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WO2025088993A1 - Procédé de fabrication de cellule solaire et cellule solaire - Google Patents

Procédé de fabrication de cellule solaire et cellule solaire Download PDF

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Publication number
WO2025088993A1
WO2025088993A1 PCT/JP2024/035142 JP2024035142W WO2025088993A1 WO 2025088993 A1 WO2025088993 A1 WO 2025088993A1 JP 2024035142 W JP2024035142 W JP 2024035142W WO 2025088993 A1 WO2025088993 A1 WO 2025088993A1
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layer
solar cell
photoelectric conversion
hole transport
nanofiber
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PCT/JP2024/035142
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English (en)
Japanese (ja)
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洋亮 中川
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富士フイルム株式会社
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Publication of WO2025088993A1 publication Critical patent/WO2025088993A1/fr

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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—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 solar cell having a layer structure in which at least a photoelectric conversion layer, a hole transport layer, and an electrode are stacked in this order, and to the solar cell, and in particular to a method for manufacturing a solar cell in which a nanofiber layer is provided on the photoelectric conversion layer, and to the solar cell.
  • Patent Document 1 proposes a solar cell in which the hole transport layer contains an organic semiconductor and an insulating polymer compound having a glass transition point of 100° C. or higher.
  • Patent Document 2 proposes a solar cell including a conductive substrate, an electrode layer arranged to face the conductive substrate, a photoelectric conversion layer containing an organic-inorganic perovskite compound arranged between the conductive substrate and the electrode layer, and an organic semiconductor layer arranged between the electrode layer and the photoelectric conversion layer, wherein the electrode layer is made of a transparent conductive material containing a metal oxide.
  • An object of the present invention is to provide a method for manufacturing a solar cell that suppresses the occurrence of peeling of the layers constituting the solar cell and suppresses deterioration of the photoelectric conversion characteristics, and to provide the solar cell.
  • invention [1] is a method for manufacturing a solar cell having a layer structure in which at least a photoelectric conversion layer, a hole transport layer, and an electrode are laminated in this order, the method comprising the steps of forming a nanofiber layer made of nanofibers on the photoelectric conversion layer, and forming a hole transport layer on the photoelectric conversion layer so as to cover the nanofiber layer, and after the hole transport layer is formed, at least a portion of the nanofiber layer protrudes from the surface of the hole transport layer opposite the photoelectric conversion layer, and further comprising the step of forming an electrode on the surface of the hole transport layer so as to cover the nanofiber layer protruding from the surface.
  • the present invention provides a solar cell manufacturing method and solar cell that suppresses the occurrence of peeling of the layers that make up the solar cell and suppresses deterioration of the photoelectric conversion characteristics.
  • angles such as “parallel” and “perpendicular” include a generally accepted error range in the relevant technical field.
  • the temperature includes a generally acceptable error range in the relevant technical field.
  • transparent means transparent to light. More specifically, “transparent” means that the light transmittance for light in the wavelength range of 400 to 800 nm is 80% or more. In the case of transparency, the light transmittance is more preferably 85% or more, and even more preferably 90% or more.
  • the light transmittance can be calculated by the method described in JIS (Japanese Industrial Standards)-K7105, that is, by measuring the total light transmittance and the amount of scattered light using an integrating sphere type light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance.
  • FIG. 1 is a schematic cross-sectional view showing a first example of a solar cell according to an embodiment of the present invention.
  • Fig. 2 is a schematic plan view showing a nanofiber layer on a photoelectric conversion layer of the first example of a solar cell according to an embodiment of the present invention.
  • Fig. 2 shows a photoelectric conversion layer 16 and a nanofiber layer 19, and does not show a hole transport layer 17 and a sealing layer side electrode 18.
  • the solar cell 10 shown in FIG. 1 has a layer structure in which, for example, a support 12, a support-side electrode 14, an electron transport layer 15, a photoelectric conversion layer 16, a hole transport layer 17, a sealing layer-side electrode 18, an adhesive layer 20, and a sealing layer 22 are laminated in this order.
  • the solar cell 10 may have a layer configuration in which at least a photoelectric conversion layer 16, a hole transport layer 17, and an electrode, i.e., a sealing layer side electrode 18, are laminated in this order.
  • the photoelectric conversion layer 16 contains, for example, a perovskite compound.
  • the solar cell 10 has a nanofiber layer 19 made of nanofibers 30 (see FIG. 2 ) provided on the photoelectric conversion layer 16. The nanofiber layer 19 is disposed between the hole transport layer 17 and the electrode, i.e., the sealing layer side electrode 18, straddling the hole transport layer 17 and the sealing layer side electrode 18 in the stacking direction Ds of the layer configuration.
  • Fig. 3 is a schematic perspective view showing the nanofiber layer of the first example of the solar cell according to the embodiment of the present invention
  • Fig. 4 is a side view showing the nanofiber layer of the first example of the solar cell according to the embodiment of the present invention.
  • Fig. 3 shows a part of one layer in the nanofiber layer 19.
  • the nanofiber layer 19 is composed of nanofibers 30 and has, for example, voids 31.
  • the nanofibers 30 extend in the longitudinal direction Dm, and a plurality of layers are laminated in the lamination direction Ds.
  • the configuration of the nanofibers 30, such as the arrangement thereof, is not particularly limited.
  • the nanofibers 30 may extend in a plurality of directions, or as shown in FIG. 4, the nanofibers 30 may extend in the longitudinal direction Dm.
  • the nanofiber layer 19 may be arranged so that the nanofibers 30 form a nonwoven fabric.
  • the nanofiber layer 19 has voids 31 as shown in FIG. 3, a part of the hole transport layer 17 and a part of the sealing layer side electrode 18 enter the voids 31, and the hole transport layer 17 and the sealing layer side electrode 18 are physically fixed more firmly.
  • nanofiber layer 19 is disposed inside hole transport layer 17 and sealing layer side electrode 18, straddling hole transport layer 17 and sealing layer side electrode 18 in stacking direction Ds. Nanofiber layer 19 is within sealing layer side electrode 18 and does not protrude from sealing layer side electrode 18.
  • the hole transport layer 17 and the sealing layer side electrode 18 are physically fixed by the above-mentioned nanofiber layer 19, and the physical adhesion between the hole transport layer 17 and the sealing layer side electrode 18 is increased. This makes it possible to suppress peeling between the hole transport layer 17 and the sealing layer side electrode 18, and to suppress peeling of each layer of the solar cell 10 due to temperature changes or the like in the surrounding environment in which the solar cell 10 is placed. This makes it possible to suppress deterioration of the photoelectric conversion characteristics of the photoelectric conversion layer 16 and maintain the power generation capacity even if there is a temperature change or the like in the surrounding environment.
  • solar cell 10 for example, sunlight Ls is irradiated from the surface 22a side of the sealing layer 22, and the electricity obtained by photoelectric conversion in the photoelectric conversion layer 16 is extracted to the outside through the support side electrode 14 and the sealing layer side electrode 18.
  • solar cell 10 may be configured such that, for example, sunlight Ls is irradiated from the side opposite support 12 to support-side electrode 14, photoelectric conversion is performed in photoelectric conversion layer 16, and the electric power obtained from support-side electrode 14 and sealing layer-side electrode 18 is extracted to the outside.
  • adhesive layer 20 sealing layer-side electrode 18, nanofiber layer 19, and hole transport layer 17 transparent
  • support 12, support-side electrode 14, and electron transport layer 15 are made transparent.
  • FIG. 5 is a schematic cross-sectional view showing a second example of a solar cell according to an embodiment of the present invention.
  • the same components as those in the solar cell 10 shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted.
  • the solar cell 11 shown in Figure 5 differs from the solar cell 10 shown in Figure 1 in that a conductive support 13 is used instead of the support 12 and the support-side electrode 14, but otherwise has the same configuration as the solar cell 10 shown in Figure 1.
  • the solar cell 11 has a layer structure in which a conductive support 13, an electron transport layer 15, a photoelectric conversion layer 16, a hole transport layer 17, a sealing layer side electrode 18, an adhesive layer 20, and a sealing layer 22 are laminated in this order.
  • the solar cell 11 does not have the support side electrode 14 shown in FIG. 1, and the electron transport layer 15 is provided on the conductive support 13.
  • the photoelectric conversion layer 16 also contains, for example, a perovskite compound.
  • the nanofiber layer 19 is disposed between the hole transport layer 17 and the sealing layer side electrode 18 in the stacking direction Ds of the layer configuration.
  • solar cell 11 for example, sunlight Ls is irradiated from the surface 22a side of sealing layer 22, photoelectrically converted in photoelectric conversion layer 16, and the obtained electric power is taken out from conductive support 13 and sealing layer side electrode 18.
  • Solar cell 11 differs from solar cell 10 described above only in that conductive support 13 is used instead of support 12 and support side electrode 14, and the same effects as solar cell 10 can be obtained.
  • the solar cell 11 may also be configured such that, for example, sunlight Ls is irradiated from the opposite side of the electron transport layer 15 of the conductive support 13, photoelectric conversion is performed in the photoelectric conversion layer 16, and the electric power obtained from the support-side electrode 14 and the sealing layer-side electrode 18 is taken out to the outside.
  • the conductive support 13 needs to be transparent.
  • the light irradiated by the solar cells 10 and 11 is not limited to sunlight Ls.
  • FIG. 6 to 9 are schematic cross-sectional views each showing a step of a first example of a manufacturing method of a solar cell according to an embodiment of the present invention.
  • Fig. 6 to Fig. 9 the same components as those in Fig. 1 to Fig. 4 are given the same reference numerals, and detailed description thereof will be omitted.
  • Fig. 7 to Fig. 9 the electron transport layer 15, the support-side electrode 14, and the support 12 below the photoelectric conversion layer 16 of the laminated base material 27 shown in Fig. 6 are omitted.
  • the hole transport layer 17 is formed on the photoelectric conversion layer 16 so as to cover the nanofiber layer 19 as shown in FIG.
  • the hole transport layer 17 is formed by applying a hole transport material solution onto the photoelectric conversion layer 16, for example, by spin coating, with the nanofiber layer 19 on the photoelectric conversion layer 16, and then drying the applied hole transport material solution.
  • the step of forming the hole transport layer 17 is also referred to as a second formation step. After the hole transport layer 17 is formed, at least a part of the nanofiber layer 19 protrudes from a surface 17 a of the hole transport layer 17 opposite to the photoelectric conversion layer 16 .
  • the step of forming the nanofiber layer includes a step of applying a voltage to a solution in which a fiber material is dissolved in a solvent, and ejecting the solution from a nozzle onto the photoelectric conversion layer.
  • FIG. 10 is a schematic diagram showing an example of an apparatus used for forming a nanofiber layer of a solar cell according to an embodiment of the present invention.
  • An apparatus 40 shown in FIG. 10 is an apparatus for forming a nanofiber layer by using an electrospinning method.
  • the apparatus 40 includes a solution preparation section 41 , a pump 42 , piping 43 , a holding member 44 , a nozzle 45 , a power source 46 , and a collector 47 .
  • the solution preparation section 41 is for preparing a solution (not shown) in which a fiber material is dissolved in a solvent, for forming nanofibers.
  • the solution preparation unit 41 prepares the solution by, for example, dissolving a cellulose-based polymer in a solvent for the cellulose-based polymer.
  • the cellulose-based polymer is an example of a fiber material.
  • the pump 42 sends the solution to the nozzle 45 via a pipe 43.
  • the flow rate of the solution coming out of the nozzle 45 can be adjusted by changing the rotation speed of the pump 42.
  • the nozzle 45 is held by a holding member 44.
  • the holding member 44 and the nozzle 45 constitute a nozzle unit.
  • the nozzle unit is disposed in an upper portion of a spinning chamber 48.
  • the tip of the nozzle 45 from which the solution exits is directed toward a collector 47 disposed below the nozzle 45.
  • the power supply 46 is a voltage application unit that applies a voltage to the nozzle 45 and the collector 47, thereby charging the nozzle 45 to a first polarity and charging the collector 47 to a second polarity opposite to the first polarity.
  • the solution becomes charged by passing through the charged nozzle 45, and comes out of the nozzle 45 in a charged state.
  • the power supply 46 applies a voltage to the solution, causing it to be ejected from the nozzle 45 onto the photoelectric conversion layer 16 (see Figure 6). This forms a nanofiber layer 19 (see Figure 7) on the photoelectric conversion layer 16 (see Figure 6).
  • the holding member 44 and the nozzle 45 are electrically connected, and a voltage is applied to the nozzle 45, i.e., the solution, via the holding member 44 by connecting the power source 46 to the holding member 44, but the method of applying a voltage to the nozzle 45 is not limited to this.
  • a configuration in which the power source 46 is connected to the nozzle 45 to apply a voltage to the nozzle 45, i.e., the solution may also be used.
  • the nozzle 45 is positively charged and the collector 47 is negatively charged by the power source 46, but the polarities of the nozzle 45 and the collector 47 may be reversed.
  • the collector 47 side may be earthed to set the potential to 0.
  • the solution is ejected from the nozzle 45 toward the collector 47 as a spinning jet 49 by charging due to the application of a voltage.
  • a voltage is applied to the nozzle 45, but this is not limiting.
  • a voltage may be applied to the pipe 43 to charge the solution, and the charged solution may be guided to the nozzle 45.
  • the collector 47 is for attracting the solution discharged from the nozzle 45 and collecting the formed nanofibers, and collects the nanofibers on the photoelectric conversion layer 16 of the laminated substrate 27 .
  • the collector 47 may be made of any material that becomes charged when a voltage is applied from the power source 46, and may be made of stainless steel, for example.
  • the collector 47 may be configured to be movable. With this, the laminated base material 27 is placed on the collector 47, and the position of the photoelectric conversion layer 16 with respect to the nozzle 45 can be adjusted by moving the collector 47 to move the laminated base material 27.
  • the spinning chamber 48 contains, for example, a nozzle unit and a collector 47.
  • the spinning chamber 48 is configured to be sealable, so that it is possible to prevent the solvent gas from leaking out of the spinning chamber 48.
  • the solvent gas is the evaporated solvent of the solution.
  • the appropriate value of the distance L between the nozzle 45 and the collector 47 varies depending on the types of cellulose-based polymer and solvent, the mass ratio of the solvent in the solution, etc., but is preferably within the range of 30 mm to 500 mm.
  • the voltage applied between the nozzle 45 and the collector 47 is not particularly limited, but is, for example, 5 kV to 200 kV. From the viewpoint of forming thin nanofibers, it is preferable that the voltage is as high as possible within this range, for example, 40 kV.
  • the fiber material used to form the nanofiber layer is, for example, a cellulose-based polymer.
  • the cellulose-based polymer is, for example, cellulose acylate.
  • Cellulose acylate is a cellulose ester in which some or all of the hydrogen atoms constituting the hydroxyl groups of cellulose are substituted with acyl groups.
  • Examples of the cellulose acylate include cellulose triacetate (TAC), cellulose diacetate (DAC), cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB).
  • TAC cellulose triacetate
  • DAC cellulose diacetate
  • CAP cellulose acetate propionate
  • CAB cellulose acetate butyrate
  • examples of the cellulose-based polymer include cellulose propionate, cellulose butyrate, nitrocellulose, ethyl cellulose, carboxymethylethyl cellulose, and mixtures thereof.
  • the fiber material preferably has electrical insulation properties.
  • the fiber material preferably has an electrical resistivity of 10 12 ⁇ cm or more.
  • a cellulosic polymer is preferred as the fiber material because it is optically transparent and electrically insulating.
  • the solvent for the fiber material is, for example, a mixture of several compounds.
  • a mixture of dichloromethane and methanol is used as the solvent for the fiber material. It is preferable to use the above-mentioned mixture of dichloromethane and methanol as the solvent, because the evaporation rate of the solvent can be adjusted to maintain high fiber productivity due to the quick drying property of dichloromethane while making it easier to obtain continuous fibers that do not break during spinning.
  • solvents that dissolve cellulose-based polymers include methanol, ethanol, isopropanol, butanol, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, dimethylformamide, N-methylpyrrolidone (NMP), diethyl ether, dioxane, tetrahydrofuran, and 1-methoxy-2-propanol.
  • NMP N-methylpyrrolidone
  • a solvent may be used alone as a solvent depending on the type of cellulose-based polymer, or a mixture of a plurality of these compounds may be used as a solvent.
  • a solvent When a solvent is used alone, the formation of foreign matter becomes significant when the boiling point of the solvent is approximately 50° C. or less.
  • a solvent with a low boiling point is prone to forming foreign matter because the evaporation rate of the solvent is fast. In order to suppress this, it is preferable to mix a solvent with a high boiling point to adjust the evaporation rate of the solvent.
  • the process of forming the nanofiber layer can be carried out by applying a voltage to a solution in which the fiber material is dissolved in the above-mentioned solvent and spraying the solution from a nozzle onto the photoelectric conversion layer, or by using, for example, an electrobubble spinning method or a fixed wire electrode method.
  • the electrobubble spinning method is a method in which compressed gas is supplied to a solution and a voltage is applied to the generated bubbles, causing the solution to fly in a linear fashion from the bubble surface, forming nanofibers. This method has been introduced by Hirose Paper Co., Ltd.
  • the fixed wire electrode method is a method for forming nanofibers by applying a solution to a wire with fixed ends and applying a voltage between the wire and a collector.
  • a fiber forming device using the fixed wire electrode method is sold by, for example, Elmarco Co., Ltd.
  • solar cell 11 shown in FIG. 5 can also be manufactured by the same manufacturing method as solar cell 10.
  • Solar cell 11 shown in FIG. 5 can be manufactured using the manufacturing method for solar cell 10 described above, except that the configuration of layered substrate 27 shown in FIG. 6 above is different.
  • Layered substrate 27 for solar cell 11 shown in FIG. 5 is configured using conductive substrate 13 (see FIG. 3), not shown, instead of substrate 12 and substrate-side electrode 14 shown in FIG. 6.
  • the support is not particularly limited as long as it can hold a solar cell composed of each layer formed thereon, and can be appropriately selected depending on the purpose, for example, glass, plastic film, etc.
  • the support is preferably a flexible material such as a plastic film.
  • the flexibility described above is preferably capable of being curved to a radius of curvature of 2 cm or less, and more preferably capable of being curved to a radius of curvature of 1 cm or less, as a guideline for preventing deterioration of photoelectric conversion characteristics even when deformed due to handling, heating, cooling, etc. during or after manufacture. Note that hereinafter, flexibility is as described above.
  • thermoplastic resins such as polyester resin, methacrylic resin, resin made of methacrylic acid-maleic acid copolymer, polystyrene resin, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, resin made of cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, fluorene ring modified polyester resin, and acryloyl compounds.
  • thermoplastic resins such as polyester resin, methacrylic resin, resin made of methacrylic acid-maleic acid copolymer, polystyrene resin, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, poly
  • the plastic film preferably has heat resistance.
  • the heat resistance preferably satisfies at least one of the physical properties of a glass transition temperature (Tg) of 100° C. or higher and a linear thermal expansion coefficient of 40 ppm/K or lower.
  • Tg and linear expansion coefficient of the plastic film are measured by the method for measuring transition temperature of plastics described in JIS-K7121 and the method for testing linear expansion coefficient of plastics by thermomechanical analysis described in JIS-K7197.
  • thermoplastic resins with excellent heat resistance include polyethylene naphthalate (PEN: 120°C (Tg, the same applies below)), polycarbonate (PC: 140°C), alicyclic polyolefins (for example, Zeonor 1600 (product name): 160°C, manufactured by Zeon Corporation), polyarylate (PAr: 210°C), polyethersulfone (PES: 220°C), polysulfone (PSF: 190°C), and cycloolefins.
  • PEN polyethylene naphthalate
  • PC 140°C
  • alicyclic polyolefins for example, Zeonor 1600 (product name): 160°C, manufactured by Zeon Corporation
  • PAr polyarylate
  • PES polyethersulfone
  • PSF polysulfone
  • Examples of such compounds include fluorene copolymers (COC: compounds in JP 2001-150584 A: 162°C), fluorene ring-modified polycarbonates (BCF-PC: compounds in JP 2000-227603 A: 225°C), alicyclic ring-modified polycarbonates (IP-PC: compounds in JP 2000-227603 A: 205°C), acryloyl compounds (compounds in JP 2002-80616 A: 300°C or higher), polyimides, etc.
  • COC fluorene copolymers
  • BCF-PC compounds in JP 2000-227603 A: 225°C
  • IP-PC compounds in JP 2000-227603 A: 205°C
  • acryloyl compounds compounds in JP 2002-80616 A: 300°C or higher
  • polyimides etc.
  • polyethylene terephthalate and polyethylene naphthalate are preferred.
  • the support may be transparent to light depending on the direction of irradiation of the light. Transparency is as described above.
  • the thickness of the support is not particularly limited, but is, for example, from 1 to 800 ⁇ m, and preferably from 10 to 300 ⁇ m.
  • the conductive support is not particularly limited as long as it has conductivity and can hold the solar cell composed of each layer formed thereon.
  • the conductive support can be made of a material having conductivity, such as a metal or a conductive resin.
  • a metal substrate is used as the conductive support.
  • the conductive support may be transparent to light depending on the direction of light irradiation, as in the case of the support.
  • the conductive support has a thickness that is not particularly limited, but is, like the support, for example, 1 to 800 ⁇ m, and preferably 10 to 300 ⁇ m.
  • the material of the support-side electrode is not particularly limited as long as it has electrical conductivity, and examples thereof include metals, metal oxides, conductive polymers, and mixtures thereof. Among these, conductive polymers are preferred in terms of flexibility.
  • metals include magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), strontium (Sr), silver (Ag), indium (In), tin (Sn), barium (Ba), and bismuth (Bi), as well as alloys thereof.
  • metal oxides include transparent conductive oxides (TCOs) such as tin oxide, fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO).
  • TCOs transparent conductive oxides
  • FTO fluorine-doped tin oxide
  • AZO antimony-doped zinc oxide
  • ITO indium oxide
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • IWO indium tungsten oxide
  • the conductive polymer is not particularly limited as long as it is a polymer compound having conductivity, and the charge carrier to be transported may be either a hole or an electron.
  • Specific examples of the conductive polymer include polythiophene, polypyrrole, polyaniline, polyphenylenevinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and the like, and polymer compounds having a plurality of these conductive skeletons.
  • polythiophenes are preferred, with polyethylenedioxythiophene and polythienothiophene being particularly preferred. These polythiophenes are usually partially oxidized to obtain electrical conductivity.
  • the electrical conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount), and the greater the doping amount, the higher the electrical conductivity. Since polythiophenes become cationic upon partial oxidation, they require a counter anion to neutralize the charge. An example of such a polythiophene is polyethylenedioxythiophene (PEDOT-PSS) with polystyrenesulfonic acid as the counter ion. As the conductive polymer, for example, the conductive polymer described in JP 2015-191916 A can be used.
  • the support-side electrode is preferably transparent to light, like the support. Transparency is as described above.
  • the thickness of the support-side electrode is not particularly limited, but is preferably, for example, 0.01 to 30 ⁇ m.
  • the layer structure of the support-side electrode is not particularly limited, and may be a single-layer structure or a multilayer structure.
  • the electron transport layer has a function of transporting electrons generated in the photoelectric conversion layer to the support-side electrode or the conductive support.
  • the electron transport layer is formed of an electron transport material capable of transporting electrons.
  • the electron transport material is not particularly limited, but an organic material (organic electron transport material) is preferred.
  • the organic electron transport material include fullerene compounds such as [6,6]-Phenyl-C61-Butyric Acid Methyl Ester (PC61BM), perylene compounds such as perylene tetracarboxydiimide (PTCDI), and other low molecular weight compounds such as tetracyano-quinodimethane (TCNQ), and polymer compounds.
  • the thickness of the electron transport layer is not particularly limited, but is preferably from 0.001 to 10 ⁇ m, and more preferably from 0.01 to 1 ⁇ m.
  • the photoelectric conversion layer has a photoelectric conversion function and obtains electric power from incident light.
  • the photoelectric conversion layer contains a perovskite compound.
  • the perovskite compound is a compound having a perovskite crystal structure.
  • the compound having a perovskite crystal structure is not particularly limited.
  • the perovskite compounds described in International Publication No. 2019/053967, JP 2017-17166 A, and JP 2015-191916 A can be used.
  • the method for forming the photoelectric conversion layer is not particularly limited, and examples thereof include vacuum deposition, sputtering, gas phase reaction methods such as CVD (Chemical Vapor Deposition), electrochemical deposition, and printing.
  • the use of the printing method allows the solar cell to be easily formed in a large area.
  • the printing method include spin coating and casting, and when the printing method is used, a roll-to-roll method can be used.
  • the thickness of the photoelectric conversion layer is not particularly limited, and is, for example, preferably from 0.001 to 100 ⁇ m, more preferably from 0.01 to 10 ⁇ m, and particularly preferably from 0.01 to 5 ⁇ m.
  • the organic hole transport material include conductive polymers such as polythiophene, polyaniline, polypyrrole, and polysilane; spiro compounds in which two rings share a central atom such as C or Si and have a tetrahedral structure; aromatic amine compounds such as triarylamine; triphenylene compounds; nitrogen-containing heterocyclic compounds; and liquid crystalline cyano compounds.
  • the hole transport material is preferably an organic hole transport material that can be applied as a solution and becomes a solid.
  • the thickness of the hole transport layer is not particularly limited, and is, for example, preferably 50 ⁇ m or less, more preferably 100 nm to 10 ⁇ m, even more preferably 100 nm to 5 ⁇ m, and particularly preferably 100 nm to 1 ⁇ m.
  • the thickness of the hole transport layer corresponds to the average distance between the sealing layer side electrode 18 and the photoelectric conversion layer 16 in the stacking direction Ds shown in FIG.
  • a cross-sectional image of the solar cell is obtained using a scanning electron microscope (SEM) or the like, and 10 points corresponding to the distance between the sealing layer side electrode 18 and the photoelectric conversion layer 16 in the stacking direction Ds are selected in the cross-sectional image.
  • the length of each of the selected 10 points on the cross-sectional image is measured to obtain the length values of the 10 points.
  • the average of the length values of the 10 points is calculated, and the average is regarded as the thickness of the hole transport layer.
  • the sealing layer side electrode functions as a positive electrode in the solar cell.
  • the sealing layer side electrode is not particularly limited as long as it has electrical conductivity.
  • the sealing layer side electrode preferably has a structure having a high current collecting effect.
  • at least one of the support or conductive support and the sealing layer side electrode must be transparent to light. The transparency is as described above. In a solar cell, when the support or the conductive support is transparent to light and sunlight or the like is incident on the support or the conductive support side, it is more preferable that the sealing layer side electrode has a property of reflecting light.
  • Examples of materials for forming the sealing layer side electrode include metals such as platinum (Pt), gold (Au), nickel (Ni), copper (Cu), silver (Ag), indium (In), ruthenium (Ru), palladium (Pd), rhodium (Rh), iridium (Ir), osnium (Os), and aluminum (Al), the above-mentioned conductive metal oxides, carbon materials, conductive polymers, etc.
  • the carbon material may be any material that is formed by bonding carbon atoms and has conductivity, and examples of the carbon material include fullerene, carbon nanotubes, graphite, and graphene.
  • the nanofiber layer is composed of nanofibers as described above.
  • the nanofiber is made of the above-mentioned fiber material.
  • the nanofiber is formed of, for example, a cellulose-based polymer.
  • the cellulose-based polymer is, for example, cellulose acylate.
  • As the cellulose acylate the above-mentioned materials can be used.
  • the nanofibers are preferably formed from a cellulose-based polymer, which is optically transparent and electrically insulating, and the cellulose-based polymer is preferably cellulose acylate.
  • the diameter of the nanofiber is not particularly limited, but the diameter of the nanofiber is preferably 10 ⁇ m or less, more preferably 0.1 to 5 ⁇ m, and particularly preferably 0.1 to 1 ⁇ m.
  • the diameter of the nanofiber is preferably 10 ⁇ m or less as described above, because the volume occupied by the nanofiber layer that supports the hole transport layer and the sealing layer side electrode is appropriate for the hole transport layer that actually contributes to the solar cell performance.Furthermore, the diameter of the nanofiber is preferably 10 ⁇ m or less as described above, because the hole transport layer and the sealing layer side electrode can be held and physically fixed sufficiently.
  • an image of 100 nanofibers is obtained using a scanning electron microscope (SEM). Then, in the image of the 100 nanofibers, one point corresponding to the diameter of each nanofiber is measured to obtain data on the diameter of the 100 nanofibers.
  • the average value of the data on the diameter of the 100 nanofibers is calculated, and the average value is regarded as the diameter of the nanofiber.
  • the nanofiber layer is disposed inside the hole transport layer 17 and the sealing layer side electrode 18, straddling the hole transport layer 17 and the sealing layer side electrode 18 in the stacking direction Ds, and is within the sealing layer side electrode 18, so long as it does not protrude from the sealing layer side electrode 18.
  • the nanofiber layer preferably has a layer configuration of 5 to 10 layers in the stacking direction Ds (see FIG. 1).
  • the adhesive layer is provided between the sealing layer and the sealing layer side electrode, and serves to adhere the sealing layer to the sealing layer side electrode and the photoelectric conversion section, thereby fixing the sealing layer to the sealing layer side electrode and the photoelectric conversion section.
  • the adhesive layer is made of, for example, a hardened acrylic resin or a hardened epoxy resin.
  • a hardened acrylic resin any known material can be used as long as it is a cured product of a monomer or oligomer having an acrylic group in the molecule
  • the cured epoxy resin any known material can be used as long as it is a cured product of a monomer or oligomer having an epoxy group in the molecule.
  • Epoxy resins include water-dispersed, solvent-free, solid, heat-cured, mixed with curing agent, and UV-cured resins. Of these, heat-cured and UV-cured resins are preferred, and UV-cured resins are more preferred. UV-cured resins can be heated, and are preferably heated even after UV-cured resins.
  • Specific examples of epoxy resins include bisphenol A, bisphenol F, novolac, cyclic aliphatic, long-chain aliphatic, glycidylamine, glycidyl ether, and glycidyl ester resins. These may be used alone or in combination of two or more. It is also preferred to mix a curing agent or various additives into the epoxy resin as necessary. Epoxy resins can be made from epoxy resin compositions that are already available on the market.
  • the curing agent is not particularly limited and can be appropriately selected according to the purpose.
  • the curing agent include amine-based, acid anhydride-based, polyamide-based, and other curing agents.
  • examples of the amine-based curing agent include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
  • Examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, het acid anhydride, and dodecenyl succinic anhydride.
  • Examples of other curing agents include imidazoles and polymercaptan. These may be used alone or in combination of two or more. It is also preferable to mix a curing agent or various additives with the epoxy resin as necessary. Commercially available epoxy resin compositions can be used.
  • the additives are not particularly limited and can be appropriately selected according to the purpose.
  • a filler, a gap agent, a polymerization initiator, a drying agent (moisture absorbent), a curing accelerator, a coupling agent, a flexibilizer, a colorant, a flame retardant assistant, an antioxidant, an organic solvent, etc. are mentioned.
  • a filler, a gap agent, a curing accelerator, a polymerization initiator, a drying agent (moisture absorbent) are preferred, and a filler and a polymerization initiator are more preferred.
  • the adhesive layer is formed using, for example, a thermosetting epoxy resin or an ultraviolet-curing epoxy resin.
  • the encapsulation layer is for protecting the solar cell.
  • the sealing layer 22 is provided to prevent substances that deteriorate the photoelectric conversion layer, such as water and oxygen, from penetrating into the photoelectric conversion layer.
  • the sealing layer 22 covers the surface 20a of the adhesive layer 20 and covers the periphery of the photoelectric conversion layer 16.
  • the sealing layer may be, for example, a film of silicon or aluminum oxide, nitride, or oxynitride formed on a PET (polyethylene terephthalate) film or a PEN film.
  • the sealing layer may have a surface functional layer on the surface opposite to the photoelectric conversion layer, if necessary.
  • the surface functional layer examples include a matting agent layer, an anti-reflection layer, a hard coat layer, an anti-fogging layer, an anti-soiling layer, and an easy-adhesion layer.
  • the surface functional layer is described in detail in JP-A-2006-289627.
  • the solar cell is not limited to the above-mentioned configuration, and may have, for example, a configuration having a blocking layer (not shown) and a porous layer (not shown) between the support-side electrode or the conductive support and the photoelectric conversion layer.
  • a configuration having a blocking layer (not shown) and a porous layer (not shown) between the support-side electrode or the conductive support and the photoelectric conversion layer In this case, the support-side electrode or the conductive support, the blocking layer, the porous layer, and the photoelectric conversion layer are laminated in this order.
  • Blocking Layer In a solar cell, for example, when the photoelectric conversion layer or the hole transport layer is electrically connected to the support side electrode or the like, a reverse current occurs.
  • the blocking layer serves to prevent this reverse current.
  • the blocking layer is also called a short circuit prevention layer.
  • the blocking layer can also function as a scaffold for supporting the photoelectric conversion layer.
  • the material for forming the blocking layer is not particularly limited as long as it can perform the above-mentioned functions, and is preferably a material that transmits light in the wavelength range of 400 to 800 nm and is insulating against the support-side electrode, the conductive support, etc.
  • the "insulating material for the support-side electrode and the conductive support” is a compound (n-type semiconductor compound) whose conduction band energy level is equal to or higher than the conduction band energy level of the material forming the support-side electrode and the conductive support, and lower than the conduction band energy level of the material forming the porous layer and the ground state energy level of the material forming the photoelectric conversion layer.
  • Examples of materials constituting the blocking layer include silicon oxide, magnesium oxide, aluminum oxide, calcium carbonate, cesium carbonate, polyvinyl alcohol, polyurethane, etc.
  • Materials generally used as photoelectric conversion materials may also be used, such as titanium oxide, tin oxide, zinc oxide, niobium oxide, tungsten oxide, etc. Among these, titanium oxide, tin oxide, magnesium oxide, aluminum oxide, etc. are preferred.
  • the thickness of the blocking layer is not particularly limited, but is preferably from 0.001 to 10 ⁇ m, more preferably from 0.005 to 1 ⁇ m, and particularly preferably from 0.01 to 0.1 ⁇ m.
  • the porous layer is provided between the blocking layer and the photoelectric conversion layer.
  • the porous layer functions as a scaffold for supporting the photoelectric conversion layer.
  • the porous layer is preferably a fine particle layer having pores, in which fine particles of the material forming the porous layer are deposited or adhered to each other.
  • the porous layer may be a fine particle layer in which two or more kinds of fine particles are deposited.
  • the amount of light absorbent carried (adsorbed) can be increased.
  • the surface area of the fine particles is preferably 10 times or more, more preferably 100 times or more, relative to the projected area.
  • the particle size of the fine particles forming the porous layer is preferably 0.001 to 1 ⁇ m as primary particles in the average particle size calculated by converting the projected area into a circle diameter.
  • the average particle size of the fine particles is preferably 0.01 to 100 ⁇ m as the average particle size of the dispersion.
  • the material constituting the porous layer is not particularly limited in terms of its conductivity, and may be an insulator (insulating material), a conductive material, or a semiconductor (semiconductive material).
  • materials that can be used to form the porous layer include metal chalcogenides (e.g., oxides, sulfides, selenides, etc.), compounds having a perovskite crystal structure (excluding perovskite compounds used as light absorbers), oxides of silicon (e.g., silicon dioxide, zeolite), and carbon nanotubes (including carbon nanowires and carbon nanorods, etc.).
  • the metal chalcogenide is not particularly limited, and preferred examples include oxides of titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, aluminum, or tantalum, cadmium sulfide, cadmium selenide, etc.
  • the crystal structure of the metal chalcogenide includes anatase type, brookite type, and rutile type, with anatase type and brookite type being preferred.
  • Compounds having a perovskite crystal structure are not particularly limited, and examples thereof include transition metal oxides.
  • transition metal oxides For example, strontium titanate, calcium titanate, barium titanate, lead titanate, barium zirconate, barium stannate, lead zirconate, strontium zirconate, strontium tantalate, potassium niobate, bismuth ferrate, strontium barium titanate, barium lanthanum titanate, calcium titanate, sodium titanate, and bismuth titanate are listed. Of these, strontium titanate and calcium titanate are preferred.
  • the present invention is basically configured as described above.
  • the solar cell manufacturing method and solar cell of the present invention have been described in detail above, but the present invention is not limited to the above-mentioned embodiment, and various improvements and modifications may of course be made within the scope of the gist of the present invention.
  • Example 1 is a solar cell having the configuration shown in FIG.
  • the organic layer coating composition shown below was applied onto a PET (polyethylene terephthalate) film having a thickness of 100 ⁇ m, and then the film was dried and irradiated with ultraviolet light to form an organic layer.
  • a 50 nm thick SiN film was formed on the organic layer by CVD using trisdimethylaminosilane.
  • the organic layer coating composition shown below was applied onto the SiN film, and then the film was dried and irradiated with ultraviolet light to form an organic layer. This was used as a support.
  • a composition was prepared containing a polymerizable compound (trimethylolpropane triacrylate (TMPTA) 100 parts by mass, manufactured by Daicel Cytec Co., Ltd.), a photopolymerization initiator (Irgacure 184, manufactured by Chiba Chemical Co., Ltd.), 3 parts by mass of a silane coupling agent shown below, and methyl ethyl ketone (MEK).
  • TMPTA trimethylolpropane triacrylate
  • Irgacure 184 manufactured by Chiba Chemical Co., Ltd.
  • MEK methyl ethyl ketone
  • R represents CH 2 CHCOOCH 2.
  • the above silane coupling agent was synthesized with reference to the method described in JP 2009-67778 A.
  • a fluorine-doped SnO2 conductive film (thickness 300 nm) was formed on the organic layer of the support.
  • the fluorine-doped SnO2 conductive film i.e., the fluorine-doped tin oxide (FTO) conductive film, is a transparent conductive film and is the support side electrode.
  • the support side electrode formed on the support is called the support side electrode/support.
  • ⁇ Preparation of Blocking Layer Solution A 15% by weight solution of titanium (IV) isopropoxide (acetylacetonate) in isopropanol (manufactured by Aldrich) was diluted with 1-butanol to prepare a 0.02 M solution for the blocking layer.
  • the prepared 0.02 M blocking layer solution was applied to the support side electrode by spraying. The solution was heated in air from room temperature (25° C.) at a rate of 10° C./min until it reached a temperature of 500° C., and then held for 1 hour to form a blocking layer (film thickness 50 nm) made of titanium oxide on the SnO 2 conductive film of the support side electrode/support.
  • the porous layer corresponds to the electron transport layer.
  • the prepared light absorber solution A was applied onto the porous layer by spin coating (2000 rpm (revolutions per minute) for 60 seconds, followed by 3000 rpm for 60 seconds), and the applied light absorber solution A was dried on a hot plate at 100°C for 40 minutes to form a photosensitive layer (film thickness 350 nm (including the film thickness of the porous layer 300 nm)) as a photoelectric conversion layer having a perovskite compound .
  • the obtained perovskite compound was CH3NH3PbI3 .
  • ⁇ Formation of nanofiber layer> A mixture of dichloromethane and NMP (N-methylpyrrolidone) was used as the mixed solvent, and TAC (cellulose triacetate) was used as the fiber material.
  • a solution for electrospinning was prepared by dissolving TAC (cellulose triacetate) as a fiber material in the mixed solvent. A voltage of 40 kV was applied while the above-mentioned solution for electrospinning was discharged from a nozzle at a flow rate of 0.5 mL/h onto the photoelectric conversion layer, to form a nanofiber layer composed of nanofibers with a diameter of 0.7 ⁇ m.
  • the hole transport material solution was applied to the photoelectric conversion layer by spin coating so as to cover the nanofiber layer, and the applied hole transport material solution was dried to form a hole transport layer (film thickness 0.5 ⁇ m). After the hole transport layer was formed, at least a part of the nanofiber layer protruded from the surface of the hole transport layer opposite to the photoelectric conversion layer.
  • sealing layer side electrode> Gold was deposited by evaporation on the surface of the hole transport layer opposite the photoelectric conversion layer to cover the nanofiber layer protruding from the opposite surface, thereby forming a sealing layer side electrode (film thickness 300 nm). In this manner, a laminate having a layer structure of sealing layer side electrode/hole transport layer/photoelectric conversion layer/porous layer/electron blocking layer/support side electrode/support was obtained.
  • sealing layer > 1.0 g of hydrotalcite and epoxy resin manufactured by Epoch Corporation (E-01-001 (product number) base: 4.0 g, curing agent: 2.0 g) were mixed and applied onto a laminate of sealing layer side electrode/hole transport layer/photoelectric conversion layer/porous layer/electron blocking layer/support side electrode/support using spin coating (1000 rpm, 120 seconds), and unnecessary parts were removed with acetone. Next, a sealing layer was attached thereon and heated at 80°C for 1 hour to form a solar cell. A PET film (Barrierox manufactured by Toray Industries, Inc.) on which aluminum oxide was vapor-deposited was used for the sealing layer. In this manner, a solar cell was produced.
  • Example 2 Example 2 was the same as Example 1, except that the fiber material dissolved in the mixed solvent was changed from TAC to DAC (cellulose diacetate).
  • Example 3 Example 3 was the same as Example 1, except that the fiber material dissolved in the mixed solvent was changed from TAC to CAP (cellulose acetate propionate).
  • Example 4 Example 4 was the same as Example 1, except that the mixed solvent was changed from a mixture of dichloromethane and NMP (N-methylpyrrolidone) to a mixture of dichloromethane and methanol.
  • NMP N-methylpyrrolidone
  • Comparative Example 1 was the same as Example 1, except that no nanofiber layer was formed.
  • the battery characteristic test was performed using a solar simulator "WXS-85H" (manufactured by WACOM Corporation) by irradiating the sealing layer side with 1000 W/ m2 artificial sunlight from a xenon lamp passed through an AM (Air Mass) 1.5 filter.
  • WACOM-85H manufactured by WACOM Corporation
  • AM Air Mass 1.5 filter
  • the current-voltage characteristics were measured using an IV tester to determine the initial photoelectric conversion efficiency ( ⁇ (%)).
  • Decrease rate (%) 100 ⁇ 100 ⁇ (photoelectric conversion efficiency after aging)/(initial photoelectric conversion efficiency) ⁇ - Moisture resistance evaluation criteria -
  • Adhesion evaluation criteria A: None of the 10 pieces peeled off. B: 1-2 pieces peeled off out of the 10 pieces. C: 3-4 pieces peeled off out of the 10 pieces. D: 5 or more pieces peeled off out of the 10 pieces.
  • Comparative Example 1 After storage for 24 hours under conditions of a temperature of 85° C. and a humidity of 85% RH (relative humidity), all 10 batteries peeled off. Therefore, after storage for 24 hours under conditions of a temperature of 85° C. and a humidity of 85% RH (relative humidity), the above-mentioned battery characteristic test could not be performed. For this reason, Comparative Example 1 is marked with a “-” in the “Moisture Resistance” column in Table 1. As shown in Table 1, in Examples 1 to 4, no peeling occurred even after storage for 24 hours under conditions of a temperature of 85° C. and a humidity of 85% RH (relative humidity). Furthermore, the decrease in photoelectric conversion efficiency was suppressed, and power generation capacity was maintained.

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Abstract

L'invention concerne un procédé de fabrication de cellule solaire et une cellule solaire dans lesquels l'apparition d'un pelage ou similaire de chacune des couches constituant une cellule solaire est supprimée et la détérioration des caractéristiques de conversion photoélectrique est supprimée. Le procédé de fabrication de cellule solaire est un procédé de fabrication d'une cellule solaire présentant une configuration en couches dans laquelle au moins une couche de conversion photoélectrique, une couche de transport de trous et une électrode sont stratifiées dans cet ordre, le procédé comprenant : une étape consistant à former une couche de nanofibres composée de nanofibres sur une couche de conversion photoélectrique ; et une étape de formation d'une couche de transport de trous sur la couche de conversion photoélectrique de façon à recouvrir la couche de nanofibres. Après la formation de la couche de transport de trous, au moins une partie de la couche de nanofibres fait saillie depuis une surface opposée à la couche de conversion photoélectrique de la couche de transport de trous. Le procédé comprend en outre une étape consistant à former une électrode sur la surface de la couche de transport de trous de façon à recouvrir la couche de nanofibres faisant saillie depuis la surface.
PCT/JP2024/035142 2023-10-27 2024-10-01 Procédé de fabrication de cellule solaire et cellule solaire WO2025088993A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013506965A (ja) * 2009-10-02 2013-02-28 サウス ダコタ ステイト ユニバーシティ 半導体ナノ粒子／ナノファイバ複合材電極
WO2018168225A1 (fr) * 2017-03-17 2018-09-20 コニカミノルタ株式会社 Composition pour la production de dispositif électronique, procédé de production de composition pour la production de dispositif électronique, film mince organique et procédé de production de film mince organique
US20190319207A1 (en) * 2018-04-16 2019-10-17 Tsinghua University Polymer solar cell
JP2021132108A (ja) * 2020-02-19 2021-09-09 シャープ株式会社 光電変換素子、及び光電変換素子の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013506965A (ja) * 2009-10-02 2013-02-28 サウス ダコタ ステイト ユニバーシティ 半導体ナノ粒子／ナノファイバ複合材電極
WO2018168225A1 (fr) * 2017-03-17 2018-09-20 コニカミノルタ株式会社 Composition pour la production de dispositif électronique, procédé de production de composition pour la production de dispositif électronique, film mince organique et procédé de production de film mince organique
US20190319207A1 (en) * 2018-04-16 2019-10-17 Tsinghua University Polymer solar cell
JP2021132108A (ja) * 2020-02-19 2021-09-09 シャープ株式会社 光電変換素子、及び光電変換素子の製造方法

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