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WO2012020657A1 - Film conducteur transparent, procédé pour sa fabrication, dispositif électronique organique et cellule solaire à film mince organique - Google Patents

Film conducteur transparent, procédé pour sa fabrication, dispositif électronique organique et cellule solaire à film mince organique Download PDF

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Publication number
WO2012020657A1
WO2012020657A1 PCT/JP2011/067542 JP2011067542W WO2012020657A1 WO 2012020657 A1 WO2012020657 A1 WO 2012020657A1 JP 2011067542 W JP2011067542 W JP 2011067542W WO 2012020657 A1 WO2012020657 A1 WO 2012020657A1
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Prior art keywords
conductive
polymer layer
layer
conductive polymer
mesh
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English (en)
Japanese (ja)
Inventor
東　耕平
塚原　次郎
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Fujifilm Corp
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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 transparent conductive film, a manufacturing method thereof, an organic electronic device, and an organic thin film solar cell.
  • a bulk hetero type photoelectric change layer (referred to as “bulk hetero layer” as appropriate) formed by mixing an electron transport material and a hole transport material between two different electrodes. What is arranged is common.
  • Bulk hetero-type organic thin-film solar cells are easier to manufacture than flexible solar cells using amorphous silicon or the like, and have the advantage of being able to manufacture solar cells of any area at a low cost. Yes.
  • the electrode on the light receiving side has high transparency.
  • a metal oxide thin film is usually used.
  • ITO indium tin oxide
  • the ITO film is formed by a vapor phase method, is expensive, and requires a manufacturing facility for vapor phase film formation.
  • an alternative electrode material is currently required.
  • a transparent conductive film that satisfies the required performance without using ITO is required.
  • a transparent conductive film in which a conductive metal mesh and a conductive polymer are combined has been disclosed (see, for example, JP 2009-76668 A and JP 2009-231194 A).
  • An object of the present invention is to provide a transparent conductive film having high conductivity and good device physical properties when used as an electrode of an organic electronic device, and a method for producing the same. Moreover, the further objective of this invention is to provide organic electronic devices, such as an organic thin-film solar cell with high electric power generation efficiency using the transparent conductive film of the said this invention.
  • a support a conductive mesh disposed on the support, and a first conductive polymer layer disposed in contact with the conductive mesh in an opening of the conductive mesh and on the conductive mesh And a second conductive polymer layer having a volume resistivity higher than that of the first conductive polymer layer and disposed on the first conductive polymer layer.
  • Conductive film
  • ⁇ 2> a support, a conductive mesh disposed on the support, a first conductive polymer layer disposed in contact with the conductive mesh in an opening of the conductive mesh, and the first A second conductive polymer layer having a volume resistivity higher than that of the conductive polymer layer, and disposed on the conductive mesh and the first conductive polymer layer.
  • Transparent conductive film ⁇ 3> The transparent conductive film according to ⁇ 1> or ⁇ 2>, wherein the conductive mesh contains silver.
  • ⁇ 4> The transparent conductive film according to any one of ⁇ 1> to ⁇ 3>, wherein the conductive mesh includes silver and a hydrophilic polymer.
  • ⁇ 5> The transparent conductive film according to any one of ⁇ 1> to ⁇ 4>, wherein a line width of the conductive mesh in plan view is 1 ⁇ m or more and 20 ⁇ m or less.
  • ⁇ 6> The transparent conductive film according to any one of ⁇ 1> to ⁇ 5>, wherein a pitch of the conductive mesh in plan view is 50 ⁇ m or more and 500 ⁇ m or less.
  • ⁇ 7> The transparent conductive film according to any one of ⁇ 1> to ⁇ 6>, wherein an area of an opening serving as a repeating unit in the conductive mesh is 1 ⁇ 10 ⁇ 8 m 2 or more and 1 ⁇ 10 ⁇ 7 m 2 or less. .
  • ⁇ 8> The transparent conductive film according to any one of ⁇ 1> to ⁇ 7>, wherein the first conductive polymer layer and the second conductive polymer layer contain a polythiophene derivative.
  • the polythiophene derivative is polyethylenedioxythiophene.
  • the volume resistivity of the first conductive polymer layer is 5 ⁇ 10 ⁇ 1 ⁇ cm or less, and the volume resistivity of the second conductive polymer layer is 10 ⁇ cm or more.
  • ⁇ 1> to ⁇ 8> The transparent conductive film according to any one of the above.
  • the first conductive polymer layer contains a polythiophene derivative with a volume resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less
  • the second conductive polymer layer contains a polythiophene derivative with a volume resistivity of 10 ⁇ cm or more.
  • ⁇ 13> The transparent conductive film according to any one of ⁇ 1> to ⁇ 11>, the photoelectric conversion layer disposed on the second conductive polymer layer of the transparent electrode film, and the transparent conductive film
  • a step of forming a conductive mesh on a support a step of forming a first conductive polymer layer in the opening of the conductive mesh and on the conductive mesh, and on the first conductive polymer layer Forming a second conductive polymer layer having a volume resistivity higher than the volume resistivity of the first conductive polymer layer.
  • a step of forming a conductive mesh on the support a step of forming a first conductive polymer layer in contact with the conductive mesh in the opening of the conductive mesh, the conductive mesh and the first conductive Forming a second conductive polymer layer having a volume resistivity higher than the volume resistivity of the first conductive polymer layer on the conductive polymer layer.
  • the step of forming a conductive mesh on the support includes a step of performing pattern exposure on the coating film for forming the conductive mesh, a step of developing the pattern-exposed coating,
  • an organic electronic device such as a transparent conductive film having high conductivity and good device physical properties when used as an electrode of an organic electronic device, a method for producing the transparent conductive film, and an organic thin film solar cell having high power generation efficiency.
  • a bulk hetero type organic thin film solar cell is an organic thin film solar cell in which a photoelectric conversion layer is a bulk hetero layer, and the bulk hetero layer is a mixed layer of a hole transport material and an electron transport material.
  • the mixed layer may be a layer in which a plurality of materials are uniformly mixed, or may be a layer that is microscopically phase-separated.
  • a transparent conductive film having a conductive mesh and a conductive polymer as a conductive layer has a lower surface resistance than ITO and is essentially preferable for electronic devices.
  • a bulk hetero type organic thin film solar cell is essentially preferable because of high conversion efficiency compared to other organic thin film solar cells (for example, planar hetero type organic thin film solar cells). For this reason, producing a bulk hetero type organic thin film solar cell using a transparent conductive film having a conductive mesh and a conductive polymer as a conductive layer is one of the most preferable methods for obtaining a highly efficient flexible organic thin film solar cell. It is thought that.
  • the cause of the leakage current is that electrons leak from the electron transport material present in the bulk hetero layer to the conductive layer.
  • the present inventors have provided a conductive polymer layer having a low volume resistivity at least in the opening of the conductive mesh, and a conductive polymer layer having a high volume resistivity is laminated thereon. It has been found that the object of the present invention is achieved. That is, in the transparent conductive film of the present invention, the conductive polymer in contact with the opening of the conductive mesh is made highly conductive rather than simply laminating the conductive mesh and the conductive polymer layer on the light transmissive support.
  • the device is designed to reduce the conductivity of the conductive polymer in contact with the photoelectric conversion layer. By this device, we succeeded in greatly suppressing the leakage current.
  • a bulk hetero type organic thin film solar cell having higher power generation efficiency than a transparent conductive film formed only of a conductive polymer or a transparent conductive film combining a conductive mesh and one conductive polymer layer. can get. This will become clear from the following examples.
  • FIG. 1A is a schematic cross-sectional view showing one embodiment of the transparent conductive film of the present invention
  • FIG. 2 is a schematic plan view showing an example of a pattern of a conductive mesh.
  • the transparent conductive film 10 of the embodiment shown in FIG. 1A includes at least a light-transmitting substrate 12 as a support, a conductive mesh 14 disposed on the substrate 12, and an opening 20 of the conductive mesh 14. And a first conductive polymer layer 16 disposed on and in contact with the conductive mesh 14 and a second conductive polymer layer 18 disposed on the first conductive polymer layer 16. It is comprised including.
  • the transparent conductive film according to this embodiment has the above-described configuration, the transparent conductive film has good conductivity, and when used as an electrode of an organic electronic device, gives a good device with little leakage current. For this reason, the transparent conductive film 10 of this invention is useful for manufacture of a lightweight flexible organic thin-film solar cell and an organic electroluminescent element.
  • the organic thin-film solar cell using the transparent conductive film 10 of the present invention is excellent in power generation efficiency.
  • the method for producing the transparent conductive film 10 of the present invention having such a configuration is not particularly limited.
  • a hole block layer an exciton diffusion prevention layer, a hole transport layer, an electron transport layer, a hole collection layer, an electron collection layer, an easily bonding layer
  • a known layer such as a layer, a protective layer, a gas barrier layer, a matting agent layer, an antireflection layer, a hard coat layer, an antifogging layer, or an antifouling layer may be further provided.
  • the surface resistance value is preferably 10 ⁇ / sq or less, more preferably 3 ⁇ / sq or less. More preferably, it is 1 ⁇ / sq or less.
  • the surface resistance value of the transparent conductive film 10 of this invention is mainly determined by the electroconductivity of a conductive mesh. That is, in the present invention, it is possible to obtain a surface resistance value of 10 ⁇ / sq or less with only the conductive mesh.
  • the power generation efficiency is low.
  • the transparent conductive film 10 of the present invention includes a low-resistance first conductive polymer layer 16 that covers the conductive mesh 14 and a high-resistance second conductive polymer on the first conductive polymer layer 16.
  • a surface electrode can be formed and a surface resistance value of 10 ⁇ / sq or less can be obtained.
  • the transparent conductive film 10 of the present invention is suitable as a transparent electrode of an organic electronic device.
  • An organic electronic device provided with the counter electrode arranged oppositely can be constituted.
  • the transparent conductive film 10 of the present invention is particularly preferably used as a member of an organic thin film solar cell.
  • the organic thin film solar cell includes at least the transparent conductive film of the present invention, a photoelectric conversion layer, and a second electrode, and the transparent conductive film of the present invention functions as a first electrode.
  • the first electrode can be used as both a positive electrode (cathode) and a negative electrode (anode).
  • the first electrode should be used as the positive electrode. Is preferred.
  • the transparent conductive film of the present invention is also suitably used as a member of an organic electroluminescent element.
  • an organic electroluminescent element is equipped with the transparent conductive film of the said this invention, a light emitting layer, and a 2nd electrode at least, and the transparent conductive film of this invention functions as a 1st electrode.
  • the first electrode can be used as both an anode (anode) and a cathode (cathode), but a hole transportable one is generally selected as the conductive polymer. Is preferred.
  • the support used for the transparent conductive film of the present invention is not particularly limited as long as it has a smooth surface capable of holding a conductive mesh or a polymer layer, and may be appropriately selected according to the purpose.
  • a plastic film substrate will be described as a representative example of the support.
  • the plastic film substrate is not particularly limited as long as it can hold a conductive mesh and a water-soluble polymer layer, which will be described later, and can be appropriately selected according to the purpose.
  • the film has excellent transparency to light in the wavelength range of 400 nm to 800 nm.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
  • thermoplastic resins such as a ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.
  • the plastic film substrate is preferably made of a heat-resistant material.
  • the glass transition temperature (Tg) has a heat resistance satisfying at least one of physical properties of 100 ° C. or higher and a linear thermal expansion coefficient of 40 ppm / ° C. or lower. Further, as described above, the exposure wavelength is adjusted. On the other hand, it is preferable to be molded from a material having high transparency.
  • the Tg and linear expansion coefficient of the plastic film are measured by the plastic transition temperature measurement method described in JIS K 7121 and the linear expansion coefficient test method based on the thermomechanical analysis of plastic described in JIS K 7197. In, the value measured by this method is used.
  • thermoplastic resin having excellent heat resistance for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C.
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • alicyclic polyolefin for example, ZEONOR 1600: 160 ° C.
  • the plastic film used as the support substrate 12 in the transparent conductive film 10 of the present invention is required to be transparent to light. More specifically, the light transmittance for light in the wavelength range of 400 nm to 800 nm is usually preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the thickness of the plastic film is not particularly limited, but is typically 1 ⁇ m to 800 ⁇ m, preferably 10 ⁇ m to 300 ⁇ m.
  • a known functional layer may be provided on the back surface of the plastic film (the surface on which the conductive mesh is not provided). Examples of the functional layer include a gas barrier layer, a mat agent layer, an antireflection layer, a hard coat layer, an antifogging layer, and an antifouling layer.
  • the functional layer is described in detail in paragraph numbers [0036] to [0038] of JP-A-2006-289627.
  • the surface of the plastic film substrate (the surface on which the conductive mesh is placed) may have an easy adhesion layer or an undercoat layer from the viewpoint of improving adhesion.
  • the easy adhesion layer or the undercoat layer may be a single layer or a multilayer.
  • Various hydrophilic undercoat polymers are used to form the easy-adhesion layer or the undercoat layer. Examples of hydrophilic undercoat polymers used in the present invention include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol and other water-soluble polymers, carboxymethylcellulose, cellulose esters such as hydroxyethylcellulose, and vinyl chloride-containing copolymers.
  • Examples include latex polymers such as vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers, and butadiene-containing copolymers, polyacrylic acid copolymers, and maleic anhydride copolymers. Is done.
  • the coating thickness after drying the easy-adhesion layer or undercoat layer is preferably in the range of 50 nm to 2 ⁇ m.
  • a support body as a temporary support body, it is also possible to give an easily peelable process to the support surface.
  • the conductive mesh 14 is formed of various metal materials.
  • the metal material include gold, platinum, iron, copper, silver, aluminum, chromium, cobalt, and stainless steel.
  • Preferable examples of the metal material include low resistance metals such as copper, silver, aluminum, and gold. Among them, silver or copper having excellent conductivity is preferably used.
  • the mesh pattern Stripes, squares, rectangles, diamonds, honeycombs, or curves may be used.
  • FIG. 2 is a schematic plan view showing an example of a square mesh network pattern. These mesh designs are adjusted so that the aperture ratio (light transmittance) and the surface resistance (conductivity) have desired values. In FIG.
  • a region 20 surrounded by the conductive mesh 14 represents an opening, and the opening ratio is 70% or more, preferably 80% or more, and more preferably 85% or more.
  • the surface resistance of the conductive mesh when no conductive polymer is installed is preferably 10 ⁇ / sq or less, more preferably 3 ⁇ / sq or less, and even more preferably 1 ⁇ / sq or less. Since the light transmittance and the conductivity are in a trade-off relationship, the larger the aperture ratio, the better. However, in practice, it becomes 95% or less.
  • the thickness of the conductive mesh 14 is not particularly limited, but is usually 0.02 ⁇ m or more and 20 ⁇ m or less.
  • the line width of the fine metal wire is in the range of 1 ⁇ m or more and 500 ⁇ m or less, preferably 1 ⁇ m or more and 100 ⁇ m or less, and more preferably 3 ⁇ m or more and 20 ⁇ m or less from the viewpoint of light transmittance and conductivity.
  • the conductive polymer layer 16 formed in contact with the conductive mesh 14 has lower carrier (hole and electron) mobility than the metal conductive mesh.
  • a finer pitch of the conductive mesh is advantageous in terms of device characteristics.
  • the finer the pitch the lower the light transmission, so a compromise is chosen.
  • the pitch in plan view is preferably 50 ⁇ m or more and 2000 ⁇ m or less, more preferably 100 ⁇ m or more and 1000 ⁇ m or less, and further preferably 150 ⁇ m or more and 500 ⁇ m or less.
  • the area of the opening 20 serving as a repeating unit of the conductive mesh 14 is preferably 1 ⁇ 10 ⁇ 9 m 2 or more and 1 ⁇ 10 ⁇ 5 m 2 or less, and 3 ⁇ 10 ⁇ 9. More preferably, it is m 2 or more and 1 ⁇ 10 ⁇ 6 m 2 or less, and further preferably 1 ⁇ 10 ⁇ 8 m 2 or more and 1 ⁇ 10 ⁇ 7 m 2 or less.
  • the conductive mesh 14 may have a bus line (thick line) for large area current collection. The thickness and pitch of the bus line are appropriately selected according to the device to be used.
  • the formation method of the conductive mesh 14 in the present invention is not particularly limited, and a known formation method can be appropriately used.
  • a method in which a metal mesh prepared in advance is bonded to the substrate surface a method in which a conductive material is applied in a pattern, a conductive film is formed on the entire surface by vapor deposition or sputtering, and then etched to form a mesh-shaped conductive film.
  • a method using a silver halide photosensitive material described in JP-A No. 352073, JP-A-2009-231194, and the like hereinafter sometimes referred to as a silver salt method).
  • the conductive mesh 14 of the present invention is preferably formed by a silver salt method because the pattern is fine.
  • a coating liquid for forming the conductive mesh is provided on the support, and a pattern exposure is performed on the coating film for forming the conductive mesh, and the pattern exposure is performed.
  • a conductive mesh having a desired pattern can be formed on the support by the step of developing the coating film and the step of fixing the developed coating film.
  • the conductive mesh produced by the silver salt method is a layer of silver and a hydrophilic polymer.
  • hydrophilic polymers examples include water-soluble polymers such as gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, and polyvinyl alcohol; cellulose esters such as carboxymethyl cellulose and hydroxyethyl cellulose.
  • the layer contains substances derived from the coating, developing and fixing processes. A method of obtaining a conductive mesh having a lower resistance by forming a conductive mesh by the silver salt method and then performing copper plating is also preferably used.
  • the conductive polymer layer has a two-layer structure. That is, in the present invention, the conductive polymer layer is formed in the opening 20 of the conductive mesh 14 and on the conductive mesh 14, and the first conductive polymer layer 16 in contact with the conductive mesh 14, and the first conductive It is comprised from the 2nd conductive polymer layer 18 which exists on the polymer layer 16 and contacts an organic compound layer (for example, photoelectric conversion layer).
  • the first conductive polymer layer 16 is a low resistance layer
  • the second conductive polymer layer 18 is a high resistance layer.
  • each of the conductive polymer layers 16 and 18 needs to be transparent in the action spectrum range of the solar cell to be applied, and usually from visible light. It needs to be excellent in light transmittance of near infrared light.
  • the average light transmittance in the wavelength region of 400 nm to 800 nm when the film thickness is 0.2 ⁇ m is preferably 75% or more, and more preferably 85% or more.
  • each conductive polymer layer 16, 18 is not particularly limited as long as it is a polymer material having conductivity. With respect to the charge to be transported, either hole conductivity or electron conductivity may be used.
  • specific conductive polymers include, for example, polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. It is done. Among these, polythiophene is preferable, and polyethylenedioxythiophene is particularly preferable. These polythiophenes are usually partially oxidized in order to obtain conductivity.
  • the conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount), and the higher the doping amount, the higher the conductivity. Since polythiophene becomes cationic by partial oxidation, it has a counter anion to neutralize the charge.
  • An example of such a polythiophene is polyethylene dioxythiophene (PEDOT-PSS) having polystyrene sulfonic acid as a counter ion.
  • polymers may be added to the respective conductive polymer layers 16 and 18 as long as the desired conductivity is not impaired. Other polymers are added for the purpose of improving coatability and increasing the film strength.
  • examples of other polymers include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, 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, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin , Fluorene ring-modified polyester resins, acryloyl compounds and other thermoplastic resins, gelatin, polyvinyl alcohol, polyacrylic acid, poly
  • the first conductive polymer layer 16 in the present invention is preferably within a volume resistivity alone contains 1 ⁇ 10 -1 ⁇ cm or less of the conductive polymer, 1 ⁇ 10 -2 ⁇ cm or less of the conductive polymer More preferably.
  • the volume resistivity of the first conductive polymer layer 16 is preferably 5 ⁇ 10 ⁇ 1 ⁇ cm or less, and preferably 5 ⁇ 10 ⁇ 2 ⁇ cm or less. More preferably.
  • the second conductive polymer layer 18 preferably contains a conductive polymer having a volume resistivity of 10 ⁇ cm or more, and more preferably contains a conductive polymer having a volume resistivity of 100 ⁇ cm or more.
  • the volume resistivity of the second conductive polymer layer 18 is preferably 10 ⁇ cm or more, and more preferably 100 ⁇ cm or more.
  • the conductive polymer is an aqueous solution or a water dispersion, and therefore, a normal aqueous coating method is used for forming the conductive polymer layers 16 and 18.
  • a hydrophilic polymer is present around the conductive mesh, which is convenient for applying an aqueous dispersion.
  • Various solvents, surfactants, thickeners and the like may be added to the conductive polymer coating solution as coating aids.
  • the film thickness of the first conductive polymer layer 16 is preferably in the range of 30 nm to 3 ⁇ m, more preferably 100 nm to 1 ⁇ m, from the viewpoints of conductivity and transparency.
  • the film thickness of the second conductive polymer layer 18 is preferably in the range of 1 to 100 nm, and more preferably 5 to 50 nm, from the viewpoint of electron blocking properties and hole conductivity.
  • the transparent conductive film of the present invention may further have a functional layer depending on the purpose in addition to the above essential components.
  • the functional layer used on the surface side include a peelable temporary protective layer.
  • functional layers used on the back side include gas barrier layers, matting agent layers, antireflection layers, hard coat layers, antifogging layers, antifouling layers, and easy adhesion. Layer and the like.
  • FIG. 1B is a schematic cross-sectional view showing another embodiment of the transparent conductive film of the present invention.
  • the transparent conductive film 10 of the embodiment shown in FIG. 1B is arranged in contact with the conductive mesh 14 in the opening of the support 12, the conductive mesh 14 disposed on the support 12, and the conductive mesh 14.
  • First conductive polymer layer 16 having a volume resistivity higher than that of the first conductive polymer layer 16 and on the conductive mesh 14 and the first conductive polymer.
  • a second conductive polymer layer 18 disposed on the layer 16. As shown in FIG.
  • the first conductive polymer layer 16 is disposed in the opening of the conductive mesh 14 so as to be in contact with the conductive mesh 14, and the second conductive polymer layer 18 having high resistance is connected to the conductive mesh 14. 14 and the first conductive polymer layer 16, the first conductive polymer layer 16 imparts conductivity to the openings of the conductive mesh 14 and the second conductive polymer layer 16. Since the movement of electrons from the photoelectric conversion layer is hindered by the conductive polymer layer 18, the conversion efficiency can be improved.
  • the first conductive polymer layer 16 disposed in the opening of the conductive mesh 14 needs to be in contact with the conductive mesh 14, but the first conductive polymer layer 16 disposed in the opening of the conductive mesh 14.
  • the thickness of the polymer layer 16 is not necessarily the same as the thickness of the conductive mesh 14.
  • the first conductive polymer layer 16 is filled up to an intermediate height in the mesh opening, and the second conductive polymer layer 18 covers the conductive mesh 14 and the first conductive polymer layer 16 thereon.
  • positioned may be sufficient.
  • a step of forming a conductive mesh 14 on the support 12 and a first contact with the conductive mesh 14 in the opening of the conductive mesh 14 A step of forming a conductive polymer layer 16 and a volume resistivity higher than the volume resistivity of the first conductive polymer layer 16 on the conductive mesh 14 and the first conductive polymer layer 16; And the step of forming the second conductive polymer layer 18.
  • the transparent conductive film of the present invention can be used for purposes such as organic EL displays, organic EL lighting, dye-sensitized solar cells, and organic thin-film solar cells. Especially, it uses suitably for the organic thin-film solar cell excellent in electric power generation efficiency.
  • the organic thin film solar cell of the present invention includes the transparent conductive film (first electrode) of the present invention, a photoelectric conversion layer disposed on the second conductive polymer layer of the transparent electrode film, and the transparent conductive film. And a counter electrode (second electrode) disposed to face the film so as to sandwich the photoelectric conversion layer.
  • the first electrode may be either a positive electrode or a negative electrode.
  • the second electrode has a polarity opposite to that of the first electrode.
  • the first electrode is usually a positive electrode.
  • the configuration in which the first electrode (the transparent conductive film 10 of the present invention) is a positive electrode will be described in detail.
  • the organic thin-film solar cell using the transparent conductive film shown in FIG. 1A will be mainly described.
  • the present invention is not limited to this, and a transparent conductive film having the form shown in FIG. 1B may be used.
  • FIG. 3 schematically shows an example of the configuration of the organic thin-film solar cell of the present invention.
  • the organic thin film solar cell 30 of the present invention is most simply configured as transparent conductive film 10 / bulk heterolayer 22 / negative electrode 24).
  • An electron trapping layer may be provided between the bulk hetero layer and the negative electrode, and other organic layers may be provided between the layers as necessary.
  • the organic thin film solar cell of the present invention may take a so-called tandem configuration in which a plurality of photoelectric conversion layers are laminated.
  • the tandem element may be a serial connection type or a parallel connection type.
  • the transparent conductive film 10 of the present invention serves as a positive electrode.
  • Molybdenum oxide may be used as part of the positive electrode. In this case, for example, molybdenum oxide may be deposited on the conductive film 10 of the present invention.
  • the negative electrode can be appropriately selected from known electrode materials. Examples thereof include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, copper, aluminum, magnesium-silver alloy, indium, nickel and the like. These may be used alone or in combination of two or more.
  • silver is particularly preferable.
  • the method for forming the negative electrode is not particularly limited, and can be performed according to a known method.
  • the negative electrode is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the negative electrode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.
  • Patterning for forming the negative electrode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or vacuum deposition or sputtering may be performed with a mask overlapped. Alternatively, the lift-off method or the printing method may be used.
  • the formation position of the negative electrode is not particularly limited as long as it is disposed opposite to the transparent conductive film so as to sandwich an organic layer such as a bulk hetero layer, and may be formed on the entire organic layer. It may be formed in a part thereof. Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the negative electrode and the organic layer in a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of the negative electrode can be appropriately selected depending on the material constituting the negative electrode and cannot be generally defined, but is usually about 10 nm to 5 ⁇ m, and preferably 50 nm to 500 nm.
  • the bulk hetero layer is an organic photoelectric conversion layer in which a hole transport material and an electron transport material are mixed.
  • the mixing ratio of the hole transport material and the electron transport material is adjusted so that the conversion efficiency is the highest, but is usually selected from the range of 10:90 to 90:10 by mass ratio.
  • a method for forming such a mixed organic layer for example, a co-evaporation method by vacuum deposition is used. Or it is also possible to produce by carrying out solvent application
  • the thickness of the bulk hetero layer is preferably 10 to 500 nm, and particularly preferably 20 to 300 nm.
  • the hole transport material is a ⁇ -electron conjugated compound having a HOMO level of 4.5 to 6.0 eV, specifically, various arenes (for example, thiophene, carbazole, fluorene, silafluorene, thienopyrazine, thienobenzothiophene). , Dithienosilol, quinoxaline, benzothiadiazole, thienothiophene, etc.) coupled polymers, phenylene vinylene polymers, porphyrins, phthalocyanines, and the like.
  • Chem. Rev. The compound group described as Hole Transport material in 2007, 107, 953-1010 and the porphyrin derivative described in Journal of the American Chemical Society Vol.
  • a conjugated polymer obtained by coupling a structural unit selected from the group consisting of thiophene, carbazole, fluorene, silafluorene, thienopyrazine, thienobenzothiophene, dithienosilole, quinoxaline, benzothiadiazole, and thienothiophene is particularly preferable.
  • Specific examples include poly-3-hexylthiophene, poly-3-octylthiophene, various polythiophene derivatives described in Journal of the American Chemical Society, Vol. 130, p. 3020 (2008), Advanced Materials, Vol. 19, p. 2295 (2007).
  • the electron transport material is a ⁇ -electron conjugated compound having a LUMO level of 3.5 to 4.5 eV.
  • fullerene and its derivatives, phenylene vinylene polymers, naphthalene tetracarboxylic imide derivatives, perylene tetra Examples thereof include carboxylic acid imide derivatives. Of these, fullerene derivatives are preferred.
  • fullerene derivative examples include C 60 , phenyl-C 61 -methyl butyrate (fullerene derivative referred to as PCBM, [60] PCBM, or PC 61 BM in the literature), C 70 , phenyl-C 71 -methyl butyrate (Fullerene derivatives referred to as PCBM, [70] PCBM, or PC 71 BM in many literatures) and fullerene derivatives described in Advanced Functional Materials, Vol. 19, pp. 779-788 (2009), journals Examples of the fullerene derivative SIMEF and the like described in The American Chemical Society Vol. 131, page 16048 (2009).
  • an electron transport layer made of an electron transport material may be provided between the bulk hetero layer and the negative electrode.
  • the electron transport material that can be used for the electron transport layer include those described above and Chem. Rev. 2007, 107, 953-1010, and those described as Electron Transport Materials.
  • the electron transport layer can be suitably formed by any of various types of wet film forming methods, dry film forming methods such as vapor deposition and sputtering, transfer methods, and printing methods.
  • An electron collection layer may be provided between the bulk hetero layer and the negative electrode.
  • an electron transport material or a compound for example, bathocuproine, titanium oxide, or the like
  • the thickness of the electron trapping layer is 1 nm to 30 nm, preferably 2 nm to 15 nm.
  • the electron collection layer can be suitably formed by any of various wet film forming methods, dry film forming methods such as vapor deposition and sputtering, transfer methods, and printing methods.
  • a recombination layer is provided between the two photoelectric conversion layers.
  • an ultrathin layer of a conductive material is used as the material of the recombination layer.
  • Preferred metals include gold, silver, aluminum, platinum, ruthenium oxide and the like. Of these, silver is preferred.
  • the thickness of the recombination layer is 0.01 to 5 nm, preferably 0.1 to 1 nm, and particularly preferably 0.2 to 0.6 nm.
  • the formation method of a recombination layer For example, it can form by a vacuum evaporation method, sputtering method, an ion plating method, etc.
  • organic layer is used as a general term for layers using organic compounds such as a bulk hetero layer, a hole transport layer, an electron transport layer, an electron block layer, a hole block layer, and an exciton diffusion prevention layer.
  • the organic thin film solar cell of the present invention may be annealed by various methods for the purpose of crystallization of the organic layer and promotion of phase separation of the bulk hetero layer.
  • the annealing method include a method of heating the substrate temperature during vapor deposition to 50 ° C. to 150 ° C. and a method of setting the drying temperature after coating to 50 ° C. to 150 ° C. Further, after the formation of the second electrode is completed, annealing may be performed by heating to 50 ° C. to 150 ° C.
  • the organic thin film solar cell of the present invention may be protected by a protective layer.
  • the material contained in the protective layer MgO, SiO, SiO 2, Al 2 O 3, Y 2 O 3, TiO metal oxides such as 2, metal nitrides such as SiN x, metal nitrides such as SiN x O y
  • examples thereof include oxides, metal fluorides such as MgF 2 , LiF, AlF 3 , and CaF 2 , and polymers such as polyethylene, polypropylene, polyvinylidene fluoride, and polyparaxylylene.
  • the protective layer may be a single layer or a multilayer structure.
  • the method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, vacuum ultraviolet CVD method, coating method, printing method, transfer method can be applied.
  • a protective layer may be used as the conductive layer.
  • the organic thin film solar cell of the present invention may have a gas barrier layer.
  • the gas barrier layer is not particularly limited as long as it has a gas barrier property.
  • the gas barrier layer is an inorganic layer.
  • the inorganic substance includes boron, magnesium, aluminum, silicon, titanium, zinc, tin oxide, nitride, oxynitride, carbide, hydride, and the like. These may be pure substances, or may be a mixture of multiple compositions or a gradient material layer. Of these, aluminum oxide, nitride or oxynitride, or silicon oxide, nitride or oxynitride is preferable.
  • the inorganic layer may be a single layer or a laminate of a plurality of layers.
  • a laminate of an organic layer and an inorganic layer may be used, or an alternating laminate of a plurality of inorganic layers and a plurality of organic layers may be used.
  • the organic layer is not particularly limited as long as it is a smooth layer, but a layer made of a polymer of (meth) acrylate is preferably exemplified.
  • the thickness of the inorganic layer is not particularly limited, but usually attached to one layer, It is in the range of 5 to 500 nm, preferably 10 to 200 nm.
  • the inorganic layer may have a laminated structure including a plurality of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as disclosed in US Patent Publication No. 2004-46497, a layer in which the interface with the organic polymer layer is not clear and the composition continuously changes in the film thickness direction may be used.
  • the thickness of the organic thin layer solar cell of the present invention is preferably 50 ⁇ m to 1 mm, and more preferably 100 ⁇ m to 500 ⁇ m.
  • the silver chlorobromide cubic grain emulsion was chemically sensitized at 40 ° C. for 80 minutes using 20 mg of sodium thiosulfate per mole of silver halide. After chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) is 500 mg per mole of silver halide and 1-phenyl-5-mercaptotetrazole is 1 mole of silver halide.
  • a silver halide emulsion was obtained by adding 150 mg per unit. This silver halide emulsion had a volume ratio of silver halide grains to gelatin (silver halide grains / gelatin) of 0.625.
  • a hardening agent H-1: tetrakis (vinylsulfonylmethyl) methane
  • a surfactant SU-2: sulfosuccinate disulfate
  • (2-ethylhexyl) .sodium was added to adjust the surface tension.
  • Polyethylene naphthalate having a coating thickness of 100 ⁇ m and a transmittance of 92% (anti-reflective treatment on the back surface) was applied to the coating solution thus obtained so that the basis weight in terms of silver was 0.625 g / m 2.
  • a curing process was carried out at 50 ° C. for 24 hours to obtain a photosensitive material.
  • the obtained photosensitive material was exposed with a UV exposure device through a mesh photomask (line width: 5 ⁇ m, pitch: 300 ⁇ m).
  • FIX-1 750 mL of pure water Sodium thiosulfate 250g Anhydrous sodium sulfite 15g Glacial acetic acid 15mL Potash alum 15g Water was added to make up a total volume of 1 liter.
  • electrolytic copper plating treatment was performed at 25 ° C. using the following electrolytic plating solution, followed by washing with water and drying treatment. In addition, the current control in electrolytic copper plating was performed over 3 minutes, 3 minutes for 1 minute and then 12 minutes for 1A. After the completion of the plating treatment, the plate was rinsed with tap water for 10 minutes to carry out a water washing treatment, and dried using a dry air (50 ° C.) until it was in a dry state.
  • Electrolytic plating solution Copper sulfate (pentahydrate) 200g 50g of sulfuric acid Sodium chloride 0.1g Water was added to make up a total volume of 1000 mL.
  • first conductive polymer layer An aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (abbreviation: PEDOT-PSS) (manufactured by HC Starck Co., Ltd.) on the surface of the transparent conductive film (A-0) (side on which the conductive mesh is formed) A solution in which 5% by mass of dimethyl sulfoxide was added to Clevios PH-500) was applied. Next, this film was heated and dried at 120 ° C. for 20 minutes to form a first conductive polymer layer, and a transparent conductive film (A-1) was obtained. At this time, the film thickness of the conductive polymer layer was 200 nm.
  • PEDOT-PSS polyethylene dioxythiophene / polystyrene sulfonic acid
  • the PEDOT-PSS aqueous dispersion was applied to the cleaned glass surface and subjected to the same treatment.
  • a single layer (B-1) of a conductive polymer having a thickness of 220 nm was obtained.
  • a high-resistance PEDOT-PSS aqueous dispersion (manufactured by HC Starck Co., Clevios P-VP-AI4083) was applied to the surface of the transparent conductive film (A-0). Next, this film was heated and dried at 130 ° C. for 10 minutes to form a first conductive polymer layer, and a transparent conductive film (A-2) was obtained. At this time, the film thickness of the conductive polymer layer was 220 nm.
  • the high-resistance PEDOT-PSS aqueous dispersion was applied to the cleaned glass surface and subjected to the same treatment.
  • a single layer (B-2) of a conductive polymer having a thickness of 210 nm was obtained.
  • a comparative film (A-3) was prepared by laminating Clevios PH-500 at 200 nm and Clevios P-VP-AI4083 at 20 nm on the PEN film.
  • Second conductive polymer layer On the surface of the transparent conductive film (A-1) (the side on which the first conductive polymer layer is formed), an aqueous dispersion of the above-mentioned high-resistance PEDOT-PSS (manufactured by HC Starck, Crevius P -VP-AI4083) was applied. Next, this film was heated and dried at 130 ° C. for 10 minutes to form a second conductive polymer layer, and a transparent conductive film (F-1) was obtained. At this time, the film thickness of the second conductive polymer layer was 20 nm.
  • PEDOT-PSS manufactured by HC Starck, Crevius P -VP-AI4083
  • a transparent conductive film (F-1) of the present invention having a layer was obtained.
  • the transparent conductive film (F-2) of the present invention was produced in the same manner as (F-1) except that the line width of the mesh was changed to 30 ⁇ m by changing the exposure conditions. Further, the transparent conductive film (F-3) of the present invention was produced in the same manner as (F-1) except that the mesh pitch was changed to 600 ⁇ m by changing the exposure conditions. It will be apparent from the following examples that the transparent conductive film of the present invention exhibits excellent performance as an electrode of an organic thin film solar cell.
  • Example 1 According to the following procedure, an organic thin film solar cell having the transparent conductive film (F-1) of the present invention as a positive electrode was produced.
  • P3HT poly-3-hexylthiophene, Lisicon SP-001 (trade name), manufactured by Merck & Co., Inc.
  • PCBM [6,6] -phenyl C 61 -butylic acid methyl ester, Nanom Spectra E-100H (product) Name
  • 14 mg 14 mg (manufactured by Frontier Carbon Co., Ltd.) was dissolved in 1 ml of chlorobenzene to obtain a photoelectric conversion layer coating solution.
  • a photoelectric conversion coating solution was spin-coated on the transparent conductive film (F-1) and dried to form a photoelectric conversion layer.
  • the rotation speed of the spin coater was 2000 rpm, and the dry film thickness was 90 nm.
  • Aluminum was deposited on the photoelectric conversion layer to a thickness of 100 nm to form a negative electrode. At this time, mask deposition was performed so that the effective area of photoelectric conversion was 4 cm 2 .
  • a comparative organic thin film solar cell (PA-0, PA-1) was prepared in the same manner as in Example 1 except that the prepared A-0, A-1, or A-2 was used instead of F-1. , PA-2).
  • a comparative organic thin-film solar cell (PA-3) was obtained in the same manner as in Example 1 except that the prepared A-3 was used instead of F-1.
  • the organic thin film solar cells obtained in the examples and comparative examples were irradiated with simulated sunlight of AM1.5G, 100 mW / cm 2 using a Pexel Technologies L12 type solar simulator, and the source measure unit (SMU2400).
  • the current value was measured in a voltage range of ⁇ 0.1 V to 0.7 V using a mold (manufactured by KEITHLEY).
  • the obtained current-voltage characteristics were evaluated using a Pexel Technologies IV curve analyzer, and the characteristic parameters were calculated. The measurement results are shown in Table 1 below.
  • the PGIP of Comparative Example 4 is preferable in terms of a high short circuit current, since the surface resistance of the positive electrode is as high as 10 ⁇ / sq, the shape factor is low and the total power generation efficiency does not reach the present invention.
  • the present invention is not limited to the above embodiment and examples.
  • the conductors constituting the conductive mesh 14 have a rectangular cross-sectional shape in the thickness direction, but the cross-sectional shape is not limited.
  • the conductive wire constituting the conductive mesh 14 may have a rounded surface shape, and the thickness of the conductive polymer layer is extremely large with respect to the height of the protrusion. It may be too thin.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne un film conducteur transparent (10) comportant un support (12), un treillis conducteur (14) disposé sur le support, une première couche (16) de polymère conducteur formée sur le treillis conducteur et les ouvertures (20) du treillis conducteur de façon à être en contact avec le treillis conducteur, et une deuxième couche (18) de polymère conducteur présentant une résistivité volumique supérieure à la résistivité volumique de la première couche de polymère conducteur et formée sur la première couche de polymère conducteur. La première couche de polymère conducteur peut n'être formée que dans les ouvertures du treillis conducteur, tandis que la deuxième couche de polymère conducteur peut être formée sur le treillis conducteur et la première couche conductrice.
PCT/JP2011/067542 2010-08-12 2011-07-29 Film conducteur transparent, procédé pour sa fabrication, dispositif électronique organique et cellule solaire à film mince organique Ceased WO2012020657A1 (fr)

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WO2013128932A1 (fr) * 2012-02-29 2013-09-06 富士フイルム株式会社 Film conducteur transparent, et cellule solaire à couche mince organique équipée de celui-ci
JP2015511771A (ja) * 2012-03-16 2015-04-20 ケンブリッジ ディスプレイ テクノロジー リミテッド 光電装置
WO2016027620A1 (fr) * 2014-08-21 2016-02-25 コニカミノルタ株式会社 Électrode transparente, procédé de production d'électrode transparente et dispositif électronique
JP2017188378A (ja) * 2016-04-08 2017-10-12 学校法人五島育英会 有機導電膜およびその製造方法
WO2017212890A1 (fr) * 2016-06-06 2017-12-14 住友化学株式会社 Procédé de fabrication de dispositif organique
CN112582567A (zh) * 2020-11-27 2021-03-30 固安翌光科技有限公司 一种有机电致发光器件及其制备方法

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GB201314497D0 (en) * 2013-08-13 2013-09-25 Cambridge Display Tech Ltd An Electrode for an Organic Electronic Device
JP2024178538A (ja) * 2023-06-13 2024-12-25 三星電子株式会社 透明電極及び測定機器

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
WO2013128932A1 (fr) * 2012-02-29 2013-09-06 富士フイルム株式会社 Film conducteur transparent, et cellule solaire à couche mince organique équipée de celui-ci
JP2013211283A (ja) * 2012-02-29 2013-10-10 Fujifilm Corp 透明導電フィルム及びそれを備えた有機薄膜太陽電池
JP2015511771A (ja) * 2012-03-16 2015-04-20 ケンブリッジ ディスプレイ テクノロジー リミテッド 光電装置
WO2016027620A1 (fr) * 2014-08-21 2016-02-25 コニカミノルタ株式会社 Électrode transparente, procédé de production d'électrode transparente et dispositif électronique
JPWO2016027620A1 (ja) * 2014-08-21 2017-07-06 コニカミノルタ株式会社 透明電極、透明電極の製造方法、及び、電子デバイス
US9923165B2 (en) 2014-08-21 2018-03-20 Konica Minolta, Inc. Transparent electrode, method for producing transparent electrode and electronic device
JP2017188378A (ja) * 2016-04-08 2017-10-12 学校法人五島育英会 有機導電膜およびその製造方法
WO2017212890A1 (fr) * 2016-06-06 2017-12-14 住友化学株式会社 Procédé de fabrication de dispositif organique
JPWO2017212890A1 (ja) * 2016-06-06 2019-03-28 住友化学株式会社 有機デバイスの製造方法
CN112582567A (zh) * 2020-11-27 2021-03-30 固安翌光科技有限公司 一种有机电致发光器件及其制备方法
CN112582567B (zh) * 2020-11-27 2022-11-04 固安翌光科技有限公司 一种有机电致发光器件及其制备方法

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