WO2012124647A1 - Procédé de fabrication d'une électrode plane pour dispositif électronique organique - Google Patents

Procédé de fabrication d'une électrode plane pour dispositif électronique organique Download PDF

Info

Publication number
WO2012124647A1
WO2012124647A1 PCT/JP2012/056225 JP2012056225W WO2012124647A1 WO 2012124647 A1 WO2012124647 A1 WO 2012124647A1 JP 2012056225 W JP2012056225 W JP 2012056225W WO 2012124647 A1 WO2012124647 A1 WO 2012124647A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
conductive polymer
organic electronic
electronic device
wire pattern
Prior art date
Application number
PCT/JP2012/056225
Other languages
English (en)
Japanese (ja)
Inventor
博和 小山
昌紀 後藤
Original Assignee
コニカミノルタホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタホールディングス株式会社 filed Critical コニカミノルタホールディングス株式会社
Priority to JP2013504715A priority Critical patent/JP5835316B2/ja
Publication of WO2012124647A1 publication Critical patent/WO2012124647A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/80—Constructional details
    • H10K10/82—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
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/341—Short-circuit prevention
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing a planar electrode for an organic electronic device, and more particularly, an electrode that provides an organic electronic device that maintains high transparency and has a low driving voltage and does not leak with a counter electrode.
  • the present invention relates to a method for producing a planar electrode for an organic electronic device that can be produced at low cost.
  • PEDOT / PSS poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid) layer is provided on a fine metal wire pattern fired by local heating is described (for example, see Non-Patent Document 1). Yes.
  • Non-Patent Document 1 a process of burying a fine metal wire pattern is performed. This requires a very complicated process and is desired to be improved. Alternatively, in order to save without performing the burying treatment, it is necessary to make the PEDOT / PSS layer extremely thick, and the transmittance of the surface electrode is greatly reduced, thereby reducing the performance of the organic electronic device.
  • a transparent electrode having a second transparent conductive layer containing a conductive polymer and a water-soluble binder resin on a first transparent conductive layer containing conductive fibers is described (for example, see Patent Document 2).
  • the present inventor has applied this technique to provide a transparent conductive layer containing a conductive polymer and a specific water-soluble binder resin on a metal fine wire pattern, thereby providing an organic electronic device such as a solar cell or organic electroluminescence. It was discovered that a short circuit with the counter electrode can be prevented when used in the above. This is a very effective technique because the transmittance of the surface electrode is not lowered and it is not necessary to perform a complicated burying process on the fine metal wire pattern.
  • a conductive polymer comprising a ⁇ -conjugated conductive polymer and a polyanion in the metal pattern is represented by the general formula (I).
  • An organic electronic device such as a solar cell or organic electroluminescence was produced using a planar electrode for an organic electronic device having a conductive polymer-containing layer formed from a transparent binder having a structural unit. It has been found that the drive voltage of the device increases despite the low sheet resistance.
  • Such a phenomenon includes a conductive fine metal wire pattern formed from metal nanoparticles on a base material, and a conductive polymer comprising at least a ⁇ -conjugated conductive polymer and a polyanion on the fine metal wire pattern.
  • a planar electrode for organic electronic devices having a conductive polymer-containing layer formed from a water-soluble binder resin containing a structural unit represented by the general formula (I), this is a newly manifested problem.
  • Patent Document 1 and Non-Patent Document 1 there is no suggestion of such a problem or suggestion of a solution.
  • a planar electrode for an organic electronic device having a conductive polymer-containing layer formed from a water-soluble binder resin containing a structural unit represented by the general formula (I) local heat treatment is applied to the thin metal wire pattern.
  • a method for producing a planar electrode for an organic electronic device comprising forming the conductive polymer-containing layer after applying the method.
  • 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 or — (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 above-described means of the present invention produces a planar electrode for an organic electronic device that provides an organic electronic device that is highly transparent, low-cost without complicated processes, low in driving voltage, and free from leakage with the counter electrode. can do.
  • the conductive polymer-containing layer on the fine metal wire pattern, it becomes possible to supply electricity to the window portion where the fine metal wire pattern does not exist, and it functions as a planar electrode.
  • a conductive polymer comprising a ⁇ -conjugated conductive polymer and a polyanion on a conductive fine metal wire pattern formed from metal nanoparticles on a substrate and represented by the general formula (I)
  • the technology for providing a conductive polymer-containing layer formed from a transparent binder has an effect of improving the conductivity of the conductive polymer layer in the water-soluble binder resin containing the structural unit represented by the general formula (I) Therefore, a very large amount can be contained in the conductive polymer-containing layer. Therefore, the film thickness of the conductive polymer-containing layer can be increased without reducing the transmittance.
  • this conductive polymer-containing layer on the conductive metal fine line pattern, it becomes possible to cover the conductive metal fine line pattern smoothly, and when viewed macroscopically, the metal fine line pattern has irregularities, When viewed microscopically, the surface can be made smooth, which requires very complicated processing such as burying of fine metal wire patterns even in organic electronic devices in which a functional layer and counter electrode are provided on the surface electrode. Without short-circuiting with the counter electrode.
  • a conductive metal wire pattern formed from metal nanoparticles on a substrate and a conductive polymer comprising at least a ⁇ -conjugated conductive polymer and a polyanion on the metal wire pattern and a general formula
  • the planar electrode for an organic electronic device having a conductive polymer-containing layer formed from a water-soluble binder resin containing the structural unit represented by (I)
  • the conductive polymer-containing layer is formed from the metal fine wire pattern. It is necessary to pass electricity without barriers.
  • electricity could flow without a barrier.
  • the water-soluble binder resin containing the structural unit represented by the general formula (I) in the conductive polymer-containing layer as in the present invention
  • the drive voltage may increase when a current is passed from the metal fine line pattern to the conductive polymer-containing layer.
  • the water-soluble binder resin containing the structural unit represented by the general formula (I) rather than the conductive polymer containing a ⁇ -conjugated conductive polymer and a polyanion.
  • the present invention for such a problem, by forming the conductive polymer-containing layer after subjecting the metal thin wire pattern to local heat treatment, it has been found that it can be applied to an organic electronic device without an increase in driving voltage, The present invention has been reached.
  • the surface state of the metal fine wire pattern is changed by performing a process of directly transmitting energy to the metal fine wire pattern, and the ⁇ -conjugated conductive conductivity is higher than that of the water-soluble binder resin containing the structural unit represented by the general formula (I). It is considered that the affinity with the interaction between the molecule and the conductive polymer containing the polyanion is higher, and current conduction from the fine metal wire pattern to the conductive polymer-containing layer is not caused.
  • a conductive fine metal wire pattern is formed on a substrate using metal nanoparticles.
  • the metal nanoparticles are simple metal species selected from the group of metal elements consisting of gold, silver, copper, platinum, palladium, nickel and aluminum, or metals consisting of gold, silver, copper, platinum, palladium, nickel and aluminum Mention may be made of alloys made of two or more metal species selected from the group of elements.
  • the particle size of the metal nanoparticles is 1 nm or more and 100 nm or less, more preferably 50 nm or less, and more preferably 30 nm or less.
  • the metal nanoparticles can be prepared by a conventional method, for example, by reducing a metal compound corresponding to the metal nanoparticles in a solvent in the presence of a protective colloid and a reducing agent.
  • Metal compounds corresponding to metal nanoparticles include, for example, metal oxides, metal hydroxides, metal sulfides, metal halides, metal acid salts [metal inorganic acid salts (oxo salts such as sulfates, nitrates, perchlorates, etc. Acid organic acid salt (acetate etc.) etc.] etc.
  • the form of the metal salt may be any of a single salt, a double salt or a complex salt, and may be a multimer (for example, a dimer). These metal compounds can be used alone or in combination of two or more.
  • metal halides, metal acid salts [metal inorganic acid salts (sulfate, nitrate, perchlorate, etc.
  • oxoacid salts etc.
  • metal organic acid salts acetates, etc.
  • a solvent for example, in the form of a solution of an aqueous solvent such as an aqueous solution.
  • Examples of the reducing agent include conventional components such as sodium borohydride (sodium borohydride, sodium cyanoborohydride, sodium triethylborohydride, etc.), lithium aluminum hydride, hypophosphorous acid or a salt thereof (sodium).
  • sodium borohydride sodium borohydride, sodium cyanoborohydride, sodium triethylborohydride, etc.
  • lithium aluminum hydride lithium aluminum hydride, hypophosphorous acid or a salt thereof (sodium).
  • reducing agents can be used alone or in combination of two or more.
  • the amount of the reducing agent used is 1 to 30 mol (for example, 1.2 to 20 mol), preferably 1.5 to 15 mol, preferably 1 to 15 mol, based on 1 equivalent (or 1 mol) of the metal compound in terms of metal atom. Preferably, it may be about 2 to 10 moles, and usually about 1 to 5 moles.
  • the reduction reaction can be performed by a conventional method, for example, about 10 to 75 ° C. (for example, 15 to 50 ° C., preferably 20 to 35 ° C.).
  • the atmosphere of the reaction system may be air, an inert gas (nitrogen gas or the like), or an atmosphere containing a reducing gas (hydrogen gas or the like).
  • the reaction may be usually performed under stirring (or while stirring).
  • the reaction solvent may be a dispersion medium described later constituting the final metal nanoparticle ink, or may be a solvent different from the dispersion medium constituting the metal nanoparticle ink, or a mixed solvent thereof. It may be.
  • the reaction solvent can be selected according to the type of the protective colloid, and for example, when the protective colloid is a water-soluble compound, the reaction solvent is often composed of a polar solvent such as water, and a hydrophobic compound. In some cases, the reaction solvent is often composed of a hydrophobic solvent.
  • the reaction solvent is a hydrophobic solvent
  • hydrocarbons for example, aliphatic hydrocarbons such as hexane, heptane, trimethylpentane, octane, decane, dodecane, and tetradecane; alicyclic such as cyclohexane) Hydrocarbons; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and trichloroethane), esters (methyl acetate, ethyl acetate, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.), Ethers (diethyl ether, dipropyl ether, etc.)], polar solvents [water, alcohols (C1-4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, etc.
  • polar solvents water, alcohols (
  • the concentration of the metal compound in the reaction solvent is, for example, 5% by mass or more (for example, 6 to 50% by mass), preferably 8% by mass or more (for example, 9 to 40% by mass) in terms of metal mass. More preferably, the concentration may be as high as 10% by mass or more (for example, 12 to 30% by mass), usually about 5 to 30% by mass.
  • the pH of the reaction system may be adjusted according to the type of reaction solvent.
  • the pH is adjusted by a conventional method, for example, an acid (an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or perchloric acid, an organic acid such as formic acid, acetic acid, propionic acid or benzoic acid), an alkali [sodium hydroxide, Inorganic bases such as ammonia and bases such as amines (for example, organic bases such as tertiary amines such as alkylamines and alkanolamines) can be used.
  • an acid an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or perchloric acid, an organic acid such as formic acid, acetic acid, propionic acid or benzoic acid
  • an alkali sodium hydroxide
  • Inorganic bases such as ammonia and bases such as amines (for example, organic bases such as tertiary amines such as alkylamines and alkanol
  • the metal colloid particles (A) can be prepared in the form of a dispersion in which the metal colloid particles (A) are dispersed in the reaction solvent.
  • finish of a reductive reaction you may refine
  • the metal nanoparticle ink can be prepared by concentrating unnecessary solvent components from the dispersion when the solvent containing the dispersion medium is used as the reaction solvent. It can be prepared by dispersing (redispersing) the metal colloidal particles (A) separated from the dispersion medium in the dispersion medium.
  • Separation of the metal colloidal particles (A) from the dispersion can be performed by a conventional method, for example, by separating and removing the reaction solvent from the dispersion.
  • a conventional concentration operation or the like can be used for removal of the reaction solvent.
  • the removal of the reaction solvent may be performed in the presence of a dispersion medium using the difference in boiling point between the reaction solvent and the dispersion medium (that is, the removal of the reaction solvent and the dispersion in the dispersion medium are the same). System may be used).
  • the reaction solvent may be removed from a mixture obtained by mixing the dispersion medium with the dispersion.
  • the amount of the dispersion medium used can be appropriately adjusted so as to obtain a desired viscosity, and may be appropriately selected from the same range as described above.
  • the viscosity may be adjusted by mixing other solvent in addition to the dispersion medium and removing the other solvent.
  • an organic protective colloid In order to use metal nanoparticles, it is preferable to use them in a state of being coated with an organic protective colloid.
  • the organic protective colloid those having a decomposition temperature or boiling point in the range of 70 to 250 ° C. are preferably used. This decomposition temperature or boiling point refers to the lower one of the decomposition temperature and boiling point.
  • the organic protective colloid When the decomposition temperature or boiling point of the organic protective colloid is within 250 ° C., the organic protective colloid can be decomposed or evaporated by low-temperature heat treatment, and low-temperature firing can be easily performed. Further, when the decomposition temperature or boiling point of the organic protective colloid is 70 ° C. or higher, there is no fear that the organic protective colloid is decomposed or evaporated during storage of the silver paste, and the storage stability of the silver paste is good.
  • the organic protective colloid it is preferable to use hydrocarbons having 3 to 18 carbon atoms. If the carbon number is 18 or less, the decomposition temperature or boiling point becomes high, and there is no fear that the organic protective colloid cannot be decomposed or evaporated by low-temperature heat treatment, and if the carbon number is 3 or more, the decomposition temperature Or there is no possibility that the boiling point becomes too low and a problem occurs in the storage stability of the silver paste.
  • the organic protective colloid satisfying the above conditions is not particularly limited, but includes octylamine (boiling point 178 to 179 ° C.), 6-methyl-2-heptylamine (boiling point 154 to 156 ° C.), dibutylamine ( Boiling point 160-162 ° C), hexylamine (boiling point 130-132 ° C), dipropylamine (boiling point 105 ° C), diisopropylamine (boiling point 83-84 ° C), butylamine (boiling point 76-78 ° C), stearic acid (boiling point 232) 19.95 hPa), palmitic acid (boiling point 271.4 ° C; 133 hPa), myristic acid (boiling point 250 ° C; 133 hPa), lauric acid (boiling point 131 ° C; 1.3 hPa), octanoic acid (
  • organic protective colloid those containing an amine (amino group) are particularly preferable.
  • amines By including amines, it is possible to obtain a high effect of protecting metal nanoparticles with an organic protective colloid, and the organic protective colloid does not remain during firing, and the organic residue has an adverse effect on the specific resistance. It is possible to prevent the effect.
  • the method of coating the surface of the metal nanoparticles with the organic protective colloid can adopt any method.
  • the surface of the metal nanoparticles can be prepared by making the organic protective colloid coexist when preparing the metal nanoparticles.
  • the coating amount of the metal nanoparticles with the organic protective colloid is not particularly limited, but is preferably set in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the metal nanoparticles.
  • a dispersion medium having a decomposition temperature or boiling point in the range of 70 to 250 ° C This decomposition temperature or boiling point refers to the lower one of the decomposition temperature and boiling point.
  • the decomposition temperature or boiling point of the dispersion medium is within 250 ° C., the dispersion medium can be decomposed or evaporated by low-temperature heat treatment, and low-temperature firing can be easily performed. Further, when the decomposition temperature or boiling point of the dispersion medium is 70 ° C. or higher, there is no fear that the dispersion medium is decomposed or evaporated during storage of the silver paste, and the storage stability of the silver paste is good.
  • hydrocarbons having 3 to 18 carbon atoms are preferably used.
  • the number of carbon atoms is 18 or less, the decomposition temperature or boiling point becomes high, and there is no fear that the dispersion medium cannot be decomposed or evaporated by low-temperature heat treatment.
  • the number of carbon atoms is 3 or more, the decomposition temperature or There is no possibility that the boiling point becomes too low and a problem occurs in the storage stability of the silver paste.
  • Such a dispersion medium is not particularly limited, but is misty 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 metal nanoparticle ink according to the present invention may contain a binder for the purpose of improving the adhesion to the substrate, in addition to the metal nanoparticles covered with the organic protective colloid and the dispersion medium.
  • a binder for the purpose of improving the adhesion to the substrate, in addition to the metal nanoparticles covered with the organic protective colloid and the dispersion medium.
  • the organic protective colloid that coats the metal nanoparticles may also play a role as a binder, it is not necessary to add a binder.
  • the metal nanoparticles covered with the organic protective colloid or the dispersion medium alone can be used to form the metal nanoparticles. It is also possible to prepare particle ink.
  • the amount of the dispersion medium in the metal nanoparticle ink varies depending on the coating method of the metal nanoparticle ink, and is appropriately set so as to obtain viscosity and fluidity according to the coating method.
  • the metal nanoparticle ink thus prepared is printed on the surface of a substrate or the like in a desired shape by various conventionally known printing methods such as gravure printing, flexographic printing, screen printing, and ink jet printing to form a fine metal line pattern. .
  • the pattern is a pattern having an opening, and as the shape of the pattern, for example, the shape of the opening is a quadrangle such as a triangle, square, rectangle, rhombus, parallelogram, trapezoid, (positive) hexagon, (positive) Examples include a mesh-like pattern made of geometric figures combining polygons such as octagons.
  • a shape in which the metal composition exists in a stripe shape composed of a plurality of parallel lines may be used.
  • the shape of the fine metal wire pattern according to the present invention is preferably a shape having a network structure in which the metal composition is continuous in a stitch shape.
  • the line width, line spacing, and height of the portion of the pattern where the metal composition is present there are no particular restrictions on the line width, line spacing, and height of the portion of the pattern where the metal composition is present, and it can be appropriately selected depending on the target sheet resistance and pattern formation method. It is preferable that the line spacing is 0.1 to 10 ⁇ m, the height is 0.1 to 10 ⁇ m.
  • the fine metal wire pattern is subjected to a firing treatment in order to develop conductivity.
  • a firing treatment method heating by an oven or heating by a hot plate, which is generally performed conventionally, can be used. Although the heating conditions differ depending on the metal nanoparticle ink, firing is usually performed at 200 to 500 ° C. for about 1 to 60 minutes. Inks that can be fired even at low temperatures have been proposed, and such inks are fired at 100 to 200 ° C. for about 1 to 60 minutes.
  • the baking treatment may use a local heat treatment described later, or may be performed by using an oven, a hot plate, and a local heat treatment in combination.
  • a heat treatment a method in which a sample to be heated is kept at a constant temperature for a relatively long time of a minute unit or more (such as an oven or a baking furnace) or a constant temperature is maintained.
  • a method (such as a hot plate) is performed in which a sample to be heated on a held metal plate is allowed to stand for a certain period of time for a relatively long time of a minute unit or more.
  • Such processing is performed while maintaining the entire sample at a constant temperature, such as a substrate or a fine metal wire pattern.
  • the above-mentioned fine metal wire pattern is subjected to local heat treatment.
  • the local heat treatment is preferably performed after the above-described firing process of the fine metal wire pattern, but may be performed in combination with the firing process.
  • the local heat treatment refers to the difference in absorption efficiency between the metal fine wire pattern for energy irradiation and other members such as a base material, or high energy is applied to the surface including the metal fine wire pattern in a short time.
  • the metal fine line pattern portion is heated before the temperature of the base material rises due to heat propagation, the metal fine wire pattern portion is heated to a temperature higher than that of other members such as the base material. It is processing.
  • Such local heat treatment is a very short-time treatment with a treatment time of 10 seconds or less, preferably 1 second or less, and it is also preferable to repeat such treatment.
  • the metal fine line pattern portion is preferably heated to a temperature higher than that of other members such as a substrate by local heat treatment, particularly preferably 20 ° C. or higher, more preferably 30 ° C. or higher. It is preferable to do.
  • a temperature difference it is necessary for the metal fine line pattern part to receive strong energy irradiation in a short time, and as a result, the surface of the metal fine line pattern part is modified by the energy treatment, thereby producing the effect of the present invention. I believe.
  • Such temperature measurement can be obtained by measuring the temperature difference between the fine metal wire pattern portion and the substrate portion using thermography. In the process in which the thermocouple is not affected by the process, the temperature can be determined by connecting a thermocouple to each of the fine metal wire pattern portion and the base material portion and monitoring the temperature.
  • a temperature difference of 20 ° C. or more is generated between the fine metal wire pattern and the substrate by the measurement method described above.
  • Examples of such treatment include plasma treatment, dielectric heating treatment, excimer light irradiation treatment, ultraviolet treatment, microwave treatment, infrared heater treatment, hot air heater treatment, and the like.
  • plasma treatment, dielectric heating treatment, excimer light irradiation treatment, or microwave treatment is preferable.
  • Plasma processing either plasma processing using a vacuum system or atmospheric pressure plasma processing performed near atmospheric pressure can be used.
  • atmospheric pressure plasma processing performed near atmospheric pressure requires no vacuum process. There is an advantage that can be simplified.
  • the outermost metal fine line pattern portion is preferably heated more instantaneously than the thick base material portion, so that the effect is obtained.
  • Atmospheric pressure plasma treatment is a treatment method in which plasma is generated under a pressure near atmospheric pressure to treat the surface of a non-treated material and can be treated by a known method using a known plasma discharge treatment apparatus.
  • a planar method is used in which high-frequency power is applied between electrodes arranged opposite to each other so as to sandwich a material to be processed, and a supply gas is turned into plasma, and a reaction gas is passed between electrodes to which a high-frequency voltage is applied.
  • a downstream system that converts to plasma, any system can be used in the present invention.
  • the power source is not particularly limited, but a pearl industrial high frequency power source (200 kHz), a pearl industrial high frequency power source (800 kHz), a JEOL high frequency power source (13.56 MHz), a pearl industrial high frequency power source (150 MHz), or the like is used. it can.
  • the value of the voltage applied from the power supply is appropriately determined.
  • the voltage is about 0.5 to 10 kV, and the power supply frequency is adjusted to more than 100 kHz and 150 MHz or less.
  • a continuous sine wave continuous oscillation mode called a continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called a pulse mode
  • the lower limit value of power is preferably 1.2 W / cm 2 or more, and the upper limit value is preferably 50 W / cm 2 or less, more preferably 20 W / cm 2 or less.
  • the voltage application area (/ cm 2 ) in the electrode refers to the area in which discharge occurs.
  • Such an electrode is preferably a metal base material coated with a dielectric. It is preferable to coat a dielectric on at least one side of the opposed application electrode and the ground electrode, and more preferably coat both of the opposed application electrode and the ground electrode with a dielectric.
  • the dielectric is preferably an inorganic substance having a relative dielectric constant of 6 to 45. Examples of such a dielectric include ceramics such as alumina and silicon nitride, silicate glass, borate glass, and the like. Glass lining material and the like.
  • the distance between the discharge electrodes is preferably 0.5 to 20 mm, more preferably 0.5 to 5 mm, and particularly preferably 1 to 3 mm from the viewpoint of uniform discharge.
  • the atmospheric pressure represents a pressure of 20 to 110 kPa
  • 93 to 104 kPa is preferable in order to preferably obtain the effects described in the present invention.
  • the gas used in the present invention is basically a mixed gas of an inert gas and a reactive gas such as an organic fluorine compound.
  • the reactive gas is preferably contained in an amount of 0.01 to 10% by volume with respect to the mixed gas.
  • inert gas examples include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc.
  • helium Argon is preferably used.
  • reaction can be promoted by containing 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen and nitrogen in the mixed gas.
  • a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen and nitrogen in the mixed gas.
  • UV treatment examples of the ultraviolet irradiation treatment include high-pressure mercury lamp, low-pressure mercury lamp, xenon lamp, and excimer light treatment.
  • the excimer light irradiation treatment can irradiate strong energy in a short time and can be preferably used in the present invention. Since the excimer light irradiation treatment receives strong energy in a short time, the metal fine line pattern portion becomes high temperature before the heat to the base material diffuses.
  • excimer light treatment at 172 nm is more preferable from the viewpoint of treatment efficiency.
  • a feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.
  • the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
  • Dielectric barrier discharge is a lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode.
  • a dielectric transparent quartz in the case of an excimer lamp
  • a high frequency high voltage of several tens of kHz to the electrode.
  • the micro discharge streamer reaches the tube wall (dielectric)
  • the electric discharge accumulates on the surface of the dielectric, and the micro discharge disappears.
  • This micro discharge spreads over the entire tube wall, and is a discharge that repeatedly generates and disappears. For this reason, flickering of light that can be seen with the naked eye occurs.
  • a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.
  • Electrodeless electric field discharge by capacitive coupling, also called RF discharge.
  • the lamp, the electrodes, and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.
  • Synthetic quartz windows are not only expensive consumables, but also cause light loss.
  • the outer diameter of the double-cylindrical lamp is about 25 mm, the difference in distance to the irradiation surface cannot be ignored directly below the lamp axis and on the side of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are arranged in close contact, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.
  • the biggest feature of the capillary excimer lamp is its simple structure.
  • the quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. Therefore, a very inexpensive light source can be provided.
  • ⁇ Double cylindrical lamps are processed to close by connecting both ends of the inner and outer tubes, so they are more likely to break during handling and transportation than thin tube lamps.
  • the outer diameter of the tube of the thin tube lamp is about 6 to 12 mm.
  • the discharge mode can be either dielectric barrier discharge or electrodeless field discharge.
  • the electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.
  • the Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, radical oxygen atomic species and ozone can be generated at a high concentration, and the ability to dissociate organic bonds is high. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, only the extreme surface portion can be efficiently removed in a short time.
  • the excimer light intensity is preferably 1 to 200 mW / cm 2 .
  • the irradiation time is preferably 0.5 to 10 seconds.
  • the integrated intensity is preferably 5 to 1000 mJ / cm 2 , and more preferably 50 to 500 mJ / cm 2 . If the integrated strength is less than 5 J / cm 2 , the effect is small, and if it exceeds 1000 mJ / cm 2 , damage due to treatment becomes large.
  • the oxygen concentration during the excimer light irradiation treatment is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.
  • Microwave irradiation can also be used for local heating. Microwave irradiation may be used.
  • the microwave may be a general-purpose microwave with a frequency of 2.45 GHz adopted in a general microwave oven, but in this case, arc discharge occurs in a part of the metal thin wire pattern, and the microwave is partially Such abnormal heating may occur or catch fire, and the electrode layer and the film substrate may be significantly damaged.
  • microwaves of 10 GHz or higher can be processed without discharge, and it is not necessary to use a discharge prevention method. Therefore, it is more preferable to perform heat treatment by applying microwave irradiation at a frequency of 10 to 60 GHz. preferable.
  • ⁇ Heating with microwaves can appropriately determine conditions such as radio wave output and irradiation time.
  • the radio wave output is in the range of 0.01 to 10 kW, preferably 0.1 to 5 kW.
  • the irradiation time is in the range of 1 second to 60 minutes, preferably 2 seconds to 30 minutes.
  • microwave device for example, an electromagnetic wave heating and sintering device (FMW-10-28, transmission frequency 28 GHz, radio wave output ⁇ 10 kW) manufactured by Fuji Radio Industry Co., Ltd. can be used.
  • FMW-10-28, transmission frequency 28 GHz, radio wave output ⁇ 10 kW an electromagnetic wave heating and sintering device manufactured by Fuji Radio Industry Co., Ltd.
  • heat conductivity such as iron, stainless steel, and copper is good on the back surface of the transparent support (the side on which the conductive metal layer and the conductive polymer layer are not formed) as necessary.
  • a heat sink or the like that can dissipate heat applied to the transparent support by installing a metal plate, an inorganic plate such as glass, or the like can be provided.
  • Induction heat treatment In the induction heating process, the magnetic field changes in accordance with the insertion and removal of the permanent magnet in the center of the coil-shaped conductor, and the electromagnetic induction action, which is a phenomenon in which current flows through the conductor, is used in the heated object in the coil magnetic field.
  • current is induced to heat. This induced current is generated by an eddy current that flows while vortexing in the object, generates Joule heat due to hysteresis loss, and generates heat in a very short time. This is a process of heating with the generated heat.
  • the induction heating is preferably performed at a frequency of 10 to 900 kHz, and more preferably at a frequency of 100 to 700 kHz.
  • Use of a frequency lower than 10 kHz is not preferable because heat generation by the frequency is weak, and use of a frequency exceeding 900 kHz is not preferable because of surface minimal heating due to the skin effect.
  • Hot air heater processing Further, using a nozzle having a 0.1 to 10 mm blowing hole or a slit-like blowing port, high-temperature hot air of 300 to 1000 ° C. is irradiated for a short time of less than 1 second, more preferably less than 0.1 second. Hot air heater treatment can also be used. For example, it can process using the high heater apparatus made from a Hibeck company.
  • the conductive polymer-containing layer includes a water-soluble binder resin containing at least a conductive polymer containing a ⁇ -conjugated conductive polymer and a polyanion and a structural unit represented by the general formula (I) And formed from.
  • the formation of the conductive polymer-containing layer according to the present invention includes a roll coating method, a bar coating method, a dip coating method, a spin coating method, and the like.
  • Various coating methods such as a coating method, a casting method, a die coating method, a blade coating method, a curtain coating method, a spray coating method, and a doctor coating method can be used.
  • the conductive polymer-containing layer according to the present invention is preferably formed within 24 hours after the local heat treatment of the fine metal wire pattern according to the present invention. If it is within 24 hours, the effect of modifying the surface of the fine metal wire pattern portion will not be reduced.
  • 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 polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like, and ease of adsorption to metal nanoparticles. Most preferred is polyethylene dioxythiophene.
  • Precursor monomers used in the formation of ⁇ -conjugated conductive polymers have a ⁇ -conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidant, a ⁇ -conjugated system is formed in the main chain. It is what is done. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
  • the precursor monomer examples include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexyl Offene, 3-heptyl
  • poly anion The polyanions used in the present invention are substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester, and co-polymers thereof.
  • a polymer comprising a structural unit having an anionic group and a structural unit having no anionic group.
  • This poly anion is a solubilized polymer that solubilizes the ⁇ -conjugated conductive polymer in a solvent.
  • the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
  • the anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable.
  • a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
  • polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Isoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be sufficient and two or more types of copolymers may be sufficient.
  • it may be a poly anion further having F (fluorine atom) in the compound.
  • F fluorine atom
  • Nafion manufactured by Dupont
  • Flemion manufactured by Asahi Glass Co., Ltd.
  • perfluoro vinyl ether containing a carboxy group can be used.
  • compounds having a sulfo group are formed by applying and drying a conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or longer before being irradiated with microwaves. May be. 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 hydroxy group-containing non-conductive polymer, and can further increase the conductivity of the obtained conductive polymer.
  • the degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.
  • Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, and an anionic group containing The method of manufacturing by superposition
  • Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, this is maintained at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
  • the oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the ⁇ -conjugated conductive polymer.
  • the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid.
  • the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like.
  • the ultrafiltration method is preferable from the viewpoint of easy work.
  • the ratio of the ⁇ -conjugated conductive polymer and the poly anion contained in the conductive polymer, “ ⁇ -conjugated conductive polymer”: “poly anion” is preferably 1: 1 to 20 by mass ratio. From the viewpoint of conductivity and dispersibility, the range of 1: 2 to 10 is more preferable.
  • the oxidant used when the precursor monomer forming the ⁇ -conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole.
  • oxidants such as iron (III) salts, eg FeCl 3 , Fe (ClO 4 ) 3 , organic acids and iron (III) salts of inorganic acids containing organic residues
  • iron (III) salts eg FeCl 3 , Fe (ClO 4 ) 3
  • organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable.
  • air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time.
  • persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are
  • iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate 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.
  • a water-soluble organic compound may be contained as the second dopant.
  • an oxygen containing compound is mentioned suitably.
  • the oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a 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.
  • Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, ⁇ -butyrolactone, and the like.
  • Examples of the ether group-containing compound include diethylene glycol monoethyl ether.
  • Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used singly or in combination of two or more, but it is preferable to use at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol.
  • the conductive polymer-containing layer according to the present invention 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 effect of the second dopant described above, even if the resin is mixed, the resistance value of the conductive polymer-containing layer is not significantly deteriorated. Depending on the conditions, the resistance value can be lowered. When the film thickness of the conductive polymer-containing layer is increased only with the conductive polymer, the transparency is deteriorated. However, by using the water-soluble binder resin together, the conductive polymer-containing layer is not reduced without decreasing the conductivity and transparency. It is possible to increase the film thickness. By increasing the film thickness, it is possible to sufficiently cover the fine metal wire pattern with the conductive polymer-containing layer, and even when used for electrodes such as organic light-emitting devices and organic solar cell devices, leakage between the electrodes can be prevented. It becomes.
  • the water-soluble binder resin is a water-soluble binder resin, and means a binder resin in which 0.001 g or more 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 according to the present invention is preferably transparent.
  • the water-soluble binder resin according to the present invention has a structure including at least the structural unit represented by the general formula (I), and may be a homopolymer represented by the general formula (I). These 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. More preferably.
  • 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, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyls
  • 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. 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 of 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 represents a substituted or unsubstituted alkylene group, — (CH 2 CHRbO) x —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.
  • these 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 substrate used for the planar 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 or a thin film glass.
  • since local heating is utilized since the temperature of a support body can be restrained to comparatively low temperature, it can apply preferably also to such a transparent resin film.
  • the transparent resin film is not particularly limited, and the material, shape, structure, thickness and the like can be appropriately selected from known ones.
  • polyolefin resins such as biaxially stretched polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, and cyclic olefin resins.
  • vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like can be mentioned. If the resin film transmittance of 80% or more at 80 nm), can be preferably applied to a transparent resin film according to the present invention.
  • PEEK polyether ether ketone
  • PSF polysulfone
  • PES polyether sulfone
  • PC polycarbonate
  • Polyamide resin film polyimide resin film
  • acrylic resin film acrylic resin film
  • TAC triacetyl cellulose
  • biaxially stretched polyethylene terephthalate film biaxially stretched polyethylene naphthalate film, polyethersulfone film, and polycarbonate film are preferable from the viewpoints of transparency, ease of handling, strength, and cost.
  • a biaxially stretched polyester such as a terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.
  • 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.
  • planar electrode for organic electronic devices of the present invention can be used as an electrode for organic electronic devices.
  • the planar electrode of the present invention may be used as either a cathode or an anode, but can be used as an anode, for example.
  • the organic electroluminescence element will be described.
  • An organic electroluminescence element (hereinafter also referred to as an organic EL element) includes an organic light emitting layer such as a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole block layer, and an electron block layer in addition to the organic light emitting layer. You may have a layer which controls light emission in combination. Since the planar electrode for organic electronic devices 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 organic light emitting layer is produced 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.
  • the counter electrode is a cathode in the organic EL element.
  • the counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a material having a 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 than this for example, a magnesium / silver mixture
  • Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • 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.
  • a polyethylene naphthalate film having a film thickness of 125 ⁇ m (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PEN Q83) was cut into 4 cm ⁇ 4 cm.
  • the easy adhesion layer the following easy adhesion layer coating solution 1 is applied by a spin coater with the rotation speed adjusted so as to have a dry film thickness of 50 nm, subjected to heat treatment at 110 ° C. for 3 minutes, and the easy adhesion layer has been prepared.
  • a substrate was used.
  • Bayronal MD1200 Toyobo 0.6g 4.7 g of H 2 O Isopropyl alcohol 4.7g
  • Inkjet silver nanopaste NPS-JL (manufactured by Harima Kasei Co., Ltd.) has a pressure applying means and an electric field applying means as an ink jet recording head, and has a nozzle diameter of 25 ⁇ m, a driving frequency of 12 kHz, a number of nozzles of 128, a nozzle density of 180 dpi (dpi). 1 represents the number of dots per inch, that is, 2.54 cm), and loaded on an inkjet printing apparatus equipped with a piezo-type head, and printed on the substrate with the easy adhesion layer as shown in FIG.
  • the take-out electrodes 1 and 4 in FIG. 1 are used as take-out electrodes with a silver solid portion of 1.2 cm ⁇ 5 mm.
  • the metal fine line pattern 2 in FIG. 1 is in contact with the extraction electrode 1 at a metal mesh pattern portion having a line width of 50 ⁇ m and a line interval of 900 ⁇ m printed in a range of 1.2 cm ⁇ 1.2 cm.
  • the blank part 3 is a 1.2 cm ⁇ 2 mm silver-free part.
  • the formed fine metal wire pattern 2 was baked at 130 ° C. for 60 minutes using an oven. The height from the base material of the metal fine wire pattern 2 was 500 nm.
  • the speed is adjusted so that the film thickness of the conductive polymer-containing layer of the blank portion 3 is 500 nm.
  • the following conductive polymer-containing coating solution 1 was applied to the region of the conductive polymer-containing layer 5 in FIG. 2 so as to adjust and pass over the fine metal wire pattern 2 in FIG.
  • region other than the metal fine wire pattern 2) of the coated sample was dried for 1 minute with warm air of 80 ° C., and the conductive polymer-containing layer 5 was wiped off with a cotton swab dipped in pure water.
  • the conductive polymer containing layer 6 was provided in the area
  • the structure and molecular weight were measured by 1 H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively.
  • the base material is 0.7 mm thick, 4 cm ⁇ 4 cm glass substrate (Eagle EG, manufactured by Corning), silver nanopaste for inkjet NPS-J (manufactured by Harima Chemicals), and the firing conditions are 250 ° C. and 30 minutes.
  • a metal pattern 2 was obtained in the same manner as the metal fine line pattern 1 except that.
  • Metal fine wire pattern 3 A fine metal wire pattern 3 was obtained in the same manner as the fine metal wire pattern 1 except that the silver nanoparticle paste MDot-SLP manufactured by Mitsuboshi Belting Co., Ltd. was gravure-printed using a K303 multicoater manufactured by Matsuo Sangyo Co., Ltd.
  • planar electrodes 108 to 110 were produced in the same manner except that the organic electronic device planar electrodes 102, 106, 107 were changed to the local heat treatment 2.
  • planar electrode 111 for organic electronic devices (Preparation of planar electrode 111 for organic electronic devices)
  • the firing condition is set to 150 ° C. for 15 minutes, and then the local heat treatment 1 is performed to perform the additional firing treatment and the local heat treatment in the same manner.
  • a planar electrode 111 was produced.
  • planar electrodes 112 to 114 for organic electronic devices In the surface electrode 102 for organic electronic devices, the surface for organic electronic devices was the same except that the time from the local heat treatment to the formation of the conductive polymer-containing layer was 12 hours, 24 hours, and 36 hours. The shaped electrodes 112 to 114 were produced.
  • planar electrodes 120 to 122 were produced in the same manner except that the local heat treatment was changed to the following local heat treatment 4 in the planar electrodes 116, 118, and 119 for the organic electronic device.
  • (Local heat treatment 4) Changed the treatment conditions for local heat treatment 3 to the following (excimer light irradiation treatment conditions) Excimer light intensity 80mW / cm 2 (172nm) 1mm distance between sample and light source Stage heating temperature 80 °C Oxygen concentration in irradiation device 0.1% Excimer irradiation time 0.2 seconds 5 times 5 times As in the case of the planar electrode 101 for organic electronic devices, it is confirmed that the direction with the fine metal wire pattern is 20 ° C. or higher than the portion without the fine metal wire pattern. did.
  • planar electrodes 123 to 127 were produced in the same manner except that the local heat treatment was changed to the following local heat treatment 5 using microwave heat treatment in the planar electrodes 115 to 119 for the organic electronic device. did.
  • Microwave treatment equipment Electromagnetic heating and sintering equipment (FMW-10-28, transmission frequency 28 GHz) manufactured by Fuji Radio Industry Co., Ltd. Output: 1kW Treatment time: 5 seconds In the same manner as the planar electrode 101 for organic electronic devices, it was confirmed that the direction with the fine metal wire pattern was 20 ° C. or higher than the portion without the fine metal wire pattern.
  • planar electrodes 128 to 132 were prepared in the same manner except that the local heat treatment was changed to the following local heat treatment 6 using induction heat treatment in the planar electrodes 115 to 119 for the organic electronic device. .
  • thermography (Thermo Tracer TH9100, NEC, manufactured by Avio Sekigaisen Technology Co., Ltd.), it was confirmed that the direction with the fine metal wire pattern was 20 ° C. or higher than the portion without the fine metal wire pattern.
  • planar electrode 133 for organic electronic devices was produced similarly except having changed the local heat processing into the following local heat processing 7 using a hot-air heater process.
  • Hot air heater treatment The treatment was performed at 500 ° C. for 0.01 seconds using a high heater (manufactured by Hibeck Co., Ltd.) having a slit-shaped blowout of 27 mm ⁇ 0.5 mm.
  • thermography (Thermo Tracer TH9100, manufactured by NEC, Avio Sekigaisen Technology Co., Ltd.), it was confirmed that the temperature with the fine metal wire pattern was about 15 ° C. higher than the temperature of the portion without the fine metal wire pattern.
  • the conductive polymer-containing coating solution 1 is the following conductive polymer-containing coating solution 6 that does not contain a water-soluble binder resin containing a structural unit represented by the general formula (I).
  • the surface shape for comparative organic electronic devices was the same except that the coating speed was adjusted so that the film thickness of the conductive polymer-containing layer in the portion without the fine metal wire pattern was 50 nm without performing the local heat treatment.
  • An electrode 201 was produced.
  • ⁇ or more is necessary, and ⁇ or more is preferable.
  • An organic EL constituent layer is formed on the obtained metal thin wire pattern of each planar electrode for organic electronic devices by the following procedure, and organic EL elements 101 to 133 and 201 corresponding to the planar electrodes for each organic electronic device are formed.
  • To 205 were prepared, and the short-circuit characteristics and driving voltage of each organic EL element were evaluated.
  • PEDOT-PSS CLEVIOS P AI 4083 (solid content 1.5%) (manufactured by HC Starck) was made into the same region as the conductive polymer-containing coating solution using a bar coater with a gap gap of 40 ⁇ m, and the dry film thickness was applied to a thickness of 30 nm, and unnecessary areas were wiped off in the same manner as the conductive polymer-containing coating solution. Further, heat treatment was performed at 130 ° C. for 30 minutes on a hot plate to form a hole injection layer.
  • 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.
  • a crucible made of a resistance heating material made of molybdenum or tungsten was used as the evaporation crucible.
  • the deposition crucible containing compound 1 was heated by energization, and deposited at a deposition rate of 0.1 nm / second on a region with a fine metal wire pattern. A hole transport layer was provided.
  • 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.
  • Co-evaporation was performed on the patterned region to form a green-red phosphorescent light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
  • the compound 4 and the compound 5 are co-deposited at a deposition rate of 0.1 nm / second in a region having a fine metal wire pattern so that the compound 4 becomes 10% by mass, and blue phosphorescence having a maximum emission wavelength of 471 nm and a thickness of 15 nm.
  • a light emitting layer was formed.
  • the hole blocking layer was formed by vapor-depositing the compound 6 in a film thickness of 5 nm in a region having a fine metal wire pattern.
  • 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 to form an electron transport layer having a thickness of 45 nm.
  • each obtained organic EL element performed subsequent evaluation under nitrogen, without taking out in air
  • Drive voltage Using a source measure unit 2400 manufactured by KEITHLEY, a DC voltage was applied, a voltage required to pass a current of 3 mA to the device was determined as a drive voltage, and evaluation was performed using the following indices.
  • ⁇ or more is preferable, and ⁇ ⁇ or more is more preferable.
  • the method for producing a planar electrode for an organic electronic device of the present invention is to produce an electrode that provides an organic electronic device with low driving voltage and no leakage with a counter electrode while maintaining high transparency at low cost. And can be suitably used for planar electrodes for organic electronic devices.

Abstract

Le problème traité par la présente invention est de fournir un procédé qui sert à fabriquer une électrode plane pour dispositif électronique organique et qui peut, à bas coût, produire une électrode qui permet d'obtenir un dispositif électronique organique n'ayant pas de fuite par rapport à une contre-électrode et une faible tension d'attaque tout en maintenant une transparence élevée. Le procédé de fabrication d'une électrode plane pour dispositif électronique organique est caractérisé par la formation d'une couche contenant un polymère conducteur après réalisation d'un traitement de chauffage local sur un motif de fil métallique mince dans l'électrode plane et qui est pour un dispositif électronique organique et qui a : le motif de fil mince métallique conducteur formé à partir de nanoparticules métalliques sur un substrat ; et la couche contenant un polymère conducteur formée à partir d'au moins un polymère conducteur, qui est formé comprenant un polymère conducteur π conjugué et un polyanion, et une résine de liant soluble dans l'eau, qui contient l'unité structurelle représentée par la formule générale (I), sur le motif de fil mince métallique.
PCT/JP2012/056225 2011-03-14 2012-03-12 Procédé de fabrication d'une électrode plane pour dispositif électronique organique WO2012124647A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013504715A JP5835316B2 (ja) 2011-03-14 2012-03-12 有機電子デバイス用面状電極の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011055246 2011-03-14
JP2011-055246 2011-03-14

Publications (1)

Publication Number Publication Date
WO2012124647A1 true WO2012124647A1 (fr) 2012-09-20

Family

ID=46830718

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/056225 WO2012124647A1 (fr) 2011-03-14 2012-03-12 Procédé de fabrication d'une électrode plane pour dispositif électronique organique

Country Status (2)

Country Link
JP (1) JP5835316B2 (fr)
WO (1) WO2012124647A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2996359A1 (fr) * 2012-10-03 2014-04-04 Hutchinson Electrode transparente conductrice et procede de fabrication associe
US9384907B2 (en) 2011-07-01 2016-07-05 Hutchinson Current-conducting electrode and corresponding manufacturing process
WO2018235594A1 (fr) * 2017-06-22 2018-12-27 住友化学株式会社 Procédé de production d'électrode transparente et procédé de production de dispositif électronique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008133322A (ja) * 2006-11-27 2008-06-12 Shin Etsu Polymer Co Ltd 導電性高分子塗料及び導電性塗膜
JP2008522369A (ja) * 2004-11-24 2008-06-26 ノバセントリックス コーポレイション ナノ材料組成物の電気的使用、めっき的使用および触媒的使用
JP2008243547A (ja) * 2007-02-28 2008-10-09 Mitsuboshi Belting Ltd 透明電極及びその製造方法
JP2010244747A (ja) * 2009-04-02 2010-10-28 Konica Minolta Holdings Inc 透明電極、透明電極の製造方法、および有機エレクトロルミネッセンス素子
WO2011148931A1 (fr) * 2010-05-28 2011-12-01 コニカミノルタホールディングス株式会社 Électrode pour dispositif électronique organique
JP2012009240A (ja) * 2010-06-24 2012-01-12 Konica Minolta Holdings Inc 透明電極とその製造方法、及び透明電極を用いた有機電子素子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008522369A (ja) * 2004-11-24 2008-06-26 ノバセントリックス コーポレイション ナノ材料組成物の電気的使用、めっき的使用および触媒的使用
JP2008133322A (ja) * 2006-11-27 2008-06-12 Shin Etsu Polymer Co Ltd 導電性高分子塗料及び導電性塗膜
JP2008243547A (ja) * 2007-02-28 2008-10-09 Mitsuboshi Belting Ltd 透明電極及びその製造方法
JP2010244747A (ja) * 2009-04-02 2010-10-28 Konica Minolta Holdings Inc 透明電極、透明電極の製造方法、および有機エレクトロルミネッセンス素子
WO2011148931A1 (fr) * 2010-05-28 2011-12-01 コニカミノルタホールディングス株式会社 Électrode pour dispositif électronique organique
JP2012009240A (ja) * 2010-06-24 2012-01-12 Konica Minolta Holdings Inc 透明電極とその製造方法、及び透明電極を用いた有機電子素子

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9384907B2 (en) 2011-07-01 2016-07-05 Hutchinson Current-conducting electrode and corresponding manufacturing process
FR2996359A1 (fr) * 2012-10-03 2014-04-04 Hutchinson Electrode transparente conductrice et procede de fabrication associe
WO2014053572A3 (fr) * 2012-10-03 2014-07-24 Hutchinson Electrode transparente conductrice et procede de fabrication associe
CN104813499A (zh) * 2012-10-03 2015-07-29 哈钦森公司 导电透明电极以及相关制造工艺
US20150262730A1 (en) * 2012-10-03 2015-09-17 Hutchinson Transparent conductive electrode and associated production method
US9905332B2 (en) 2012-10-03 2018-02-27 Hutchinson Transparent conductive electrode and associated production method
WO2018235594A1 (fr) * 2017-06-22 2018-12-27 住友化学株式会社 Procédé de production d'électrode transparente et procédé de production de dispositif électronique
JP2019008942A (ja) * 2017-06-22 2019-01-17 住友化学株式会社 透明電極の製造方法及び電子デバイスの製造方法

Also Published As

Publication number Publication date
JPWO2012124647A1 (ja) 2014-07-24
JP5835316B2 (ja) 2015-12-24

Similar Documents

Publication Publication Date Title
JP5741581B2 (ja) 透明導電膜、および有機エレクトロルミネッセンス素子
WO2017056797A1 (fr) Élément électroluminescent organique transparent
JP6319090B2 (ja) 透明電極の製造方法
JP2012009240A (ja) 透明電極とその製造方法、及び透明電極を用いた有機電子素子
WO2014034920A1 (fr) Électrode transparente, procédé de production et dispositif électronique organique correspondants
JP5835316B2 (ja) 有機電子デバイス用面状電極の製造方法
JP5983173B2 (ja) 透明電極の製造方法および有機電子素子の製造方法
JPWO2013172399A1 (ja) 導電性基板の製造方法、導電性基板および有機電子素子
JP5782855B2 (ja) 透明電極及び有機エレクトロルミネッセンス素子
JP5849834B2 (ja) 透明電極、透明電極の製造方法、及び該透明電極を用いた有機電子素子
JP2012138310A (ja) 有機電子デバイス用給電電極およびその製造方法
JP2014104409A (ja) 透明電極の製造方法
JP5750908B2 (ja) 透明導電膜の製造方法、透明導電膜および有機エレクトロルミネッセンス素子
JPWO2015050081A1 (ja) 導電性基板、その製造方法及び当該導電性基板が備えられている有機電子デバイス
JP2016110769A (ja) 透明電極の製造方法、透明電極、透明電極の製造装置、電子機器
WO2016143201A1 (fr) Électrode transparente, son procédé de fabrication, et élément électroluminescent organique
JP5691472B2 (ja) 透明電極の製造方法及び有機エレクトロルミネッセンス素子の製造方法
WO2017056814A1 (fr) Élément organique transparent à électroluminescence et son procédé de fabrication
JP6032271B2 (ja) 透明電極の製造方法および有機電子素子の製造方法
JP5741366B2 (ja) 透明電極の製造方法
JP5609797B2 (ja) 透明導電膜、その形成方法および有機エレクトロルミネッセンス素子
JP2012138311A (ja) 透明導電膜基板および有機エレクトロルミネッセンス素子
JP2012243492A (ja) 透明電極の製造方法および有機電子デバイス
JP5494390B2 (ja) 透明導電膜、および有機エレクトロルミネッセンス素子
JP2012160391A (ja) 透明導電膜、および有機エレクトロルミネッセンス素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12757883

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013504715

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12757883

Country of ref document: EP

Kind code of ref document: A1