WO2013121912A1 - Procédé pour fabriquer une électrode transparente, électrode transparente et élément électronique organique - Google Patents

Procédé pour fabriquer une électrode transparente, électrode transparente et élément électronique organique Download PDF

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WO2013121912A1
WO2013121912A1 PCT/JP2013/052482 JP2013052482W WO2013121912A1 WO 2013121912 A1 WO2013121912 A1 WO 2013121912A1 JP 2013052482 W JP2013052482 W JP 2013052482W WO 2013121912 A1 WO2013121912 A1 WO 2013121912A1
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group
transparent electrode
firing
layer
light
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PCT/JP2013/052482
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English (en)
Japanese (ja)
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松村　智之
昌紀 後藤
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コニカミノルタ株式会社
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Priority to JP2014500171A priority Critical patent/JP6032271B2/ja
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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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent 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
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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

Definitions

  • the present invention relates to a method for producing a transparent electrode, a transparent electrode, an organic EL (electroluminescence) element using the same, and an organic electronic element used for an organic electronic device such as a solar battery.
  • organic electronic devices such as organic EL elements and organic solar cells have attracted attention.
  • transparent electrodes have become an essential component technology.
  • a transparent electrode in which a transparent conductive film of indium tin oxide (ITO) and a metal conductive layer formed in a pattern are combined (for example, Patent Documents) 1), no mention is made of organic electronic devices that require high smoothness.
  • ITO indium tin oxide
  • Patent Documents Patent Documents
  • a patterning method by etching using a photolithography method, or after exposing and developing a photosensitive material having a silver salt-containing layer, a plating process is performed to form a metal conductive pattern for example, refer to Patent Document 2.
  • the photolithography method and the silver salt method are costly and have a problem that the process is complicated.
  • a method of directly forming a metal conductive pattern that has been miniaturized by a printing method has recently been attracting attention.
  • the formation of the conductive pattern by the printing method has a feature that the process is simple and can be performed at low cost.
  • a method of forming a conductive pattern with an ink containing a conductor such as metal nanoparticles on a substrate on which the conductive pattern is formed is employed.
  • the conductivity of the conductive pattern is improved by heating and baking at a high temperature.
  • films such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) are used for the substrate, but in order not to damage the substrate, the conductive material formed from metal nanoparticles. It is known that a fine metal wire pattern is fired by local heating. For example, an example of firing by irradiation with pulsed light (flash) is disclosed (for example, see Patent Document 3).
  • the accumulated energy of the pulsed light that is, the product of the illuminance of the pulsed light and the pulse width
  • the resistance value of the fine metal wire pattern sufficiently low
  • surface irregularities and disconnections will occur in the fine metal wire pattern. Defects such as disappearance due to ablation occur, or if the fine metal wire pattern is baked on the resin substrate, the resin substrate surface may be deformed or melted along the fine metal wire pattern, resulting in defects such as the substrate. Therefore, it was difficult to obtain a sufficient effect even if the resistance value was reduced.
  • the solvent to be evaporated rapidly evaporates and diffuses simultaneously with the irradiation (firing) of pulsed light. Therefore, as a means for preventing defects in the fine metal line pattern, it is conceivable to heat and dry the fine metal line pattern prior to firing by irradiation with pulsed light. Heating and drying at a high temperature in order to sufficiently remove the high-boiling organic solvent necessary for the enhancement may cause deformation of the substrate when using a resin substrate, particularly a relatively inexpensive PET film, PEN film or the like. is there. Therefore, it is actually difficult to heat and dry at high temperature in order to avoid substrate deformation.
  • the pulsed light irradiation is divided into a plurality of times and firing is performed a plurality of times.
  • the pulsed light irradiation is divided into a plurality of times and firing is performed a plurality of times.
  • the pulsed light irradiation is performed a plurality of times. It is considered difficult to obtain the effect of lowering resistance even if it is divided.
  • a main object of the present invention is to provide a method for producing a transparent electrode capable of reducing the resistance value while preventing the occurrence of defects in the fine metal wire pattern and the substrate.
  • the present inventor has examined the cause of the above-mentioned problem and the like.
  • firing by light irradiation of the fine metal wire pattern is performed by preliminary firing (first firing step) and main firing (second firing step).
  • the firing is performed so that the integrated energy of the irradiation light in the first baking step is larger than the integrated energy of the irradiation light in the second baking step, so that the defects of the metal fine line pattern described above are obtained. And found that resistance can be reduced while preventing defects in the substrate.
  • the second firing process (light irradiation), which is positioned as the main firing in a situation where the residual solvent in the metal fine wire pattern is reduced by the pre-firing
  • integration of irradiation light in the second firing process is performed.
  • the efficiency used to fuse metal nanoparticles is expected to increase. Therefore, the integrated energy of the irradiation light in the second baking step is more efficient than the case where baking is performed with a single pulse light so far, that is, the effect of lowering resistance is obtained with lower energy.
  • the energy since the energy is lower, it is assumed that defects in the substrate are less likely to occur.
  • the integrated energy in the first baking step is maximum.
  • E-P1m (max) is the integrated energy amount of a single pulse
  • E-P2m (max) is the single pulse integrated energy amount that maximizes the integrated energy in the second firing process. It has been found that the above-described effect is further increased by performing firing by light irradiation so that the value of P2m (max) / E-P1m (max) is 1.5 or more.
  • the above-mentioned problem according to the present invention is solved by the following means:
  • the method for producing a transparent electrode having a transparent substrate and a conductive fine metal wire pattern Forming the metal fine line pattern with metal nanoparticles on the transparent substrate;
  • a step of firing the fine metal wire pattern by light irradiation In the step of firing the fine metal wire pattern, A first firing step of pre-firing the metal fine wire pattern;
  • a method for producing a transparent electrode wherein the integrated energy of irradiation light in the second baking step is made larger than the integrated energy of irradiation light in the first baking step.
  • the light irradiation of each step is constituted by one or a plurality of times of pulsed light
  • the integrated energy amount of the single pulse that maximizes the accumulated energy in the first firing process is E ⁇ P1m (max)
  • the accumulated energy amount of the single pulse that maximizes the accumulated energy in the second firing process is E ⁇ .
  • P2m (max) The value of E ⁇ P2m (max) / E ⁇ P1m (max) is preferably 1.5 or more and 40 or less.
  • the present invention it is possible to reduce the resistance value while preventing the metal fine line pattern or the substrate from being defective.
  • the transparent electrode according to a preferred embodiment of the present invention has at least a transparent substrate and a conductive fine metal wire pattern, and the fine metal wire pattern is formed on the transparent substrate.
  • a conductive polymer layer is preferably formed on the fine metal wire pattern.
  • the transparent substrate used for the transparent electrode of the present invention is not particularly limited as long as it is a resin substrate having high light transparency.
  • a resin substrate and a resin film are mentioned suitably, it is preferable to use a transparent resin film from a viewpoint of productivity, a viewpoint of performance, such as lightness and a softness
  • the transparent resin film that can be preferably used is not particularly limited, and the material, shape, structure, thickness, and the like can be appropriately selected from known ones.
  • polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc.
  • Resin films vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like. If the resin film transmittance of 80% or more at 80 ⁇ 780 nm), can be preferably applied to a transparent resin film according to the present invention.
  • biaxial stretching of biaxially stretched polyethylene terephthalate resin film, biaxially stretched polyethylene naphthalate resin film, polyethersulfone resin film, polycarbonate resin film, etc. in terms of transparency, heat resistance, ease of handling, strength and cost It is preferably a polyester resin film, more preferably a biaxially stretched polyethylene terephthalate resin film or a biaxially stretched polyethylene naphthalate resin film.
  • 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.
  • an inorganic or organic film or a hybrid film of both may be formed on the front or back surface of the transparent substrate, and the water vapor transmission rate (25 ⁇ 0) measured by a method in accordance with JIS K 7129-1992. .5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less barrier film, and further conforms to JIS K 7126-1987
  • the oxygen permeability measured by the above method is 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less (1 atm is 1.01325 ⁇ 10 5 Pa), water vapor permeability (25 ⁇ 0.5 ° C.
  • the relative humidity (90 ⁇ 2)% RH) is preferably a high barrier film having 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the fine metal wire pattern of the present invention is formed from metal nanoparticles.
  • the metal material of the metal nanoparticles is not particularly limited as long as it has excellent conductivity.
  • an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium may be used. Silver is preferred from the viewpoint.
  • the average particle size of the metal nanoparticles is preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 30 nm.
  • the average particle diameter of the metal nanoparticles in the present invention is determined by observing 200 or more metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse at random from an electron microscope observation of the metal nanoparticles. It is obtained by determining the particle size of the nanoparticles and determining the number average value thereof.
  • the average particle diameter according to the present invention refers to the minimum distance among the distances between the outer edges of the metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines. . When measuring the average particle diameter, the ones that clearly represent the side surfaces of the metal nanoparticles are not measured.
  • the pattern shape of the fine metal wire pattern in the present invention is not particularly limited.
  • the pattern shape may be a stripe shape or a mesh shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency. .
  • An aperture ratio is the ratio which the electroconductive part which has translucency accounts 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. When the line width of the thin wire is 10 ⁇ m or more, desired conductivity is obtained, and when it is 200 ⁇ m or less, sufficient transparency as a transparent electrode is obtained.
  • the height of the fine wire is preferably 0.1 to 5 ⁇ m. If the height of the fine wire is 0.1 ⁇ m or more, desired conductivity is obtained, and if it is 5 ⁇ m or less, the unevenness difference does not affect the film thickness distribution of the functional layer in the formation of the organic electronic element.
  • a method of forming an electrode having a conductive or striped conductive portion a method of printing an ink containing metal nanoparticles in a desired shape is preferable.
  • a printing method It can print and form in a desired shape with well-known printing methods, such as gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing.
  • the pattern of the thin wire electrode is not limited to the regular pattern as described above, and may have a random network structure.
  • a random network structure for example, 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 transparent electrode according to the present invention over the fired thin metal wire pattern formed on a transparent substrate, a conductive polymer-containing layer it is preferred that the coated. That is, the case where it uses as transparent electrodes, such as organic electroluminescent (EL) element, organic electronic elements, such as a solar cell, etc. corresponds.
  • the configuration of the conductive polymer-containing layer is arbitrary, but a configuration formed from a conductive polymer including a ⁇ -conjugated conductive polymer and a polyanion is preferable.
  • the conductive polymer-containing layer includes a conductive polymer containing at least a ⁇ -conjugated conductive polymer and a polyanion and a structural unit represented by the following general formula (I). It is preferable that it is formed from a water-soluble binder resin from the viewpoint of obtaining high surface smoothness while maintaining high transparency and conductivity.
  • R represents a hydrogen atom or a methyl group
  • Q represents —C ( ⁇ O) O— or —C ( ⁇ O) NRa—
  • Ra represents a hydrogen atom or an alkyl group
  • A represents a substituted or unsubstituted alkylene group, — (CH 2 CHRbO) x CH 2 CHRb—.
  • Rb represents a hydrogen atom or an alkyl group
  • x represents the average number of repeating units.
  • the dry film thickness of the conductive polymer-containing 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 more preferably 300 nm or more. Further, from the viewpoint of transparency, the thickness is more preferably 1000 nm or less, and further preferably 800 nm or less.
  • the conductive polymer-containing layer is applied in roll coating, bar coating, dip coating, spin coating, casting, and die coating.
  • Coating methods such as a method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, and an ink jet method can be used.
  • the conductive polymer according to the present invention comprises 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 polythiophene, the same shall apply hereinafter), polypyrroles, and polyindoles.
  • a chain conductive polymer of polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazils Can be used.
  • polythiophenes and polyanilines are preferred from the viewpoints of conductivity, transparency, stability, and the like, and ease of adsorption to metal nanoparticles.
  • Most preferred is polyethylene dioxythiophene.
  • the precursor monomer used to form the ⁇ -conjugated conductive polymer has a ⁇ -conjugated system in the molecule and acts as an appropriate oxidizing agent. Even when the polymer is polymerized by ⁇ , a ⁇ -conjugated system is formed in the main chain. 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 poly anion used in the present invention is an acidic polymer in a free acid state, a polymer of a monomer having an anionic group, or a monomer having an anionic group and a monomer having no anionic group. It is a copolymer.
  • the free acid may be in the form of a partially neutralized salt.
  • 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. and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
  • the compound having a sulfonic acid may be formed by applying and drying the conductive polymer-containing layer, followed by heat drying at 100 to 120 ° C. for 5 minutes or more. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.
  • 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 superposing
  • 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. It is reacted in 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 ⁇ -conjugated conductive polymer and polyanion contained in the conductive polymer, “ ⁇ -conjugated conductive polymer”: “polyanion” is preferably 1: 1 to 1:20 by mass ratio. From the viewpoint of conductivity and dispersibility, the range of 1: 2 to 1:10 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 half esters of alkanols such as lauryl sulfate; alkyl sulfonic acids of 1 to 20 carbons, For example, methane or dodecanesulfonic acid; aliphatic carboxylic acids having 1 to 20 carbon atoms such as 2-ethylhexylcarboxylic acid; aliphatic perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acids such as sulphur Mention may be made of acids and in particular Fe (III) salts of aromatic, optionally alkyl-substituted sulphonic acids having 1 to 20 carbon atoms, such as benzenecene sulphonic acid, p-toluenesulphonic acid and dodecylbenzenesulphonic
  • 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.
  • the conductive polymer-containing layer may contain a water-soluble organic compound as the second dopant.
  • a water-soluble organic compound which can be used by this invention, It can select suitably from well-known things,
  • 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 conductive polymer-containing layer of the present invention preferably contains a water-soluble binder resin containing at least the structural unit represented by the general formula (I). Since such a resin can be easily mixed with a conductive polymer and also has the above-mentioned second dopant effect, by using this water-soluble binder resin in combination, the conductivity and transparency are not reduced.
  • the film thickness of the conductive polymer-containing layer can be increased. By increasing the film thickness, high surface smoothness can be obtained, and the metal fine wire pattern can be sufficiently covered with the conductive polymer-containing layer, even when used for electrodes such as organic light-emitting devices and organic solar cell devices. The rectification ratio is excellent, and it becomes possible to prevent leakage between the electrodes.
  • the water-soluble binder resin is a water-soluble binder resin and means a binder resin in which 0.001 g or more of the resin component is dissolved in 100 g of water at 25 ° C.
  • the dissolution can be measured with a haze meter or a turbidimeter.
  • the water-soluble binder resin is transparent.
  • the water-soluble binder resin preferably has a structure including the structural unit represented by the general formula (I).
  • the homopolymer represented by the general formula (I) may be used, or other components may be copolymerized.
  • the structural unit represented by the general formula (I) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. it is more preferable.
  • the water-soluble binder resin is preferably contained in the conductive polymer-containing layer in an amount of 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.
  • R represents a hydrogen atom or a methyl group.
  • Q represents —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, more preferably a methyl group. Moreover, 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 further preferably 1 to 8.
  • Examples of 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. and most preferably.
  • Examples of the alkoxy group 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 1-20, more preferably 1-12, and still more preferably 1-6, Most preferred is 1 to 4.
  • Examples of the alkylthio group include a methylthio group and an ethylthio group.
  • the carbon number of the arylthio group is preferably 6-20, and more preferably 6-12.
  • 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 number of carbon atoms of the aryl group is preferably 6-20, and more preferably 6-12.
  • 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 number of carbon atoms in the heterocycloalkyl group is preferably 2 to 10, and more preferably 3 to 5.
  • Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.
  • the number of carbon atoms in the heteroaryl group is preferably 3-20, and more preferably 3-10.
  • Examples of the heteroaryl group include a thienyl group and a pyridyl group.
  • the number of carbon atoms of the acyl group is preferably 1-20, and more preferably 1-12.
  • Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
  • the number of carbon atoms in the alkylcarbonamide group is preferably 1-20, and more preferably 1-12.
  • Examples of the alkylcarbonamide group include an acetamide group.
  • the number of carbon atoms in the arylcarbonamide group is preferably 1-20, and more preferably 1-12.
  • Examples of the arylcarbonamide group include a benzamide group and the like.
  • the number of carbon atoms of the alkylsulfonamide group is preferably 1-20, and more preferably 1-12.
  • Examples of the sulfonamide group 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 number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12.
  • Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the number of carbon atoms of the alkoxycarbonyl group is preferably 1-20, and more preferably 2-12.
  • 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 number of carbon atoms in the aralkyloxycarbonyl group is preferably 8-20, and more preferably 8-12.
  • Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.
  • the number of carbon atoms of the acyloxy group is preferably 1-20, and more preferably 2-12.
  • Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
  • the number of carbon atoms of the alkenyl group is preferably 2-20, and more preferably 2-12.
  • Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group.
  • the number of carbon atoms of the alkynyl group is preferably 2-20, and more preferably 2-12.
  • Examples of the alkynyl group include an ethynyl group.
  • the number of carbon atoms of the alkylsulfonyl group is preferably 1-20, and more preferably 1-12.
  • Examples of the alkylsulfonyl group 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 number of carbon atoms in the alkyloxysulfonyl group is preferably 1-20, and more preferably 1-12.
  • Examples of the alkyloxysulfonyl group 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 number of carbon atoms of the alkylsulfonyloxy group is preferably 1-20, and more preferably 1-12.
  • Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.
  • the arylsulfonyloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • 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 is a substituted or unsubstituted alkylene group, - (CH 2 CHRbO) x represents a -CH 2 CHRb-.
  • 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 substituent described above.
  • 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, more preferably a methyl group.
  • alkyl groups may be substituted with the above-mentioned substituent.
  • x represents the average number of repeating units, and is preferably 0 to 100, more preferably 0 to 10. The number of repeating units has a distribution, and the notation indicates an average value and may be expressed with one decimal place.
  • the water-soluble binder resin 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 water-soluble binder resin 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 solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH 2 Cl 2 are preferable, more preferably THF and DMF, and still more preferably DMF.
  • the measurement temperature is not particularly limited, but 40 ° C. is preferable.
  • the total light transmittance of the transparent electrode in the present invention is 70% or more, preferably 80% or more.
  • the total light transmittance can be measured according to a known method using a spectrophotometer or the like.
  • the electric resistance value of the conductive portion of the transparent electrode in the present invention is preferably 100 ⁇ / ⁇ or less, more preferably 20 ⁇ / ⁇ or less, for use in a large-area organic electronic device. preferable.
  • the surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
  • Method for producing transparent electrode In the method for producing a transparent electrode according to a preferred embodiment of the present invention, mainly, (I) forming a fine metal wire pattern with metal nanoparticles on a transparent substrate; (Ii) a step of firing the metal fine wire pattern by light irradiation; It has.
  • heating and firing by light irradiation of (ii) is realized, for example, by irradiation of pulsed light using a flash lamp, and a conductive metal fine wire pattern formed from metal nanoparticles is fired, This is performed in order to improve conductivity.
  • heating and baking by light irradiation with pulsed light is divided into a first baking step (10) for performing preliminary baking and a second baking step (20) for performing main baking.
  • the total of the integrated energy of the irradiation light in the 2nd baking process is made larger than the total of the integrated energy of the irradiation light in the 1st baking process.
  • the light irradiation in each step in the first baking step and the second baking step is constituted by one or a plurality of times of pulse light irradiation, and integration of irradiation light in the first baking step.
  • E-P1m (max) is the integrated energy amount of the single pulse that maximizes the energy
  • E-P2m (max) is the integrated energy amount of the single pulse that maximizes the integrated energy of the irradiation light in the second firing process.
  • the value of E-P2m (max) / E-P1m (max) is 1.5 or more and 40 or less.
  • the total amount of light irradiation energy in the first baking step in which preliminary baking is performed is preferably 0.1 to 10 J / cm 2 .
  • 0.1 J / cm hardly effect of precalcination is obtained is less than 2, exceeds 10J / cm 2, it is more likely to result in an adverse effect on the shape of the metal thin wire pattern.
  • a range of 0.1 to 3 J / cm 2 is more preferable.
  • the light irradiation time, that is, the pulse width is preferably 10 ⁇ sec to 100 msec, and more preferably 100 ⁇ sec to 10 msec.
  • the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1 to 50 times.
  • the pulse interval in the case of performing multiple irradiations is arbitrary.
  • a preferable range of the integrated energy amount E-P1m (max) of the single pulse that maximizes the integrated energy of the irradiation light in the first firing step is 0.1 to 3 J / cm 2 . If it is 0.1 J / cm 2 or more, the effect of pre-firing can be easily obtained, and if it is 3 J / cm 2 or less, the possibility of adversely affecting the shape of the metal fine line pattern is lowered.
  • the total amount of light irradiation energy in the second baking step for performing the main baking is preferably 0.3 to 50 J / cm 2 . If it is 0.3 J / cm 2 or more, the firing effect is easily obtained, and if it is 50 J / cm 2 or less, the possibility of adversely affecting the shape of the fine metal wire pattern is lowered. A range of 0.3 to 10 J / cm 2 is more preferable.
  • the light irradiation time, that is, the pulse width is preferably 10 ⁇ sec to 100 msec, and more preferably 100 ⁇ sec to 10 msec.
  • the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed in the range of 1 to 50 times.
  • the pulse interval in the case of performing multiple irradiations is arbitrary.
  • a preferable range of the integrated energy amount E-P1m (max) of the single pulse that maximizes the integrated energy of the irradiation light in the second firing step is 0.3 to 4 J / cm 2 . If it is 0.3 J / cm 2 or more, it is easy to obtain the effect of preliminary firing, and if it is 4 J / cm 2 or less, the possibility of adversely affecting the shape of the metal fine line pattern is lowered.
  • the relationship between the total light irradiation energy of the first baking step and the total light irradiation energy of the second baking step is large in the total light irradiation energy of the latter second baking step. Is the premise.
  • the interval between the first baking step and the second baking step is arbitrary, but is preferably 5 milliseconds or more. If it is 5 ms or more, the effect of separating the pre-firing and the main firing is easily obtained. More preferably, it is 10 milliseconds or more. On the contrary, there is no particular effect on the length of the interval and influence on the performance of the transparent electrode, but it is advantageous in terms of the production rate of the transparent electrode, and it is preferably within 1 minute.
  • the distinction between the first baking step and the second baking step will be described, for example, in accordance with the contents shown in FIG. 1. When the pulsed light in each step is “pulsed light 11-13, 21-23” In addition, the amount of energy of the pulsed light tends to attenuate in each step.
  • the pulse light 21 exceeding the energy amount of the pulse light 13 having the minimum energy amount among the pulse lights 11 to 13 in the first firing step is newly irradiated, the pulse light 13 and the pulse light 13 It is assumed that the first baking step and the second baking step are divided with the point between the light 21 as a boundary.
  • Table 1 illustrates examples of firing conditions by more specific light irradiation.
  • xenon As the discharge tube of the flash lamp of the present invention, xenon, helium, neon and argon can be used, but xenon is preferably used.
  • Preferred spectral band of the flash lamp in the present invention in the range of 240 nm ⁇ 2000 nm is preferred because it does not damage such as conductive lowered to the conductive polymer-containing layer of the present invention by light irradiation.
  • the light irradiation of the flash lamp to the substrate may be performed not only from the front side on which the metal fine line pattern is printed, but also from the back side or from both sides. .
  • the light irradiation using the flash lamp of the present invention may be performed in the air, but can also be performed in an inert gas atmosphere such as nitrogen, argon, helium or the like, if necessary.
  • the substrate temperature at the time of light irradiation is the boiling point (vapor pressure) of the dispersion medium of the ink containing the metal nanoparticles, the type and pressure of the atmospheric gas, the thermal behavior such as the dispersibility and oxidation of the metal nanoparticles, the substrate It may be determined in consideration of the heat-resistant temperature of the film, and is preferably performed at room temperature to 150 ° C.
  • the substrate on which the fine metal wire pattern has been formed may be subjected to heat treatment in advance before performing light irradiation using a flash lamp.
  • the light irradiation device of the flash lamp satisfies the above irradiation energy and irradiation time, any device can be used.
  • Organic electronic devices The organic electronic device in the present invention has a transparent electrode and an organic functional layer produced by the method of the present invention.
  • the transparent electrode formed by the method of the present invention is used as a first electrode portion, an organic functional layer is formed on the first electrode portion, and a second electrode portion is formed on the organic functional layer as a counter electrode.
  • an organic electronic device can be obtained.
  • the organic functional layer examples include an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like without any particular limitation, but the present invention includes an organic light emitting layer in which the organic functional layer is a thin film and a current-driven system, This is particularly effective in the case of an organic photoelectric conversion layer.
  • the organic electronic device of the present invention is an organic EL device and an organic photoelectric conversion device will be described.
  • Organic EL element (1.1) Organic functional layer structure (organic light emitting layer)
  • organic functional layer structure organic light emitting layer
  • an organic EL element having an organic light-emitting layer as the organic functional layer in addition to the organic light emitting layer, hole injection layer, a hole transport layer, an electron transporting layer, an electron injection layer, a hole blocking layer, an electron blocking layer, etc.
  • a layer for controlling the light emission may be used in combination with the organic light emitting layer.
  • the conductive polymer layer on the transparent electrode of the present invention can also function as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.
  • the light emitting layer may be a monochromatic light emitting layer having a light emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm, respectively, or by laminating at least three of these light emitting layers.
  • a white light emitting layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers.
  • the organic EL device of the present invention is preferably a white light emitting layer.
  • the organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer.
  • Electrode The transparent electrode of the present invention is used in the first or second electrode portion described above.
  • the first electrode portion is an anode and the second electrode portion is a cathode.
  • the second electrode portion may be a conductive material single layer, but in addition to a conductive material, a resin for holding these may be used in combination.
  • a material having a low work function (4 eV or less) metal referred to as an electron injecting metal
  • an alloy referred to as an electrically conductive compound
  • a mixture thereof as an electrode material is used.
  • Electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light coming to the second electrode side is reflected and returns to the first electrode part side.
  • a metal material as the conductive material of the second electrode portion, this light can be reused and the extraction efficiency is further improved.
  • the organic photoelectric conversion element includes a first electrode part, a photoelectric conversion layer having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer) (hereinafter also referred to as a bulk heterojunction layer), and a second electrode. It is preferable to have a structure in which the portions are laminated.
  • the transparent electrode of the present invention is used at least on the incident light side.
  • An intermediate layer such as an electron transport layer may be provided between the photoelectric conversion layer and the second electrode part.
  • the photoelectric conversion layer is a layer that converts light energy into electric energy, and constitutes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. It is preferable.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which does not simply donate or accept electrons as in the case of an electrode, but donates or accepts electrons by a photoreaction.
  • Examples of p-type semiconductor materials include various condensed polycyclic aromatic compounds and conjugated compounds.
  • condensed polycyclic aromatic compound for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene, Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and derivatives and precursors thereof.
  • conjugated compound examples include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.
  • thiophene hexamer ⁇ -seccithiophene ⁇ , ⁇ -dihexyl- ⁇ -sexithiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3- An oligomer such as butoxypropyl) - ⁇ -sexithiophene can be preferably used.
  • polymer p-type semiconductor examples include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like.
  • Substituted-unsubstituted alternating copolymer polythiophenes such as JP-A-2006-36755, JP-A-2007-51289, JP-A-2005-76030, J. Pat. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc.
  • porphyrin copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenedithiotetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex, TCNQ-iodine complex, etc.
  • Organic molecular complexes such as C60, C70, C76, C78, and C84, carbon nanotubes such as SWNT, dyes such as merocyanine dyes and hemicyanine dyes, and ⁇ -conjugated polymers such as polysilane and polygerman Organic / inorganic hybrid materials described in Kai 2000-260999 can also be used.
  • At least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable. Further, pentacenes are more preferable.
  • pentacenes examples include substituents described in International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, JP-A-2004-107216, etc.
  • Examples thereof include substituted acenes described in No. 14.4986 and the like and derivatives thereof.
  • Such compounds include those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), No. Acene-based compounds substituted with a trialkylsilylethynyl group described in US Pat. No. 9,2706, etc., and pentacene precursors described in US Patent Application Publication No. 2003/136964, etc., and Japanese Patent Application Laid-Open No. 2007-224019 Examples include precursor type compounds (precursors) such as porphyrin precursors.
  • the latter precursor type can be preferably used.
  • the p-type semiconductor material is a compound that has undergone a chemical structural change by a method such as exposing the precursor of the p-type semiconductor material to vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material.
  • a method such as exposing the precursor of the p-type semiconductor material to vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material.
  • compounds that cause a scientific structural change by heat are preferred.
  • n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic acid
  • n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide, perylenetetracarboxylic acid
  • Fullerene-containing polymer compounds include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Examples thereof include a polymer compound having a skeleton.
  • a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.
  • fullerene-containing polymers are roughly classified into polymers in which fullerene is pendant from a polymer main chain and polymers in which fullerene is contained in the polymer main chain. Fullerene is contained in the polymer main chain. compounds there are preferred.
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the photoelectric conversion element of the present invention may be used as a photoelectric conversion device such as a solar cell
  • the photoelectric conversion element may be used in a single layer or may be used by being laminated (tandem type).
  • the photoelectric conversion device is preferably sealed by a known method so as not to be deteriorated by oxygen, moisture, etc. in the environment.
  • a transparent electrode capable of reducing the resistance value while preventing defects in the fine metal wire pattern and the substrate (see the following examples).
  • Such a transparent electrode is excellent in transparency and conductivity, and also has a flexible characteristic by using a transparent resin substrate.
  • the transparent electrode it is possible to provide an organic electronic device that can be driven at a low voltage in response to an increase in area.
  • a flexible resin substrate it has become possible to provide a high-speed and mass production form by a roll-to-roll process, and to provide an inexpensive and high-performance transparent electrode.
  • the resin film substrate on which the fine metal wire pattern obtained above was formed was baked by light irradiation under the baking conditions (light irradiation pattern A) in Table 1 described above to produce “transparent electrode TCF-1”.
  • a flash lamp a xenon lamp 2400WS (made by COMET) equipped with a short wavelength cut filter of 250 nm or less was used.
  • Transparent Electrode TCF-R3 (Comparative) In preparation of transparent electrode TCF-1, the firing conditions were an energy amount of 1.5 J / cm 2 , a pulse width of 3 ms, and a pause of 1 second, Two irradiations were performed. Otherwise, the same process as that of the transparent electrode TCF-1 was performed to produce a comparative “transparent electrode TCF-R3”.
  • PEDOT-PSS CLEVIOS P AI 4083 solid content 1.5%) (manufactured by Heraeus) is applied to the glass substrate so that the dry film thickness becomes 30 nm using an applicator with a coating width of 150 mm. It was applied and wiped off unnecessary peripheral parts so as to have an area of 150 mm ⁇ 150 mm, and then dried.
  • the transparent electrode was set in a commercially available vacuum deposition apparatus, and each of the deposition materials in the vacuum deposition apparatus was filled with the constituent material of each layer in an optimum amount for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • each light emitting layer was provided in the following procedures. First, after depressurizing to a vacuum of 1 ⁇ 10 ⁇ 4 Pa, the deposition crucible containing the following ⁇ -NPD was energized and heated, evaporated at a deposition rate of 0.1 nm / second, and a 30 nm hole transport layer Was provided. Thereafter, Ir-1, Ir-14 and the following compound 1-7 were added at a deposition rate of 0.1 nm / second so that the following Ir-1 had a concentration of 13% by mass and the following Ir-14 had a concentration of 3.7% by mass.
  • Co-evaporation was performed to form a green-red phosphorescent layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
  • E-66 and compound 1-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the following E-66 was 10% by mass, and a blue phosphorescent light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.
  • M-1 below is deposited to a thickness of 5 nm to form a hole blocking layer
  • CsF is co-deposited with M-1 to a thickness ratio of 10% to form an electron transport layer having a thickness of 45 nm. Formed.
  • Al was mask-deposited under a vacuum of 5 ⁇ 10 ⁇ 4 Pa as a material for forming an external lead terminal for the first electrode and a second electrode (cathode) of 150 mm ⁇ 150 mm. A 100 nm second electrode was formed.
  • an adhesive is applied to the periphery of the second electrode except for the end portions so that external lead terminals of the first electrode and the second electrode can be formed, and a polyethylene terephthalate resin film is used as a substrate to form Al 2 O 3 with a thickness of 300 nm. after pasting the deposited flexible sealing member to form a sealing film to cure the adhesive in a heat treatment, to produce an organic EL element of the light emitting area 150 mm ⁇ 150 mm.
  • a two-component epoxy compounded resin manufactured by Three Bond
  • 2103 were blended at a ratio of 100: 3.
  • Rectification ratio current value when +4 V is applied / current value when ⁇ 4 V is applied ⁇ : Rectification ratio of 10 3 or more ⁇ : Rectification ratio of 10 2 or more and less than 10 3 ⁇ : Rectification ratio of 10 1 or more and less than 10 2 ⁇ : Rectification ratio of 10 1 Less than
  • a driving voltage KEITHLEY source measure unit MODEL 2400 manufactured by luminance by applying a DC current to each organic EL element to emit light so as to be 1000 cd / m 2, the voltage values at 1000 cd / m 2 It was measured. The lower the voltage value, the lower the driving voltage. 5V or less is a practical range.
  • the present invention relates to a method for producing a transparent electrode, and can be particularly suitably used for reducing a resistance value while preventing defects in a fine metal wire pattern or a substrate.

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Abstract

L'invention porte sur un procédé pour fabriquer une électrode transparente, qui a un substrat transparent, et un motif de câblage fin en métal conducteur. Ce procédé comporte : une étape de formation, sur le substrat transparent, du motif de câblage fin en métal à l'aide de nanoparticules de métal ; et une étape de calcination du motif de câblage fin en métal à l'aide d'irradiation de lumière. L'étape de calcination du motif de câblage fin en métal a : une première étape de calcination (10) consistant à pré-calciner le motif de câblage fin en métal ; et une seconde étape de calcination (20) constituant à calciner le motif de câblage fin en métal. Une énergie cumulative de la lumière d'irradiation dans la seconde étape de calcination est établie de façon à être supérieure à une énergie cumulative de la lumière d'irradiation dans la première étape de calcination.
PCT/JP2013/052482 2012-02-15 2013-02-04 Procédé pour fabriquer une électrode transparente, électrode transparente et élément électronique organique WO2013121912A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015050081A1 (fr) * 2013-10-01 2015-04-09 コニカミノルタ株式会社 Substrat conducteur, procédé permettant de produire ce dernier et dispositif électronique organique comprenant ledit substrat conducteur
WO2016052878A1 (fr) * 2014-09-30 2016-04-07 한양대학교 산학협력단 Électrode transparente à base de nanofil métallique et d'oxyde de graphène utilisant une source lumineuse combinée, et son procédé de fabrication

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