WO2006104230A1 - 有機エレクトロルミネッセンス素子 - Google Patents

有機エレクトロルミネッセンス素子 Download PDF

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WO2006104230A1
WO2006104230A1 PCT/JP2006/306988 JP2006306988W WO2006104230A1 WO 2006104230 A1 WO2006104230 A1 WO 2006104230A1 JP 2006306988 W JP2006306988 W JP 2006306988W WO 2006104230 A1 WO2006104230 A1 WO 2006104230A1
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Prior art keywords
organic
layer
cathode
metal
aromatic hydrocarbon
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PCT/JP2006/306988
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English (en)
French (fr)
Japanese (ja)
Inventor
Kenichi Nakayama
Masaaki Yokoyama
Shinichi Morishima
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Sumitomo Chemical Company, Limited
Osaka University
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Priority to GB0721118A priority Critical patent/GB2439887B/en
Priority to DE112006000714T priority patent/DE112006000714T5/de
Publication of WO2006104230A1 publication Critical patent/WO2006104230A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/157—Hole transporting layers between the light-emitting layer and the cathode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/167—Electron transporting layers between the light-emitting layer and the anode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • 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
    • H10K59/10—OLED displays
    • 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
    • H10K59/10—OLED displays
    • H10K59/18—Tiled displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom

Definitions

  • the present invention relates to an organic electoluminescence device (hereinafter sometimes referred to as an organic EL device).
  • An organic EL element is an EL element using an organic material as a light emitting material, and has a light emitting layer between an anode and a cathode as a basic structure.
  • an organic EL device having a layer containing an organic compound and an alkali metal in contact with the cathode between the cathode and the light emitting layer is disclosed.
  • Japanese Laid-Open Patent Publication No. Hei 10-2 7 0 1 7 1 Japanese Laid-Open Patent Publication No. Hei 10-2 7 0 1 7 1
  • An object of the present invention is to provide an organic EL device having excellent electron injection properties, durability, and the like.
  • the present invention is an organic electoluminescence device having a light emitting layer between an anode and a cathode, wherein the layer (L) is provided between and in contact with the cathode between the cathode and the light emitting layer.
  • a containing an aromatic hydrocarbon ring or heterocyclic ring and a carbonyl group and a metal (B) selected from an alkaline earth metal and a group III metal.
  • An oral luminescence element is provided.
  • the present invention is an organic electoluminescence device having a light emitting layer between an anode and a cathode, the layer having a layer (L) between the cathode and the light emitting layer, in contact with the cathode,
  • the layer (L) uses an organic compound (A) containing an aromatic hydrocarbon ring or heterocyclic ring and a carbonyl group, and a metal (B) selected from an alkaline earth metal and a group III metal.
  • FIG. 1 is a schematic view showing a cross section of an example of a laminated structure of an organic electoluminescence device according to the present invention.
  • FIG. 2 A graph showing current density-voltage characteristics of the organic electroluminescence device of the present invention and a comparative example.
  • FIG. 3 A graph showing luminance-voltage characteristics of the organic electoluminescence device of the present invention and a comparative example.
  • FIG. 4 is a graph showing current density-time characteristics of the organic electroluminescence device of the present invention and a comparative example.
  • FIG. 5 A graph showing a mixture contained in the layer (L) used in the organic electoluminescence device of the present invention and an absorption spectrum of a comparative example.
  • FIG. 6 A graph showing the ES R spectrum of the mixture contained in the layer (L) used in the organic electoluminescence device of the present invention.
  • FIG. 7 A graph showing an absorption spectrum of a comparative example.
  • FIG. 8 A graph showing an ESR spectrum of a comparative example. BEST MODE FOR CARRYING OUT THE INVENTION
  • the organic EL device of the present invention is an organic electoluminescence device having a light emitting layer between an anode and a cathode, wherein the layer is in contact with the cathode between the cathode and the light emitting layer.
  • the device of the present invention has a laminated structure represented by cathode / layer (L) / light emitting layer / anode.
  • the cathode and layer (L) must be in contact.
  • Another layer may be provided between the layer (L) and the light emitting layer, and between the light emitting layer and the anode.
  • the cathode the layer (L), the light emitting layer, and the anode will be described in order.
  • Materials used for the cathode of the organic EL device of the present invention include metals, graphitic or graphite intercalation compounds, inorganic semiconductors such as ZnO (zinc oxide), Examples include conductive transparent electrodes such as ITO (indium, tin, oxide) and IZO (indium, zinc, oxide), and metal oxides such as strontium oxide and barium oxide.
  • metals examples include alkaline metals such as lithium, sodium, potassium, rubidium, and cesium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; gold, silver, platinum, copper, manganese, and titanium. From transition metals such as copper, nickel, tungsten; tin, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, sucrose, terbium, ytterbium; and two or more of these metals And the like.
  • alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, calcium-aluminum alloys, and the like.
  • the cathode may have a laminated structure of two or more layers.
  • a cathode in which a metal, an alloy, or the like is laminated on a layer made of a metal fluoride such as lithium fluoride or cesium fluoride or a conductive polymer, or a layer made of an organic insulating material and having an average film thickness of 5 nm or less.
  • the organic EL device of the present invention has a layer (L) in contact with the cathode between the cathode and the light emitting layer.
  • the film thickness of the layer (L) is usually about 0.1 nm to 500 nm, preferably 1 nm to 100 nm, and more preferably 5 nm to 20 nm.
  • Layer (L) contains an organic compound (A) and a metal (B) selected from alkaline earth metals and Group III metals, or contains an aromatic hydrocarbon ring or heterocycle and a force sulfonyl group. It is obtained using an organic compound (A) and a metal (B) selected from an alkaline earth metal and a group VIII metal. Two or more layers (L) may be stacked.
  • Examples of the alkaline earth metal in the metal (B) used for the layer (L) include magnesium, calcium, strontium, and barium. Examples thereof include aluminum, gallium, indium, and thallium. From the viewpoint of durability, a Group III metal is preferable, and indium is more preferable.
  • the organic compound (A) used for the layer (L) is an organic compound containing an aromatic hydrocarbon ring or heterocyclic ring and a carbonyl group.
  • Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pendecacene ring, a pyrene ring, and a phenanthrene ring.
  • Examples include a phosphorus ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, and a pyrrole ring.
  • the aromatic hydrocarbon ring and the heterocyclic ring may have a substituent such as an alkyl group, an alkoxy group, or an alkylthio group.
  • the organic compound (A) As the organic compound (A), the following formulas (1), (2), (3) and (4) are preferable.
  • Ar represents an organic group containing an aromatic hydrocarbon ring or a heterocyclic ring.
  • X represents ⁇ or NH.
  • n is an integer from 1 to 4. If there are multiple Xs, they may be the same or different.
  • 8 1 ", 2 “ and 1 " 3 each independently represents an organic group containing an aromatic hydrocarbon ring or a heterocyclic ring.
  • m represents an integer from 1 to 4.
  • a r 3 When a plurality of A r 3 are present, they may be the same or different.
  • Ar 2 is a 2m-valent organic group
  • Ar 3 is a divalent organic group
  • Ar 4 is a divalent organic group
  • Ar 5 is a divalent organic group
  • ⁇ 7 each independently represents an organic group containing an aromatic hydrocarbon ring or a heterocyclic ring.
  • k is an integer from 1 to 4.
  • a r 7 When a plurality of A r 7 are present, they may be the same or different.
  • Ar 6 is a 2 k valent organic group
  • Ar 7 is a divalent organic group.
  • NTCDA Naphthalene-1,8: 4, 5-tetracarboxylic dianhydride
  • PTCDA Perylene-3, 4, 9, 10-tetracarboxyl dianhydride
  • NTCDI 4, 7, 8-naphthalene-tetracarboxyl ic-diimide
  • formula (3) examples include isoviolanthrone (9, 18-dihydrobenzo [rst] phenanthro [10, 1, 2-cde] pentaphene-9, 18-dione).
  • the formula (1) is preferable, tetracarboxylic anhydride or tetrastruccinimide is more preferable, and NTCDA, PTCDA, NTCDI are more preferable.
  • the number of carbonyl groups possessed by the organic compound (A) is 1 or more, preferably in the range of 1-8.
  • Two or more organic compounds (A) and metals (B) may be used.
  • the total weight of organic compound (A) and metal (B) is usually 50 wt% or more, preferably 8 owte, and more preferably based on the total weight of layer (L) Is over 90w ⁇ '.
  • the number of metal atoms of the metal (B) is preferably about 0.025 to 25, more preferably 0.06, per one force sulfonyl group in the organic compound (A). ⁇ 2.25, more preferably 0.16 to 0.38.
  • the electric conductivity of the mixture that is obtained from the organic compound (A) and the metal (B) is 1 0- 6 S Bruno cm or more, 1 0- 4 SZ cm by more preferably more than, 1 0- 2 SZ cm or more in a more preferred arbitrariness.
  • the number ratio of metal atoms of metal (B) per carbonyl group in organic compound (A) in the mixture is made the same as the number ratio in layer (L).
  • the absorption peak wavelength of the thin film composed of the organic compound (A) and the metal (B) is 5 nm or more longer than the absorption peak wavelength of the thin film composed of the organic compound (A).
  • the wavelength is 1 O nm or longer, more preferably 3 O nm or longer.
  • the absorption peak of the organic compound (A) shows that when the organic compound (A) consists of two or more types, the organic compound (A) contains the most molecules (mol ratio in the organic compound (A)). Is the absorption peak of the organic compound.
  • the mixture used for the measurement of the absorption peak wavelength is the same as the number ratio in the layer (L) of the number of metal atoms of the metal (B) per carbonyl group in the organic compound (A) in the mixture.
  • the light emitting layer of the organic EL device of the present invention usually contains an organic light emitter.
  • organic light emitters organic fluorescent molecules and polymeric fluorescent materials usually used in organic EL devices can be used.
  • organic fluorescent molecules examples include benzoxazol derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthylimide derivatives, coumarin derivatives, perylene derivatives, Perinone derivatives, Oxadiazole derivatives, Ardazine derivatives, Viralizine derivatives, Cyclopentene derivatives, Bisstyrylanthracene derivatives, Quinacridone derivatives, Pyrophine pyridines Derivatives, thiadiazolopyridine derivatives, cyclopentagen derivatives, styrylamine derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives, rare earth complexes, and various metal complexes represented by Ir and Pt complexes .
  • JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, JP-A-3-37992 And those disclosed in Japanese Patent Publication No. 3-152184 are preferably used.
  • Polymer phosphors have a molecular structure in which ⁇ -electron systems such as polyarylene and polyarylene vinylene are non-polarized along the molecular chain, exhibit fluorescence in the solid state, and are converted to polystyrene.
  • a polymeric fluorescent substance having a number average molecular weight of 1 ⁇ 10 4 to 1 ⁇ 10 7 is preferably used.
  • the film thickness of the light-emitting layer varies depending on the material used, and it may be selected so that the drive voltage and light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the drive voltage of the element will increase, which is not preferable. Accordingly, the thickness of the light emitting layer is, for example, 1 nm to 1 mm, and is preferable. It is preferably 2 nm to 500 nm, more preferably 5 nn! ⁇ 200 nm.
  • At least one of the anode and the cathode is transparent or translucent.
  • the anode is preferably transparent or translucent.
  • a conductive metal oxide film, a translucent metal thin film, or the like is used as the material of the anode. Specifically, it was fabricated using conductive glass made of indium oxide, zinc oxide, tin oxide, and their composites such as indium tin oxide (ITO), indium zinc, and oxide. Films (NESA, etc.), gold, platinum, silver, copper, etc. are used, and ITo, indium / zinc / oxide, and tin oxide are preferred.
  • an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
  • the film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity. For example, 10 0 ⁇ ⁇ ! ⁇ 10 ju m, preferably 20 mn m: L m, more preferably 50 ⁇ ! ⁇ 5 0 0 nm.
  • the organic EL device of the present invention may have layers such as a hole transport layer and an electron transport layer in addition to the light emitting layer, the anode, the cathode, and the layer (L).
  • layers such as a hole transport layer and an electron transport layer in addition to the light emitting layer, the anode, the cathode, and the layer (L).
  • the following structures are specifically mentioned.
  • the hole transport layer is a layer having a function of transporting holes
  • the electron transport layer is a layer having a function of transporting electrons.
  • the hole transport layer and the electron transport layer are collectively referred to as a charge transport layer.
  • those having the function of improving the charge injection efficiency from the electrode are sometimes generally called charge injection layers (hole injection layers, electron injection layers).
  • those having a function of blocking electrons injected from the cathode between the anode and the light-emitting layer are particularly similar to the electron block layer.
  • a material generally called and having a function of blocking holes injected from the anode between the cathode and the light emitting layer may be generally called a hole blocking layer.
  • an electron transport layer a hole transport layer, a layer (L), or a layer having a function of mitigating a decrease in light emission intensity of the light emitting layer caused by stacking the electrodes, Sometimes called a quenching prevention layer.
  • two or more light emitting layers, anodes, cathodes, hole transport layers, and electron transport layers may be used independently.
  • the position where the second layer is used is not particularly limited, and can be appropriately used in consideration of light emission efficiency and device lifetime.
  • the hole transport material used for the hole transport layer is N, N-diphenyl-N, N-bis (3-methylphenyl) -1, Aromatic amine compounds such as di-4,4-diamine (TPD), hydrazone compounds, metal phthalocyanines, porphyrins, styrylamine compounds, polyvinylcarbazole, polysilane (App Phys. Lett. 59, 2760 (1991)), a suspension of poly (3,4) ethylenedioxythiophene Z polystyrene sulfonic acid (manufactured by Bayer, Bytron PTP AI 4083), and the like are preferably used.
  • the film thickness of the hole transport layer varies depending on the material used and may be selected so that the drive voltage and light emission efficiency are appropriate. At least, the thickness should be such that no pinholes are generated. If the thickness is too thick, the drive voltage of the element increases, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • the electron transport material used for the electron transport layer includes a triazole derivative, an oxazole derivative, an oxadiazole derivative, a fluorenone derivative, an anthraquinodimethane derivative, an anthrone derivative, Diphenylquinone derivatives, thiopyran dioxide derivatives, carpositimide derivatives, fluorenylidenemethane derivatives, distyrylvirazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, phthalocyanine derivatives, 8_quinolinol derivative metals Complex metal phthalocyanine, various metal complexes represented by benzoxazol benzothiazole as a ligand, benzoquinone or its derivative, naphthoquinone or its derivative, anthraquinone or its Derivatives, diphenyl dicyanethylene or derivatives thereof, diphenoquinone
  • Examples include those described in No. 8, No. 3-3 7 9 92 No. 2, No. 3 _ 1 5 2 1 8 No. 4, etc.
  • the film thickness of the electron transport layer varies depending on the material used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. Yes, if it is too thick, the drive voltage of the element will increase, which is not preferable. Therefore, the film thickness of the electron transport layer is, for example, 1 nm to 1 m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • the organic EL device of the present invention may have a protective layer outside the cathode or anode.
  • a protective layer and Z or a protective cover in order to protect the element from the outside.
  • the protective layer is provided on the cathode side, the protective layer is attached from the cathode side so as to be sandwiched between the substrate on which the element is laminated after the cathode is manufactured.
  • a polymer compound, a metal oxide, a metal fluoride, a metal boride and the like can be used as the material of the protective layer.
  • a glass plate, a plastic plate having a surface subjected to low water permeability treatment, or the like can be used, and the cover is attached to the element substrate with a heat-effect resin or a photo-curing resin and sealed.
  • a spacer it is easy to prevent the element from being damaged.
  • an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and moisture adsorbed in the manufacturing process can be obtained by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the device.
  • a film that protects the organic EL element can be formed by forming one or more organic / inorganic layered films on the organic EL element. Of these, it is preferable to take one or more measures.
  • the element of the present invention is as described above.
  • the layer (L) and the light emitting layer may be provided, and another layer may be provided between the light emitting layer and the anode.
  • the cathode the layer (L), the light emitting layer, the anode, and the layers used as necessary, a method for producing the hole transport layer and the electron transport layer will be described in order.
  • the method for producing the cathode is not particularly limited.
  • the metal is formed by a vacuum deposition method, a sputtering method, an electron beam method, or the like.
  • a vacuum deposition method is preferably used as a method for forming the layer (L).
  • vacuum deposition include a method of co-evaporating metal (B), organic compound (A) and the like. Specifically, raw materials such as metal (B) and organic compound (A) are filled in a crucible, a port, etc., and the raw materials are heated and evaporated by resistance heating. At this time, co-evaporation can be performed at an arbitrary ratio by monitoring and controlling the deposition rate of the metal (B) and the organic compound (A), and an arbitrary composition ratio and film thickness can be obtained.
  • vacuum deposition includes a method of depositing an organic compound (A) and then depositing metal (B). Metal diffuses into organic compounds Can be formed.
  • the method for laminating the organic compound (A) is not limited to the vacuum vapor deposition method, and there is a method of applying (on the substrate) a solution in which the organic compound (A) is dissolved or dispersed in a solvent. Examples of the coating method include a drop casting method, a spin coating method, and an ink jet method, but are not particularly limited.
  • Metal (B) deposition includes sputtering, electron beam, ion plating, and laser ablation.
  • Examples of the method for forming a light emitting layer of the organic electoluminescence device of the present invention include a vacuum deposition method when the organic light emitter is an organic fluorescent molecule, and a coating from a solution when the organic light emitter is a polymer fluorescent material.
  • a phosphor solution may be used, or a mixed solution with a polymer binder may be used.
  • the solvent used for film formation from a solution is not particularly limited as long as it can dissolve a light emitter.
  • the solvent include chlorine solvents such as chloroform, methylene chloride and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; Examples include ester solvents such as ethyl, butyl acetate, and ethyl cellosolve acetate.
  • film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, and spray coating.
  • Application methods such as a printing method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
  • polymer binder to be mixed those not extremely disturbing the light emitting property are preferable, and those not strongly absorbing visible light are preferably used.
  • the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • polysilane or a derivative thereof polysiloxane 13 having an aromatic amine compound group in the side chain or main chain, a polyaniline or a derivative thereof
  • a polymeric hole transport material such as polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-cenylenylene) or a derivative thereof may be used.
  • Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • the organic EL device of the present invention has a hole transport layer
  • a method for forming the layer will be described.
  • vacuum deposition, film formation by coating from a solution, and the like can be mentioned.
  • a solution of a hole transport material may be used, or a mixed solution with a polymer binder may be used.
  • the solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material.
  • the solvent include chlorine solvents such as chloroform, methylene chloride and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone.
  • the solvent include ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate.
  • Film deposition methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire-bar coating method, dip coating method, spray coating method Application methods such as screen printing, flexographic printing, offset printing, and inkjet printing can be used.
  • polymer binder to be mixed those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are preferably used.
  • the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • polysilane or a derivative thereof polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain
  • polyaniline or a derivative thereof polythiophene or a derivative thereof
  • poly (P_Phenylene vinylene) also Alternatively, a derivative thereof, or a polymer hole transport material such as poly (2,5-Chenylenevinylene) or its derivative may be used.
  • the method for forming the electron transport layer is not particularly limited.
  • a vacuum deposition method from a powder, a solution or a melt is used.
  • Examples of the method of film formation from the state, and methods of film formation from a solution or a molten state are exemplified for the polymer electron transport material.
  • a polymer binder may be used in combination.
  • the solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and Z or a polymer binder.
  • the solvent include chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, and ketones such as acetone and methylethylketone.
  • Examples of such solvents include ester solvents such as cetyl acetate, butyl acetate, butyl acetate, and cetyl cellosolvate.
  • Film formation methods from solution or molten state include spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spraying Coating methods such as a coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
  • polymer binder those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used.
  • the polymer binder include poly (N-vinylcarbazol), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, and poly (2,5-chainylene vinylene. Or derivatives thereof, poly force monoponate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.
  • the organic EL device of the present invention may be manufactured in the order of cathode, layer (L), (if necessary, electron transport layer, etc.), light emitting layer, (if necessary, electron transport layer, etc.), anode, They may be manufactured in the reverse order.
  • a substrate is usually used when forming the organic EL device of the present invention, but the substrate may be any material that does not change when an electrode is formed and an organic layer is formed.
  • the substrate may be any material that does not change when an electrode is formed and an organic layer is formed.
  • glass, plastic, polymer film Examples include silicon substrates.
  • the opposite electrode is preferably transparent or translucent.
  • Poly (9,9-dioctylfluorene) (PFO) was synthesized by the method described in W00 / 53656.
  • the number average molecular weight of the P FO is 4. was 8 xl 0 4.
  • TFB (2,7- (9,9-dioctylfluorene) -alt- (1,4-phenylene- ((4-sec butylphenyl) imino) -1,4-phenylene))
  • a coating solution was prepared by dissolving the polymers PFO and TFB in Synthesis Example 1 in toluene. (In the coating solution, the concentration of?
  • the organic EL device was fabricated by co-evaporation with a deposition rate of 0.021 111/3 to a film thickness of 10 nm, and further with a gold deposition of 20 nm using gold as the cathode.
  • the degree of vacuum during the deposition was all less than 1.0xlO— 5 Torr.
  • This indium source for one NTCDA molecule '' The number of children is 1 (0.25 indium atoms per carbonyl group).
  • a coating solution was prepared by dissolving the polymers PF0 and TFB of Synthesis Example 1 in toluene. (The concentration of ??? cho ??? 8 in the coating solution is 1.5w% respectively.)
  • a suspension of xithiphene polystyrene sulfonic acid (Bayer, By tron P TP AI 4083) was spin-coated to a thickness of 60 nm and dried on a hot plate at 200 ° C for 10 minutes. On top of that, a light emitting layer was formed to a thickness of 200 nm by spin coating using the above coating solution.
  • bathocuproine BCP was deposited as an electron transport layer (quenching prevention layer) at a deposition rate of 0.45 nmZs to a thickness of 4 Onm.
  • layer (L) NTCDA was co-evaporated to a thickness of 10 nm with a deposition rate of 0.4 nmZs and indium at a deposition rate of 0.02 nmZs.
  • 2 O nm was vapor-deposited using gold as a cathode to produce an organic EL device.
  • the degree of vacuum during deposition was 1.0 xl (T 5 Torr or less.)
  • the ratio of indium atoms to one NTCDA molecule was one (0.25 indium atoms per carbonyl group).
  • Example 2 In the device of Example 2, a device in which the layer (L) was not deposited was produced.
  • the absorption spectrum was measured with an ultraviolet-visible absorption spectrum measuring apparatus.
  • the measurement environment is air and room temperature.
  • the absorption spectrum peak of the sample is shifted by about 7 Onm on the longer wavelength side compared to that of NTCDA alone. ( Figure 5)
  • the cleaned glass substrate was set in a vacuum evaporation machine, and BCP was co-evaporated to a film thickness of 200 nm with a deposition rate of 0.45 nmZs and indium at a deposition rate of 0.02 nmZs.
  • the ratio of indium atoms to one BCP molecule is one.
  • a sample was also prepared by depositing BCP to a thickness of 200 nm at a deposition rate of 0.45 nmZ s without depositing metal.
  • the degree of vacuum was less than all 1.0 X 10- 5 Torr.
  • the measurement environment is the same as in Example 3.
  • the absorption spectrum peak of the sample obtained by co-evaporation of B C / indium has an absorption spectrum peak shifted by 1 Onm or more on the short wavelength side compared to that of BCP alone. ( Figure 7)
  • the cleaned glass substrate is set in a vacuum evaporation machine, and the layer (L) is NTCDA with a deposition rate of 0.4 nm Zs and metal atoms with a deposition rate of 0.02 nm s, resulting in a film thickness of 200 nm. Co-deposited.
  • the ratio of metal atoms to one NTCDA molecule is 1 (0.25 metal atom per carbonyl group).
  • a gold electrode was vapor-deposited as a parallel electrode having an interval of 1.00 m using a vapor deposition mask.
  • BCP was co-evaporated to a film thickness of 200 nm with a deposition rate of 0.45 nmZs and metal atoms at a deposition rate of 0.02 ns.
  • a gold electrode was deposited. The degree of vacuum at this time was less than 1.0 x lO— 5 Torr.
  • the electrical conductivity of the co-deposited film doped with metal atoms in NTCDA or BCP was determined by measuring the amount of current when a voltage was applied between the gold electrodes. An electrometer was used for the measurement. The measurement environment is in vacuum and at room temperature.
  • Table 1 shows the measured electrical conductivity of NTCDA or BCP doped with metal atoms.
  • the amount of metal doping is the ratio of one metal atom to one NTCDA or BCP molecule. Some have improved conductivity by 6 orders of magnitude or more compared to the case where nothing is doped.
  • doping with alkali metals such as lithium and sodium improves electrical conductivity, but alkali metals are extremely reactive with moisture and oxygen, so the composition of these metal atoms and organic compounds is exposed to the atmosphere. They are unstable.
  • indium is relatively stable against moisture and oxygen.
  • the indicator ⁇ When arm is compared doped NTCDA and BCP is more indium-doped NTCDA 9. 1 10- 2 S / cm and about 5 orders of magnitude more high electric conductivity Natsuta.
  • the organic EL device of the present invention is excellent in durability, electron injection property and the like. Industrial applicability
  • a planar light source, a segment display device, and a dot matrix display device can be created using the organic electoluminescence device of the present invention.
  • a liquid crystal display device can be produced by using the organic electoluminescence device of the present invention as a backlight.
  • the planar anode and cathode may be arranged so as to overlap each other.
  • a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-
  • a method of emitting light a method of forming either the anode or the cathode, or both electrodes in a pattern.
  • both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal. Partial color display and multi-color display are possible by coating multiple types of polymer phosphors with different emission colors, or by using color filter or fluorescence conversion filters.
  • the dot matrix element can be driven passively or may be driven actively in combination with TFT or the like.
  • planar light-emitting element is a self-luminous thin type and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

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  • Electroluminescent Light Sources (AREA)
PCT/JP2006/306988 2005-03-28 2006-03-27 有機エレクトロルミネッセンス素子 WO2006104230A1 (ja)

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JP2018006772A (ja) * 2010-10-04 2018-01-11 株式会社半導体エネルギー研究所 複合材料、発光素子、発光装置、電子機器、及び照明装置

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JP5196764B2 (ja) * 2006-11-17 2013-05-15 キヤノン株式会社 有機ｅｌ素子及びその製造方法
KR101468592B1 (ko) * 2008-06-25 2014-12-05 삼성전자주식회사 유기 광전 변환막, 광전 변환 소자 및 이미지 센서
CN109698281B (zh) * 2019-01-11 2022-07-08 中国科学院重庆绿色智能技术研究院 一种含有吡啶聚合物的光伏器件

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH10270171A (ja) * 1997-01-27 1998-10-09 Junji Kido 有機エレクトロルミネッセント素子
JP2000196140A (ja) * 1998-12-28 2000-07-14 Sharp Corp 有機エレクトロルミネッセンス素子とその製造法
JP2000306676A (ja) * 1999-04-21 2000-11-02 Chemiprokasei Kaisha Ltd 有機エレクトロルミネッセンス素子
JP2003292587A (ja) * 2002-04-05 2003-10-15 National Institute Of Advanced Industrial & Technology 共重合体及びエレクトロルミネッセンス素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10270171A (ja) * 1997-01-27 1998-10-09 Junji Kido 有機エレクトロルミネッセント素子
JP2000196140A (ja) * 1998-12-28 2000-07-14 Sharp Corp 有機エレクトロルミネッセンス素子とその製造法
JP2000306676A (ja) * 1999-04-21 2000-11-02 Chemiprokasei Kaisha Ltd 有機エレクトロルミネッセンス素子
JP2003292587A (ja) * 2002-04-05 2003-10-15 National Institute Of Advanced Industrial & Technology 共重合体及びエレクトロルミネッセンス素子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018006772A (ja) * 2010-10-04 2018-01-11 株式会社半導体エネルギー研究所 複合材料、発光素子、発光装置、電子機器、及び照明装置

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