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WO2013031346A1 - Élément organique à électroluminescence, dispositif d'affichage et dispositif d'éclairage - Google Patents

Élément organique à électroluminescence, dispositif d'affichage et dispositif d'éclairage Download PDF

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WO2013031346A1
WO2013031346A1 PCT/JP2012/065691 JP2012065691W WO2013031346A1 WO 2013031346 A1 WO2013031346 A1 WO 2013031346A1 JP 2012065691 W JP2012065691 W JP 2012065691W WO 2013031346 A1 WO2013031346 A1 WO 2013031346A1
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group
layer
emitting layer
ring
light emitting
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みゆき 岡庭
和博 及川
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent 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
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to an organic electroluminescence element, and more particularly to an organic electroluminescence element excellent in luminous efficiency, luminous lifetime and luminance unevenness, and a display device and an illumination device using the same.
  • organic electroluminescence elements using organic substances are promising for use as solid light-emitting inexpensive large-area full-color display elements and writing light source arrays.
  • the organic EL element is composed of an organic functional layer (single layer portion or multilayer portion) having a thickness of only about 0.1 ⁇ m containing an organic light emitting material between a pair of anode and cathode formed on a film. It is a thin film type all solid state device.
  • a relatively low voltage of about 2 to 20 V is applied to such an organic EL element, electrons are injected from the cathode and holes are injected from the anode into the organic compound layer.
  • emission is obtained by releasing energy as light when the electrons and holes recombine in the light emitting layer and the energy level returns from the conduction band to the valence band. This technology is expected as a flat display and lighting.
  • an anode made of ITO Indium Tin Oxide
  • a film made with an aqueous solvent hole injection layer
  • a light emitting layer an alkali metal such as LiF
  • an alkali metal such as LiF
  • an alkali such as LiF
  • an alkali such as LiF
  • an alkali such as LiF
  • an alkali such as LiF
  • an alkali such as LiF
  • an alkali such as LiF
  • the light emitting layer manufactured by the coating process has a problem that the film thickness is not uniform compared to the light emitting layer formed by using the vapor deposition process, and luminance unevenness is likely to occur.
  • the film formed using the coating process is a coarse film as compared with the film formed using the vapor deposition process, and is easily affected by the diffusion material from the peripheral layer. Also in the film production, it is affected by the physical properties of the coating liquid, the coating process and the drying process, and it is very difficult to produce a uniform film particularly in a large area.
  • Patent Document 2 discloses a method for increasing the density of a film. Specifically, a method is disclosed in which the entire organic EL element is compressed with a laminate material to uniformly pressurize the film to increase the film density and raise the rough film formed by coating to the vapor deposition level.
  • Patent Document 3 discloses a method of suppressing luminance unevenness. More specifically, a method of providing a partition and reducing luminance unevenness by making the film surface uniform by an ink jet method / nozzle coating method is disclosed (Patent Document 3).
  • Patent Document 3 discloses a method of suppressing luminance unevenness. More specifically, a method of providing a partition and reducing luminance unevenness by making the film surface uniform by an ink jet method / nozzle coating method is disclosed (Patent Document 3).
  • Patent Document 3 the effect of suppressing luminance unevenness is insufficient for a large area.
  • the thickness of the electron injection layer composed of a chemically unstable material is increased to about 5 to 10 nm, the lifetime of the organic EL element, that is, the reliability is lowered.
  • the lifetime of the organic EL element that is, the reliability is lowered.
  • an anode and a hole injection layer made of a transparent conductive material such as ITO (Indium Tin Oxide) are generally formed.
  • ITO Indium Tin Oxide
  • the light emitting layer formed using the coating method is a rough film, the lifetime of the light emitting layer may be reduced by indium atoms diffused from the anode to the light emitting layer.
  • various problems occur in the organic EL element mainly due to the fact that the light emitting layer formed using the coating method is a rough film.
  • a main object of the present invention is to provide an organic electroluminescence element excellent in luminous efficiency, light emission lifetime and luminance unevenness
  • another object of the present invention is a display device using the organic electroluminescence element and The object is to provide a lighting device.
  • an organic electroluminescence device comprising: The film density of the light emitting layer is ⁇ EM, the film density of the hole transport layer is ⁇ HT, the film density of the electron transport layer is ⁇ ET, and the film density of the light emitting layer and the film density of the hole transport layer are When the difference between ⁇ (EM ⁇ HT) and the difference between the film density of the light emitting layer and the film density of the electron transport layer is ⁇ (EM ⁇ ET), both conditional expressions (i) and (ii) An organic electroluminescence device characterized by satisfying the above is provided.
  • ⁇ (EM ⁇ HT) ( ⁇ EM ⁇ HT) ⁇ 0.03 (i) ⁇ (EM ⁇ ET)
  • the present invention it is possible to improve the light emission efficiency and the light emission lifetime, and to suppress the occurrence of luminance unevenness.
  • an organic electroluminescence element 100 (hereinafter also referred to as an organic EL element) according to a preferred embodiment of the present invention has a flexible support substrate 1.
  • An anode 2 is formed on the flexible support substrate 1
  • an organic functional layer 20 is formed on the anode 2
  • a cathode 8 is formed on the organic functional layer 20.
  • the organic functional layer 20 refers to each layer constituting the organic electroluminescence element 100 provided between the anode 2 and the cathode 8.
  • the organic functional layer 20 includes, for example, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and in addition, a hole block layer, an electron block layer, and the like. May be included.
  • the anode 2, the organic functional layer 20, and the cathode 8 on the flexible support substrate 1 are sealed with a flexible sealing member 10 through a sealing adhesive 9.
  • these layer structures (refer FIG. 1) of the organic electroluminescent element 100 show only the preferable specific example, and this invention is not limited to these.
  • the organic EL device 100 according to the present invention may have a layer structure of (i) to (viii).
  • Organic functional layer 20 of organic EL element >> Subsequently, the detail of the organic functional layer which comprises the organic EL element of this invention is demonstrated.
  • the injection layer can be provided as necessary.
  • the injection layer includes an electron injection layer and a hole injection layer, and may be present 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 as described above.
  • the injection layer referred to in the present invention is a layer provided between the electrode and the organic functional layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998, NT.
  • Injection materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives.
  • the details of the electron injection layer are described in, for example, JP-A-6-325871, JP-A-9-17574, and JP-A-10-74586, and specific examples thereof include strontium and aluminum.
  • the buffer layer (injection layer) is desirably a very thin film, and potassium fluoride and sodium fluoride are preferable.
  • the film thickness is about 0.1 nm to 5 ⁇ m, preferably 0.1 to 100 nm, more preferably 0.5 to 10 nm, and most preferably 0.5 to 4 nm.
  • Hole transport layer 4 As the hole transport material constituting the hole transport layer, the same compounds as those applied in the hole injection layer can be used, and further, porphyrin compounds, aromatic tertiary amine compounds, and styryl. It is preferable to use an amine 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
  • 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.
  • the hole transport layer is 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. Can do.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • n described in the above exemplary compounds represents the degree of polymerization and represents an integer having a weight average molecular weight in the range of 50,000 to 200,000. If the weight average molecular weight is less than this range, there is a concern of mixing with other layers during film formation due to the high solubility in the solvent. Even if a film can be formed, the light emission efficiency does not increase at a low molecular weight. When the weight average molecular weight is larger than this range, problems arise due to difficulty in synthesis and purification. Since the molecular weight distribution increases and the residual amount of impurities also increases, the light emission efficiency, voltage, and life of the organic EL element deteriorate. These polymer compounds are disclosed in Makromol. Chem. , Pages 193, 909 (1992) and the like.
  • Electron transport layer 6 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. Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the cathode side with respect to the light emitting layer is injected from the cathode. As long as it has a function of transmitting electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds.
  • fluorene derivatives for example, fluorene derivatives, carbazole derivatives, azacarbazole And metal complexes such as derivatives, oxadiazole derivatives, triazole derivatives, silole derivatives, pyridine derivatives, pyrimidine derivatives, 8-quinolinol derivatives, and the like.
  • 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.
  • a carbazole derivative, an azacarbazole derivative, a pyridine derivative, and the like are preferable in the present invention, and an azacarbazole derivative is more preferable.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a spin coating method, a casting method, a printing method including an ink jet method, an LB method, and the like, preferably
  • the electron transport material can be formed by a wet process using a coating solution containing a fluorinated alcohol solvent.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • an electron transport layer with high n property doped with impurities as a guest material can be used.
  • 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.
  • the electron transport layer in the present invention preferably contains an organic alkali metal salt.
  • organic substance but formate, acetate, propionic acid, butyrate, valerate, caproate, enanthate, caprylate, oxalate, malonate, succinate Benzoate, phthalate, isophthalate, terephthalate, salicylate, pyruvate, lactate, malate, adipate, mesylate, tosylate, benzenesulfonate ,
  • the type of alkali metal of the alkali metal salt of the organic substance is not particularly limited, and examples thereof include Na, K, and Cs, preferably K, Cs, and more preferably Cs.
  • Examples of the alkali metal salt of the organic substance include a combination of the organic substance and the alkali metal, preferably, formic acid Li, formic acid K, formic acid Na, formic acid Cs, acetic acid Li, acetic acid K, Na acetate, acetic acid Cs, propionic acid Li, Propionic acid Na, propionic acid K, propionic acid Cs, oxalic acid Li, oxalic acid Na, oxalic acid K, oxalic acid Cs, malonic acid Li, malonic acid Na, malonic acid K, malonic acid Cs, succinic acid Li, succinic acid Na, succinic acid K, succinic acid Cs, benzoic acid Li, benzoic acid Na, benzoic acid K, benzoic acid Li,
  • the light emitting layer constituting the organic EL device of the present invention 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, and the light emitting portion is the light emitting layer. It may be in the layer or the interface between the light emitting layer and the adjacent layer.
  • the light emitting layer according to the present invention is not particularly limited in its configuration as long as the contained light emitting material satisfies the above requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. It is preferable to have a non-light emitting intermediate layer between each light emitting layer.
  • the total thickness of the light emitting layers in the present invention is preferably in the range of 1 to 100 nm, and more preferably 50 nm or less because a lower driving voltage can be obtained.
  • the sum total of the film thickness of the light emitting layer as used in this invention is a film thickness also including the said intermediate
  • the film thickness of each light emitting layer is preferably adjusted in the range of 1 to 50 nm.
  • each light emitting layer may emit light of each color of blue, green, and red, and there is no particular limitation on the relationship between the thickness of each light emitting layer.
  • a plurality of light emitting materials may be mixed in each light emitting layer, or a phosphorescent light emitting material and a fluorescent light emitting material may be mixed and used in the same light emitting layer.
  • the structure of the light-emitting layer preferably contains a host compound and a light-emitting material (also referred to as a light-emitting dopant compound) and emits light from the light-emitting material.
  • (4.1) Host compound As the host compound contained in the light emitting layer of the organic EL device of the present invention, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.
  • 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. Moreover, it becomes possible to mix different light emission by using multiple types of luminescent material mentioned later, and can thereby obtain arbitrary luminescent colors.
  • 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).
  • a polymer material it is difficult to purify, and the phenomenon that the compound is difficult to escape such as swelling and gelation due to incorporation of the solvent is likely to occur. It is preferably not high, and specifically, a material having a molecular weight of 2,000 or less at the time of coating is preferably used, and a material having a molecular weight of 1,000 or less at the time of coating is more preferably used.
  • the known host compound a compound having a hole transporting ability and an electron transporting ability, preventing an increase in the wavelength of light emission, and having a high Tg (glass transition temperature) is preferable.
  • the glass transition point (Tg) is a value determined by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).
  • Specific examples of known host compounds include compounds described in the following documents. For example, Japanese Patent Laid-Open Nos.
  • the host compound used in the present invention is preferably a carbazole derivative.
  • the host compound is preferably a compound represented by the general formula (1).
  • X represents NR ′, O, S, CR′R ′′ or SiR′R ′′.
  • R ′ and R ′′ each represent a hydrogen atom or a substituent.
  • Ar represents an aromatic ring.
  • N represents an integer of 0 to 8.
  • examples of the substituent represented by R ′ and R ′′ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a pentyl group, Hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl group, etc.), alkynyl group ( For example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesity
  • These substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • X is preferably NR ′ or O
  • R ′ is an aromatic hydrocarbon group (also referred to as an aromatic carbocyclic group, an aryl group, etc., for example, a phenyl group, a p-chlorophenyl group, a mesityl group, A tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a biphenylyl group, or an aromatic heterocyclic group (for example, a furyl group, a thienyl group, a pyridyl group) Group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group,
  • aromatic hydrocarbon group and aromatic heterocyclic group each may have a substituent represented by R ′ or R ′′ in X of the general formula (1).
  • examples of the aromatic ring represented by Ar include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • the aromatic ring may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent represented by R ′ or R ′′ in X of the general formula (1).
  • examples of the aromatic hydrocarbon ring represented by Ar include a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, Examples include a pyranthrene ring and anthraanthrene ring. These rings may further have substituents represented by R ′ and R ′′ in X of the partial structure represented by the general
  • examples of the aromatic heterocycle represented by Ar include a furan ring, a dibenzofuran ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, and a pyrimidine ring.
  • These rings may further have substituents represented by R ′ and R ′′ in the general formula (1).
  • the aromatic ring represented by Ar is preferably a carbazole ring, a carboline ring, a dibenzofuran ring, or a benzene ring, and more preferably a carbazole ring, A carboline ring and a benzene ring, more preferably a benzene ring having a substituent, and particularly preferably a benzene ring having a carbazolyl group.
  • the aromatic ring represented by Ar is preferably a condensed ring of three or more rings, and the aromatic hydrocarbon condensed ring condensed with three or more rings is specifically exemplified.
  • aromatic heterocycle condensed with three or more rings include an acridine ring, a benzoquinoline ring, a carbazole ring, a carboline ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, Kindin ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (any one of the carbon atoms constituting the carboline ring is a nitrogen atom Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzod
  • n represents an integer of 0 to 8, preferably 0 to 2, particularly preferably 1 to 2 when X is O or S.
  • a host compound having both a dibenzofuran ring and a carbazole ring is particularly preferable.
  • Luminescent dopant compound (also referred to as a luminescent dopant) will be described.
  • a fluorescent dopant also referred to as a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
  • a fluorescent dopant also referred to as a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
  • Fluorescent dopant also called fluorescent compound
  • fluorescent dopants coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, rare earth complex phosphors, and the like, and compounds having a high fluorescence quantum yield such as laser dyes.
  • the phosphorescent dopant compound according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition.
  • the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • the other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant compound is obtained.
  • a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant compound is obtained.
  • it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.
  • the light-emitting dopant according to the present invention may be used in combination of a plurality of types of compounds, or may be a combination of phosphorescent dopants having different structures, or a combination of a phosphorescent dopant and a fluorescent dopant.
  • the film density of the light emitting layer has a certain relationship with the film density of the other layers.
  • the film density of the light emitting layer is ⁇ EM
  • the film density of the hole transport layer is ⁇ HT
  • the film density of the electron transport layer is ⁇ ET
  • the difference between the film density of the light emitting layer and the film density of the hole transport layer is When ⁇ (EM ⁇ HT) and the difference between the film density of the light emitting layer and the film density of the electron transport layer are ⁇ (EM ⁇ ET), both of the conditional expressions (i) and (ii) are satisfied.
  • ⁇ (EM ⁇ HT) ( ⁇ EM ⁇ HT) ⁇ 0.03
  • ⁇ (EM ⁇ ET) ( ⁇ EM ⁇ ET) ⁇ 0.03 (ii)
  • the value of ⁇ EM is preferably 1.40 or more.
  • the light emitting layer and the non-light emitting layer are formed.
  • the value of ⁇ EM is the largest, and the non-light emitting layer has a higher film density as the layer is closer to the light emitting layer.
  • hole injection is performed on the anode.
  • the film density of the light emitting layer is larger than the film density of each of the hole injection layer and the hole transport layer, Of the hole injection layer and the hole transport layer of the non-light emitting layer, the film density of the hole transport layer close to the light emitting layer is higher than the film density of the hole injection layer.
  • a cathode is formed on the support substrate, and two non-light-emitting layers, ie, an electron injection layer and an electron transport layer, are formed between the cathode and the light-emitting layer.
  • the film density of the light-emitting layer is larger than the film density of the electron injection layer and the electron transport layer, and the electron injection layer of the non-light-emitting layer And the electron transport layer, the film density of the electron transport layer close to the light emitting layer is larger than the film density of the electron injection layer.
  • the film density of the present invention can be determined by an X-ray reflectance measurement method. It is obtained by measuring the reflectance at a very low angle, for example, in the range of 0.2 to 2 degrees, and fitting the obtained reflectance curve to the reflectance formula of the multilayer film sample obtained from the Fresnel formula. .
  • the X-ray generation source is operated at 50 kV-300 mA with copper as a target. X-rays monochromatized with a multilayer mirror and a Ge (111) channel cut monochromator are used.
  • GXRRVer. 2.1.0.0 Measurements can be made using analysis software.
  • each layer of organic functional layer it is sufficient that at least one light emitting layer as a constituent layer is formed by a coating method, and the method for forming the other layers is not particularly limited to the coating method, and is necessary. In accordance with the above, it is also possible to form a film using a vapor deposition method or the like.
  • a coating method (also referred to as a coating film forming method) is used as a method for forming a light emitting layer.
  • a method for forming the light emitting layer there are a spin coat method, a cast method, an ink jet method, a spray method, a printing method, a slot type coater method and the like.
  • the light emitting layer is preferably formed by a coating method such as a spin coating method, an ink jet method, a spray method, a printing method, or a slot coater method.
  • the slot type coater method is preferably used.
  • the coating solution is dried.
  • spin drying hot air drying, far-infrared drying, vacuum drying, reduced pressure drying, or the like can be applied.
  • the “coating film-forming method” as used herein means a process from application of a coating solution to completion of drying of the coating solution.
  • the present inventors prepared low molecular organic thin films formed so as to have the same film thickness by various coating film forming methods, and suppressed the size and content of contained microcrystals in the low molecular organic thin films.
  • one type of host material is mixed in the light emitting layer, preferably three or more types are mixed, more preferably five or more types are mixed, and still more preferably seven or more types are mixed. Is good.
  • the light emitting layer at least two kinds of dopant materials are preferably mixed, and more preferably three or more kinds are mixed.
  • the solvent of the coating solution for the light emitting layer a low boiling point solvent having a boiling point of 100 ° C. or less is used, and preferably isopropyl acetate or npropyl acetate is used.
  • the coating solution for the light emitting layer is preferably composed of two or more mixed solvents.
  • the film is preferably formed in a coating environment of 35 ° C. or higher, and is preferably formed at 40 ° C. or higher.
  • the coating solution for the light emitting layer may be subjected to a drying treatment within 5 seconds after being applied (after completion of the coating), and is preferably subjected to a drying treatment within 3 seconds after being applied. Good.
  • cooling may be performed after coating and drying.
  • spin drying, hot air drying, far infrared drying, vacuum drying, reduced pressure drying, or the like can be applied.
  • the “film thickness that is 5% more than the final film thickness after drying” means that, for example, when a thin film having a final film thickness after drying of 50 nm is to be produced, the film thickness is 52.5 nm. It corresponds to.
  • a spectroscopic ellipsometer for example, UVISEL manufactured by Joban Yvon
  • UVISEL manufactured by Joban Yvon
  • 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.
  • 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 desired shape pattern 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.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually in the range of 10 to 1000 nm, preferably in the range of 10 to 200 nm.
  • Cathode 8 a material having a low 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 the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light emission luminance is improved, which is convenient.
  • a transparent or translucent cathode can be produced by forming the above metal on the cathode with a film thickness of 1 to 20 nm and then forming the conductive transparent material mentioned in the description of the anode thereon. By applying this, an organic EL element in which both the anode and the cathode are transmissive can be produced.
  • the support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. Since the effect of suppressing high-temperature storage stability and chromaticity variation appears greatly in a flexible substrate than a rigid substrate, a particularly preferable support substrate has flexibility that can give flexibility to an organic EL element. Resin film.
  • 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, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (
  • an inorganic film, an organic film or a hybrid film of both may be formed on the surface of the resin film.
  • the film is preferably a high-barrier film having a degree of 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the degree is 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • a material for forming the barrier film any material may be used as long as it has a function of suppressing entry of factors that cause deterioration of the organic EL element such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like is used. Can do.
  • the method for forming the barrier film is not particularly limited.
  • 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 support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.
  • the external extraction efficiency of light emission at room temperature is preferably 1% or more, more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element ⁇ 100.
  • Sealing (sealing adhesive 9, sealing member 10)
  • a sealing means applicable to the organic EL element of the present invention for example, a method of adhering a sealing member, an electrode, and a support substrate with an adhesive can be mentioned.
  • a sealing member it should just be arrange
  • Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • Examples of 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, silicone, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the element can be thinned.
  • the polymer film has an oxygen permeability 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.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by the above method is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • sandblasting, chemical etching, or the like is used for processing the sealing member into a concave shape.
  • 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. Can be mentioned. Moreover, heat
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
  • the material for forming the film may be a material having 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.
  • 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
  • a polymerization method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • an inert gas such as nitrogen or argon, an inert gas such as fluorinated hydrocarbon or silicon oil is used. It is preferable to inject a liquid. A vacuum is also possible.
  • 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 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, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • Sealing includes casing type sealing (can sealing) and close contact type sealing (solid sealing), but solid sealing is preferable from the viewpoint of thinning. Moreover, when producing a flexible organic EL element, since sealing is also required for the sealing member, solid sealing is preferable.
  • thermosetting adhesive such as an epoxy resin, an acrylic resin, or a silicone resin, more preferably moisture resistant.
  • a thermosetting adhesive such as an epoxy resin, an acrylic resin, or a silicone resin, more preferably moisture resistant.
  • It is an epoxy thermosetting adhesive resin that is excellent in water resistance and water resistance and has little shrinkage during curing.
  • the water content of the sealing adhesive according to the present invention is preferably 300 ppm or less, more preferably 0.01 to 200 ppm, and most preferably 0.01 to 100 ppm.
  • the moisture content referred to in the present invention may be measured by any method.
  • a volumetric moisture meter Karl Fischer
  • an infrared moisture meter a microwave transmission moisture meter
  • a heat-dry weight method GC / MS , IR, DSC (differential scanning calorimeter), TDS (temperature programmed desorption analysis).
  • a precision moisture meter AVM-3000 Omnitech
  • moisture can be measured from a pressure increase caused by evaporation of moisture, and moisture content of a film or a solid film can be measured.
  • the moisture content of the sealing adhesive can be adjusted by, for example, placing it in a nitrogen atmosphere with a dew point temperature of ⁇ 80 ° C. or lower and an oxygen concentration of 0.8 ppm, and changing the time.
  • the sealing adhesive can be dried in a vacuum state of 100 Pa or less while changing the time.
  • the sealing adhesive can be dried only with an adhesive, but can also be placed in advance on the sealing member and dried.
  • the sealing member for example, a 50 ⁇ m thick PET (polyethylene terephthalate) laminated with an aluminum foil (30 ⁇ m thick) is used.
  • a sealing adhesive is placed in advance, the resin substrate 1 and the sealing member 5 are aligned, and both are pressure-bonded ( 0.1-3 MPa) and a temperature of 80-180 ° C. for close contact / bonding (adhesion), and close sealing (solid sealing).
  • Heating or pressure bonding time varies depending on the type, amount, and area of the adhesive, but temporary bonding is performed at a pressure of 0.1 to 3 MPa, and heat curing time is in the range of 5 seconds to 10 minutes at a temperature of 80 to 180 ° C. Just choose.
  • the use of a heated crimping roll is preferred because it allows simultaneous crimping (temporary bonding) and heating, and eliminates internal voids at the same time.
  • a coating method such as roll coating, spin coating, screen printing, or spray coating, or a printing method can be used depending on the material.
  • solid sealing is a form in which there is no space between the sealing member and the organic EL element substrate and the resin is covered with a cured resin.
  • the sealing member include metals such as stainless steel, aluminum and magnesium alloys, polyethylene terephthalate, polycarbonate, polystyrene, nylon, plastics such as polyvinyl chloride, and composites thereof, glass, and the like.
  • a laminate of gas barrier layers such as aluminum, aluminum oxide, silicon oxide, and silicon nitride can be used as in the case of a resin substrate.
  • the gas barrier layer can be formed by sputtering, vapor deposition or the like on both surfaces or one surface of the sealing member before molding the sealing member, or may be formed on both surfaces or one surface of the sealing member after sealing by a similar method.
  • the oxygen permeability is 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is 1 ⁇ It is preferably 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the sealing member may be a film laminated with a metal foil such as aluminum.
  • a generally used laminating machine can be used.
  • the adhesive polyurethane-based, polyester-based, epoxy-based, acrylic-based adhesives and the like can be used. You may use a hardening
  • a hot melt lamination method, an extrusion lamination method and a coextrusion lamination method can also be used, but a dry lamination method is preferred.
  • the metal foil is formed by sputtering or vapor deposition and is formed from a fluid electrode material such as a conductive paste, it may be created by a method of forming a metal foil on a polymer film as a base. Good.
  • a protective film or a protective plate may be provided outside the sealing film on the side facing the support substrate with the organic functional layer interposed therebetween or on the outer side of the sealing film.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.
  • a light extraction member between the flexible support substrate and the anode, or at any location on the light emission side from the flexible support substrate.
  • the light extraction member include a prism sheet, a lens sheet, and a diffusion sheet.
  • a diffraction grating or a diffusion structure introduced into an interface or any medium that causes total reflection can be used.
  • an organic electroluminescence element that emits light from a substrate
  • a part of the light emitted from the light emitting layer causes total reflection at the interface between the substrate and air, causing a problem of loss of light.
  • prismatic or lens-like processing is applied to the surface of the substrate, or prism sheets, lens sheets, and diffusion sheets are affixed to the surface of the substrate, thereby suppressing total reflection and light extraction efficiency.
  • prismatic or lens-like processing is applied to the surface of the substrate, or prism sheets, lens sheets, and diffusion sheets are affixed to the surface of the substrate, thereby suppressing total reflection and light extraction efficiency.
  • a method of introducing a diffraction grating or a method of introducing a diffusion structure in an interface or any medium that causes total reflection is known.
  • Method for Manufacturing Organic EL Element 100 As an example of the method for producing an organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
  • a desired electrode material for example, a thin film made of an anode material is formed on a suitable substrate by a thin film forming method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm.
  • An anode is produced.
  • a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic functional layer (organic compound thin film) of an electron injection layer, which are organic EL element materials, are formed thereon.
  • the process of forming the organic functional layer mainly includes (I) a step of coating and laminating the coating liquid constituting the organic functional layer on the anode of the support substrate; and (ii) a step of drying the coating liquid after coating and laminating; Consists of.
  • the light emitting layer forming method (coating film forming method) is as described above.
  • a vapor deposition method for example, spin coating method, casting method, die coating method, blade coating method, roll coating method, ink jet method, printing method, spray coating.
  • Method, curtain coating method, LB method Liangmuir Brodgett method and the like can be used
  • at least the light emitting layer of the present invention is preferably formed by a wet process.
  • a wet process in the present invention from the viewpoint that a homogeneous film is easily obtained and pinholes are difficult to be generated, among others, a spin coating method, a casting method, Film formation by a coating method such as a die coating method, a blade coating method, a roll coating method, or an ink jet method is preferable.
  • liquid medium for dissolving or dispersing the organic EL material according to the present invention examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene.
  • Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane
  • organic solvents such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO) can be used.
  • the preparation step for dissolving or dispersing the organic EL material according to the present invention and the coating process until coating on the base material are preferably performed under an inert gas atmosphere. Since the film can be formed without degrading the performance of the organic EL element even if it is not carried out in step 1, it may not necessarily be carried out in an inert gas atmosphere. In this case, the manufacturing cost can be suppressed, which is more preferable.
  • the coated and laminated organic functional layer is dried.
  • drying refers to a reduction to 0.2% or less when the solvent content of the film immediately after coating is 100%.
  • those generally used can be used, and examples thereof include reduced pressure or pressure drying, heat drying, air drying, IR drying, and electromagnetic wave drying.
  • heat drying is preferable, the temperature is equal to or higher than the boiling point of the solvent having the lowest boiling point in the organic functional layer coating solvent, and the temperature is lower than (Tg + 20) ° C. of the material having the lowest Tg among the Tg of the organic functional layer material. Most preferably, it is held at In the present invention, more specifically, it is preferable to hold and dry at 80 ° C.
  • the atmosphere when drying the coating liquid after coating / lamination is preferably an atmosphere having a volume concentration of a gas other than the inert gas of 200 ppm or less, but it is not necessarily in an inert gas atmosphere as in the liquid preparation coating process. It may not be necessary. In this case, the manufacturing cost can be suppressed, which is more preferable.
  • the inert gas is preferably a rare gas such as nitrogen gas and argon gas, and most preferably nitrogen gas in terms of production cost.
  • the coating / laminating and drying steps of these layers may be single wafer manufacturing or line manufacturing. Further, the drying process may be performed while being conveyed on the line, but from the viewpoint of productivity, it may be deposited or rolled in a non-contact manner in a roll form.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 nm to 200 nm.
  • a desired organic EL element can be obtained.
  • the organic EL element can be produced by adhering the close-sealing or sealing member to the electrode and the support substrate with an adhesive.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, and light sources for optical sensors.
  • it can be used in a wide range of applications such as general household appliances that require a display device, but it can be used effectively as a backlight for a liquid crystal display device combined with a color filter, and as a light source for illumination. it can.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.
  • Example Sample 1 Production of Gas Barrier Flexible Film First of polyethylene naphthalate film (Teijin DuPont film, hereinafter abbreviated as PEN) as the flexible film.
  • An inorganic gas barrier film made of SiOx is continuously formed on the flexible film on the entire surface on the electrode forming side using an atmospheric pressure plasma discharge treatment apparatus having the structure described in JP-A-2004-68143.
  • first electrode layer 120 nm thick ITO (Indium Tin Oxide) film is formed on the prepared gas barrier flexible film by sputtering and patterned by photolithography. An electrode layer (anode) was formed. The pattern was such that the light emission area was 50 mm square.
  • ITO Indium Tin Oxide
  • the patterned ITO substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
  • a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (abbreviated as PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds.
  • the film was formed by spin coating and held at 200 ° C. for 1 hour to provide a hole injection layer having a thickness of 30 nm.
  • a light-emitting layer composition having the following composition was formed by a spin coating method at 1500 rpm for 30 seconds and held at 120 ° C. for 30 minutes to form a light-emitting layer having a thickness of 40 nm. .
  • ⁇ Light emitting layer composition> Host material ... Exemplified compound a-6 13.95 parts by mass Dopant material ... Exemplified compound D-24: D-25: D-26: D-51: D-55 equimolar mixture 2.45 parts by mass Dopant material ... Exemplified compound D-1 0.025 parts by mass Dopant material ... Exemplary compound D-10 0.025 parts by mass Solvent species ...
  • Toluene: isopropyl acetate 1: 1 2,000 parts by mass
  • the coating film was kept at 30 ° C., and after 5 seconds (within 5 seconds) from the end of the application of the light emitting layer composition, the coating film was dried by applying dry air to the coating film.
  • a sealing member a flexible aluminum foil (made by Toyo Aluminum Co., Ltd.) having a thickness of 30 ⁇ m, a polyethylene terephthalate (PET) film (12 ⁇ m thickness) and an adhesive for dry lamination (two-component reaction type urethane) (Adhesive layer thickness 1.5 ⁇ m) was used.
  • a thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 ⁇ m along the adhesive surface (shiny surface) of the aluminum foil using a dispenser. This was dried under a vacuum of 100 Pa or less for 12 hours. Furthermore, it moved to a nitrogen atmosphere with a dew point temperature of ⁇ 80 ° C.
  • thermosetting adhesive an epoxy adhesive mixed with the following (A) to (C) was used.
  • DGEBA Bisphenol A diglycidyl ether
  • DIY Dicyandiamide
  • C Epoxy adduct curing accelerator
  • Example sample 1 (organic EL element) was manufactured by closely sealing at a temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min.
  • Example Sample 1 Production of Example Samples 2 to 7
  • the application environment of the light-emitting layer (application temperature, time from the end of application to the start of drying, solvent type of application liquid) is shown in Table 1, respectively The environment was changed. Other than that was the same as Example Sample 1.
  • Example Sample 8 In the production of Example Sample 1, the application environment of the light emitting layer (application temperature, time from the end of application to the start of drying, solvent type of the application liquid) are shown in Table 1, respectively. And the host material was an equal mass mixture of a-1, a-6, and a-41. Other than that was the same as Example Sample 1.
  • Example Sample 9 (4) Production of Comparative Sample 9
  • the application environment of the light emitting layer was changed to the environment shown in Table 1. Other than that was the same as Example Sample 1.
  • Example Samples 1 to 8 and Comparative Samples 9 to 13 were subjected to (1) measurement of the film density of the light emitting layer and the evaluations (2) to (4).
  • Example Samples 1 to 8 and Comparative Samples 9 to 13 were measured by the measurement method described above. The results are shown in Table 2.
  • ⁇ HIL represents the film density of the hole injection layer
  • ⁇ HT represents the film density of the hole transport layer
  • ⁇ EM represents the film density of the light emitting layer
  • ⁇ ET represents the film of the electron transport layer. Each density is shown.
  • ⁇ (EM-HT) is the difference between the film density of the light emitting layer and the film density of the hole transport layer ( ⁇ EM ⁇ HT)
  • ⁇ (EM-ET) is the film density of the light emitting layer and the electron ( ⁇ EM ⁇ ET), which is the difference from the film density of the transport layer, is shown.
  • Example Samples 1 to 8 have good results in each evaluation. there were. From the above, in order to improve the light emission efficiency, the light emission lifetime, and the suppression of luminance unevenness, both of the conditional expressions (i) and (ii) are satisfied ( ⁇ (EM ⁇ HT) and ⁇ (EM ⁇ It can be seen that it is useful to set both the value of (ET) to 0.03 or more.
  • the present invention can be particularly suitably used for improving luminous efficiency and luminous lifetime and suppressing occurrence of luminance unevenness.

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Abstract

La présente invention concerne un élément organique électroluminescent pourvu des éléments suivants : un substrat de support (1) ; une électrode positive (2) et une électrode négative (8) formées sur le substrat de support (1) ; une couche émettrice de lumière (5) formée entre l'électrode positive (2) et l'électrode négative (8) ; une couche de transport de trous (4) formée entre la couche émettrice de lumière (5) et l'électrode positive (2) ; et une couche de transport d'électrons (6) formée entre la couche émettrice de lumière (5) et l'électrode négative (8). Les deux équations conditionnelles (i) et (ii) suivantes sont satisfaites : (i) Δρ(EM-HT)=(ρEM-ρHT)≥0,03 et (ii) Δρ(EM-ET)=(ρEM-ρET)≥0,03 (où ρEM représente la densité de film de la couche émettrice de lumière (5), ρHT représente la densité de film de la couche de transport de trous (4), ρET représente la densité de film de la couche de transport d'électrons (6), Δρ(EM-HT) représente la différence entre la densité de film de la couche émettrice de lumière (5) et la densité de film de la couche de transport de trous (4), et Δρ(EM-ET) représente la différence entre la densité de film de la couche émettrice de lumière (5) et la densité de film de la couche de transport d'électrons (6)).
PCT/JP2012/065691 2011-08-29 2012-06-20 Élément organique à électroluminescence, dispositif d'affichage et dispositif d'éclairage Ceased WO2013031346A1 (fr)

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WO2007020718A1 (fr) * 2005-08-18 2007-02-22 Konica Minolta Holdings, Inc. Élément électroluminescent organique, dispositif d’affichage et dispositif d’éclairage
JP2007059244A (ja) * 2005-08-25 2007-03-08 Konica Minolta Holdings Inc 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
JP2007059687A (ja) * 2005-08-25 2007-03-08 Konica Minolta Holdings Inc 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
JP2007110097A (ja) * 2005-09-14 2007-04-26 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、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
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