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WO2012039240A1 - Procédé de production d'électrode transparente et dispositif électronique organique - Google Patents

Procédé de production d'électrode transparente et dispositif électronique organique Download PDF

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Publication number
WO2012039240A1
WO2012039240A1 PCT/JP2011/069413 JP2011069413W WO2012039240A1 WO 2012039240 A1 WO2012039240 A1 WO 2012039240A1 JP 2011069413 W JP2011069413 W JP 2011069413W WO 2012039240 A1 WO2012039240 A1 WO 2012039240A1
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group
polymer
conductive layer
transparent
transparent electrode
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Japanese (ja)
Inventor
孝敏 末松
昌紀 後藤
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Konica Minolta Inc
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Konica Minolta Inc
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom

Definitions

  • the present invention relates to a method for producing a transparent electrode excellent in electrical conductivity, transparency, washing resistance, and current uniformity, and excellent in driving voltage when used in an organic electronic device, and an organic electronic device using the same. It is.
  • a transparent electrode is an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate by a vacuum deposition method or a sputtering method. From the viewpoint of performance such as conductivity and transparency, It has been mainly used. However, the transparent electrode using the vacuum evaporation method or the sputtering method has a problem that the production cost is high because of poor productivity. Furthermore, in recent years, transparent electrodes used in organic electronic devices have been required to have a large area and a low resistance value, and the resistance value of ITO transparent electrodes has become insufficient.
  • ITO indium-tin composite oxide
  • a transparent conductive layer such as a conductive polymer, is laminated on a thin metal wire formed in a pattern so that it can be used for products that require a large area and low resistance.
  • Transparent with both current surface uniformity and high conductivity An electrode has been developed (see, for example, Patent Documents 1 and 2).
  • the transparent electrode is composed of an opening made of a thin metal wire portion and a transparent conductive layer such as a conductive polymer.
  • the resistance of the transparent conductive layer is preferably as low as possible. As the resistance of the transparent conductive layer is lower, even if the area of the opening is increased, the surface uniformity of the current can be maintained, so that an electrode having a large opening and excellent transparency can be produced.
  • a method for reducing the coloring of the transparent conductive layer it is known to use a polymer obtained by mixing a conductive polymer and a hydroxyl group-containing non-conductive polymer as the transparent conductive layer.
  • a polymer obtained by mixing a conductive polymer and a hydroxyl group-containing non-conductive polymer as the transparent conductive layer.
  • a polymer selected from the group consisting of polyvinyl alcohol (PVA), polymethacrylic acid (PMAA) and the like is disclosed (for example, Patent Document 3, 4).
  • PVA polyvinyl alcohol
  • PMAA polymethacrylic acid
  • the present invention has been made in view of the above problems, and its purpose is to provide excellent conductivity, transparency, washing resistance, surface uniformity of current, and a transparent electrode excellent in driving voltage when used in an organic electronic device. And an organic electronic device using the same.
  • the patterned conductive layer is a metal oxide or a metal material
  • the contained nonconductive polymer is a polymer (A) containing a structural unit selected from the following general formula (I) and general formula (II), and the transparent conductive layer is heated in a temperature range of 150 ° C. or higher and 300 ° C. or lower.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • Q 1 and Q 2 each independently represent —C ( ⁇ O) O— or —C ( ⁇ O) NRa—.
  • Ra represents a hydrogen atom, an alkyl group
  • a 1 each independently represent a substituted or unsubstituted alkylene group
  • - (CH 2 CHRbO) x represents a -CH 2 CHRb-.
  • Rb represents a hydrogen atom or an alkyl group
  • x represents the average number of repeating units.
  • y represents 0 or 1;
  • Z represents an alkyl group, —C ( ⁇ O) —Rc, —SO 2 —Rd, —SiRe 3 .
  • Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, and an aryl group.
  • a method for producing a transparent electrode that can be suitably used for an organic electronic device has excellent conductivity, transparency, washing resistance, and surface uniformity of current, and has excellent driving voltage when used in an organic electronic device.
  • a transparent electrode that can be suitably used for an organic electronic device, has excellent conductivity, transparency, washing resistance, and surface uniformity of current, and has excellent driving voltage when used in an organic electronic device.
  • the present inventor uses a conductive polymer and a conventional hydroxyl group-containing non-conductive polymer by using the polymer (A) as the conductive polymer and the hydroxyl group-containing non-conductive polymer.
  • the decrease in transparency due to coloring and the decrease in conductivity due to the addition of a nonconductive polymer can be suppressed.
  • a transparent conductive layer composed of a conductive polymer and a polymer (A) is formed by heat treatment, it is found that when used in an organic electronic device, a transparent electrode excellent in driving voltage can be obtained. It is up to you.
  • the transparent substrate used in the present invention is not particularly limited as long as the substrate is not deformed even if a high temperature treatment at 150 ° C. or higher is performed, and a material having a glass transition temperature (Tg) of 150 ° C. or higher is preferably used.
  • Tg glass transition temperature
  • the material, shape, structure, thickness, hardness and the like can be appropriately selected from known materials, but preferably have high transparency. Examples thereof include a glass substrate and a polyimide film, but a glass substrate is more preferable from the viewpoints of transparency, heat resistance, ease of handling, and barrier properties.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesiveness of the coating solution.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • a barrier coat layer may be formed in advance as necessary, or a hard coat layer may be formed in advance.
  • a barrier coat layer an inorganic film, an organic film or a hybrid film of both may be formed on the front surface or the back surface, and the water vapor transmission rate (25 ⁇ 0) measured by a method according to JIS K 7129-1992. 0.5 ° C.
  • relative humidity (90 ⁇ 2)% RH) is preferably a transparent substrate having a barrier property of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less, and JIS K 7126- Oxygen permeability measured by a method according to 1987 is 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the material for forming the barrier layer may be any material that has a function of suppressing the intrusion of devices that cause deterioration of the device such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the conductive polymer according to the present invention is a conductive polymer having a ⁇ -conjugated conductive polymer and a polyanion.
  • a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a ⁇ -conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a poly anion described later. .
  • the ⁇ -conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.
  • Precursor monomers used in the formation of ⁇ -conjugated conductive polymers have a ⁇ -conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidant, a ⁇ -conjugated system is formed in the main chain. It is what is done. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
  • the precursor monomer examples include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexyl Offene, 3-heptyl
  • the polyanion used in the present invention includes a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a co-polymer thereof. It is a polymer and has at least a structural unit having an anionic group.
  • This poly anion is a solubilized polymer that solubilizes the ⁇ -conjugated conductive polymer in a solvent.
  • the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
  • the anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable.
  • a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
  • polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned.
  • it may be a poly anion further having F (fluorine atom) in the compound.
  • F fluorine atom
  • Nafion made by Dupont
  • Flemion made by Asahi Glass Co., Ltd.
  • perfluoro vinyl ether containing a carboxylic acid group
  • polystyrene sulfonic acid polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polybutyl acrylate sulfonic acid are preferable.
  • These poly anions have high compatibility with the hydroxyl group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.
  • the degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.
  • Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and an anionic group containing The method of manufacturing by superposition
  • Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
  • the oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the ⁇ -conjugated conductive polymer.
  • the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid.
  • the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like.
  • the ultrafiltration method is preferable from the viewpoint of easy work.
  • the ratio of the ⁇ -conjugated conductive polymer and the poly anion contained in the conductive polymer, “ ⁇ -conjugated conductive polymer”: “poly anion” is preferably 1: 1 to 20 by mass ratio. From the viewpoint of conductivity and dispersibility, the range of 1: 2 to 10 is more preferable.
  • the oxidant used when the precursor monomer forming the ⁇ -conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole.
  • oxidants such as iron (III) salts, eg FeCl 3 , Fe (ClO 4 ) 3 , organic acids and iron (III) salts of inorganic acids containing organic residues
  • iron (III) salts eg FeCl 3 , Fe (ClO 4 ) 3
  • organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable.
  • air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time.
  • persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are
  • iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate hemiesters having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, such as Methane or dodecanesulfonic acid; carboxylic acid having 1 to 20 aliphatic carbon atoms such as 2-ethylhexyl carboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And in particular aromatic, optionally substituted alkyl sulfonic acids having 1 to 20 carbon atoms such as benzenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid Fe (III) salts.
  • Such a conductive polymer is preferably a commercially available material.
  • a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. It is commercially available from Starck as the Clevios series, from Aldrich as PEDOT-PSS 483095 and 560596, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.
  • a water-soluble organic compound may be contained as the second dopant.
  • an oxygen containing compound is mentioned suitably.
  • the oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound.
  • the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like.
  • ethylene glycol and diethylene glycol are preferable.
  • the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, ⁇ -butyrolactone, and the like.
  • the ether group-containing compound include diethylene glycol monoethyl ether.
  • the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.
  • the hydroxyl group-containing non-conductive polymer according to the present invention is characterized by containing a certain amount of the polymer (A).
  • the present invention it is possible to improve the conductivity of the conductive polymer-containing layer by using the conductive polymer and the polymer (A) in combination with the transparent conductive layer, and the compatibility with the conductive polymer is also good. Can achieve high transparency. As a result, the thickness of the transparent conductive layer can be increased, and foreign matter adhering to the substrate surface and unevenness of the pattern conductive layer can be embedded without reducing the transparency. Can be suppressed.
  • the hydroxyl group-containing non-conductive polymer of the present invention is preferably water-soluble, and the polymer (A) is preferably dissolved in 0.001 g or more in 100 g of water at 25 ° C.
  • the solubility can be measured with a haze meter or a turbidimeter.
  • the polyanion has a sulfo group
  • the sulfo group effectively acts as a dehydration catalyst
  • the conductive polymer and the polymer (A) are densely cross-linked without using an additional agent such as a cross-linking agent.
  • a layer can be formed, and a strong transparent conductive layer can be formed. Therefore, it has high durability and is advantageous when cleaning the substrate.
  • Crosslinking can be measured by a change in glass transition temperature and nanoindentation elastic modulus of the transparent conductive layer, and a change in functional group by FTIR measurement.
  • the polymer (A) is a polymer containing a structural unit selected from the following general formula (I) and general formula (II).
  • the constituent ratio of the structural unit of the general formula (I) in the polymer (A) is m and the constituent ratio of the structural unit of the general formula (II) is n, the constituent ratio (mol%) of m + n is 50 ⁇ m + n ⁇ 100 and m / (m + n) ⁇ 0.2.
  • the total of the components of the structural unit of the general formula (I) and the general formula (II) is 50 mol% or more and 100% or less, and the component of the structural unit of the general formula (I) is 20% or more. It is a copolymer. More preferably, the sum of the components of the structural units of the general formulas (I) and (II) is 80 mol% or more and 100% or less.
  • the polymer (A) of the present invention may contain a structural unit other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).
  • the component of the structural unit of the general formula (I) in the polymer (A) is less than 20%, the number of hydroxyl groups decreases, the number of hydroxyl groups as crosslinking points decreases, and the stability and denseness of the film decrease. Deterioration in water resistance and lifespan.
  • R 1 and R 2 each independently represents a hydrogen atom or a methyl group.
  • Q 1 and Q 2 each independently represent —C ( ⁇ O) O— or —C ( ⁇ O) NRa—, and Ra represents a hydrogen atom or an alkyl group.
  • the alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. These alkyl groups may be substituted with a substituent.
  • substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxyl groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, acyls.
  • a hydroxyl group and an alkyloxy group are preferable.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and more preferably 1 to 8. Further preferred.
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.
  • the number of carbon atoms of the cycloalkyl group is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • the alkoxy group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably.
  • alkoxy group examples include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, preferably an ethoxy group.
  • the alkylthio group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6, Most preferred is 1 to 4.
  • Examples of the alkylthio group include a methylthio group and an ethylthio group.
  • the arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylthio group include a phenylthio group and a naphthylthio group.
  • the number of carbon atoms of the cycloalkoxy group is preferably 3 to 12, and more preferably 3 to 8.
  • Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group.
  • the aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
  • the heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms.
  • Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.
  • the heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the heteroaryl group include a thienyl group and a pyridyl group.
  • the acyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
  • the alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the alkylcarbonamide group include an acetamide group.
  • the arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the arylcarbonamide group include a benzamide group and the like.
  • the alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • alkylsulfonamide group examples include a methanesulfonamide group.
  • the arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the arylsulfonamido group include a benzenesulfonamido group and p-toluenesulfonamido group.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms.
  • Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
  • the aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms.
  • Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
  • the aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.
  • the acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms.
  • Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
  • the alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.
  • the alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group.
  • the alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • alkylsulfonyl group examples include a methylsulfonyl group and an ethylsulfonyl group.
  • the arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.
  • the alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • alkyloxysulfonyl group examples include a methoxysulfonyl group and an ethoxysulfonyl group.
  • the aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.
  • the alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.
  • the number of carbon atoms in the arylsulfonyloxy group is preferably 6-20, and more preferably 6-12.
  • Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group.
  • the substituents may be the same or different, and these substituents may be further substituted.
  • a 1 and A 2 are each independently a substituted or unsubstituted alkylene group, — (CH 2 CHRbO) x —, — (CH 2 CHRbO) x —CH 2 CHRb— is represented.
  • the alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the above-described substituents.
  • Rb represents a hydrogen atom or an alkyl group.
  • the alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Further, these alkyl groups may be substituted with the above-described substituents. Further, x represents the average number of repeating units, preferably 1 to 100, more preferably 1 to 10. The number of repeating units has a distribution, the notation indicates an average value, and may be expressed by one digit after the decimal point.
  • Ra, Rb, and x have the same meaning as defined in the general formula (I).
  • y represents 0 or 1.
  • Z represents an alkyl group, —C ( ⁇ O) —Rc, —SO 2 —Rd, —SiRe 3 , and the alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group And more preferably a methyl group.
  • alkyl groups may be substituted with the substituent described above.
  • Rc, Rd and Re represent an alkyl group, a perfluoroalkyl group or an aryl group, and the alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. .
  • These alkyl groups may be substituted with the substituent described above.
  • the perfluoroalkyl group preferably has, for example, 1 to 8 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably a trifluoromethyl group.
  • the aryl group is preferably, for example, a phenyl group or a toluyl group, and more preferably a toluyl group. Furthermore, these alkyl groups, perfluoroalkyl groups, and aryl groups may be substituted with the above-described substituents.
  • Polymer (A) can be obtained by copolymerization of monomers (I) and (II) whose main copolymerization components form structural units represented by general formulas (I) and (II), respectively.
  • the polymer (A) of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst.
  • the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization.
  • the polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.
  • the number average molecular weight of the polymer (A) of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, still more preferably in the range of 5,000 to 100,000.
  • the number average molecular weight and molecular weight distribution of the polymer (A) of the present invention can be measured by generally known gel permeation chromatography (GPC).
  • the solvent to be used is not particularly limited as long as the polymer (A) is dissolved, and THF, DMF, and CH 2 Cl 2 are preferable, THF and DMF are more preferable, and DMF is more preferable.
  • the measurement temperature is not particularly limited, but 40 ° C. is preferable.
  • the polymer (A) preferably has a number average molecular weight of 0 to 5% by mass with a molecular weight of 1000 or less.
  • the amount of the low molecular component is small, it is possible to further reduce the storage stability of the device and the behavior of having a barrier in the direction perpendicular to the layer when exchanging charges in the direction perpendicular to the conductive layer.
  • the content of the molecular weight of 1000 or less is 0 to 5% by mass or less.
  • a redispersion method or preparative GPC is synthesized by synthesizing a monodisperse polymer by living polymerization.
  • a method of removing the low molecular weight component or suppressing the generation of the low molecular weight component can be used.
  • the reprecipitation method the polymer is dissolved in a solvent in which the polymer can be dissolved and dropped into a solvent having a lower solubility than the solvent in which the polymer is dissolved, thereby precipitating the polymer and removing low molecular weight components such as monomers, catalysts, and oligomers.
  • preparative GPC can be separated by molecular weight by, for example, recycling preparative GPCLC-9100 (manufactured by Nippon Analytical Industrial Co., Ltd.), polystyrene gel column, and passing the polymer-dissolved solution through the column. It is a method that can be removed.
  • the living polymerization the generation of the starting species does not change with time, and there are few side reactions such as termination reaction, and a polymer having a uniform molecular weight can be obtained. Since the molecular weight can be adjusted by the amount of monomer added, for example, if a polymer having a molecular weight of 20,000 is synthesized, the production of low molecular weight substances can be suppressed. From the viewpoint of production suitability, reprecipitation and living polymerization are preferred.
  • the molecular weight distribution of the polymer (A) according to the present invention is preferably 1.01 to 1.30, more preferably 1.01 to 1.25.
  • the molecular weight distribution is represented by a ratio of (weight average molecular weight / number average molecular weight).
  • Content with molecular weight of 1000 or less was converted to a ratio by integrating the area of molecular weight of 1000 or less and dividing by the area of the entire distribution in the distribution obtained by GPC.
  • the ratio of the conductive polymer to the polymer (A) is preferably from 30 to 900 parts by mass of the polymer (A) when the conductive polymer is 100 parts by mass. From the viewpoint of properties, the polymer (A) is more preferably 100 to 900 parts by mass.
  • the heat treatment in the present invention is performed at 150 ° C. or higher and 300 ° C. or lower.
  • the transparent conductive layer containing the conductive polymer and the polymer (A) is formed by heat treatment in a temperature range of 150 ° C. or more and 300 ° C. or less, the drive voltage is lowered when used for an organic electronic device.
  • the details of the principle about lowering the driving voltage are unknown, by treating the transparent conductive layer made of the polymer (A) and the conductive polymer at a high temperature, the polymer between the polymer in the transparent conductive layer and the patterned conductive layer is removed. This is thought to be because some kind of reaction occurs, making it easier to make contacts at the molecular level and creating a conductive path.
  • the film structure of the transparent conductive layer is stabilized, and becomes a dense film, so that it becomes strong, has an excellent cleaning resistance, and has an electrode with little deterioration under a high temperature environment.
  • the heat treatment temperature is less than 150 ° C.
  • the drive voltage does not decrease because the reaction between the transparent conductive layer and the patterned conductive layer is insufficient. Furthermore, moisture remains in the transparent conductive layer, deteriorating the life of the organic electronic device and the storage stability at high temperatures.
  • heat treatment is performed at a temperature higher than 300 ° C., a part of the bond of the conductive polymer starts to break and the resistance increases, so that it cannot be suitably used for an organic electronic device.
  • the heat treatment method is not particularly limited as long as it can be performed at 150 ° C. or more and 300 ° C. or less, and a known treatment method can be used. For example, a heater, an IR heater, vacuum heating, etc. can be mentioned, but it is not limited to this.
  • the heat treatment time is preferably 10 seconds or longer and 30 minutes or shorter, and more preferably 10 seconds or longer and 10 minutes or shorter. When the heat treatment time is 10 seconds or more, the moisture in the transparent conductive layer can be sufficiently reduced, and deterioration of the lifetime of the organic electronic device can be prevented. On the other hand, when the heat treatment is performed for 30 minutes or less, it is possible to prevent partial bond of the transparent conductive layer from starting to be broken and to prevent the resistance from being affected.
  • the patterned conductive layer according to the present invention is characterized in that a metal material or a metal oxide is formed in a pattern on a substrate.
  • a known metal oxide such as ITO or IZO may be used for the pattern conductive layer, or a metal material may be used.
  • a metal oxide is used, the transparency is superior to that using a metal material, but inferior to a metal material from the viewpoint of the resistance of the transparent electrode. Therefore, a metal material is more preferable for producing a large-area transparent electrode.
  • the metal material When a metal material is used for the pattern conductive layer, it becomes a substrate having both a light-impermeable conductive portion made of a metal material and a light-transmitting window portion, and an electrode substrate excellent in conductivity can be manufactured.
  • the metal material is not particularly limited as long as it is excellent in conductivity.
  • the metal material may be an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium.
  • the shape of the metal material is preferably metal fine particles or metal nanowires from the viewpoint of ease of pattern formation as described later, and the metal material is preferably silver from the viewpoint of conductivity.
  • the pattern shape is not particularly limited.
  • the conductive portion may be a stripe shape, a mesh shape, or a random network shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency.
  • the aperture ratio is the ratio of the light-impermeable conductive portion to the whole.
  • the aperture ratio of the stripe pattern having a line width of 100 ⁇ m and a line interval of 1 mm is about 90%.
  • the line width of the pattern is preferably 10 to 200 ⁇ m.
  • Desirable conductivity is obtained by setting the line width of the fine wire to 10 ⁇ m or more, and transparency is improved by setting the line width to 200 ⁇ m or less.
  • the height of the fine wire is preferably 0.1 to 10 ⁇ m. If the height of the fine wire is 0.1 ⁇ m or more, desired conductivity can be obtained, and if it is 10 ⁇ m or less, it causes current leakage and poor function layer thickness distribution in the formation of organic electronic devices. Can be prevented.
  • a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method.
  • a conductor layer is formed on the entire surface using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, etc., or a metal foil is used as an adhesive.
  • the film After being laminated on the base material, the film can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.
  • a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, followed by plating treatment As another method, a method using silver salt photographic technology can also be used.
  • a method using silver salt photographic technology can be carried out, for example, referring to paragraphs 0076 to 0112 of JP2009-140750A and examples.
  • the method for carrying out the plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, JP-A-2007-281290.
  • a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 can be used.
  • a method for forming a random network structure of metal nanowires by applying and drying a coating solution containing metal nanowires as described in JP-T-2009-505358 can be used.
  • Metal nanowire refers to a fibrous structure having a metal element as a main component.
  • the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.
  • the average length is preferably 3 ⁇ m or more, more preferably 3 to 500 ⁇ m, and particularly preferably 3 to 300 ⁇ m.
  • the relative standard deviation of the length is preferably 40% or less.
  • the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm.
  • the relative standard deviation of the minor axis is preferably 20% or less.
  • the basis weight of the metal nanowire is preferably 0.005 to 0.5 g / m 2 , and more preferably 0.01 to 0.2 g / m 2 .
  • metal used for the metal nanowire copper, iron, cobalt, gold, silver or the like can be used, but silver is preferable from the viewpoint of conductivity.
  • a single metal may be used, in order to achieve both conductivity and stability (sulfurization, oxidation resistance, and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.
  • the method for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction
  • a method for producing silver nanowires Adv. Mater. , 2002, 14, 833-837, Chem. Mater. 2002, 14, 4736-4745
  • a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252
  • a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871.
  • the above-described method for producing silver nanowires can be preferably applied because silver nanowires can be easily produced in an aqueous solution, and the conductivity of silver is maximum in metals.
  • the surface specific resistance of the thin line portion of the pattern conductive layer is preferably 100 ⁇ / ⁇ or less, and more preferably 20 ⁇ / ⁇ or less for increasing the area.
  • the surface specific resistance can be measured, for example, according to JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
  • the heating temperature is preferably 150 ° C. or higher and 500 ° C. or lower, and more preferably 200 ° C. or higher and 350 ° C. or lower, if it is metal fine particles.
  • the transparent conductive layer may completely cover the patterned patterned conductive layer, or may partially cover or contact it.
  • the transparent conductive layer is formed into a film by applying and drying a dispersion containing a conductive polymer and polymer (A).
  • the application of the transparent conductive layer is performed by roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, Coating methods such as blade coating, bar coating, gravure coating, curtain coating, spray coating, doctor coating, and ink jet can be used.
  • a pattern conductive layer may be formed and transcribe
  • the pattern conductive layer is formed on the transfer film by the above-described method, and the transparent conductive layer is further formed by the above-described method.
  • the method etc. which form a transparent conductive layer by the well-known method by the inkjet method etc. in the nonelectroconductive part of a pattern conductive layer are mentioned.
  • the transparent conductive layer is further characterized by containing a polymer (A).
  • A a polymer
  • the conductive layer of the present invention By forming the conductive layer of the present invention having such a structure, high conductivity that cannot be obtained with a metal or metal oxide fine wire or a conductive polymer layer alone can be obtained uniformly in the electrode plane. .
  • the dry film thickness of the transparent conductive layer is preferably 30 to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is further preferably 200 nm or more. Moreover, it is more preferable that it is 1000 nm or less from the point of transparency.
  • the transparent conductive layer After applying the transparent conductive layer, it can be appropriately dried. It is preferable to heat at a temperature equal to or lower than the heat treatment temperature as a drying treatment condition. For example, a drying treatment at 80 to 120 ° C. for 1 minute or more and 10 minutes or less can be performed.
  • a drying treatment at 80 to 120 ° C. for 1 minute or more and 10 minutes or less can be performed.
  • the resistance of a transparent conductive layer can be lowered
  • the film structure of the transparent conductive layer is stabilized and strengthened by processing at a high temperature. In addition, the resistance is remarkably improved by heating the electrode. With these effects, particularly in the case of an organic EL element, effects such as improvement of life and improvement of storage stability of the element under a high temperature environment can be obtained.
  • the dispersion containing the conductive polymer and the polymer (A) according to the present invention is a transparent non-conductive polymer, additive or cross-linking agent as long as the conductivity, transparency and smoothness of the conductive layer are simultaneously satisfied. It may contain.
  • the transparent non-conductive polymer a wide variety of natural polymer resins or synthetic polymer resins can be used, and a water-soluble polymer or an aqueous polymer emulsion is particularly preferable.
  • water-soluble polymers include natural polymers such as starch, gelatin, and agar, semi-synthetic polymers such as hydroxypropylmethylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, cellulose derivatives, synthetic polymers such as polyvinyl alcohol, and polyacrylic acid polymers.
  • Polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, etc., and aqueous polymer emulsions include acrylic resins (acrylic silicone modified resins, fluorine modified acrylic resins, urethane modified acrylic resins, epoxy modified acrylic resins, etc.), polyester resins, urethane Resin, vinyl acetate resin and the like can be used.
  • Synthetic polymer resins include transparent thermoplastic resins (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride), A transparent curable resin (for example, a melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, or a silicone resin such as an acrylic-modified silicate) that can be cured by heat, light, electron beam, or radiation can be used.
  • transparent thermoplastic resins for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride
  • a transparent curable resin for example, a melamine acrylate, urethane acrylate, epoxy resin, polyimide resin, or a silicone resin such as an acrylic-modified silicate
  • additives examples include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments.
  • solvents for example, organic solvents such as water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc. are used. May be included.
  • crosslinking agent for the polymer (A) for example, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an aldehyde crosslinking agent, or the like is used alone or in combination. be able to.
  • the transparent electrode of the present invention can be used for various organic electronic devices.
  • An organic electronic device has an anode electrode and a cathode electrode on a support, and has at least one organic functional layer between the electrodes.
  • the organic functional layer include, but are not particularly limited to, an organic light emitting layer, an organic photoelectric conversion layer, and a liquid crystal polymer layer.
  • INDUSTRIAL APPLICABILITY The present invention is particularly effective when the functional layer is a thin film and is an organic light emitting layer or an organic photoelectric conversion layer that is a current-driven device, and can be applied to organic electronic devices such as organic EL devices and solar cells.
  • Preparation of conductive layer The following coating liquids A to I are applied onto a glass substrate by adjusting the slit gap of the extrusion head so as to have a dry film thickness of 300 nm using an extrusion method, and heated at 100 ° C. for 1 minute to form a conductive layer A. ⁇ I.
  • Synthesis Example 3 (Synthesis of P-3 as polymer (A)) After adding 100 ml of THF to a 200 ml three-necked flask and heating to reflux for 10 minutes, the mixture was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (4.1 g, 35 mmol, molecular weight: 116.05), Bremmer PME-900 (7.4 g, 15 mmol, molecular weight: 496.29), AIBN (0.8 g, 5 mmol, molecular weight: 164.11) ) And heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK and stirred for 1 hour.
  • Synthesis Example 4 (Synthesis of P-4) After adding 100 ml of THF to a 200 ml three-necked flask and heating to reflux for 10 minutes, the mixture was cooled to room temperature under nitrogen. 2-hydroxyethyl acrylate (0.6 g, 5 mmol, molecular weight: 116.05), Bremer PME-900 (21 g, 45 mmol, molecular weight: 496.29), AIBN (0.8 g, 5 mmol, molecular weight: 164.11). The mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK and stirred for 1 hour.
  • Conductive layers A to I were heat-treated at the following temperatures to prepare electrodes 1 to 24, respectively. The heating time was 2 minutes.
  • the conductive layer A was heated at 150 ° C. and 200 ° C. to form electrodes 1 and 2.
  • Conductive layer B was heated at 130 ° C., 150 ° C., 200 ° C., 250 ° C., 300 ° C., and 330 ° C. to form electrodes 3-8.
  • the conductive layer C was heated at 200 ° C. and 250 ° C. to form electrodes 9 and 10.
  • the conductive layer D was heated at 200 ° C. and 250 ° C. to form electrodes 11 and 12.
  • the conductive layer E was heated at 150 ° C., 200 ° C., and 250 ° C. to form electrodes 13 to 15.
  • the conductive layer F was heated at 150 ° C., 200 ° C., and 250 ° C. to form electrodes 16 to 18.
  • the conductive layer G was heated at 200 ° C. and 250 ° C. to form electrodes 19 and 20.
  • the conductive layer H was heated at 200 ° C. and 250 ° C. to form electrodes 21 and 22.
  • the conductive layer I was heated at 200 ° C. and 250 ° C. to form electrodes 23 and 24.
  • Total light transmittance was measured using a HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. Since it is used for an organic electronic device, it is preferably 80% or more.
  • the surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
  • the surface resistance is preferably 1500 ⁇ / ⁇ or less, and more preferably 1000 ⁇ / ⁇ or less in order to increase the area of the organic electronic device.
  • the cleaning liquid is ultra-pure water prepared using Milli-Q water production equipment Milli-Q Advantage (Nippon Millipore Corporation). A substrate is attached to the cleaning liquid for 10 minutes, and the surface of the transparent conductive layer is not visually disturbed. The following criteria evaluated.
  • the organic EL devices 1 to 14 were formed by using the organic EL electrodes 1 to 14 by the following method so as to have a combination of the composition of the substrate and the conductive layer shown in Table 2 and the heat treatment temperature. Details of the production will be described below.
  • a thin wire grid was created in the center of a 3 cm square glass substrate with a size of 1.5 cm ⁇ 1.5 cm.
  • the fine wire lattice metal material was produced by the inkjet method shown below.
  • a silver nanoparticle ink (Harima NPS-J manufactured by Harima Kasei Co., Ltd.) is used as an ink jet recording head, and has a pressure applying means and an electric field applying means, and has a nozzle diameter of 25 ⁇ m, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi Is an ink jet printing apparatus equipped with a piezo head of 1 inch, that is, 2.54 cm), and the line width is within a range of 1.5 cm ⁇ 1.5 cm at the center of a 3 cm square glass substrate.
  • a drying process was performed at 220 ° C. for 60 minutes.
  • the silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m 2 , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate. Produced. The excess part was wiped off.
  • Silver nanowire dispersions are available from Adv. Mater. , 2002, 14, 833 to 837 with reference to the method described in PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 ⁇ m were produced. Silver nanowires are filtered off using a filtration membrane, washed, and then redispersed in an aqueous solution containing 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a silver nanowire dispersion. did.
  • ITO substrate An ITO (indium tin oxide) film having a thickness of 150 nm was formed on a 3 cm square glass substrate by a sputtering method to form an ITO substrate, and was patterned by a photolithographic method so that the ITO remained in a central area of 15 mm ⁇ 15 mm.
  • organic EL devices were produced as anode electrodes by the following procedure.
  • the hole transport layer and subsequent layers were formed by vapor deposition.
  • the electrodes 1 and 2 laminated with the conductive polymer were not cleaned because a part of the conductive layer was peeled off by cleaning. After cleaning, the organic EL electrodes 1 to 14 were subjected to the same treatment to produce organic EL devices 1 to 14, respectively.
  • Each of the deposition crucibles in a commercially available vacuum deposition apparatus was filled with a constituent material for each layer in a necessary amount for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • an organic EL layer composed of a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed in a range of a central portion of 17 mm ⁇ 17 mm.
  • each light emitting layer was provided in the following procedures.
  • Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass.
  • Co-evaporation was performed in the same region as the hole transport layer at a rate of 0.1 nm / second to form a green-red phosphorescent organic light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
  • compound 4 and compound 5 are deposited in the same region as the organic light-emitting layer emitting green-red phosphorescence at a deposition rate of 0.1 nm / second so that compound 4 is 10.0% by mass and compound 5 is 90.0% by mass.
  • Co-evaporation was performed to form a blue phosphorescent organic light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.
  • a hole blocking layer was formed by depositing compound 6 in a thickness of 5 nm on the same region as the formed organic light emitting layer.
  • CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% to form an electron transport layer having a thickness of 45 nm.
  • a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al 2 O 3 is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed.
  • the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm ⁇ 15 mm was produced.
  • the surface uniformity of the current was determined by evaluating the light emission uniformity. Using a source measure unit type 2400 manufactured by KEITHLEY, a direct current voltage was applied to each organic EL element to emit light so that the luminance became 1000 cd / m 2 , and the light emission state was visually evaluated according to the following criteria.
  • ⁇ Uniform light emission, no problem
  • ⁇ Light emission unevenness is partially observed (drive voltage)
  • An organic EL device made of ITO instead of a transparent electrode for organic EL prepared as an anode electrode was prepared by the same method as described above, with the voltage when light was emitted at an initial luminance of 5000 cd / m 2 as a drive voltage, and the ratio to this was evaluated using the following indicators. It is preferably less than 95% and more preferably less than 90%.
  • the obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m 2 , the voltage was fixed, and the time until the luminance was reduced by half was determined.
  • An organic EL device made of ITO instead of the transparent electrode for organic EL prepared as the anode electrode was prepared by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. 100% or more is preferable, and 150% or more is more preferable.
  • An organic EL device made of ITO instead of the organic EL transparent electrode prepared as the anode electrode was prepared in the same manner as described above, the ratio to this was determined, and the following indicators were evaluated. 100% or more is preferable, and 120% or more is more preferable.

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Abstract

L'invention concerne un procédé servant à produire une électrode transparente présentant des niveaux supérieurs de conductivité, transparence, résistance au lavage et uniformité superficielle, et ayant une tension de commande supérieure quand on l'utilise dans un dispositif électronique organique. L'invention concerne également un dispositif électronique organique utilisant ladite électrode. Le procédé de production d'électrode transparente ci-décrit vise à produire une électrode transparente dotée d'une couche conductrice structurée sur un substrat transparent et une couche conductrice transparente contenant au moins un polymère conducteur et un polymère non-conducteur comportant un groupe hydroxyle. Le procédé se caractérise en ce que la couche conductrice structurée est un oxyde métallique ou un matériau métallique. Le procédé se caractérise également en ce que le polymère non conducteur qui comporte un groupe hydroxyle est un polymère (A) doté d'une unité structurelle sélectionnée parmi la formule générale (I) et la formule générale (II) et la couche conductrice transparente est formée par traitement thermique sur une fourchette de température de 150 à 300 °C.
PCT/JP2011/069413 2010-09-24 2011-08-29 Procédé de production d'électrode transparente et dispositif électronique organique Ceased WO2012039240A1 (fr)

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US20130285041A1 (en) * 2010-12-13 2013-10-31 Konica Minolta, Inc. Transparent surface electrode, organic electronic element, and method for manufacturing transparent surface electrode
WO2019049470A1 (fr) * 2017-09-11 2019-03-14 日東電工株式会社 Composition conductrice et biocapteur
WO2022239107A1 (fr) * 2021-05-11 2022-11-17 シャープディスプレイテクノロジー株式会社 Élément électroluminescent, dispositif électroluminescent et procédé de fabrication d'élément électroluminescent

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