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WO2012032850A1 - Élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage - Google Patents

Élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage Download PDF

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Publication number
WO2012032850A1
WO2012032850A1 PCT/JP2011/065947 JP2011065947W WO2012032850A1 WO 2012032850 A1 WO2012032850 A1 WO 2012032850A1 JP 2011065947 W JP2011065947 W JP 2011065947W WO 2012032850 A1 WO2012032850 A1 WO 2012032850A1
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group
organic
layer
light emitting
light
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Japanese (ja)
Inventor
秀雄 ▲高▼
片倉　利恵
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Konica Minolta Inc
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Konica Minolta Inc
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • H10K59/80524—Transparent cathodes, e.g. comprising thin metal layers

Definitions

  • the present invention relates to an organic electroluminescence element having a plurality of light emitting units laminated through a charge generation layer and having improved luminance or lifetime, and further relates to an illumination device and a display device including the element.
  • an organic electroluminescence element (hereinafter also referred to as an organic EL element) is an all-solid-state element composed of an organic material film having a thickness of only about 0.1 ⁇ m between electrodes and emits light of 2 V. Since it can be achieved at a relatively low voltage of about ⁇ 20 V, it is a technology expected as a next-generation flat display and illumination.
  • Japanese Patent No. 3884564, Japanese Patent No. 3933591, and the like include an organic EL having a multi-unit structure in which organic EL elements are connected in series by a charge generation layer. Devices have been reported.
  • the optical distance is adjusted by performing optical design of the element, and in particular, the light is emitted from the element in which the plurality of light emitting layers are stacked. It is important to increase the amount of light (light extraction).
  • the organic EL element having a multi-unit structure has a problem that optical design is remarkably difficult because there are a plurality of light emitting regions.
  • a cavity adjustment layer for example, see Patent Document 1 for adjusting an optical distance, adjustment by a light scattering layer (for example, see Patent Document 2), and the like are known. It becomes a limitation and it cannot be said that it is sufficient yet, and drastic improvement is desired.
  • An object of the present invention is to provide an organic EL element having a multi-unit structure with high light extraction efficiency, and further to provide an illumination device and a display device including the element.
  • an organic electroluminescence element having a plurality of light emitting units sandwiched between an anode and a cathode
  • the organic electroluminescence device wherein the anode or the cathode is a transparent electrode containing a conductive polymer formed on a transparent support.
  • the charge generating layer is provided between the plurality of light emitting units, and the charge generating layer generates holes and electrons by applying a voltage between the plurality of light emitting units. 6.
  • the organic electroluminescence device according to any one of 5 above.
  • An illuminating device comprising the organic electroluminescent element according to any one of 1 to 7 above.
  • a display device comprising the organic electroluminescence element according to any one of 1 to 7 above.
  • an element configuration in which a plurality of light emitting units are laminated also referred to as having a multi-unit structure
  • a transparent electrode made of a conductive polymer is used in combination as at least one electrode of an anode or a cathode.
  • ITO indium tin oxide
  • aluminum, and other metal / metal oxide-based electrodes it is possible to improve the light extraction efficiency without applying a special optical design.
  • FIG. 4 is a schematic diagram of a display unit A.
  • FIG. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is a schematic diagram of an illuminating device.
  • organic electroluminescence element (organic EL element) of the present invention, by having the configuration according to any one of claims 1 to 4, high luminance is achieved at a constant current, and could provide an organic electroluminescence device (organic EL device) having a long life.
  • the present inventors have found that in an organic EL element in which a plurality of light emitting units are provided between an anode and a cathode, either the anode or the cathode is placed on a transparent support.
  • the formed transparent electrode containing a conductive polymer the inventors succeeded in significantly increasing the light extraction efficiency, which was not sufficient with a conventionally known tandem element having an ITO electrode exhibiting a large refractive index.
  • Either the anode or the cathode according to the organic EL device of the present invention is characterized in that it is a transparent electrode containing a conductive polymer formed on a transparent support.
  • the “transparent” of the transparent electrode of the present invention means that it shows a transmittance of 70% or more for visible light having a wavelength of 550 nm.
  • the conductive polymer constituting the transparent electrode of the present invention, the electrical characteristics of the electrode, etc. will be described in detail later.
  • Transparent support As the transparent support according to the present invention, glass, quartz, a transparent resin film and the like are preferable, and a transparent resin film which can give flexibility to the organic EL element is more preferable.
  • transparent of the transparent support means to exhibit a transmittance of 80% or more for visible light having a wavelength of 550 nm.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfone , Polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, cyclone resins such as Arton (trade name, manufactured by JSR) or Appel (trade
  • An inorganic or organic film or a hybrid film of both may be formed on the surface of the transparent resin film, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • a barrier film having a relative humidity (90 ⁇ 2)% RH) of 0.01 g / (m 2 ⁇ 24 h) or less is preferable.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 is preferable.
  • a high barrier film having 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ MPa) or less and a water vapor permeability of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferably used.
  • the material for forming the barrier film may be any material that has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the formation method of the barrier layer is not particularly limited.
  • the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method An atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, etc. can be used, but the atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is used. Is particularly preferred.
  • Conductive polymer >> The conductive polymer according to the present invention will be described.
  • the conductive polymer according to the present invention refers to a non-conjugated or ⁇ -conjugated polymer exhibiting conductivity of 10 ⁇ 6 S ⁇ cm ⁇ 1 or more.
  • Preferred examples of the conductive polymer according to the present invention include a polymer mixture containing a ⁇ -conjugated conductive polymer and a polyanion and a water-soluble polymer. Among these, a water-soluble polymer is preferably used.
  • Water-soluble polymer examples include a synthetic water-soluble polymer and a natural water-soluble polymer, both of which can be preferably used.
  • the synthetic water-soluble polymer includes, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.
  • nonionic group examples include an ether group, an ethylene oxide group, and a hydroxy group.
  • anionic group examples include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like. Is mentioned.
  • These synthetic water-soluble polymers may be homopolymers or copolymers with one or more monomers.
  • this copolymer may be a copolymer with a partially hydrophobic monomer as long as it remains water-soluble. However, it is preferable to make the composition range that does not cause side effects upon addition.
  • examples of the natural water-soluble polymer include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.
  • the “water-soluble” of the water-soluble polymer according to the present invention means that it exhibits a solubility of 0.05 g or more with respect to 100 g of water at 20 ° C., preferably 0.1 g or more. .
  • the water-soluble polymer has a weight average molecular weight of 1,000 or more and preferably 40,000 or less, more preferably 20,000 or less, and still more preferably 10,000 or less.
  • the weight average molecular weight of the water-soluble resin according to the present invention can be measured by GPC (Gel Permeation Chromatography).
  • the GPC measurement conditions are shown below.
  • the weight average molecular weight measurement method by GPC is diluted with THF so that the sample solid content concentration becomes 0.8 mass%, and the measurement is performed at a column temperature of 25 ° C. under the following conditions.
  • R 1 and R 2 are each a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group).
  • a halogen atom for example, chlorine atom, bromine atom, iodine atom, fluorine atom and the like
  • M represents a hydrogen atom, Li + , Na + or K + ).
  • L represents —CONH—, —NHCO—, —COO—, —OCO—, —CO—, —SO 2 —, —NHSO 2 —, —SO 2 NH— or —O—.
  • J represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, such as methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc., arylene group (for example, phenylene group, naphthylene) Group), an aralkylene group (eg, —CH 2 —C 6 H 4 — etc.), or — (CH 2 CH 2 O) m — (CH 2 ) n —, — (CH 2 CH (OH) CH 2 O ) M- (CH 2 ) n- , wherein m represents an integer from 0 to 40 and n represents an integer from 0 to 4.
  • Q represents a hydrogen atom or any of the groups shown below.
  • M represents a hydrogen atom
  • R 9 represents an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group).
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group, hexyl group, decyl group, hexadecyl group etc.), alkenyl group (eg vinyl group, aryl group etc.), phenyl group (eg phenyl group, methoxyphenyl group, chloroenyl group etc.), aralkyl group (eg benzyl) Group).
  • alkyl group having 1 to 20 carbon atoms for example, a methyl group, an ethyl group, a propyl group, Butyl group, hexyl group, decyl group, hexadecyl group etc.
  • alkenyl group eg vinyl group, aryl group etc.
  • X - X of the anion represented by represents a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), p and q each represents a 0 or 1 .
  • halogen atom e.g., fluorine atom, chlorine atom, bromine atom, iodine atom
  • Y represents a hydrogen atom or-(L) p- (J) q -Q (wherein the groups represented by L, J, and Q are the same as L, J , Each having the same meaning as the group represented by Q).
  • the synthetic water-soluble monomer which is an example of the water-soluble polymer according to the present invention, can be copolymerized with an ethylenically unsaturated monomer.
  • ethylenically unsaturated monomer for example, styrene, alkyl styrene, hydroxyalkyl styrene (wherein hydroxyalkyl is preferably alkyl having 1 to 4 carbon atoms, such as hydroxymethyl styrene, hydroxyethyl Styrene, hydroxybutylstyrene, etc.), vinylbenzenesulfonic acid and its salts, ⁇ -methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of fatty acids (eg, vinyl acetate, vinyl propionate, etc.) Ethylenically unsaturated monocarboxylic or dicarboxylic acids and salts thereof (eg acrylic acid, methacrylic acid) maleic anhydride, ethylenically unsaturated monocarboxylic or dicarboxylic acid esters (
  • Water-soluble polyester Another example of the water-soluble polymer according to the present invention is a water-soluble polyester.
  • water-soluble polyester examples include an aqueous polyester obtained by a condensation polymerization reaction of a mixed dicarboxylic acid component and a glycol component.
  • the dicarboxylic acid component preferably contains a dicarboxylic acid component having a sulfonate (a dicarboxylic acid having a sulfonate or an ester-forming derivative thereof).
  • the dicarboxylic acid having a sulfonic acid salt or an ester-forming derivative thereof used in the present invention is particularly preferably one having an alkali metal sulfonate group, such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalate.
  • Acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, alkali metal salts such as 5- [4-sulfophenoxy] isophthalic acid or ester-forming derivatives thereof can be used.
  • Sodium salts or ester-forming derivatives thereof are particularly preferred.
  • the dicarboxylic acid or ester-forming derivative thereof having these sulfonates is preferably contained in an amount of 5 mol% or more based on the total dicarboxylic acid component in order to impart water solubility.
  • dicarboxylic acid components include aromatic dicarboxylic acid components (aromatic dicarboxylic acids and / or ester-forming derivatives thereof), alicyclic dicarboxylic acid components (alicyclic dicarboxylic acids and / or ester-forming derivatives thereof), Aliphatic dicarboxylic acid components (aliphatic dicarboxylic acid and / or ester-forming derivatives thereof) and the like.
  • aromatic dicarboxylic acid components examples include terephthalic acid components (terephthalic acid and / or ester-forming derivatives thereof), isophthalic acid components (isophthalic acid and / or ester-forming derivatives thereof), and the like.
  • aromatic dicarboxylic acid component examples include aromatic dicarboxylic acids such as phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like. These ester-forming derivatives are mentioned.
  • Examples of the alicyclic dicarboxylic acid or its ester-forming derivative include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 4,4 '-Bicyclohexyldicarboxylic acid or the like, or an ester-forming derivative thereof is used.
  • a linear aliphatic dicarboxylic acid and / or an ester-forming derivative thereof may be used within a range of 15 mol% or less of the total dicarboxylic acid component.
  • dicarboxylic acid components include aliphatic dicarboxylic acids such as adipic acid, pimelic acid, speric acid, azelaic acid, and sebacic acid, and ester-forming derivatives thereof.
  • ethylene glycol is preferably used in an amount of 50 mol% or more based on the total glycol component from the viewpoint of mechanical properties and adhesiveness of the polyester copolymer.
  • 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol and the like may be used in combination with ethylene glycol in addition to ethylene glycol.
  • polyethylene glycol can be preferably used in combination.
  • Another example of the water-soluble polymer of the present invention is a natural water-soluble polymer.
  • Natural water-soluble polymers are described in detail in the Comprehensive Technical Documents for Water-soluble Polymer Water-dispersed Resin (Management Development Center Publishing Department), but lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum Gum arabic, pectin, casein, agar, xanthan gum, cyclodextrin, locust bean gum, tragacanth gum, carrageenan, glycogen, laminaran, lichenin, nigeran, and derivatives thereof are preferred.
  • Derivatives of natural water-soluble polymers include sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkyl phosphorylated, and salts thereof, polyoxyalkylenes (eg, ethylene, glycerin, propylene, etc.) ) And alkylation (methyl, ethyl, benzylation, etc.) are preferred.
  • glucose polymers and derivatives thereof are preferable, and among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, dextrin, cyclodextrin, nigeran and the like are particularly preferable. Cellulose, dextrin, cyclodextrin and derivatives thereof are preferred.
  • cellulose derivatives include carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose and the like.
  • a polymer mixture of ⁇ -conjugated conductive polymer and polyanion is used, and each will be described below.
  • the ⁇ -conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaffins.
  • a chain conductive polymer of phenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyls can be used.
  • polythiophenes and polyanilines are preferable from the viewpoint 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.
  • polyanion examples include, for example, 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 2 or more types of copolymers may be sufficient.
  • it may be a polyanion having F in the compound.
  • Nafion made by Dupont
  • Flemion made by Asahi Glass Co., Ltd.
  • perfluoro vinyl ether containing a carboxylic acid group and the like can be mentioned.
  • 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 4 to 100,000 monomer units, and more preferably in the range of 4 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.
  • an 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.
  • 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) 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-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 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.
  • hydroxy group-containing compound examples 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.
  • a transparent electrode made of the above conductive polymer on the above transparent support using a solution coating process such as a printing method and a coating method ( (Anode and / or cathode) is preferably produced.
  • the transmittance is preferably adjusted to 80% or more, more preferably 90% or more.
  • the “transmittance” of the transparent electrode indicates the transmittance of the transparent electrode with respect to visible light having a wavelength of 550 nm.
  • the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode used as the transparent electrode depends on the conductive polymer material to be constituted, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is preferably in the range of 10 nm to 5 ⁇ m, more preferably in the range of 50 nm to 200 nm.
  • the transmittance of the transparent electrode is preferably 80% or more, and more preferably adjusted to show a transmittance of 90% or more.
  • transmittance indicates the transmittance of visible light having a wavelength of 550 nm.
  • an organic EL device having both a positive electrode and a negative electrode having a transparent electrode (showing a light transmittance of 80% or more with respect to visible light of 550 nm) can be produced.
  • the transparent electrode according to the present invention may contain a filler in addition to the above conductive polymer.
  • [Light emitting unit n-1] is the (n-1) th light emitting unit of (n-1) light emitting units
  • [Light emitting unit n] is the nth light emitting unit of n light emitting units
  • ⁇ 1] indicates the (n ⁇ 1) th CGL of (n ⁇ 1) CGLs.
  • n is an integer of 1 to 100, and each light emitting unit may be the same or different. When a plurality of CGLs are present, each CGL may be the same or different.
  • the “light-emitting unit” is expressed as one unit of a light-emitting layer or a laminate of organic layers (organic compound layers) including at least one light-emitting layer.
  • the light emitting unit of the organic EL element of the present invention is composed of an organic compound layer (organic EL layer), and preferred specific examples thereof are shown below, but the present invention is not limited thereto.
  • the organic EL device of the present invention preferably has a plurality of organic compound layers as a constituent layer, and examples of the organic compound layer include a hole transport layer, a light emitting layer, and a hole blocking layer in the above-described layer configuration.
  • the organic compound layer according to the present invention an organic compound contained in a constituent layer of the organic EL element, such as a hole injection layer or an electron injection layer, is included. Defined.
  • an organic compound is used for the anode buffer layer, the cathode buffer layer, etc.
  • the anode buffer layer, the cathode buffer layer, etc. each form an organic compound layer.
  • the organic compound layer includes a layer containing “organic EL element material that can be used for a constituent layer of an organic EL element” or the like.
  • the organic EL element of the present invention is preferably a white light emitting layer, and is preferably a display device or a lighting device using these.
  • all of the plurality of light emitting units may have a white light emitting layer, or may be white by a combination of light emitting units exhibiting different light emission colors.
  • one light emitting unit emits white light
  • one or two or more light emitting layers may be laminated to form a white light emitting layer.
  • a non-light emitting intermediate layer may be provided between the light emitting layers.
  • CGL Charge generation layer
  • a charge generation layer is provided between a plurality of light emitting units, and the charge generation layer is positively applied by applying an electric field between the light emitting units.
  • Generation of holes and electrons is an example of a preferable structure of the element.
  • the layer structure of the charge generation layer according to the present invention can be used as the charge generation layer according to the present invention by combining the layers shown in the following (1) to (10) singly or arbitrarily in combination.
  • the charge generation layer according to the present invention is preferably formed from at least one layer and has a conductivity higher than that of a semiconductor, but the present invention is not limited thereto.
  • the charge generation layer according to the present invention is a layer that is provided between a plurality of light emitting units and generates holes and electrons when an electric field is applied between the light emitting units. It may be in the charge generation layer, or may be the interface between the charge generation layer and another adjacent layer, or the vicinity thereof.
  • the charge generation layer is a single layer
  • the generation of electrons and holes may be in the charge generation layer or at the adjacent charge generation layer interface.
  • the charge generation layer has a structure of two or more layers and includes one or both of a p-type semiconductor layer and an n-type semiconductor layer.
  • the charge generation layer according to the present invention may function as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer, which will be described later, and can be used as the same layer.
  • the structure of the charge generation layer in the present invention is as follows.
  • A Light-emitting unit / bipolar layer (one layer) / light-emitting unit
  • b Light-emitting unit / n-type layer / p-type layer / light-emitting unit
  • c Light-emitting unit / n-type layer / intermediate layer / p-type layer / light-emitting unit
  • the bipolar layer is a layer that can generate and transport holes and electrons inside the layer by an external electric field.
  • the n-type layer is a transport layer in which majority carriers are electrons, and preferably has conductivity higher than that of a semiconductor.
  • the p-type layer is a transport layer in which majority carriers are holes, and preferably has conductivity higher than that of a semiconductor.
  • the intermediate layer may be provided if necessary from the viewpoint of improving the charge generation ability and long-term stability.
  • the reaction between the n-type layer and the p-type diffusion prevention layer and the n-type layer and the pn-type layer may be provided.
  • examples thereof include a suppression layer, a level adjusting layer that adjusts the charge level of the p-type layer and the n-type layer.
  • a bipolar layer, a p-type layer, and an n-type layer may be provided between the light emitting unit and the charge generation layer.
  • these layers are included in the light emitting unit and are not regarded as charge generating layers. Absent.
  • charge generation layer such as a bipolar layer, a p-type layer, and an n-type layer are shown below, but are not limited thereto.
  • the charge generation layer is formed of at least one layer, and in the cathode direction of the device when a voltage is applied. It refers to a layer having a function of injecting holes toward the anode and electrons.
  • the layer interface of the charge generation layer composed of two or more layers may have an interface (heterointerface, homointerface), A multidimensional interface such as a bulk heterostructure, an island shape, or a phase separation may be formed.
  • the two thicknesses are preferably in the range of 1 nm to 100 nm, more preferably in the range of 10 nm to 50 nm.
  • the light transmittance of the charge generation layer according to the present invention desirably has a high transmittance with respect to the light emitted from the light emitting layer from the viewpoint of sufficiently extracting light and obtaining sufficient luminance.
  • the transmittance of visible light having a wavelength of 550 nm is desirably 50% or more, and more preferably 80% or more.
  • organic compounds and inorganic compounds described later can be used singly or in combination.
  • Organic compounds include nanocarbon materials, organic metal complex compounds that function as organic semiconductor materials (organic acceptors, organic donors), organic salts, aromatic hydrocarbon compounds, and derivatives thereof, heteroaromatic hydrocarbon compounds, and derivatives thereof Etc.
  • inorganic compound constituting the charge generation layer examples include metals, inorganic oxides, and inorganic salts.
  • Nanocarbon material refers to a carbon material having a particle diameter of 1 nm to 500 nm, and representative examples thereof include carbon nanotubes, carbon nanofibers, fullerenes and derivatives thereof, carbon nanocoils, carbon onion fullerenes and derivatives thereof, diamond, and diamond-like materials. Examples include carbon and graphite.
  • fullerenes and fullerene derivatives can be preferably used.
  • the fullerene in the present invention is a closed polyhedral cage molecule having 12 pentagonal planes and 20 (n / 2-10) hexagonal planes composed of 20 or more carbon atoms.
  • the derivative is called a fullerene derivative.
  • the carbon number of the fullerene skeleton is not particularly limited as long as it is 20 or more, but preferably 60, 70, and 84 carbon atoms.
  • fullerene and fullerene derivatives include compounds represented by the following general formula (1).
  • R represents a hydrogen atom or a substituent
  • n represents an integer of 1 to 12.
  • the substituent represented by R is an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group).
  • aromatic hydrocarbon group also called aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, Tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group) Group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, Zolyl group, thiazolyl group, quinazoliny
  • substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • fullerene and fullerene derivative used in the present invention is a compound represented by any one of the following general formulas (2-1), (2-2), and (2-3). It is done.
  • each of R 1 , R 2 and R 3 represents a hydrogen atom or a substituent
  • n represents an integer of 1 to 12
  • X represents — (CR 1 R 2 ) m— or —CH 2 —NR 3
  • X, R 1 , R 2 and R 3 each represents a hydrogen atom or a substituent
  • m represents an integer of 1 to 4
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 to R 13 each represents a hydrogen atom or a substituent, and n is an integer of 1 to 4 Represents.
  • M represents an alkali metal atom or a transition metal element (also simply referred to as a transition metal atom), and L represents a ligand coordinated to this metal atom.
  • the ligand is not limited as long as it is a molecule or ion constituting the ligand in a normal metal complex.
  • m represents an integer of 1 to 5.
  • the alkali metal atom represented by M is preferably a Cs atom.
  • the transition metal element represented by M is preferably a group 8 to group 10 transition metal element of the periodic table.
  • the ligand represented by L includes oxycarboxylic acid, oxyaldehyde and derivatives thereof (for example, salicylaldehyde, oxyacetophenonate, etc.) ), Dioxy compounds (for example, biphenolate), diketones (for example, acetylacetonato, dibenzoylmethanato, diethylmalonate, ethylacetoacetate, etc.), oxyquinones (for example, pyromeconato, oxynaphthoquinato, oxyanthraquino) Natto, etc.), tropolones (eg, troponate, hinokitiolato, etc.), N-oxide compounds, aminocarboxylic acids and similar compounds (eg, glycinato, alaninato, anthranilate, picolinato, etc.), hydroxylamines (eg, aminophenolato, ethanol) Amin
  • ligands may also be used.
  • Nitrogen heterocyclic ligands for example, bipyridyl, phenanthroline, etc.
  • diketone ligands for example, bipyridyl, phenanthroline, etc.
  • Organic semiconductor material An organic donor is mentioned as an example of the organic-semiconductor material used for this invention.
  • Organic donor used in the present invention will be described.
  • organic donors include phthalocyanine derivatives, porphyrin derivatives, tetrathiafulvalene (TTF) derivatives, tetrathiatetracene (TTT) derivatives, metallocene derivatives, thiophene derivatives, imidazole radical derivatives, condensed polycyclic aromatic hydrocarbon derivatives, arylamine derivatives, An azine derivative, a transition metal coordination complex derivative, and a compound represented by the following general formula (N) (wherein a, b, c, d and e are —NR n1 —, —CR c1 R c2 —, respectively) E represents N or —CR c3 —, M represents Mo or W, and n and m each represent an integer of 0 to 5), and triarylamine derivatives.
  • N general formula
  • Phthalocyanine derivative As an example of a phthalocyanine derivative, the compound represented by general formula (A) is mentioned.
  • X 1 , X 2 , X 3 and X 4 each independently represent N or CR (R represents a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • R represents a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the alkyl group, alkoxy group, aromatic hydrocarbon ring group and aromatic heterocyclic group represented by R are each an alkyl group described as a substituent represented by R in the general formula (1).
  • M is H 2 or a metal atom (as the metal atom, for example, Co, Fe, Mg, Li 2 , Ru, Zn, Cu, Ni, Na 2 , Cs 2 , Sb, etc.).
  • the phthalocyanine derivative may further have a substituent on the ring.
  • Porphyrin derivative As an example of a porphyrin derivative, the compound represented by the following general formula (B) is mentioned.
  • X 1 , X 2 , X 3 and X 4 each independently represent N or —CR (R represents a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • R represents a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • each of the alkyl group, alkoxy group, aromatic hydrocarbon ring group, and aromatic heterocyclic group represented by R is an alkyl group described as a substituent represented by R in the general formula (1).
  • M represents H 2 or a metal atom (examples of the metal atom include Co, Fe, Mg, Li 2 , Ru, Zn, Cu, Ni, Na 2 , Cs 2 , and Sb).
  • the porphyrin derivative may have a substituent on the ring.
  • porphyrin derivative used in the present invention is shown below, but the present invention is not limited thereto.
  • TTF Tetrathiafulvalene
  • X 1 , X 2 , X 3 and X 4 each independently represent S, Se or Te, and R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a substituent. .
  • R 1 , R 2 , R 3 , and R 4 each have the same definition as the substituent represented by R in General Formula (1).
  • R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.
  • TTF derivative represented by the general formula (C) are shown below, but the present invention is not limited thereto.
  • TTT Tetrathiatetracene
  • X 1 , X 2 , X 3 and X 4 each independently represent S, Se or Te, and R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a substituent. .
  • each of R 1 , R 2 , R 3 , and R 4 is the same as the substituent represented by R in General Formula (1).
  • R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.
  • TTT derivative represented by the general formula (D) are shown below, but the present invention is not limited thereto.
  • Metallocene derivatives examples include, for example, ferrocene derivatives represented by the following formula (DM-1) or (DM-2), cobaltcene derivatives represented by the following formula (DM-3), Examples thereof include a nickelocene derivative represented by the following formula (DM-4).
  • the imidazole radical derivative used in the present invention is a compound that generates an imidazole radical by light or heat, and specifically includes a compound represented by the following general formula (E).
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or a substituent.
  • R 1 , R 2 and R 3 have the same meaning as the substituent represented by R in the general formula (1).
  • R 2 and R 3 may form a ring.
  • Condensed polycyclic aromatic hydrocarbon derivatives examples include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, tetracene, pentacene, perylene, obalen, and circum.
  • Anthracene, anthanthrene, pyrasenselene, rubrene and the like can be mentioned.
  • Arylamine derivatives examples include diethylaminobenzene, aniline, toluidine, anisidine, chloroaniline, diphenylamine, indole, skatole, p-phenylenediamine, durenediamine, N, N, N , N tetramethyl-p-phenylenediamine, benzidine, N, N, N, N tetramethylbenzidine, tetrakisdimethylaminopyrene, tetrakisdimethylaminoethylene, biimidazole, m-MDTATA, ⁇ -NPD.
  • azine derivatives used in the present invention are cyanine dyes, carbazole, acridine, phenazine, N, N-dihydrodimethylphenazine, phenoxazine, and phenothiazine.
  • Transition metal coordination complex derivative (compound represented by formula (F) or (N))
  • Examples of transition metal coordination complex derivatives used in the present invention include compounds represented by the following general formula (F).
  • each of X 1 , X 2 , X 3 and X 4 is independently S, Se, Te or NR (where R is a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group).
  • R is a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the alkyl group, alkoxy group, aromatic hydrocarbon ring group, and aromatic heterocyclic group represented by R are each described as a substituent represented by R in the general formula (1).
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a substituent.
  • M is H 2 or a metal atom (examples of the metal atom include Co, Fe, Mg, Li 2 , Ru, Zn, Cu, Ni, Na 2 , Cr, Ag, Cs 2 , and Sb).
  • R 1 , R 2 , R 3 and R 4 have the same meaning as the substituent represented by R in the general formula (1).
  • R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.
  • examples of the transition metal coordination complex derivative further include a compound represented by the following general formula (N).
  • a, b, c, d and e each represent —NR n1 — or —CR c1 R c2 —, and R n1 , R c1 and R c2 each independently represent a hydrogen atom or a substituent.
  • E represents N or —CR c3 — (R c3 represents a hydrogen atom or a substituent).
  • M represents Mo or W, and n and m represent 0 to 5.
  • Triarylamine derivative Specific examples of the triarylamine derivative used in the present invention are shown below, but the present invention is not limited thereto.
  • Organic semiconductor material An example of the organic semiconductor material used in the present invention is an organic acceptor.
  • Organic acceptors include quinone derivatives, polycyano derivatives, tetracyanoquinodimethane derivatives, DCNQI derivatives, polynitro derivatives, transition metal coordination complex derivatives, phenanthroline derivatives, azacarbazole derivatives, quinolinol metal complex derivatives, aromatic heterocyclic compounds (hetero And aromatic carbon compounds), nanocarbon materials (fullerene derivatives, etc.), phthalocyanine derivatives, porphyrin derivatives, fluorinated heterocyclic derivatives, and the like.
  • quinone derivatives examples include compounds represented by the following general formula (O).
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a substituent, and R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring. .
  • R 1 , R 2 , R 3 and R 4 are preferably a halogen atom or a cyano group.
  • polycyano derivatives examples include compounds represented by the following, but the present invention is not limited thereto.
  • Tetracyanoquinodimethane derivative examples include compounds represented by the following general formula (G).
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a substituent, and R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring. .
  • DCNQI Derivatives include compounds represented by the following general formula (H).
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a substituent, and R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring. .
  • polynitro derivatives examples include trinitrobenzene, picric acid, dinitrophenol, dinitrobiphenyl, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, Examples thereof include 9-dicyanomethylene 2,4,7-trinitrofluorenone and 9-dicyanomethylene 2,4,5,7-tetranitrofluorenone.
  • the above derivative may further have a substituent represented by R in the general formula (1).
  • Transition metal coordination complex derivative examples include transition metal coordination complex salts represented by the following general formula (I) or (J) or derivatives thereof.
  • X 1 , X 2 , X 3 and X 4 are each independently S, Se, Te or N (R) (R is a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic group. Represents a heterocyclic group.
  • X 5 to X 8 each represents an oxygen, a sulfur atom or an imino group ( ⁇ NH), and R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a substituent. However, these substituents have at least one electron-withdrawing group such as a fluorine-substituted alkyl group such as a fluorine atom, a cyano group or a trifluoromethyl group, or a carboalkoxy group. R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.
  • M is H 2 or a metal atom (examples of the metal atom include Co, Fe, Mg, Li 2 , Ru, Zn, Cu, Ni, Na 2 , Cr, Ag, Cs 2 , and Sb). To express.
  • an alkyl group represented by R an alkoxy group, an aromatic hydrocarbon ring group, an aromatic complex
  • a cyclic group is synonymous with an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group, which are each described as a substituent represented by R in the general formula (1).
  • transition metal coordination complex derivative represented by the general formula (I) or (J) will be given, but the present invention is not limited thereto.
  • Phenanthroline derivative examples include compounds represented by the following general formula (K).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each represent a hydrogen atom or a substituent.
  • each of the substituents represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is represented by R in the general formula (1). It is synonymous with the substituent.
  • Azacarbazole derivative examples include compounds represented by the following general formula (L).
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 are each independently N or CR (where R is a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring) Represents a group or an aromatic heterocyclic group), and R 1 represents a hydrogen atom or a substituent.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 each independently represented by CR, an alkyl group represented by R, an alkoxy group
  • the aromatic hydrocarbon ring group and the aromatic heterocyclic group are each described as a substituent represented by R in the general formula (1), an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group, an aromatic group
  • Quinolinol metal complex derivative examples include compounds having a partial structure represented by the following general formula (M).
  • M is preferably a metal atom represented by any of Al, Co, Fe, Mg, Ru, Zn, Cu or Ni.
  • Aromatic heterocyclic compounds also called heteroaromatic hydrocarbon compounds
  • the aromatic heterocyclic compound represents an aromatic hydrocarbon compound in which one or more of carbon atoms are substituted with a heteroatom such as oxygen, sulfur, nitrogen, phosphorus, or boron.
  • a pyridine derivative substituted with a nitrogen atom can be preferably used.
  • Nanocarbon material As an example of the nanocarbon material, the nanocarbon material described in the above organic donor can be used as appropriate. Moreover, the above-mentioned fullerene derivative is raised as a preferable nanocarbon material.
  • Phthalocyanine derivatives examples include compounds represented by the following general formula (P).
  • X 1 , X 2 , X 3 and X 4 are each independently N or —CR (where R is a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group)
  • M represents a group containing H 2 or a metal atom.
  • X 1 , X 2 , X 3 , and X 4 are each independently an R of —CR, an alkyl group represented by R, an alkoxy group, an aromatic hydrocarbon ring group,
  • the aromatic heterocyclic group has the same meaning as the alkyl group, alkoxy group, aromatic hydrocarbon ring group, and aromatic heterocyclic group, respectively, which are described as the substituent represented by R in the general formula (1). is there.
  • Porphyrin derivatives examples include compounds represented by the following general formula (Q).
  • X 1 , X 2 , X 3 and X 4 are each independently N or —CR (where R is a hydrogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group)
  • M represents a group containing H 2 or a metal atom.
  • X 1 , X 2 , X 3 , and X 4 are each independently an R of —CR, an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group represented by R,
  • the aromatic heterocyclic group has the same meaning as the alkyl group, alkoxy group, aromatic hydrocarbon ring group, and aromatic heterocyclic group, respectively, which are described as the substituent represented by R in the general formula (1). is there.
  • Fluorinated heterocyclic derivatives include fluorinated aromatic hydrocarbon compounds and aromatic heterocyclic compounds, among which fluorinated phthalocyanine, fluorinated porphyrin, fluorinated fullerene, etc. Is a preferred compound.
  • Aromatic hydrocarbons of aromatic hydrocarbon compounds include aromatic monocyclic hydrocarbons, condensed polycyclic hydrocarbons, and a combination of a plurality of independent aromatic monocyclic hydrocarbons or condensed polycyclic hydrocarbons. Is also included.
  • one or more atoms are heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron among the carbon atoms of the elements constituting the aromatic hydrocarbon ring. It refers to a substituted one, and includes a monocyclic aromatic heterocycle, a condensed polycyclic aromatic heterocycle, a plurality of independent aromatic heterocycles or a condensed polycyclic aromatic heterocycle bonded thereto.
  • the inorganic compound contained in the inorganic compound layer is preferably an inorganic compound having a semiconductor or higher conductivity.
  • Metals, inorganic salts, and inorganic oxides having conductivity higher than semiconductivity can be selected.
  • a fine particle dispersion, a precursor fine particle dispersion or a precursor solution, or a solution is applied by a coating process, and if necessary, energy is supplied from the outside, so that an inorganic compound is provided. It is possible to obtain a layer.
  • the external energy source heat, light (ultraviolet, visible, infrared, etc.), electromagnetic waves (microwave, etc.), plasma, discharge, etc. can be selected, but preferably the substrate temperature is 180 ° C. or lower. A condition that is preferably maintained at 130 ° C. or lower is preferable.
  • the conduction band, valence band, and Fermi level of the inorganic compound layer can be changed by external energy.
  • a fine particle dispersion, a precursor fine particle dispersion or a precursor solution, or a solution is formed by a non-discharge type coating process. It is a dispersion liquid dispersed in The fine particles preferably have an average particle size of 10 ⁇ m or less, more preferably an average particle size of 100 nm or less, and still more preferably particles having an average particle size of 20 nm or less.
  • the particle size of the fine particle dispersion is uniform.
  • Examples of the fine particle dispersion for forming the inorganic compound layer include a fine particle metal dispersion, a fine particle inorganic oxide dispersion, and a fine particle inorganic salt dispersion.
  • Examples of the metal in the fine particle metal dispersion include metals such as gold, silver, copper, aluminum, nickel, iron, and zinc, but silver and aluminum are preferable, but not limited thereto. Furthermore, these metals may be alloys.
  • inorganic oxides in the fine particle inorganic oxide dispersion include titanium oxide, zirconium oxide, niobium oxide, zinc oxide, tin oxide, iron oxide, molybdenum oxide, vanadium oxide, lithium oxide, calcium oxide, magnesium oxide, ITO, Examples include IZO, In—Ga—Zn—Oxide, but are not limited thereto. Moreover, these inorganic oxides may be mixed.
  • the inorganic salt of the fine particle inorganic salt dispersion includes a copper metal salt (such as CuI), a silver metal salt (such as AgI), an iron salt (such as FeCl 3 ), a compound semiconductor (such as gallium-arsenic and cadmium-selenium), and titanic acid. Salts (SrTiO 3 , BaTiO 3 etc.) can be mentioned but are not limited to these. Furthermore, these may be mixed.
  • the precursor fine particle dispersion or precursor solution is a dispersion or solution of a precursor that obtains a metal or inorganic oxide thin film by using a sol-gel reaction, oxidation, or reduction reaction.
  • an inorganic oxide can be obtained from a metal halide salt, alkoxide, acetate, or the like through hydrolysis polycondensation or the like.
  • the sol-gel reaction can be rapidly advanced by mixing and applying a catalytic amount of water, acid (inorganic acid, organic acid), base (indefinite base, organic base) in the solution.
  • the obtained inorganic oxide film has a large amount of carbon, and is often not a complete inorganic oxide film, and may have low conductivity. If necessary, an inorganic oxide having high conductivity can be obtained by applying external energy. External energy is shown above.
  • the conduction band, valence band, and Fermi level can be changed by adding external energy.
  • metals for the sol-gel reaction include, but are not limited to, titanium, zirconium, zinc, tin, niobium, molybdenum, vanadium, and the like.
  • oxidation and reduction reactions are methods in which a precursor is changed to a semiconducting or more conductive inorganic compound by adding an oxidizing agent and a reducing agent.
  • a combination of a metal and an oxidizing agent such as a combination of a metal salt and a reducing agent, or a metal oxide with a metal and an oxidizing agent so that Ag metal can be obtained by reducing AgI.
  • the above methods can be combined with each other.
  • a combination of a sol-gel method and inorganic fine particles, a combination of inorganic salt fine particles and an inorganic salt solution, or a combination of an inorganic compound and an organic compound can be performed.
  • organic compounds examples include those described above.
  • the film thickness of the inorganic compound layer is 1 nm to 1 ⁇ m, preferably 1 nm to 200 nm, and more preferably 1 nm to 20 nm.
  • the structure and materials of the charge generation layer include Yusuke Husband, Proceedings of the 10th Annual Meeting of the Organic EL Conference, page 53, and Yong-Ki Kim et. Al. , Appl. Phys. Lett. , No. 94, page 63305 (2009).
  • each organic compound layer (organic EL layer) constituting the light emitting unit Will be described in detail.
  • the light-emitting layer according to the organic EL device of the present invention is a layer that emits light by recombination of electrons and holes injected from an electrode, a charge generation layer, an electron transport layer, or a hole transport layer, and emits light. May be in the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
  • the total thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of a high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 ⁇ m, more preferably in the range of 2 nm to 200 nm, and particularly preferably in the range of 10 nm to 20 nm.
  • a light emitting dopant or a host compound described later can be formed by, for example, a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method.
  • the light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant) or fluorescent dopant). .
  • phosphorescent dopant also referred to as phosphorescent dopant
  • fluorescent dopant also referred to as phosphorescent dopant
  • a host compound (also referred to as a light-emitting host) and a light-emitting dopant (also referred to as a light-emitting dopant compound) included in the light-emitting layer are described below.
  • the host compound in the present invention is a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. Is defined as a compound of less than 0.1.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • a compound having a carbazole ring as a partial structure, a compound having a polymerizable group and having a carbazole ring as a partial structure, and a polymer of the compound are particularly preferably used as the host compound.
  • a host compound a well-known host compound may be used together, and may be used in combination of multiple types. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.
  • a compound having a hole transporting ability and an electron transporting ability, which prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is used. preferable.
  • Luminescent dopant The light emitting dopant according to the present invention will be described.
  • a fluorescent dopant also referred to as a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
  • the above-mentioned host compound may be used as the luminescent dopant (simply referred to as a luminescent material) used in the light emitting layer or the light emitting unit of the organic EL device of the present invention. It is preferable to contain a phosphorescent dopant at the same time as containing.
  • the phosphorescent compound according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield.
  • the phosphorescence quantum yield is preferably 0.1 or more, although it is defined as a compound of 0.01 or more at 25 ° C.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence emitting compound according to the present invention achieves the above phosphorescence quantum yield (0.01 or more) in any solvent. It only has to be done.
  • phosphorescent compounds There are two types of light emission of phosphorescent compounds. In principle, the recombination of carriers occurs on the host compound to which carriers are transported, and an excited state of the host compound is generated. This energy is phosphorescent. An energy transfer type that obtains light emission from the phosphorescent compound by transferring to the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, and recombination of carriers on the phosphorescent compound is performed. And a carrier trap type in which light emission from the phosphorescent compound is obtained.
  • the phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.
  • the phosphorescent compound according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table, more preferably an iridium compound (Ir complex), an osmium compound, or a platinum compound. (Platinum complex compounds) and rare earth complexes, with iridium compounds (Ir complexes) being most preferred among them.
  • Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • Injection layer electron injection layer, hole injection layer >> The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.
  • An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
  • Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • anode buffer layer hole injection layer
  • copper phthalocyanine is used.
  • examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc.
  • the buffer layer (injection layer) is preferably a thin film, and the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m, depending on the material.
  • ⁇ Blocking layer hole blocking layer, electron blocking layer>
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the hole blocking layer preferably contains the azacarbazole derivative mentioned as the host compound described above.
  • the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers.
  • 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
  • the ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.
  • Gaussian 98 Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.
  • the ionization potential can be obtained as a value obtained by rounding off the second decimal place of a value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
  • the structure of the hole transport layer described later can be used as an electron blocking layer as necessary.
  • the film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably in the range of 3 nm to 100 nm, more preferably in the range of 5 nm to 30 nm.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any one of hole injection property or transport property and electron barrier property, and may be either organic or inorganic.
  • triazole derivatives for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives,
  • stilbene derivatives silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
  • No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.
  • NPD 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the
  • polymer materials in which these materials are introduced into polymer chains or these materials are used as polymer main chains can also be used.
  • inorganic compounds such as p-type-Si and p-type-SiC can be used as the hole injection material and the hole transport material.
  • JP-A-11-251067 J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.
  • organic EL device material of the present invention containing a polymerizable compound described later or a polymer compound having a structural unit derived from the polymerizable compound can be used, and the above materials may be used in combination.
  • the hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a printing method including a casting method, an LB method, In the present invention, it is preferably produced by a coating method (coating process).
  • the thickness of the hole transport layer is not particularly limited, but is preferably in the range of 5 nm to 5 ⁇ m, and more preferably in the range of 5 nm to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • a hole transport layer having a high p property doped with impurities can be used.
  • examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. J. et al. Appl. Phys. 95, 5773 (2004), and the like.
  • a hole transport layer having such a high p property because a device with lower power consumption can be produced.
  • the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer or a plurality of layers.
  • an electron transport material also serving as a hole blocking material used for an electron transport layer adjacent to the cathode side with respect to the light emitting layer is injected from the cathode.
  • Any material may be used as long as it has a function of transferring electrons to the light-emitting layer, and any material can be selected from conventionally known compounds.
  • Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material.
  • quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a printing method including a casting method, or an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is preferably in the range of 5 nm to 5 ⁇ m, and more preferably in the range of 5 nm to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • an electron transport layer having a high n property doped with impurities can be used.
  • examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-2001. 102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
  • an electron transport layer having such a high n property because an element with lower power consumption can be produced.
  • anode that is not a transparent electrode is a transparent electrode made of a conductive polymer formed on a transparent support.
  • the transparent electrode has been described in detail above.
  • an anode that is not a transparent electrode is preferably an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more).
  • Electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 ⁇ m or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • the sheet resistance of an anode that is not a transparent electrode is preferably several hundred ⁇ / ⁇ or less. Further, the film thickness is preferably in the range of 10 nm to 1000 nm, more preferably in the range of 10 nm to 200 nm, although it depends on the constituent materials.
  • Cathode that is not a transparent electrode
  • a cathode 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 is used. It is done.
  • 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.
  • a metal foil film formed by coating a dispersion of metal nanoparticles such as silver nano ink and then heating and baking may be used.
  • 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 nm to 200 nm.
  • the light emission luminance is improved, which is convenient.
  • a cathode can be produced with the transparent electrode made of the conductive polymer mentioned in the description of the anode, and by applying this, an element in which both the anode and the cathode are transmissive can be produced.
  • the transparent support according to the present invention and the transparent electrode according to the present invention (when the anode is a transparent electrode, when the cathode is a transparent electrode, when both the anode and the cathode are transparent electrodes) Etc.)), and it is preferable to provide a light-scattering nanostructure as the nanostructure.
  • the fine metal wire according to the present invention represents a fine metal wire having a line width of 1 ⁇ m to 20 ⁇ m, and the metal is preferably an element having a conductivity in a bulk state of 1 ⁇ 10 6 S / m or more.
  • metal elements examples include Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, and Ti.
  • two or more kinds of metals can be used in combination, but from the viewpoint of conductivity, it is preferable to use an element selected from at least Ag, Cu, Au, Al, and Co.
  • the nanostructure according to the present invention represents a 1 nm to 1000 nm spherical, wire (fiber), rod, cube, network, mesoporous, piece-like structure or the like.
  • Such a structure is composed of an organic material, an inorganic material, a metal, or the like, and may be a mixture thereof.
  • nanostructures include organic nanostructures, inorganic nanostructures, and metal nanostructures.
  • organic nanostructures include DNA, proteins, viruses, nanocellulose particles, and dendrimers.
  • inorganic nanostructures include carbon nanotubes, carbon nanocoils, fullerenes, zeolites, mesoporous silica, titania nanoparticles, and examples of metal nanostructures include metal nanocrystals and metal nanowires.
  • the present invention is not limited to these.
  • Light scattering nanostructure Among the above nanostructures, in the present invention, a light scattering nanostructure is particularly preferably used.
  • ⁇ Sealing> As a sealing means used for this invention, the method of adhere
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the element can be thinned.
  • the polymer film has an oxygen permeability of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ MPa) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured in (1) is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • heat- and chemical-curing types such as epoxy type can be mentioned.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • the method for forming these films is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, plasma CVD method, laser CVD method, thermal CVD method, coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil
  • a vacuum is also possible.
  • a hygroscopic compound can also be enclosed inside.
  • the hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.
  • Metal halides eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.
  • perchloric acids eg, barium perchlorate,
  • anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.
  • a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film.
  • the sealing is performed by the sealing film, the mechanical strength is not necessarily high. Therefore, it is preferable to provide such a protective film and a protective plate.
  • a material that can be used for this the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • the organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said.
  • a method of improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate and preventing total reflection at the transparent substrate and the air interface (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from the substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device of the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • the low refractive index layer examples include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction.
  • Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • the ⁇ max of light emission of the organic EL element is preferably 480 nm or less.
  • the organic EL element of the present invention is processed on the light extraction side of the substrate, for example, so as to provide a microlens array-like structure, or in combination with a so-called condensing sheet, for example, with respect to a specific direction, for example, the element emission surface By condensing in the front direction, the luminance in a specific direction can be increased.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 ⁇ m to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the upper layer material is dissolved in a solvent outside the solubility range of the solubility parameter of the lower layer main material to disturb the lower layer thin film surface.
  • a technique of laminating without causing such a problem has been disclosed (for example, JP-A-2002-299061).
  • the insolubilization used in the present invention refers to an insolubilization treatment described below after film formation by a coating process, so that it is in an inert state, that is, insoluble, and solute components are eluted or diffused. It means changing to an inert state that can suppress this.
  • Dissolution refers to a phenomenon in which a solute is solvated and diffuses into the solvent.
  • insolubilization is achieved by suppressing solvation or suppressing diffusion.
  • the ratio of the solvation is reduced to suppress the solvation and to reduce the diffusion of the solute (mobility), thereby suppressing the diffusion of the solute into the solvent.
  • the high molecular weight material in the present invention is an aromatic condensed ring derivative or heteroaromatic condensed ring derivative having a molecular weight of 800 or more and 1500 or less, more preferably an aromatic condensed ring derivative or heteroaromatic condensed ring derivative having a molecular weight of 800 or more and 1200 or less. It is.
  • the polymer material include vinyl polymers having a number average molecular weight of 10,000 to 1,000,000, polyesters, polyamides, polyethers, polysulfides, polyimides, and polyarylenes.
  • A Crosslinking reaction: Multi-dimensional cross-linking using low-molecular weight materials, high-molecular weight materials, or multiple cross-linking groups (polysynthetic reactive groups) present in a polymer, after application / film formation, by stimulation of heat, light, electromagnetic waves, etc. This is a method for insolubilizing.
  • a thermal / photopolymerization initiator or a crosslinking agent may be used in combination.
  • crosslinking group examples include groups represented by the following general formula (LP). Each crosslinking group may be used alone or in combination.
  • L represents a simple bond or a divalent linking group
  • P represents a polymerizable substituent represented by the following.
  • the divalent linking group used herein include an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, etc.), alkenylene group (for example, vinylene).
  • arylene group for example, o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, Naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group Biphenyldiyl group (eg, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.
  • arylene group for example, o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, Naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group
  • Biphenyldiyl group eg, [1,1′
  • R represents an alkyl group
  • x is an integer of 2 or more
  • y pieces so as to satisfy the valence of the metal M
  • the substituent B is bonded. When a plurality of B are present, they may be different from each other.
  • examples of the substituent represented by B include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group).
  • cycloalkyl group for example, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group for example, vinyl group, allyl group, 1 -Propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, isopropenyl group, etc.
  • alkynyl group eg, ethynyl group, propargyl group, etc.
  • aromatic hydrocarbon group aromatic hydrocarbon
  • aromatic hydrocarbon aromatic hydrocarbon
  • aromatic hydrocarbon aromatic hydrocarbon
  • aromatic hydrocarbon aromatic hydrocarbon
  • aromatic carbocyclic group for example, phenyl group, p-chlorophenyl group, mesityl group, Aryl, xylyl, naphthyl, anth
  • the group represented by the general formula (LP) can be used by substituting with any hydrogen atom of the material constituting the light emitting unit or the charge generation layer.
  • the number of substitutions is 1 to 10, preferably 1 to 4, in the case of a non-polymer compound having no repeating unit, and in the case of a polymer compound having a repeating structure, the number of crosslinking groups per 10,000 number average molecular weight is 10,000. 1 to 100, preferably 1 to 10.
  • the number of crosslinkable groups in a polymer having a number average molecular weight of 50,000 is 5 to 500, preferably 5 to 50.
  • Sol-gelation reaction It refers to a chemical synthesis method of ceramic (metal oxide) by hydrolysis dehydration condensation (sol-gel) reaction of metal alkoxide.
  • (C) Complexation reaction The reaction between the metal species and the ligand promotes the formation of a metal-crosslinked polymer (coordinating-bonded polymer complex) having coordination bond crosslinking, and insolubilization is performed.
  • the metal species include group 1 (alkali metal), group 2 (alkaline earth metal), group 12 to group 15 metal elements and group 4 to group 11 transition metal elements of the periodic table of elements. Can be mentioned.
  • metal species examples include Cs, Mg, Ca, Ba, Ti, V, Mo, W, Fe, Co, Ir, Ni, Pt, Cu, Zn, Al, and Sn.
  • the ligand has a substituent having a lone electron pair, and the substituent can form a complex with a metal by a coordinate bond, and can form two or more coordinate bonds in the molecule. If you have one, you can use it without problems.
  • Examples of the substituent capable of forming a coordination bond include amino group, ethylenediamino group, pyridyl group, bipyridyl group, terpyridyl group, carbonyl group, carboxyl group, thiol group, porphyrin ring, crown ether, carbene and the like. .
  • (D) Use of precursors After the coating and film formation of the soluble precursor compound, it is converted into a compound that cannot be re-dissolved by decomposition or substitution accompanied by chemical or physical changes caused by internal or external stimuli such as heat, light, and electromagnetic waves.
  • the precursor that can be used in the present invention compounds described in JP-A-2008-135198 can be preferably used.
  • insoluble fine particles of a soluble precursor can be formed by chemical change due to internal or external stimulation such as heat, light, electromagnetic waves, etc. after coating and film-forming of a soluble precursor compound in a solvent.
  • the solvent as used in the present invention is a name for a liquid that dissolves a solid or a liquid.
  • aromatic hydrocarbons toluene, chlorobenzene, pyridine
  • saturated hydrocarbons cyclohexane, Decane, perfluorooctane
  • alcohols isopropyl alcohol, hexafluoroisopropanol
  • ketones methyl ethyl ketone, cyclohexanone
  • esters butyl acetate, phenyl acetate
  • dichloroethane tetrahydrofuran, acetonitrile.
  • the inert state means that (i) a change in film thickness due to a change in UV absorption, (ii) a change in state of the light emitting layer due to a PL change, and (iii) at least one item of the rectification ratio satisfies an evaluation reference value described later. Refers to the state.
  • the yield was improved, and improvements were also observed with respect to the suppression of voltage rise over time, and a production method suitable for the present invention could be provided.
  • Examples of the solution coating process related to the production of the organic EL device of the present invention include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, and curtain coating.
  • a non-discharge type solution coating process is particularly preferable from the viewpoint of being able to form a precise thin film and high productivity.
  • the non-ejection type solution coating process means a method that does not involve the flying / ejection of fine droplets of the coating solution, that is, a method that does not include an inkjet method, and preferably a slit coating method, a spin coating method, a casting method, a printing method, etc.
  • a particularly preferable non-discharge type solution coating process there is a slit coating method.
  • a desired electrode material for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably 10 nm to 200 nm.
  • a method for forming each of these layers there are a vapor deposition method, a coating process (slit coating method, die coating method, spin coating method, casting method, printing method) and the like as described above.
  • film formation by a coating method such as a slit coating method, a die coating method, a spin coating method, or a printing method is preferable from the viewpoint that holes are hardly generated.
  • the layer containing a compound having a carbazole ring as a partial structure according to the present invention, the compound having a polymerizable group, and a polymer of the compound is preferably formed by the above-described coating method. Is preferably a light emitting layer.
  • the total number of layers (the constituent layers of the organic EL element) existing between the anode and the cathode 50% or more of the total number of layers is preferably formed by a coating method.
  • the hole injection layer In the case where the total number of layers / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer is 6, it is preferable that at least three layers are formed by a coating method.
  • examples of the liquid medium for dissolving or dispersing various organic EL materials used for coating include ketones such as methyl ethyl ketone and cyclohexano, and fatty acids such as ethyl acetate.
  • a dispersion method it is possible to apply a dispersion method such as ultrasonic wave, high shear force dispersion or media dispersion.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 nm to 200 nm.
  • a desired organic EL element can be obtained.
  • a DC voltage When a DC voltage is applied to the multicolor display device obtained in this way, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • Examples of light-emitting light sources include lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, Examples include, but are not limited to, a light source of an optical sensor. In particular, it can be effectively used as a backlight of a liquid crystal display device and a light source for illumination.
  • the organic EL element of the present invention may be patterned by a metal mask, a printing method, or the like when forming a film, if necessary.
  • the electrode In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.
  • the light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.
  • the display device of the present invention comprises the organic EL element of the present invention.
  • the display device of the present invention may be single color or multicolor, but here, the multicolor display device will be described.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, slit coating, die coating, casting, spin coating, printing, or the like.
  • the method is not limited, but is preferably a vapor deposition method, a slit coating method, a die coating method, a spin coating method, or a printing method.
  • the configuration of the organic EL element included in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
  • the manufacturing method of an organic EL element is as having shown in the one aspect
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc.
  • the present invention is not limited to these examples.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
  • the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal.
  • the image information is sequentially emitted to scan the image and display the image information on the display unit A.
  • FIG. 2 is a schematic diagram of the display unit A.
  • the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on the substrate.
  • the main members of the display unit A will be described below.
  • the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)
  • the pixel 3 When the scanning signal is applied from the scanning line 5, the pixel 3 receives the image data signal from the data line 6 and emits light according to the received image data.
  • a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 3 is a schematic diagram of a pixel.
  • the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
  • the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
  • the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
  • the holding of the potential of the capacitor 13 may be continued until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 4 is a schematic view of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
  • the lighting device of the present invention will be described.
  • the illuminating device of this invention has the said organic EL element.
  • the organic EL element of the present invention may be used as an organic EL element having a resonator structure.
  • the purpose of use of the organic EL element having such a resonator structure is as follows.
  • the light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However, It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.
  • the organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.
  • an electrode film can be formed by vapor deposition, slit coating, die coating, casting, spin coating, printing, etc., and productivity is improved.
  • the elements themselves are luminescent white.
  • luminescent material used for a light emitting layer For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.
  • CF color filter
  • the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 ⁇ m is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material.
  • LC0629B is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and an illumination device as shown in FIGS. Can be formed.
  • FIG. 5 shows a schematic diagram of a lighting device, and the organic EL element 201 of the present invention is covered with a glass cover 202 (in addition, the sealing operation with the glass cover is to bring the organic EL element 201 into contact with the atmosphere. And a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more).
  • FIG. 6 shows a cross-sectional view of the lighting device.
  • 205 denotes a cathode
  • 206 denotes an organic EL layer
  • 207 denotes a glass substrate with a transparent electrode.
  • the glass cover 202 is filled with nitrogen gas 208 and a water catching agent 209 is provided.
  • Example 1 Manufacture of Organic EL Element 1-1 (Comparative Example) >> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode. The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • a substrate NH-Technoglass NA-45
  • ITO indium tin oxide
  • H. C A solution obtained by diluting Stark PEDOT-PSS (CLEVIOS P VP AI 4083) to 70% with pure water was formed by spin coating, then dried at 200 ° C. for 1 hour, and the first hole having a thickness of 30 nm was formed. A transport layer was provided.
  • Stark PEDOT-PSS CLEVIOS P VP AI 4083
  • OC-9 was deposited at a deposition rate of 0.1 nm / second
  • D-15 was deposited at a deposition rate of 0.006 nm / second
  • a 40 nm light-emitting layer, OC-45 was deposited at a deposition rate of 0.1 nm / second.
  • Vapor deposition was performed at a rate of 2 seconds, and a 30 nm electron transport layer was provided.
  • lithium fluoride 1.0 nm was deposited as an electron injection layer and aluminum 110 nm was deposited as a cathode, to produce an organic EL device 1-1.
  • a transparent electrode made of a conductive polymer having a film thickness of 30 nm was provided.
  • an organic EL element 1-2 was produced in the same manner except that the transparent support substrate provided with the transparent electrode was dried in a dry nitrogen gas atmosphere.
  • H. C A solution obtained by diluting Stark PEDOT-PSS (CLEVIOS P VP AI 4083) to 70% with pure water was formed by spin coating, then dried at 200 ° C. for 1 hour, and the first hole having a thickness of 30 nm was formed. A transport layer was provided.
  • Stark PEDOT-PSS CLEVIOS P VP AI 4083
  • Each material to be described later was packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the above-mentioned transparent electrode was formed in a vacuum vapor deposition apparatus.
  • degree of vacuum became 1 ⁇ 10 ⁇ 4 Pa or less
  • OC-1 was deposited at a deposition rate of 0.1 nm / second by 20 nm to provide a second hole transport layer.
  • OC-9 was deposited at a deposition rate of 0.1 nm / second
  • D-15 was deposited at a deposition rate of 0.006 nm / second
  • a 40 nm light-emitting layer, OC-45 was deposited at a deposition rate of 0.1 nm / second.
  • Evaporation was performed at a rate of seconds, a 10 nm electron transport layer was provided, and a first light emitting unit was produced.
  • OC-45 Li (99: 1% by volume) was co-evaporated at a rate of 10 nm and 0.1 nm / second, and then molybdenum oxide was added at a rate of 0.05 nm / second to 5 nm and 0 nm. 20 nm of OC-1 was vacuum deposited at a rate of 1 nm / sec.
  • the second light emitting unit was manufactured as follows.
  • the hole transport layer in the second light emitting unit shares the above-described OC-1 layer of the charge generation layer, on which OC-9 is deposited at a deposition rate of 0.1 nm / second, and D-15 is deposited at a deposition rate. Evaporation was performed at a rate of 0.006 nm / sec, a 40 nm light-emitting layer and OC-45 were deposited at a deposition rate of 0.1 nm / sec, and a 30 nm electron transport layer was provided to produce a second light-emitting unit.
  • the organic EL element 1-4 of the present invention a power efficiency improvement of about 9% was observed based on the organic EL element 1-3 having a conventional ITO as an anode, which is a direct comparison.
  • organic EL element 1-4 of the present invention is superior to the organic EL elements 1-1 and 1-2, which are single configuration elements.
  • the power efficiencies of the organic EL elements 1-1 to 1-4 are the same, which suggests that the difference in power efficiency is due to an improvement in light extraction efficiency.
  • the organic EL element of the present invention that does not require a special optical design is a particularly important technology compared to a tandem organic EL element having a plurality of light emitting units that has conventionally required a complicated optical design. It is clear.
  • Example 2 ⁇ Manufacture of Organic EL Element 2-1 >>: According to the present invention, after masking in accordance with the anode pattern on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as the anode, C. PEDOT-PSS (CLEVIOS PH510) manufactured by Starck was formed by a spin coating method. After drying at 150 ° C. for 30 minutes, the masking was removed, and a transparent support substrate provided with a transparent electrode made of a conductive polymer having a film thickness of 30 nm was produced.
  • C. PEDOT-PSS CLEVIOS PH510
  • H. C A solution obtained by diluting Stark PEDOT-PSS (CLEVIOS P VP AI 4083) to 70% with pure water was formed by spin coating, then dried at 200 ° C. for 1 hour, and the first hole having a thickness of 30 nm was formed. A transport layer was provided.
  • Stark PEDOT-PSS CLEVIOS P VP AI 4083
  • Each material to be described later was packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate on which the transparent electrode was formed in a vacuum vapor deposition apparatus.
  • OC-61 was deposited at a deposition rate of 0.1 nm / second to 20 nm to provide a second hole transport layer.
  • OC-16 was deposited at a deposition rate of 0.1 nm / second
  • D-15 was deposited at a deposition rate of 0.006 nm / second
  • OC-50 was deposited at a deposition rate of 0.1 nm / second.
  • Vapor deposition was performed at a rate of 2 seconds, a 20 nm electron transport layer was provided, and a first light emitting unit was produced.
  • OC-50 cesium carbonate (99: 1% by volume) was co-evaporated at a rate of 10 nm and 0.1 nm / second, and then molybdenum oxide was 5 nm at a rate of 0.05 nm / second. 20 nm of OC-1 was vacuum-deposited at a rate of 0.1 nm / second.
  • the second light emitting unit was manufactured.
  • the hole transport layer in the second light emitting unit shares the above-described OC-1 layer of the charge generation layer, on which OC-5 is deposited at a deposition rate of 0.1 nm / second, and D-14 is deposited. Evaporation was performed at a rate of 0.006 nm / sec, a 40 nm light-emitting layer and OC-49 were deposited at a deposition rate of 0.1 nm / sec, and a 30 nm electron transport layer was provided to produce a second light-emitting unit.
  • the power efficiency was evaluated in the same manner as described in Example 1. The power efficiency was evaluated relative to the comparative organic EL element 2-2 as 100%.
  • the organic EL elements using the transparent support substrate provided with the transparent electrodes all showed a superior difference compared to those using the ITO electrodes.
  • Example 4 Manufacture of organic EL element 11-1 >> After masking in accordance with the anode pattern on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode, a separately prepared emeraldine salt polyaniline derivative (manufactured by Aldrich) m-cresol solution was formed by spin coating.
  • a transparent support substrate provided with a transparent electrode made of a conductive polymer having a film thickness of 30 nm was produced.
  • Organic EL element 11-1 was produced in exactly the same manner as organic EL element 2-1, except that this transparent support substrate was used.

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un élément électroluminescent organique qui assure une luminosité accrue avec un courant fixe et qui offre en outre une durée de vie prolongée avec une luminosité fixe. L'élément électroluminescent organique comprend une pluralité d'unités électroluminescentes prises en sandwich entre une électrode positive et une électrode négative et est caractérisé en ce que l'électrode positive ou l'électrode négative est une électrode transparente contenant un polymère conducteur formé sur un support transparent.
PCT/JP2011/065947 2010-09-06 2011-07-13 Élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage Ceased WO2012032850A1 (fr)

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