WO2011148931A1 - Électrode pour dispositif électronique organique - Google Patents

Électrode pour dispositif électronique organique Download PDF

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WO2011148931A1
WO2011148931A1 PCT/JP2011/061848 JP2011061848W WO2011148931A1 WO 2011148931 A1 WO2011148931 A1 WO 2011148931A1 JP 2011061848 W JP2011061848 W JP 2011061848W WO 2011148931 A1 WO2011148931 A1 WO 2011148931A1
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electrode
organic electronic
conductive polymer
pattern
layer
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PCT/JP2011/061848
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English (en)
Japanese (ja)
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博和 小山
宏明 伊東
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コニカミノルタホールディングス株式会社
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Priority to JP2012517274A priority Critical patent/JP5720680B2/ja
Publication of WO2011148931A1 publication Critical patent/WO2011148931A1/fr

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    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

Definitions

  • the present invention relates to an electrode for an organic electronic device, and more particularly, to an electrode for an organic electronic device having improved optical performance without causing leakage between the electrodes or disturbance of the device performance around the pattern of the fine metal wire. .
  • a transparent conductive film in which a transparent conductive film is laminated on a fine metal wire pattern so as to be compatible with a device having a large area is known (see, for example, Patent Documents 1 and 2).
  • organic EL organic electroluminescence
  • an organic solar cell leakage occurs between opposing electrodes, or in the organic EL, around the metal pattern.
  • the device performance may be abnormal in the vicinity of the thin metal wire pattern, for example, the light may only shine brightly or the life of the element may be reduced from the periphery of the metal pattern.
  • the pattern of the fine metal wire has a step, so that the thickness of the conductive layer on the fine metal wire pattern becomes thin when the transparent conductive film is formed, and it is easy to leak from the grid. It seems that the step between the metal thin wire pattern and the portion not having the metal fine line pattern is large, and the organic device configuration is disturbed at the step portion, which makes it easy to leak. Furthermore, from only the functional layer at the step portion, the organic EL may shine brightly only around the metal pattern, or the lifetime of the element may decrease from around the metal pattern.
  • Patent Document 3 a technique of providing a transparent conductive layer after transferring a pattern of fine metal wires formed on a smooth surface to another support provided with an adhesive layer and forming a fine metal wire pattern without steps. This is a preferable mode because it is possible to prevent leakage due to the influence of the step as described above.
  • An object of the present invention is to provide an electrode for an organic electronic device with improved optical performance without causing leakage between the electrodes or disorder of the device performance around the pattern of the fine metal wire.
  • An electrode for an organic electronic device in which a conductive fine metal wire pattern is provided on a substrate and a conductive polymer-containing layer is further provided thereon, and the conductive polymer-containing layer film on a portion where the fine metal wire is present
  • the surface of the conductive polymer-containing layer having a thickness of 100 nm to 2000 nm and on the portion with the fine metal wire, and the conductive polymer in the portion without the fine metal wire in the region provided with the pattern of the fine metal wire
  • An electrode for an organic electronic device wherein a level difference from the surface of the containing layer is 100 nm or more and 800 nm or less.
  • the level difference between the outermost surface of the conductive polymer-containing layer above the portion with the fine metal wire and the outermost surface of the conductive polymer-containing layer at the portion without the fine metal wire pattern is 150 nm or more and 600 nm or less, 2.
  • X 1 , X 2 and X 3 each independently represents a hydrogen atom or a methyl group, and R 1 , R 2 and R 3 each independently represents an alkylene group having 5 or less carbon atoms.
  • M, and n represent the composition ratio (mol%), where 50 ⁇ l + m + n ⁇ 100, and l, m, and n are 0 to 100, respectively. 7).
  • an electrode for an organic electronic device with improved optical performance without causing leakage between the electrodes or disorder of the device performance around the pattern of the fine metal wire.
  • a conductive fine metal wire pattern is used to suppress a voltage drop at the electrode. Furthermore, a conductive polymer-containing layer is provided on at least a part of the portion without the metal fine wire pattern so that electricity flows also through the portion without the metal fine wire pattern. Thereby, it can function as a surface electrode.
  • Organic electronic devices such as organic EL and organic solar cells are usually thin films with a functional layer of several hundred nm or less. For this reason, if there is a convex portion such as a pattern of a fine metal wire, it may cause a leak. Therefore, it is conceivable to smooth the pattern portion of the fine metal wire as in Patent Document 3 described above. In addition, the fine metal wire portion is not completely smoothed, and the upper portion of the conductive polymer-containing layer on the fine metal wire pattern portion is made higher than the upper portion of the conductive polymer-containing layer in the portion without the fine metal wire pattern by 100 nm or more. .
  • the step between the upper portion of the conductive polymer-containing layer on the fine metal wire pattern portion and the upper portion of the conductive polymer-containing layer in the portion without the thin metal wire pattern is set to 800 nm or less, and further, the conductivity on the fine metal wire pattern portion is further reduced. It has been found that by setting the film thickness of the conductive polymer-containing layer to 100 nm to 2000 nm, it is possible to prevent leakage and disturbance of device performance around the pattern portion of the fine metal wire while maintaining the efficiency of the electronic device. I went to.
  • FIG. 1 the ink containing metal fine particles for inkjet is printed on an easily contacted substrate as follows using an inkjet coating apparatus. Extraction electrodes (1) and (4) of the solid metal portion, a pattern (2) of the fine metal wire in contact with the extraction electrode (1), and a fine metal wire between the pattern (2) of the fine metal wire and the extraction electrode (4) A blank part (3) having no pattern is provided. The pattern of fine metal wires is fixed by heat treatment.
  • a conductive polymer-containing layer (5) is provided on the fine metal wire pattern (2) by coating.
  • the conductive polymer-containing layer (5) which has no fine metal wire pattern, is wiped away with pure water to remove the conductive polymer-containing layer ( 5 ').
  • the conductive polymer-containing layer (5 ′) is also fixed by heat treatment to obtain an electrode for organic electronic devices (10).
  • FIG. 4 shows a cathode electrode (6) finally produced after an organic layer necessary as an organic EL element is formed on the electrode for organic electronic devices (10) of the present invention.
  • the conductive polymer according to the present invention is preferably a conductive polymer comprising a ⁇ -conjugated conductive polymer and a polyanion.
  • a conductive polymer can be easily produced by chemically oxidatively polymerizing a precursor monomer that forms a ⁇ -conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion 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, A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds 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.
  • the precursor monomer has a ⁇ -conjugated system in the molecule, and a ⁇ -conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent.
  • an appropriate oxidizing agent examples 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 is 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 copolymer thereof. It consists of a structural unit having a group and a structural unit having no anionic group.
  • This polyanion is a solubilized polymer that solubilizes a ⁇ -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 a functional group capable of undergoing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate group A monosubstituted phosphate group, a phosphate group, a carboxy group, a 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, polyisoprene sulfone. 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 and the like. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
  • it may be a polyanion having F in the compound.
  • Specific examples include Nafion containing a perfluorosulfonic acid group (manufactured by Dupont), Flemion made of perfluoro vinyl ether containing a carboxylic acid group (manufactured by Asahi Glass Co., Ltd.), and the like.
  • polystyrene sulfonic acid polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polybutyl acrylate sulfonic acid are preferable.
  • These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive polymer.
  • the polymerization degree 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 methods for producing polyanions 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 anionic group-containing polymerization. And a method of production by polymerization of a functional monomer.
  • 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 polyanion 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.
  • Such a conductive polymer is preferably a commercially available material.
  • a conductive polymer (abbreviated as PEDOT-PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is H.264. C. It is commercially available from Starck as the CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, 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.
  • the water-soluble organic compound which can be used by this invention It can select suitably from well-known things, For example, 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 hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound.
  • the hydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable.
  • the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and ⁇ -butyrolactone.
  • 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 water-soluble polymer used in the present invention is not particularly limited as long as it is a polymer that can be dissolved or dispersed in an aqueous solvent (described later).
  • a polyester resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin examples thereof include polycarbonate resins, cellulose resins, polyvinyl acetal resins, polyvinyl alcohol resins, and the like.
  • Specific examples of the compound include Vylonal MD1200, MD1400, MD1480 (manufactured by Toyobo Co., Ltd.) as polyester resins.
  • the water-soluble polymer according to the present invention a compound having a group that reacts with a crosslinking agent described later is more preferable because it forms a stronger film.
  • the group that reacts with the crosslinking agent varies depending on the crosslinking agent, and examples thereof include a hydroxy group, a carboxyl group, and an amino group. Among these, it is most preferable to have a hydroxy group in the side chain.
  • Specific compounds of the water-soluble polymer according to the present invention include polyvinyl alcohol PVA-203, PVA-224, PVA-420 (manufactured by Kureha), hydroxypropyl methylcellulose 60SH-06, 60SH-50, 60SH-4000.
  • the water-soluble polymer contains a certain amount of the polymer (A)
  • the polyanion has a sulfo group
  • the polymer (A) is used, the sulfo group effectively acts as a dehydration catalyst, and a dense cross-linked layer can be formed without using an additional agent such as a cross-linking agent. This is a more preferred embodiment because it can be formed.
  • the water-soluble polymer (A) is composed mainly of the following monomers M1, M2, and M3, and 50 mol% or more of the copolymer components are any of the monomers, or the total is 50 mol% or more. It is a copolymer.
  • the total of the monomer components is more preferably 80 mol% or more, and it may be a homopolymer formed from any single monomer, which is a preferred embodiment.
  • X 1 , X 2 , and X 3 each independently represent a hydrogen atom or a methyl group, and R 1 , R 2 , and R 3 each independently represent an alkylene group having 5 or less carbon atoms.
  • polymer (A) other monomer components may be copolymerized as long as they are soluble in an aqueous solvent, but a monomer component having high hydrophilicity is more preferable.
  • the polymer (A) preferably has a content of 1000 or less in the number average molecular weight of 0 to 5%.
  • the content of 1000 or less is 0 to 5% or less, such as reprecipitation method, preparative GPC, or synthesis of monodisperse polymer by living polymerization, etc.
  • a method of removing the low molecular weight component or suppressing the generation of the low molecular weight component can be used.
  • 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. It is a method to do.
  • preparative GPC is, for example, recycled preparative GPCLC-9100 (manufactured by Nippon Analytical Industrial Co., Ltd.), polystyrene gel column, and a polymer-dissolved solution can be separated by molecular weight to cut the desired low molecular weight. This is how you can do it.
  • Living polymerization does not change the generation of the starting species over time, and there are few side reactions such as termination reaction, and a polymer with uniform molecular weight can be obtained. Since the molecular weight can be adjusted by the addition amount of the monomer, for example, if a polymer having a molecular weight of 20,000 is synthesized, the formation of a low molecular weight body can be suppressed.
  • the reprecipitation method and living polymerization are preferable from the viewpoint of production suitability.
  • the number average molecular weight and the weight average molecular weight of the water-soluble polymer of the present invention can be measured by a generally known gel permeation chromatography (GPC).
  • the molecular weight distribution can be expressed by a ratio of (weight average molecular weight / number average molecular weight).
  • the solvent to be used is not particularly limited as long as the water-soluble binder resin dissolves, 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 number average molecular weight of the polymer (A) according to 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 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 content with a number average molecular weight of 1000 or less was converted to a ratio by integrating the area with a number average molecular weight of 1000 or less and dividing by the area of the entire distribution.
  • the living polymerization solvent is inactive under the reaction conditions and is not particularly limited as long as it can dissolve the monomer and the polymer to be formed, but a mixed solvent of an alcohol solvent and water is preferable.
  • the living 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 conductive polymer-containing layer contains, for example, at least a conductive polymer containing a ⁇ -conjugated conductive polymer component and a polyanion component and a solvent, more preferably a coating solution containing a water-soluble polymer. Can be formed by coating and drying.
  • an aqueous solvent can be preferably used.
  • the aqueous solvent represents a solvent in which 50% by mass or more is water.
  • pure water containing no other solvent may be used.
  • the component other than water in the aqueous solvent is not particularly limited as long as it is a solvent compatible with water, but an alcoholic solvent can be preferably used, and isopropyl alcohol having a boiling point relatively close to water can be used. This is advantageous for the smoothness of the film to be formed.
  • coating methods roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method
  • a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.
  • the pattern shape is not particularly limited, but for example, a triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid or other quadrangle, a (regular) hexagon, a (positive) octagon It is possible to raise a mesh-like pattern composed of geometric figures combining the above.
  • a stripe shape composed of a plurality of parallel lines may be used. For example, stripes or lattices having a line width of 10 to 200 ⁇ m and a line interval of 200 to 3000 ⁇ m can be given.
  • the height of the fine metal wire pattern is not particularly limited as long as the relationship of the conductive polymer-containing layer can be satisfied. However, in order to easily satisfy the relationship of the present invention, it is preferably 200 nm or more and 2000 nm or less, and 300 nm or more. More preferably, it is 1000 nm or less.
  • the pattern of the fine metal wire does not use the conductive polymer-containing layer, and preferably has a conductivity of 30 ⁇ / ⁇ or less as a single film, more preferably 5 ⁇ / ⁇ or less, and preferably 1 ⁇ / ⁇ or less. Most preferred.
  • the metal material examples include gold, silver, copper, iron, nickel, and chromium.
  • the metal may be an alloy, and the pattern of the fine metal wire may be a single layer or multiple layers.
  • 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 of the substrate using one or more physical or chemical forming methods such as vapor deposition, sputtering, and plating, or a metal foil is formed with an adhesive. After being laminated on the material, it 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 various printing methods such as screen printing, flexographic printing, gravure printing, or an ink jet method, and various similar catalytic inks that can be plated are used.
  • a method of applying a silver salt photographic technique can be used as a method of applying a desired shape by a printing method and then performing a plating treatment, and as another method.
  • the method of printing ink containing metal fine particles in a desired shape by various printing methods can be manufactured in a simple process, so that it is possible to reduce the entrainment of foreign matters that may cause leakage at the time of manufacture. Since ink is used only at the location, there is little loss of liquid, and since there is no need for special chemical treatment such as plating, there is no concern about contamination of chemicals that cannot be removed. This is the most preferred embodiment.
  • the metal fine particle-containing ink As the metal fine particle-containing ink, known inks can be used. Examples of the metal fine particles include metal fine particles containing any one of silver, gold, copper, palladium, platinum, aluminum and nickel, or alloy fine particles containing these metals.
  • These metal fine particles are coated with a film (coating material) such as an organic substance on the surface in order to improve dispersibility.
  • an organic protective colloid In order to use metal fine particles of 0.1 ⁇ m or less, it is preferable to use the fine particles coated with an organic protective colloid.
  • this organic protective colloid one having a decomposition temperature or boiling point in the range of 70 to 250 ° C. is used. This decomposition temperature or boiling point means the lower one of the decomposition temperature and boiling point. If the decomposition temperature or boiling point of the organic protective colloid exceeds 250 ° C., the organic protective colloid cannot be decomposed or evaporated by low-temperature heat treatment, and low-temperature firing cannot be performed. If the decomposition temperature or boiling point of the organic protective colloid is less than 70 ° C., the organic protective colloid may be decomposed or evaporated during storage of the silver paste, which causes a problem in storage stability of the silver paste.
  • the organic protective colloid it is preferable to use hydrocarbons having 3 to 18 carbon atoms. If the carbon number is 19 or more, the decomposition temperature or boiling point becomes high, and the organic protective colloid may not be decomposed or evaporated by low-temperature heat treatment, and if the carbon number is 2 or less, the decomposition temperature Alternatively, the boiling point becomes too low, which may cause a problem in the storage stability of the silver paste.
  • Such a dispersion medium is not particularly limited, but myristyl alcohol (boiling point 167 ° C .; 20 hPa), lauryl alcohol (boiling point 258 to 265 ° C.), undecanol (boiling point 129 to 131 ° C .; 16 hPa), decanol ( Examples include boiling point 220 to 235 ° C., nonanol (boiling point 214 to 216 ° C.), octanol (boiling point 188 to 198 ° C.), and the like. These may be used alone or in combination of two or more. It is.
  • decanol as a dispersion medium.
  • decanol As a dispersion medium, a silver paste suitable for drawing by screen printing or the like can be obtained.
  • the amount of the dispersion medium in the silver paste varies depending on the silver paste application method, and is appropriately set so as to obtain viscosity and fluidity according to the application method.
  • the silver paste thus prepared can be applied to the surface of a substrate or the like by a conventionally known method such as screen printing, ink jet printing, dipping, applicator application, spin coat application.
  • the organic protective colloid covering the metal nanoparticles also plays a role as a binder, so that a coating film can be formed by printing a silver paste without the need for blending a binder.
  • the dispersoid concentration when the metal fine particles are dispersed in a dispersion medium is 1% by mass or more and 80% by mass or less, and can be adjusted according to a desired film thickness of the conductive film. If it exceeds 80% by mass, aggregation tends to occur and it is difficult to obtain a uniform film.
  • the precious metal colloidal particles are easily exposed on the surface of the catalyst ink pattern, and these catalyst carriers can give thixotropy to the catalyst ink, and the ink breaks at the contour of the image area. Sharpens and makes it difficult for bleeding and fatness to occur.
  • the binder resin of the catalyst ink for example, urethane resin such as two-component curable urethane resin, epoxy resin, acrylic resin, alkyd resin, polyester resin, or the like is used as one or two or more mixed resins.
  • the catalyst ink is composed of such a binder resin, an electroless plating catalyst composed of the above-mentioned noble metal, and an appropriate solvent.
  • additives such as a pigment, surfactant, and a coloring agent.
  • extender pigments for example, powders such as calcium carbonate, barium sulfate, and silica are used.
  • the catalyst ink By adding a colorant, it is possible to easily check the quality of the catalyst ink pattern printed and formed in a pattern before electroless plating.
  • a known colorant such as carbon black may be used as the colorant.
  • the catalyst ink may be any of organic solvent type, water type, emulsion type and the like.
  • a plating treatment may be performed in order to increase conductivity.
  • electroless plating is performed, or electrolytic plating is performed following electroless plating.
  • electrolytic plating and electroless plating can be carried out alone or in combination.
  • metals that can be used for plating For example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used.
  • electrolytic copper sulfate plating can be preferably used.
  • pressurization the surface is pressed on the plate with the plate / surface pressurization, the nip roll pressurization is performed while passing the base film between the rolls, and the combined pressurization is performed on the plate with the roll.
  • the magnitude of the pressurization is arbitrarily possible in the range of 1 kPa to 100 MPa, preferably 10 kPa to 10 MPa, more preferably 50 kPa to 5 MPa.
  • the pressure is less than 1 kP, the effect of contact between the particles cannot be obtained, and when the pressure is 100 MPa or more, it is difficult to keep the surface smooth, and the haze increases.
  • heating since heating is effective when heated, it is preferable to heat in the range of 40 ° C to 300 ° C.
  • the substrate used for the electrode for organic electronic devices of the present invention is preferably a transparent substrate.
  • the transparent substrate is not particularly limited as long as it has high light transmittance.
  • a glass substrate, a resin substrate, a resin film, and the like are preferable in terms of excellent hardness as a base material and ease of formation of a conductive layer on the surface. From the viewpoint, it is preferable to use a transparent resin film.
  • the transparent resin film that can be preferably used as the transparent substrate in the present invention 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.
  • biaxially stretched polyethylene terephthalate film preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.
  • 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 adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion 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.
  • examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer and the like.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the electrode for organic electronic devices of the present invention can be used as an electrode for organic electronic devices.
  • the organic EL element will be described.
  • 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,
  • 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.
  • the thickness of the organic light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.
  • 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 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 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 like an electrode, but donates or accepts electrons by a photoreaction.
  • 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.
  • 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.
  • 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.
  • 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 trialkylsilylethynyl groups described in US Pat. No. 9,2706, etc., 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 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.
  • 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.
  • heat Preferably there is.
  • compounds that cause a chemical 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. 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).
  • (1) and (4) in FIG. 1 are used as extraction electrodes with a silver solid portion of 1.2 cm ⁇ 5 mm.
  • (2) in FIG. 1 is in contact with (1) at a metal mesh pattern portion having a line width of 50 ⁇ m and a line interval of 950 ⁇ m printed in a range of 1.2 cm ⁇ 1.2 cm.
  • (3) is a 1.2 cm ⁇ 2 mm silver-free portion.
  • the formed fine metal wire pattern was heat-treated at 130 ° C. for 60 minutes.
  • the height of the metal fine wire pattern from the base material (hereinafter referred to as metal fine wire height) was 600 nm.
  • the film thickness of the conductive polymer-containing layer on the portion of the obtained organic electronic device electrode where the fine metal wire pattern is located (hereinafter referred to as the thickness of the fine metal wire portion) is 200 nm.
  • the film thickness of the conductive polymer-containing layer in the portion not present (hereinafter referred to as the film thickness of the metal-free portion) was 500 nm.
  • Conductive polymer-containing coating solution 1 PEDOT-PSS CLEVIOS PH510 (Solid content 1.89%) (manufactured by HC Starck) 1.59 g Polyhydroxyethyl acrylate (Synthesis Example 2, 20% solid content aqueous solution) 0.35g Dimethyl sulfoxide (DMSO) 0.08g "Synthesis of initiators" Synthesis example 1 2-Bromoisobutyryl bromide (7.3 g, 35 mmol), triethylamine (2.48 g, 35 mmol) and THF (20 ml) were added to a 50 ml three-necked flask, and the internal temperature was kept at 0 ° C. with an ice bath.
  • the structure and number average molecular weight were measured by 1 H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.
  • This palladium colloidal solution was desalted by ultrafiltration, and 5 parts by mass of alumina was added to the filtered colloidal solution, and the heteroaggregated and precipitated portion was filtered and crushed to obtain alumina-supported palladium particles.
  • 8 parts by mass of ethyl cellulose resin was dissolved in 100 parts by mass of toluene, and 1 part by mass of the palladium particles prepared earlier was added to the liquid to obtain a catalyst-containing ink for electroless plating.
  • the pH was adjusted to 5.90 at 40 ° C., and finally a silver chlorobromide cubic grain emulsion containing 10 mol% of silver bromide and having an average grain size of 0.09 ⁇ m and a coefficient of variation of 10% was obtained.
  • the volume ratio of silver halide grains to gelatin was 0.625.
  • a hardening agent H-1: tetrakis (vinylsulfonylmethyl) methane
  • SU-2 sulfosuccinate disulfate
  • 2-ethylhexyl) .sodium was added to adjust the surface tension.
  • the coating solution thus obtained was applied on one side of the substrate, and then cured at 50 ° C. for 24 hours.
  • the produced adhesive substrate and the metallic silver pattern produced in the same manner as D030 were pressure-bonded so that the adhesive layer and the metallic silver pattern faced to form a laminate.
  • ultraviolet rays were irradiated from the adhesive substrate side to cure the ultraviolet curable resin, and the adhesive substrate and the metal silver pattern were joined.
  • the bonded adhesive substrate and the metal silver pattern were immersed in the following enzyme solution at 40 ° C. for 5 minutes, washed with water and dried.
  • the pH of the enzyme solution was 7.0.
  • Table 1 shows the metal wire height, the metal wire portion thickness, and the metal-free portion film thickness of the organic electronic device electrodes D002 to D022 and D030 to D032 obtained as described above.
  • the obtained organic electronic device electrodes D001 to D022 and D030 to D032 were used as electrodes of organic EL elements.
  • the obtained organic electronic device electrode D001 was formed as the organic EL element 1 by forming the following layers on the metal fine wire pattern.
  • Each of the vapor deposition crucibles in a commercially available vacuum vapor deposition apparatus was filled with the optimum amount of the constituent material of each layer 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.
  • the compound 2, the compound 3 and the compound 5 were deposited at a deposition rate of 0.1 nm / second so that the concentration of the compound 2 was 13% by mass and the compound 3 was 3.7% by mass.
  • a green-red phosphorescent light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm was formed by co-evaporation in a region having the above pattern.
  • the compound 4 and the compound 5 are co-deposited on a region having a pattern of fine metal wires at a deposition rate of 0.1 nm / second so that the compound 4 becomes 10% by mass, and a blue light having a maximum emission wavelength of 471 nm and a thickness of 15 nm.
  • a phosphorescent light emitting layer was formed.
  • the hole blocking layer was formed by depositing the compound 6 in a film thickness of 5 nm on the formed light emitting layer in a region having a pattern of fine metal wires.
  • CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% in a region having a fine metal wire pattern, thereby forming an electron transport layer having a thickness of 45 nm.
  • the organic EL element was subjected to the subsequent evaluation under nitrogen without being exposed to the atmosphere even after vapor deposition.
  • the rectification ratio Inverts the plus or minus of the applied voltage.
  • the rectification ratio was defined as (absolute value of current during light emission) / (absolute value of current during inversion). This ratio decreases if there is an influence of foreign matter or protrusions, or if the level difference at the grid portion is too large.
  • this ratio is 1, the leakage state is complete, and the EL element is preferably 100 or more, more preferably 1000 or more.
  • the following indicators were used for evaluation.
  • Luminous (luminous efficiency) Using a KEITHLEY source measure unit 2400 type, the luminous efficiency (lumen / W) when a direct current voltage was applied and light was emitted at 300 cd was measured, and evaluated according to the following index at the level with respect to the luminous efficiency of the organic EL element 32. .
  • Improvement range 15% or more 2 Improvement range 10% or more and less than 15% 1: Improvement range 3% or more and 10% or less 0: Improvement range 3% or less
  • the organic EL element using the electrode of the present invention has improved luminous efficiency without breaking performance such as rectification ratio and uneven emission.
  • an electrode in which a step between the outermost surface of the conductive polymer-containing layer on the portion with the fine metal wire pattern and the outermost surface of the conductive polymer-containing layer on the portion without the fine metal wire pattern is 150 nm or more and 600 nm or less It can be seen that the light emission efficiency is improved without using light emission unevenness.
  • the rectification ratio can be improved without reducing the improvement in luminous efficiency.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une électrode pour un dispositif électronique organique, qui possède de meilleures performances optiques sans entraîner de fuite entre les électrodes, ni de perturbation des performances du dispositif autour d'un motif de fil fin métallique ou analogue. L'invention concerne plus précisément une électrode pour un dispositif électronique organique qui comprend un matériau de base, un motif de fil fin métallique conducteur d'électricité formé sur le matériau de base, et une couche contenant un polymère conducteur d'électricité formé sur le motif. L'électrode est caractérisée en ce qu'une partie de la couche contenant un polymère conducteur d'électricité qui se trouve sur une zone comportant le fil fin métallique possède une épaisseur de 100 à 2000 nm, et en ce que la différence de niveau entre la surface de la partie de la couche contenant un polymère conducteur d'électricité qui se trouve sur une zone comportant le fil fin métallique et la surface d'une partie de la couche contenant un polymère conducteur d'électricité qui se trouve sur une zone ne comportant pas de fil fin métallique dans la zone comportant le motif de fil fin métallique varie de 100 à 800 nm compris.
PCT/JP2011/061848 2010-05-28 2011-05-24 Électrode pour dispositif électronique organique WO2011148931A1 (fr)

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Cited By (4)

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WO2012124647A1 (fr) * 2011-03-14 2012-09-20 コニカミノルタホールディングス株式会社 Procédé de fabrication d'une électrode plane pour dispositif électronique organique
JP2015508218A (ja) * 2012-02-10 2015-03-16 サン−ゴバン グラス フランス Ｏｌｅｄのための透明支持電極
JP2017507368A (ja) * 2013-12-23 2017-03-16 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． ディスプレイデバイス
CN110024138A (zh) * 2016-12-08 2019-07-16 株式会社钟化 太阳能电池模块

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WO2000067531A1 (fr) * 1999-04-30 2000-11-09 Idemitsu Kosan Co., Ltd. Dispositif organique electroluminescent et procede de fabrication
JP2004504693A (ja) * 2000-06-26 2004-02-12 アグフア−ゲヴエルト，ナームローゼ・フエンノートシヤツプ 導電性パターンの作製のための材料及び方法
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Publication number Priority date Publication date Assignee Title
WO2012124647A1 (fr) * 2011-03-14 2012-09-20 コニカミノルタホールディングス株式会社 Procédé de fabrication d'une électrode plane pour dispositif électronique organique
JP2015508218A (ja) * 2012-02-10 2015-03-16 サン−ゴバン グラス フランス Ｏｌｅｄのための透明支持電極
JP2017507368A (ja) * 2013-12-23 2017-03-16 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． ディスプレイデバイス
CN110024138A (zh) * 2016-12-08 2019-07-16 株式会社钟化 太阳能电池模块

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