[go: up one dir, main page]

WO2012002245A1 - Élément électroluminescent organique - Google Patents

Élément électroluminescent organique Download PDF

Info

Publication number
WO2012002245A1
WO2012002245A1 PCT/JP2011/064377 JP2011064377W WO2012002245A1 WO 2012002245 A1 WO2012002245 A1 WO 2012002245A1 JP 2011064377 W JP2011064377 W JP 2011064377W WO 2012002245 A1 WO2012002245 A1 WO 2012002245A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
organic
layer
light emitting
intermediate layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/064377
Other languages
English (en)
Japanese (ja)
Inventor
隼 古川
硯里　善幸
朱里 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2012522582A priority Critical patent/JP5835217B2/ja
Publication of WO2012002245A1 publication Critical patent/WO2012002245A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

Definitions

  • the present invention relates to an organic electroluminescence device, and more particularly to an organic electroluminescence device that improves half-luminance life and suppresses a voltage increase in continuous driving.
  • ELD electroluminescence display
  • inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).
  • organic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.
  • an organic EL element has a configuration in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer to recombine excitons. It is an element that emits light by utilizing the emission of light (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoint of space saving and portability.
  • Non-Patent Document 1 As the development of organic EL elements for practical application, since Princeton University has reported organic EL elements that use phosphorescence emission from excited triplets (see, for example, Non-Patent Document 1), phosphorescence at room temperature. Research on materials exhibiting the above has become active (see, for example, Non-Patent Document 2 and Patent Document 1).
  • the recently discovered organic EL device using phosphorescence emission can in principle achieve light emission efficiency about 4 times that of the previous device using fluorescence emission.
  • Research and development of light-emitting element layer configurations and electrodes are performed all over the world.
  • Non-Patent Document 3 many compounds have been studied focusing on heavy metal complexes such as iridium complexes (see, for example, Non-Patent Document 3).
  • the organic EL device using phosphorescence emission is greatly different from the organic EL device using fluorescence emission, and the method for controlling the position of the emission center, particularly the emission layer. How to recombine inside the element and stabilize the light emission is an important technical issue for grasping the efficiency and life of the device.
  • a method of suppressing diffusion by treating the lower layer with an organic acid to produce a hardly soluble layer, or by devising that the surface is crosslinked / polymerized for example, refer to Patent Documents 2 and 3.
  • the impurities are introduced by the acid treatment, or the hardly soluble layer or the crosslinked layer works as an injection barrier or a trap component, sufficient performance has not been achieved.
  • there have been contrivances such as reducing the injection barrier at the interface by providing an interface region containing a charge transfer complex at the interface (see, for example, Patent Document 4), but further measures for improving performance are required. .
  • An object of the present invention is to provide an organic electroluminescence device having improved half-luminance life and voltage rise with time of driving, and more specifically, by using an intermediate layer having a critical surface tension of 10 mN / m to 30 mN / m, An organic electroluminescence device having improved voltage rise with time is provided.
  • an organic electroluminescence device having an anode and a cathode on a substrate, and a plurality of organic functional layers sandwiched between both electrodes, the plurality of organic functional layers include at least a hole injection layer, a hole transport layer, and An organic electroluminescence device comprising a light emitting layer and an intermediate layer containing at least one fluorinated polymer between any two organic functional layers of the plurality of organic functional layers.
  • R 1 and R 2 are an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group , Alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or hetero At least one selected from arylsulfonyl group, amino group, halogen atom, fluorinated hydrocarbon group, cyano group, nitro group, hydroxy group, thiol group, silyl group, phosphon
  • X is at least one cyclic selected from cyclic ether, cyclic thioether, cyclic azaether, crown ether, thiacrown ether, and azacrown ether, which contains at least one of oxygen, nitrogen, and sulfur. Represents a partial structure, and n2 represents an integer of 10 to 10,000.
  • n2 represents an integer of 10 to 10,000.
  • the organic EL device according to the present invention by providing an intermediate layer containing at least one fluorinated polymer between the organic functional layers, it was possible to provide a device having an improved half-luminance lifetime.
  • the intermediate layer according to the present invention is characterized by containing the fluorinated polymer (also referred to as a fluorine-substituted polymer) according to the present invention.
  • the intermediate layer according to the present invention is a fluorinated polymer.
  • the intermediate layer according to the present invention may further contain a material known as a conventionally known organic EL element material.
  • the intermediate layer according to the present invention preferably has a critical surface tension in the range of 10 mN / m to 30 mN / m.
  • the present invention can also be used as a material for obtaining the intermediate layer exhibiting the critical surface tension as described above.
  • a fluorinated polymer can be preferably used.
  • many of the fluorinated polymers according to the present invention can be formed by a wet process if a fluorine-substituted organic solvent is selected, and the productivity is higher than that by a dry process such as a vapor deposition method. preferable.
  • a fluorinated polymer as represented by the general formula (a) or (b) because the crystallinity is suppressed and a transparent amorphous film is easily formed.
  • the calculation of the critical surface tension and the measurement of the contact angle used for the calculation can be performed by the method described in, for example, Plastic Encyclopedia 1059 (Asakura Shoten (published March 1992)).
  • the layer satisfying the above conditions improves the half-luminance lifetime and the voltage rise over time is not clear, but when the organic material at the interface becomes an anion radical, a cation radical or an excited state, a reaction between the materials can occur
  • the provision of the intermediate layer may have an effect of mitigating reactions and deterioration between organic materials, but details are not clear.
  • a water-dispersed hole injection material such as polyethylenedioxythiophene-polysulfonic acid (hereinafter also referred to as PEDOT-PSS) generally used in coating is used.
  • PEDOT-PSS polyethylenedioxythiophene-polysulfonic acid
  • the thickness of the intermediate layer is not particularly limited, but is preferably adjusted to a range of 1 nm to 20 nm, more preferably from the viewpoint of the uniformity of the film to be formed and the prevention of unnecessary application of high voltage during light emission. The adjustment is made within the range of 1 nm to 10 nm.
  • the fluorinated polymer has substituents R 1 and R 2 and a cyclic substituent X, respectively, and R 1 , R It is preferable that any one of 2 contains at least one oxygen, nitrogen, sulfur, or at least one oxygen, nitrogen, sulfur in the cyclic substituent X.
  • substituents may be introduced into the substituents R 1 and R 2 as long as the above characteristics are satisfied.
  • substituents R 1 and R 2 include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, Tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg 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 group (
  • the fluorinated polymer has a cyclic substituent X, and the cyclic substituent X contains at least one of oxygen, nitrogen, and sulfur.
  • the cyclic substituent X may be any substituent as long as the above conditions are satisfied.
  • Specific examples of the cyclic substituent X include cyclic ether, cyclic thioether, cyclic azaether, crown ether, thiacrown ether, azacrown ether and the like.
  • any number of hydrogen atoms in the above substituents may be substituted with fluorine atoms.
  • n represents a range of 10 to 10,000, but from the viewpoint of solubility in a solvent during film formation, a range of 10 to 1,000 is preferable.
  • Examples of the polymer material represented by the general formula (a) or (b) according to the present invention include, for example, US Pat. No. 3,418,302, US Pat. No. 3,978,030, Polymers described in JP-A-63-238111, JP-A-63-238115, JP-A-1-131214, JP-A-1-131215 and the like are preferably used.
  • Anode / hole injection layer / hole transport layer / intermediate layer / light emitting layer / electron transport layer / cathode (ii) Anode / hole injection layer / intermediate layer / hole transport layer / light emitting layer / electron transport layer / Cathode (iii) Anode / hole injection layer / intermediate layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iv) Anode / hole injection layer / intermediate layer / hole transport layer / Emission layer / electron transport layer / electron injection layer / cathode (v) anode / hole injection layer / hole transport layer / emission layer / electron transport layer / intermediate layer / electron injection layer / cathode Among these, anode, cathode, The layers excluding the intermediate layer are collectively referred to as an organic functional layer.
  • the light-emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer. May be an interface between the light emitting layer and the adjacent layer, but is preferably within the layer of the light emitting layer because of deactivation of excitons between layers.
  • the film thickness of the light emitting layer is not particularly limited, but it is 2 nm from the viewpoint of the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color with respect to the driving current. It is preferable to adjust to a range of ⁇ 200 nm, and more preferably to a range of 5 nm to 100 nm.
  • a host compound also referred to as a light emitting host
  • a light emitting dopant contained in the light emitting layer will be described.
  • 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 a compound having a phosphorescence quantum efficiency of less than 0.01.
  • known host compounds may be used alone or in combination of two or more. 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.
  • the light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (polymerizable light emission). Host).
  • the host compound a compound that has a hole transporting ability and an electron transporting ability, prevents an increase in emission wavelength, and has a high Tg (glass transition temperature) is preferable.
  • Specific examples of the host compound also include compounds described in the following documents.
  • a fluorescent dopant or a phosphorescent dopant can be used. From the viewpoint of obtaining an organic EL element with higher luminous efficiency, light emission used in the light-emitting layer or light-emitting unit of the organic EL element.
  • a dopant it is preferable to contain a phosphorescent dopant simultaneously with the host compound.
  • the phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL element.
  • the phosphorescent dopant according to the present invention is preferably a complex compound containing a transition metal element of group 8 to 10 in the periodic table of elements (also simply referred to as transition metal), more preferably an iridium compound or osmium.
  • a transition metal element of group 8 to 10 in the periodic table of elements also simply referred to as transition metal
  • iridium compound or osmium Compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.
  • 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.
  • polystyrene sulfonic acid PSS
  • the film thickness of the hole injection layer is not particularly limited, but is preferably adjusted in the range of 2 nm to 200 nm, more preferably in the range of 5 nm to 100 nm, from the viewpoint of the uniformity of the film to be formed.
  • 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 is preferably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m.
  • ⁇ 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. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the compounds mentioned as the host compound can be preferably used.
  • 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 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, and 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, an electron blocking layer is 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 either hole injection or transport or electron barrier properties, 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
  • 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.
  • inorganic compounds such as p-type-Si and p-type-SiC can also 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 as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials because a light emitting element with high luminous efficiency can be obtained.
  • 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 casting method, a printing method including an ink jet method, or an LB method. it can.
  • 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.
  • JP-A-4-297076 JP-A-2000-196140, 2001-102175, J. Pat. 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 light emitting layer on the cathode side is injected from the cathode.
  • any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an 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 casting method, a printing method including an ink jet method, or an LB method.
  • the film thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • n-type electron transport layer doped with impurities examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. 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 As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • ITO indium tin oxide
  • ZnO 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.
  • a wet film forming method such as a printing method or a coating method can be used.
  • the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • 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 material.
  • cathode As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used.
  • Electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as a 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.
  • either one of the anode or the cathode of the organic EL element is transparent or semi-transparent from the viewpoint of transmitting the emitted light and improving the emission luminance.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a film thickness of 1 nm to 20 nm. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
  • substrate As a substrate (hereinafter also referred to as a support substrate) that can be used in the organic EL element of the present invention, there is no particular limitation on the type of glass, plastic and the like, and it may be transparent or opaque. When extracting light from the substrate side, the substrate is preferably transparent. Examples of the transparent substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable substrate is a resin film capable of giving flexibility to the organic EL element.
  • 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, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (manufactured by J
  • An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and a barrier film having a water vapor permeability of 0.01 g / (m 2 ⁇ 24 h) or less is preferable.
  • the oxygen permeability is 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less (1 atm is 1.01325 ⁇ 10 5 Pa)
  • the water vapor permeability is 10 ⁇ 5 cm 3 / (m 2 ⁇ 24 h.
  • -It is preferable that it is a high barrier film below atm).
  • 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 method for forming the barrier film 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, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction quantum 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.
  • external extraction quantum efficiency (%) (number of photons emitted to the outside of the organic EL element) / (number of electrons passed through 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 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 organic EL element can be thinned.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less, and conforms to JIS K 7129-1992. was measured by the method, the water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably those of 1 ⁇ 10 -3 g / (m 2 / 24h) 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. Moreover, heat
  • hot melt type polyamides, polyesters and polyolefins 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.
  • an inorganic or organic layer as a sealing film by covering the electrode and the organic layer on the outer side of the electrode facing the substrate with the organic layer interposed therebetween, and in contact with the substrate.
  • 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.
  • 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.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside.
  • Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • 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 perchloric acid) Barium, magnesium perchlorate, etc.), and anhydrous salts are preferably used in sulfates, metal halides and perch
  • the organic functional layer sandwiched between the anode and the cathode may be formed using either a dry process or a wet process, but from the viewpoint of productivity, a film is formed by a wet process. It is preferable. It is also preferable to form the entire organic laminate by a wet process.
  • the wet process referred to in the present invention is to form a layer by supplying a layer forming material in the form of a solution when forming a layer.
  • 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 thickness of 1 ⁇ m or less, preferably 10 nm to 200 nm. .
  • organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are organic EL element materials, are formed thereon.
  • Examples of methods for forming these layers include vapor deposition methods, wet processes (spin coating method, die coating method, casting method, ink jet method, spray method, printing method) and the like as described above.
  • a homogeneous film can be easily obtained and pinholes are not easily generated.
  • a composition by a coating method such as a spin coating method, a die coating method, an ink jet method, a spray method, or a printing method is used.
  • a membrane is preferred.
  • examples of the liquid medium for dissolving or dispersing the material include ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, ethyl acetate, butyl acetate, and the like.
  • ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, ethyl acetate, butyl acetate, and the like.
  • the organic solvent or water can be used.
  • 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, and a cathode is provided.
  • 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.
  • a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the 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 providing light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an organic EL element (Japanese Patent Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (Japanese Patent Laid-Open No.
  • a method of introducing a flat layer having a structure Japanese Patent Laid-Open No. 2001-202827, a method of forming a diffraction grating between any one of the substrate, the transparent electrode layer and the light emitting layer (including between the substrate and the outside world) No. 283751) That.
  • 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, more 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.
  • Bragg diffraction such as first-order diffraction and second-order diffraction.
  • 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 one 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 gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL device of the present invention can be processed to provide, for example, a microlens array-like structure on the light extraction side of the substrate, or combined with a so-called condensing sheet, for example, in a specific direction, for example, the device light emitting surface.
  • luminance in a specific direction can be raised by condensing in a front direction.
  • microlens array square 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 sheet for example, Sumitomo 3M brightness enhancement film (BEF) can be used.
  • BEF Sumitomo 3M brightness enhancement film
  • the shape of the prism sheet for example, a triangle stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m may be formed on the substrate, the vertex angle may be rounded, and the pitch may be 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 organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • 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, light
  • the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
  • 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.
  • 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 light emitting layer of the organic EL device of the present invention preferably contains at least one of a light emitting host compound and a light emitting dopant as a guest material.
  • Example 1 Production of Organic EL Element 101 >> After patterning a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate made of ITO (Indium Tin Oxide) 100 nm as an anode, the transparent support substrate provided with the ITO transparent electrode was superposed with normal propyl alcohol. Sonic cleaning, drying with dry nitrogen gas, and UV ozone cleaning were performed for 5 minutes.
  • ITO Indium Tin Oxide
  • This transparent support substrate was attached to a vacuum deposition apparatus, the vacuum layer was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and the compound HI-1 was deposited by vapor deposition to form a 20 nm thick hole injection layer (HIL). .
  • a film was formed by vapor deposition of the compound HT-1, and a hole transport layer (HTL) having a thickness of 20 nm was obtained. Further, Compound H-27 and Compound D-1 were co-evaporated so that Compound D-1 had a film thickness ratio of 16% to form a light emitting layer (EML) having a thickness of 40 nm.
  • EML light emitting layer
  • a film was formed by vapor deposition of the compound ET-1, and an electron transport layer (ETL) having a thickness of 20 nm was obtained. Thereafter, LiF was deposited as an electron injection layer with a thickness of 1 nm, and aluminum was deposited with a thickness of 110 nm to form a cathode.
  • ET-1 electron transport layer
  • ETL electron transport layer
  • FIG. 1 shows a schematic diagram of an organic EL element, and the organic EL element 101 is covered with a glass cover 102.
  • the sealing operation with the glass cover was performed in a glove box (in an atmosphere of high purity nitrogen gas having a purity of 99.999% or more) in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere.
  • FIG. 2 shows a cross-sectional view of the organic EL element.
  • 105 denotes a cathode
  • 106 denotes an organic EL layer
  • 107 denotes a glass substrate with a transparent electrode.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • Organic EL Elements 103 and 104 In the production of the organic EL element 102, a film obtained by dissolving PE in 40 mg and 20 mg in 10 ml of chlorobenzene was spin-coated at 5000 rpm for 60 seconds, and heated at 150 ° C. for 30 minutes under nitrogen to form a film thickness. Organic EL elements 103 and 104 were produced in the same manner except that an intermediate layer of 20 nm and 10 nm was formed.
  • Organic EL Elements 107 and 108 In the production of the organic EL element 106, using a solution in which 40 mg and 20 mg of PVDF were dissolved in 10 ml of 2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethyl ether, respectively. Organic EL elements 107 and 108 were produced in the same manner except that spin coating was performed at 5000 rpm for 60 seconds and heating was performed at 150 ° C. for 30 minutes under nitrogen to form an intermediate layer having a thickness of 20 nm and 10 nm.
  • the manufactured organic EL element was continuously driven by applying a current that would give a front luminance of 1000 cd / m 2 .
  • the time required for the front luminance to reach the initial half value (500 cd / m 2 ) is obtained as a half life, and the half lives of the organic EL elements 102 to 110 are 100 as measured values of the organic EL element 101 (comparative example). It was expressed as a relative value.
  • Vt Voltage increase at half brightness
  • A Voltage increase when half luminance reached less than 0.5 V
  • B Voltage increase when half luminance reached 0.5 V or more and less than 1.0 V
  • C Voltage increase when half luminance reached 1.0 V or more and less than 2.0 V
  • D Half The voltage rise when the luminance reaches 2.0 V or more
  • a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing was used for measuring the luminance.
  • ranks A and B are practical levels.
  • the organic EL element of the present invention has a half life by forming an intermediate layer containing a fluorinated polymer between the hole injection layer and the hole transport layer. It is apparent that the voltage increase when the half luminance is reached is suppressed.
  • Example 2 Production of Organic EL Element 115 >> In the production of the organic EL element 114 of Example 1, an intermediate layer was not provided between the hole injection layer (HIL) and the hole transport layer (HTL), but a hole transport layer (HTL) was formed. Later, the substrate was moved to a glove box under a nitrogen atmosphere, and spin-coated under a condition of 5000 rpm for 60 seconds using a solution in which I-1 (20 mg) was dissolved in 10 ml of chlorobenzene in the glove box, 150 An organic EL element 115 was produced in the same manner except that an intermediate layer having a film thickness of 10 nm was formed by heating under nitrogen at 30 ° C. for 30 minutes, and then a light emitting layer (EML) was formed.
  • HIL hole injection layer
  • HTL hole transport layer
  • the intermediate layer is not provided between the hole transport layer (HTL) and the light emitting layer (EML), and after the light emitting layer is formed, the substrate is moved to a glove box in a nitrogen atmosphere.
  • spin-coating was performed on the light-emitting layer (EML) using a solution obtained by dissolving I-1 (20 mg) in 10 ml of chlorobenzene at 5000 rpm for 60 seconds.
  • An organic EL element 118 was produced in the same manner except that the film was heated under nitrogen for 10 minutes to provide an intermediate layer having a thickness of 10 nm, and then an electron transport layer (ETL) was formed.
  • the organic EL device in which an intermediate layer is provided between the hole transport layer and the light emitting layer and the organic EL device in which an intermediate layer is provided between the light emitting layer and the electron transport layer are the same as in Example 1. It can be seen that the half-life is increased and the voltage rise when the half-luminance is reached is suppressed.
  • the half life (%) is further extended in the structure having a plurality of intermediate layers, such as the organic EL elements 117 to 120 of the present invention.
  • Example 3 Production of Organic EL Element 201 >> As a positive electrode, patterning was performed on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate, and then this ITO transparent electrode was provided.
  • the transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • the substrate was moved to a glove box under a nitrogen atmosphere, and spin coating (film thickness: about 20 nm) was performed at 1500 rpm for 30 seconds using a solution in which compound HT-2 (50 mg) was dissolved in 10 ml of monochlorobenzene. And dried under nitrogen at 160 ° C. for 30 minutes to form a hole transport layer (HTL).
  • spin coating film thickness: about 20 nm
  • spin coating (film thickness of about 40 nm) was performed at 1500 rpm for 30 seconds using a solution in which compound H-27 (73 mg) and compound D-1 (14 mg) were dissolved in 10 ml of isopropyl acetate. It dried under nitrogen for 30 minutes and was set as the light emitting layer (EML).
  • EML light emitting layer
  • the substrate is attached to a vacuum deposition apparatus, the vacuum chamber is depressurized to 4 ⁇ 10 ⁇ 4 Pa, LiF is deposited as an electron injection layer at 2 nm, then aluminum 110 nm is deposited to form a cathode, and the organic EL element 201 is formed. Produced.
  • Organic EL Elements 203 and 204 were produced in the same manner except that an intermediate layer of 20 nm and 10 nm was formed.
  • Organic EL Element 206 In the production of the organic EL element 202, 60 mg of polyvinylidene fluoride (PVDF) was dissolved in 10 ml of 2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethyl ether instead of PE. The organic EL element 206 was fabricated in the same manner except that the solution was spin-coated at 5000 rpm for 60 seconds and heated under nitrogen at 150 ° C. for 30 minutes to form a 30 nm thick intermediate layer. did.
  • PVDF polyvinylidene fluoride
  • an organic EL device in which a plurality of organic functional layers (for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc.) are produced by a wet process is also an intermediate containing a fluorinated polymer. It is clear that the organic EL element of the present invention provided with a layer has a longer half-life (%) than that of a comparative organic EL element that is not so, and suppresses an increase in voltage when the half-luminance is reached. is there.
  • Example 4 Production of Organic EL Element 215 >>
  • the substrate was placed under a nitrogen atmosphere.
  • An organic EL element 215 was produced in the same manner as described above except that the coating was heated at 150 ° C. for 30 minutes under nitrogen to provide an intermediate layer having a thickness of 10 nm, and then the light emitting layer (EML) was formed.
  • the positive hole transport layer HTL
  • an example in which the effect is more remarkable is that an intermediate layer is provided between the hole injection layer and the light emitting layer. It has also been clarified that an effect can be obtained even in a configuration having a plurality of intermediate layers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un élément électroluminescent organique caractérisé par une demi-vie de luminance et une augmentation de tension améliorées pendant la période d'excitation. L'élément électroluminescent organique décrit comporte un substrat, une anode et une cathode situées sur le substrat, et une pluralité de couches fonctionnelles organiques prises en sandwich entre les électrodes. Les couches fonctionnelles organiques comportent au moins une couche d'injection de trous et une couche luminescente, au moins une couche intermédiaire contenant des polymères fluorés se situant entre deux couches fonctionnelles organiques arbitraires parmi la pluralité de couches fonctionnelles organiques.
PCT/JP2011/064377 2010-07-02 2011-06-23 Élément électroluminescent organique Ceased WO2012002245A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012522582A JP5835217B2 (ja) 2010-07-02 2011-06-23 有機エレクトロルミネッセンス素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010151745 2010-07-02
JP2010-151745 2010-07-02

Publications (1)

Publication Number Publication Date
WO2012002245A1 true WO2012002245A1 (fr) 2012-01-05

Family

ID=45401963

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/064377 Ceased WO2012002245A1 (fr) 2010-07-02 2011-06-23 Élément électroluminescent organique

Country Status (2)

Country Link
JP (1) JP5835217B2 (fr)
WO (1) WO2012002245A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016204275A1 (fr) * 2015-06-17 2016-12-22 国立大学法人山形大学 Couche organique de transport de charge, dispositif el organique, dispositif semiconducteur organique, et dispositif photoélectrique organique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010073A1 (fr) * 1990-11-30 1992-06-11 Idemitsu Kosan Company Limited Dispositif a electroluminescence organique
JPH0711247A (ja) * 1993-06-28 1995-01-13 Idemitsu Kosan Co Ltd 有機ｅｌ素子の封止方法およびこの封止方法により得られた発光装置
JP2000323280A (ja) * 1999-05-07 2000-11-24 Seiko Epson Corp 電界発光素子およびその製造方法
JP2004119303A (ja) * 2002-09-27 2004-04-15 Sanyo Electric Co Ltd 有機エレクトロルミネッセンス素子およびその製造方法
JP2006222195A (ja) * 2005-02-09 2006-08-24 Seiko Epson Corp 有機ｅｌ装置、その製造方法、及び電子機器
WO2009096342A1 (fr) * 2008-01-28 2009-08-06 Asahi Glass Company, Limited Composition durcissable, produit durci contenant du fluor, matériau optique utilisant le produit durci, et dispositif émettant de la lumière
WO2010074038A1 (fr) * 2008-12-24 2010-07-01 旭硝子株式会社 Module électroluminescent et son procédé de fabrication

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002072930A (ja) * 2000-08-28 2002-03-12 Toshiba Corp 表示素子及びその駆動方法
JP2005310742A (ja) * 2004-03-25 2005-11-04 Sanyo Electric Co Ltd 有機エレクトロルミネッセンス素子
JP4466594B2 (ja) * 2005-03-30 2010-05-26 セイコーエプソン株式会社 有機ｅｌ装置及び有機ｅｌ装置の製造方法
JP2008033284A (ja) * 2006-07-04 2008-02-14 Semiconductor Energy Lab Co Ltd 表示装置の作製方法
US20080286566A1 (en) * 2007-05-18 2008-11-20 Shiva Prakash Process for forming an organic light-emitting diode and devices made by the process
EP2232527A4 (fr) * 2007-12-27 2012-04-18 Du Pont Bicouches tampons pour dispositifs électroniques
WO2009107549A1 (fr) * 2008-02-27 2009-09-03 東レ株式会社 Matériau pour élément luminescent et élément luminescent
WO2009107548A1 (fr) * 2008-02-29 2009-09-03 Semiconductor Energy Laboratory Co., Ltd. Procédé de dépôt et procédé de fabrication de dispositif électroluminescent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010073A1 (fr) * 1990-11-30 1992-06-11 Idemitsu Kosan Company Limited Dispositif a electroluminescence organique
JPH0711247A (ja) * 1993-06-28 1995-01-13 Idemitsu Kosan Co Ltd 有機ｅｌ素子の封止方法およびこの封止方法により得られた発光装置
JP2000323280A (ja) * 1999-05-07 2000-11-24 Seiko Epson Corp 電界発光素子およびその製造方法
JP2004119303A (ja) * 2002-09-27 2004-04-15 Sanyo Electric Co Ltd 有機エレクトロルミネッセンス素子およびその製造方法
JP2006222195A (ja) * 2005-02-09 2006-08-24 Seiko Epson Corp 有機ｅｌ装置、その製造方法、及び電子機器
WO2009096342A1 (fr) * 2008-01-28 2009-08-06 Asahi Glass Company, Limited Composition durcissable, produit durci contenant du fluor, matériau optique utilisant le produit durci, et dispositif émettant de la lumière
WO2010074038A1 (fr) * 2008-12-24 2010-07-01 旭硝子株式会社 Module électroluminescent et son procédé de fabrication

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016204275A1 (fr) * 2015-06-17 2016-12-22 国立大学法人山形大学 Couche organique de transport de charge, dispositif el organique, dispositif semiconducteur organique, et dispositif photoélectrique organique
JPWO2016204275A1 (ja) * 2015-06-17 2018-04-05 国立大学法人山形大学 有機電荷輸送層、有機ｅｌデバイス、有機半導体デバイス及び有機光電子デバイス
EP3312898A4 (fr) * 2015-06-17 2018-12-26 National University Corporation Yamagata University Couche organique de transport de charge, dispositif el organique, dispositif semiconducteur organique, et dispositif photoélectrique organique
US10381566B2 (en) 2015-06-17 2019-08-13 National University Corporation Yamagata University Organic charge transport layer, organic EL device, organic semiconductor device, and organic photoelectric device

Also Published As

Publication number Publication date
JPWO2012002245A1 (ja) 2013-08-22
JP5835217B2 (ja) 2015-12-24

Similar Documents

Publication Publication Date Title
JP5967057B2 (ja) 有機エレクトロルミネッセンス素子とその製造方法、照明装置及び表示装置
JP5493333B2 (ja) 有機エレクトロルミネッセンス素子、白色有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5697856B2 (ja) 有機エレクトロルミネッセンス素子、白色有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5499890B2 (ja) 有機エレクトロルミネッセンス素子、及びその製造方法
JP5201054B2 (ja) 有機エレクトロルミネッセンス材料、有機エレクトロルミネッセンス素子、青色燐光発光素子、表示装置及び照明装置
JP5163642B2 (ja) 有機エレクトロルミネセンス素子
WO2009084413A1 (fr) Dispositif électroluminescent organique et procédé de fabrication de dispositif électroluminescent organique
JP2008207520A (ja) 有機薄膜、有機薄膜の製造方法、電子デバイス、有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5417763B2 (ja) 有機エレクトロルミネッセンス素子用化合物
JPWO2008090795A1 (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP6225915B2 (ja) 有機エレクトロルミネッセンス素子
JP2015109470A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
WO2011052250A1 (fr) Élément électroluminescent organique, matériau pour éléments électroluminescents organiques, dispositif d'affichage et dispositif d'éclairage
JP5076899B2 (ja) 有機エレクトロルミネッセンス素子、その製造方法、該有機エレクトロルミネッセンス素子を有する表示装置及び照明装置
JP5521753B2 (ja) 有機エレクトロルミネッセンス素子
JP2011009517A (ja) 有機エレクトロルミネッセンス素子
JP5218185B2 (ja) 有機エレクトロルミネッセンス素子、それを用いた表示装置及び照明装置
JP5636630B2 (ja) 有機エレクトロルミネッセンス素子材料、有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2010040967A (ja) 有機エレクトロルミネッセンス素子、重合膜の製造方法、白色有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2009152435A (ja) 白色有機エレクトロルミネッセンス素子、白色有機エレクトロルミネッセンス素子の製造方法、表示装置及び照明装置
WO2012039241A1 (fr) Élément électroluminescent organique et procédé de fabrication d'un élément électroluminescent organique
JP5835217B2 (ja) 有機エレクトロルミネッセンス素子
JP5761388B2 (ja) 有機エレクトロルミネッセンス素子
WO2011114870A1 (fr) Procédé de production d'un élément électroluminescent organique
JP6056909B2 (ja) 有機エレクトロルミネッセンス素子

Legal Events

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

Ref document number: 11800710

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012522582

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11800710

Country of ref document: EP

Kind code of ref document: A1