114424A (ja) * 2010-11-02 2012-06-14 Susumu Yoshikawa 太陽電池および太陽電池の製造方法
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
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004165474A (ja) * 2002-11-14 2004-06-10 Matsushita Electric Ind Co Ltd 光電変換素子及びその製造方法
JP2008078113A (ja) * 2006-08-25 2008-04-03 Fujikura Ltd 透明導電性基板の製造装置
US20120060924A1 (en) * 2010-09-09 2012-03-15 Alion, Inc. Methods and systems for forming functionally graded films by spray pyrolysis
JP2012114424A (ja) * 2010-11-02 2012-06-14 Susumu Yoshikawa 太陽電池および太陽電池の製造方法
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
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

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