WO2013031662A1 - Élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage - Google Patents

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

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WO2013031662A1
WO2013031662A1 PCT/JP2012/071377 JP2012071377W WO2013031662A1 WO 2013031662 A1 WO2013031662 A1 WO 2013031662A1 JP 2012071377 W JP2012071377 W JP 2012071377W WO 2013031662 A1 WO2013031662 A1 WO 2013031662A1
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秀雄 ▲高▼
片倉　利恵
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コニカミノルタホールディングス株式会社
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • 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
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    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Definitions

  • the present invention relates to an organic electroluminescence element, an illumination device using the same, and a display device.
  • An organic electroluminescence element (hereinafter also referred to as an organic EL element) has a structure in which a light emitting layer containing a light emitting compound is sandwiched between a cathode and an anode, and by applying an electric field, holes injected from the anode and Excitons are generated by recombination of electrons injected from the cathode in the light-emitting layer. It is a light emitting element utilizing light emission (fluorescence / phosphorescence) when this exciton is deactivated.
  • Non-Patent Document 1 As for development of organic EL elements for practical use, Princeton University has reported organic EL elements that use phosphorescence emission from excited triplets (see, for example, Non-Patent Document 1). Research on the materials shown has been active (see, for example, Patent Document 1 and Non-Patent Document 2).
  • 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, is particularly different. How to perform recombination inside and stabilize light emission is an important technical issue in capturing the efficiency and life of the organic EL element.
  • a multilayer stacked organic EL device having a hole transport layer (located on the anode side of the light emitting layer) and an electron transport layer (located on the cathode side of the light emitting layer) adjacent to the light emitting layer has been developed. It is well known (for example, see Patent Document 2). In addition, a mixed layer using a host compound and a phosphorescent compound as dopants is often used for the light emitting layer.
  • FIrpic is known as a typical blue phosphorescent compound, and a short wave is realized by substituting fluorine for the main ligand phenylpyridine and using picolinic acid as a secondary ligand. Yes.
  • These dopants achieve high-efficiency organic EL devices by combining carbazole derivatives and triarylsilanes as host compounds.
  • the light emission lifetime of organic EL devices is greatly deteriorated, so the trade-off can be improved. It was sought after.
  • Patent Document 3 As a blue phosphorescent compound having a high potential, a metal complex having a specific ligand has been disclosed in Patent Document 3 and improved in terms of luminous efficiency and luminous lifetime. However, it is still not sufficient in terms of light emission lifetime, which is an index for practical use. For example, when light is continuously emitted for a long time or under high temperature and high humidity, the carrier balance in the light emitting layer changes, and as a result, there is a concern about deterioration of device performance mainly due to a decrease in light emission luminance. Patent Document 3 does not describe such a viewpoint of stability over time, and it has been found that further improvement is necessary.
  • wet methods also called wet processes.
  • the wet method allows film formation at a lower temperature than film formation in a vacuum process, so that damage to the underlying organic layer can be reduced, and there are great expectations for improving luminous efficiency and device life. ing.
  • processability such as solubility in solvents, solution stability, and driving voltage, and it has been found that further improvement techniques are indispensable.
  • the present invention has been made in view of the above-mentioned problems, and its problems are organic electroluminescence having high luminous efficiency, low driving voltage, long life, excellent stability over time, and suitability for production by a wet process.
  • An object of the present invention is to provide a luminescence element, a lighting device and a display device including the organic electroluminescence element.
  • an organic electroluminescence device in which an organic layer composed of at least a plurality of light emitting layers is sandwiched between an anode and a cathode, the light emitting layer is coordinated with a ligand represented by the following general formula (1).
  • a ligand represented by the following general formula (1).
  • An aromatic oligoamine compound containing a blue phosphorescent organometallic complex, having at least one layer between the anode and the light emitting layer, and the layer having four or more nitrogen atoms in the molecule An organic electroluminescence device comprising:
  • ring A and ring B represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring
  • Ar represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, or a non-aromatic hydrocarbon ring.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, or an arylalkyl.
  • the organic electroluminescence device according to 1 above, wherein a fluorine compound is
  • the blue phosphorescent organometallic complex coordinated with the ligand represented by the general formula (1) is a blue phosphorescent organometallic complex represented by the following general formula (2)
  • ring A and ring B represent a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring
  • Ar represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, or a non-aromatic hydrocarbon ring.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, or an arylalkyl.
  • R 1 and R 2 has 2 carbon atoms
  • Ra, Rb and Rc are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, An arylalkyl group, an aryl group, a heteroaryl group, a non-aromatic hydrocarbon ring group, or a non-aromatic heterocyclic group, which may further have a substituent, na and nc represent 1 or 2, and nb Represents an integer of 1 to 4.
  • L ′ is one or more of monoanionic bidentate ligands coordinated to M
  • M represents a transition metal atom having an atomic number of 40 or more and 8-10 groups in the periodic table
  • n' represents an integer of 1 to 3
  • m '+ n' is 2 or 3.
  • 4 The organic electroluminescence device according to any one of 1 to 3, wherein the aromatic oligoamine compound is an aromatic oligoamine salt.
  • R 1 and R 2 in the general formula (1) or the general formula (2) are an alkyl group or a cycloalkyl group having 2 or more carbon atoms.
  • the organic electroluminescent element of description is any one of the above 1 to 4, wherein R 1 and R 2 in the general formula (1) or the general formula (2) are an alkyl group or a cycloalkyl group having 2 or more carbon atoms.
  • the blue phosphorescent organometallic complex represented by the general formula (2) is a blue phosphorescent organometallic complex represented by the following general formula (2-1): 10.
  • Ar represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, Atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group, heteroaryl group, non-aromatic hydrocarbon ring group or non-aromatic heterocyclic group Further, it may have a substituent, and at least one of R 1 and R 2 is an alkyl group or a cycloalkyl group having 2 or more carbon atoms, and Ra, Rb and Rc each independently represent a hydrogen atom, a halogen atom, Atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, ary
  • L ′ is one or more of monoanionic bidentate ligands coordinated to M
  • M represents a transition metal atom having an atomic number of 40 or more and 8-10 groups in the periodic table
  • n' is at least 1
  • m '+ n' is 2 or 3.
  • the blue phosphorescent organometallic complex represented by the general formula (2) is a blue phosphorescent organometallic complex represented by the following general formula (2-2): 10.
  • Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may further have a substituent.
  • R 1 and R 2 are each independently a halogen atom, an alkyl group, an alkoxy group or an aryl group. And at least one of R 1 and R 2 represents an alkyl group having 2 or more carbon atoms, and Ra, Rb and Rc each independently represents a hydrogen atom, a halogen atom, an alkyl group, a silyl group or an aryl group.
  • na and nc represent 1 or 2
  • nb represents an integer of 1 to 4.
  • L ′ is a monoanionic bidentate ligand coordinated to Ir, m ′ is 0 or 1, and n 'Is 2 or 3, and m' + n 'is 3.) 13. 13.
  • the organic electroluminescence device as described in any one of 1 to 12 above, which emits white light.
  • An illumination device comprising the organic electroluminescence element according to any one of 1 to 13 above.
  • a display device comprising the organic electroluminescence element as described in any one of 1 to 13 above.
  • an organic electroluminescence element having high luminous efficiency, low driving voltage, long life, excellent stability over time, and production suitability by a wet process, and an illuminating device and a display including the organic electroluminescence element
  • An apparatus can be provided.
  • FIG. 4 is a schematic diagram of a display unit A.
  • FIG. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.
  • the present inventors have obtained a blue phosphorescent organometallic complex (metal complex dopant) coordinated with a ligand represented by the general formula (1).
  • a blue phosphorescent organometallic complex metal complex dopant
  • the light emitting layer contains high light emission luminance and low driving voltage.
  • the inventors have found that the light emission life can be extended at the same time, and have reached the present invention.
  • the organic EL device of the present invention can provide an organic EL device that is improved in terms of stability over time.
  • Blue phosphorescent organometallic complex coordinated with a ligand represented by the general formula (1) refers to a phosphorescent organometallic complex having an emission maximum wavelength in the range of 440 to 490 nm.
  • examples of the 5-membered or 6-membered aromatic hydrocarbon ring represented by the ring A and the ring B include a benzene ring.
  • examples of the 5-membered or 6-membered aromatic hydrocarbon ring represented by the ring A and the ring B include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, Examples include a pyrimidine ring, a pyrazine ring, a triazine ring, an oxadiazole ring, a triazole ring, an imidazole ring, a pyrazole ring, and a thiazole ring. More preferably, ring B is a benzene ring, and more preferably ring A is a benzene ring.
  • examples of the aromatic hydrocarbon ring of the aromatic hydrocarbon ring group represented by Ar include a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a 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, Examples include a pentaphen ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.
  • examples of the aromatic heterocyclic ring of the aromatic heterocyclic group represented by Ar include a silole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, and a pyrimidine ring.
  • examples of the non-aromatic hydrocarbon ring of the non-aromatic hydrocarbon ring group represented by Ar include a cycloalkane (for example, a cyclopentane ring, a cyclohexane ring, etc.), a cycloalkoxy group (for example, Cyclopentyloxy group, cyclohexyloxy group and the like), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group and the like), cyclohexylaminosulfonyl group, tetrahydronaphthalene ring, 9,10-dihydroanthracene ring, biphenylene ring and the like.
  • a cycloalkane for example, a cyclopentane ring, a cyclohexane ring, etc.
  • a cycloalkoxy group for example, Cyclopentyloxy group,
  • examples of the non-aromatic heterocyclic ring of the non-aromatic heterocyclic group represented by Ar include an epoxy ring, an aziridine ring, a thiirane ring, an oxetane ring, an azetidine ring, a thietane ring, a tetrahydrofuran ring, Dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ⁇ -caprolactone ring, ⁇ -caprolactam ring, piperidine ring, hexahydropyrimazine ring, hexahydropyrimidine ring, piperazine Ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring
  • These groups represented by Ar in the general formula (1) may further have a substituent, and the substituents may be bonded to each other to form a ring.
  • substituents include an alkyl group (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.)
  • a cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • an alkenyl group eg, vinyl group, allyl group, etc.
  • alkynyl group eg, ethynyl group, propargyl group, etc.
  • aromatic hydrocarbon group aromatic hydrocarbon
  • cyclic group aromatic carbocyclic group, aryl group, etc.
  • aromatic carbocyclic group aromatic carbocyclic group, aryl group, etc.
  • aromatic compound A cyclic group for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2 , 3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, benzoxazolyl group, benzoxazolyl group, benzoxazolyl
  • Ar is an aromatic hydrocarbon ring group or an aromatic heterocyclic group, more preferably an aromatic hydrocarbon ring group, and still more preferably a phenyl group.
  • R 1 and R 2 are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, silyl group, arylalkyl group, aryl group , A heteroaryl group, a non-aromatic hydrocarbon ring group or a non-aromatic heterocyclic group, which may further have a substituent, and at least one of R 1 and R 2 is an alkyl having 2 or more carbon atoms Group or a cycloalkyl group.
  • the aryl group and heteroaryl group represented by R 1 and R 2 are the aromatic hydrocarbon ring group and the aromatic heterocyclic group represented by Ar in the general formula (1). And a monovalent group derived from the above.
  • the non-aromatic hydrocarbon ring group and the non-aromatic heterocyclic group represented by R 1 and R 2 are the non-aromatic carbon groups represented by Ar in the general formula (1).
  • R 1 and R 2 are an alkyl group or cycloalkyl group having 2 or more carbon atoms, and at least one of R 1 and R 2 is preferably a branched alkyl group having 3 or more carbon atoms. More preferably, R 1 and R 2 are branched alkyl groups having 3 or more carbon atoms.
  • Ra, Rb and Rc are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a silyl group, an arylalkyl group, an aryl group.
  • the aryl group and heteroaryl group represented by Ra, Rb and Rc include the aromatic hydrocarbon ring group and the aromatic heterocyclic group represented by Ar in the general formula (1). And a monovalent group derived from the above.
  • the non-aromatic hydrocarbon ring group and non-aromatic heterocyclic group represented by Ra, Rb and Rc the non-aromatic carbon represented by Ar in the above-mentioned general formula (1) And monovalent groups derived from a hydrogen ring group and a non-aromatic heterocyclic group.
  • na and nc represent 1 or 2
  • nb represents an integer of 1 to 4.
  • R d ′, R d ′′ and R d ′′ ′′ represent a hydrogen atom or a substituent
  • the substituent represented by R d ′, R d ′′ and R d ′′ ′′ may be represented by the general formula (1)
  • the substituents for the group represented by Ar are exemplified.
  • M represents a transition metal atom having an atomic number of 40 or more and a periodic group of 8 to 10 in the periodic table of elements. Among them, Os, Ir, and Pt are preferable, and Ir is more preferable.
  • n ′ represents an integer of 0 to 2
  • n ′ represents an integer of 1 to 3
  • m ′ + n ′ represents 2 or 3.
  • n ′ is 3 or 2
  • m ′ is 0.
  • the organometallic complex represented by the general formula (2-1) is preferable.
  • the aromatic oligoamine compound used in the present invention is an aromatic amine compound represented by the following general formula (3) and having 4 or more nitrogen atoms in the molecule.
  • Ar 1 and Ar 2 are each independently an arylene group having 6 to 30 nuclear carbon atoms or an aromatic heterocyclic group having 5 to 30 nuclear atoms, and A is a single bond or 6 carbon atoms.
  • B 1 and B 2 represent a hydrogen atom, a fluorine atom, or a cyano group.
  • n1 represents 0 or 1
  • n2 represents an integer of 1 to 1,000, and when n2 is 2 or more, each Ar 1 , Ar 2 , A, B 1 , B 2 may be the same or different.
  • Ar 1 , Ar 2 , A, B 1 and B 2 may have one or more substituents, and may be bonded to each other to form a ring. When forming a ring, it is preferable to form a condensed aromatic ring.
  • the number of nitrogen atoms in the molecule does not include the number of nitrogen atoms contained in the substituents on Ar 1 , Ar 2 , A, B 1 , B 2 .
  • the ends of the molecular chains of OHT-2 to OHT-16 and OHT-22 to OHT-24 in the aromatic oligoamine compound are hydrogen atoms or halogen atoms. Furthermore, the following compound structures can be used as the aromatic oligoamine compound.
  • Aromatic tertiary amine compounds and styrylamine compounds (US Pat. No. 4,127,412, JP-A-53-27033, 54-58445, 54-149634, 54- 64299, 55-79450, 55-144250, 56-119132, 61-295558, 61-98353, 63-295695), pyridine derivatives ( JP-A-2003-282270), porphyrin compounds (see JP-A-63-295695, etc.), aniline copolymers (see JP-A-2-282263, WO08 / 129947, etc.), phenylenediamine Derivatives (US Pat. No. 3,615,404, Japanese Patent Publication No. 51-10105, No. 4) -3712, JP same 47-25336, JP-Sho 54-53435, JP same 54-110536 and JP reference like JP same 54-119925).
  • the fluorine compound contained between the anode and the light emitting layer according to the present invention has a fluorine substituent in the molecule.
  • the present invention is not limited to these.
  • a fluorine-containing polymer in which some or all of the hydrogen atoms in the polymer are substituted with fluorine atoms such as polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride, six And a fluorinated propylene copolymer (abbreviation: FEP), an ethylene / tetrafluoroethylene copolymer (abbreviation: ETFE), and an ethylene / chlorotrifluoroethylene copolymer.
  • fluorine atoms such as polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride, six And a fluorinated propylene copolymer (abbreviation: FEP), an ethylene / tetrafluoroethylene copolymer (abb
  • (2) Represents a compound in which some or all of the replaceable hydrogen atoms in the Bronsted acid are substituted with fluorine atoms, and examples thereof include fluorinated organic acids.
  • examples of the fluorinated organic acid include fluorinated carboxylic acid and fluorinated sulfonic acid.
  • Examples include inorganic acid salts. Specific examples include fluoroborate, fluoroantimonate, and fluorophosphate doors, and more specific compounds include bis (4-methylphenyl) iodonium hexafluorophosphate (FP-2) and the like. .
  • Alcohols in which some or all of the substitutable hydrogen atoms are substituted with fluorine atoms can be mentioned. Specific examples include trifluoroethanol and hexafluoroisopropanol.
  • Anode / light emitting layer / electron transport layer / cathode ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode // hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode Buffer layer / Hole transport layer / Light emitting layer / Electron
  • an organic compound layer including a light emitting layer excluding an anode and a cathode can be used as one light emitting unit, and a plurality of light emitting units can be stacked.
  • the plurality of stacked light emitting units may have a non-light emitting intermediate layer between the light emitting units, and the intermediate layer may further include a charge generation layer.
  • the organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.
  • the light emitting layer according to 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 in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
  • the total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 ⁇ m, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 5 to 100 nm.
  • a light emitting dopant or host compound described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, for example, a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method,
  • the film can be formed by an inkjet method, a printing method, a spray coating method, a curtain coating method, an LB method (including Langmuir-Blodgett method)) and the like.
  • the light emitting layer of the organic EL device of the present invention contains a light emitting dopant (phosphorescent dopant (phosphorescent dopant, also referred to as phosphorescent dopant group) or fluorescent dopant) compound and a light emitting host compound, At least one light-emitting dopant is a blue phosphorescent organometallic complex represented by the aforementioned general formula (1) or (2).
  • Luminescent dopant compound A light-emitting dopant compound (also referred to as a light-emitting dopant) will be described.
  • Fluorescent dopants also referred to as fluorescent compounds
  • phosphorescent dopants also referred to as phosphorescent emitters, phosphorescent compounds, phosphorescent compounds, etc.
  • the luminescent dopant can be used as the luminescent dopant.
  • Phosphorescent dopant also called phosphorescent dopant
  • the phosphorescent dopant according to the present invention will be described.
  • 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 phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • the phosphorescent dopant There are two types of light emission of the phosphorescent dopant in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the luminescent host compound, and this energy is used as the phosphorescent dopant.
  • the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.
  • the light-emitting layer according to the present invention may be used in combination with compounds described in the following patent publications.
  • fluorescent dopant also called fluorescent compound
  • fluorescent dopants include 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 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 host compound has a mass ratio of 20% or more among the compounds contained in the light emitting layer, and a phosphorescence quantum yield of phosphorescence emission is 0 at room temperature (25 ° C.). Defined as less than 1 compound.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • a conventionally known compound may be used in combination with the host compound according to the present invention.
  • the compound that may be used in combination typically has a basic skeleton such as a carbazole derivative, triarylamine derivative, aromatic derivative, nitrogen-containing heterocyclic compound, thiophene derivative, furan derivative, oligoarylene compound, or A carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative represents one in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom). Can be mentioned.
  • Tg glass transition temperature
  • the light emitting host used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (polymerizable light emitting host). Of course, one or more of such compounds may be used.
  • Injection layer hole injection layer (anode buffer layer), electron injection layer (cathode buffer 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.
  • anode buffer layer hole injection layer
  • copper phthalocyanine is used.
  • Representative phthalocyanine buffer layer oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, polymer buffer layer using conductive polymer such as polyaniline (emeraldine) or polythiophene, tris (2-phenylpyridine) )
  • Orthometalated complex layers represented by iridium complexes and the like.
  • 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, alkali metal compound buffer layer typified by lithium fluoride, sodium fluoride and potassium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, and aluminum oxide And an oxide buffer layer.
  • the buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m, although it depends on the material.
  • the materials used for the anode buffer layer and the cathode buffer layer can be used in combination with other materials.
  • they can be mixed in the hole transport layer or the electron transport layer.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • the above-mentioned aromatic oligoamine compound is contained in at least one of the plurality of organic layers, and the layer containing the aromatic oligoamine compound is preferably a hole transport layer.
  • the hole transport layer an aromatic oligoamine compound and a commonly known hole transport material can be used in combination.
  • 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. It is particularly preferable to use 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
  • 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.
  • the polymer has a weight average molecular weight having 4 or more nitrogen atoms, it corresponds to the aromatic oligoamine compound of the present invention.
  • inorganic compounds such as p-type-Si and p-type-SiC can be used as the hole injection material and the hole transport material.
  • cyclometalated complexes and orthometalated complexes such as copper phthalocyanine and tris (2-phenylpyridine) iridium complex can also be used as the hole transport material.
  • JP-A-11-251067 J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. 139
  • so-called p-type hole transport materials can also be used.
  • these materials are preferably used because a light-emitting element with higher 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 usually in the range of 5 nm to 5 ⁇ m, preferably in the range of 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. 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 with a single layer or a plurality of layers.
  • An electron transport material (including a hole blocking material and an electron injection material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • electron transport materials examples include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, And azacarbazole derivatives including carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives, and the like.
  • heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, And azacarbazole derivatives including carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives
  • an azacarbazole derivative refers to a compound in which one or more carbon atoms constituting the carbazole ring are replaced with nitrogen atoms.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.
  • 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 in which the terminal is substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material.
  • inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.
  • the thickness of the electron transport layer is not particularly limited, but is usually in the range of 5 to 5000 nm, preferably in the range of 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials, or may have a stacked structure in which a plurality of layers are stacked.
  • an electron transport layer having a high n property 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.
  • ⁇ Blocking layer hole blocking layer, electron blocking layer>
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the above-described configuration of the electron transport layer can be used as a hole blocking layer according to the present invention, if necessary.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the hole blocking layer contains carbazole derivatives, azacarbazole derivatives (where azacarbazole derivatives are those in which one or more carbon atoms constituting the carbazole ring are replaced by nitrogen atoms), pyridine derivatives, and the like. It is preferable to contain a nitrogen compound.
  • the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers.
  • 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
  • the ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.
  • Gaussian 98 Gaussian 98, Revision A.11.4, MJ Frisch, et al., Gaussian, Inc., Pittsburgh PA, 2002
  • a value eV unit converted value
  • This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
  • the above-described structure of the hole transport layer can be used as an electron blocking layer as necessary.
  • the film thicknesses of the hole blocking layer and the electron blocking layer according to the present invention are preferably in the range of 3 to 100 nm, and more preferably in the range of 3 to 30 nm.
  • 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.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • the anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, 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 be greater than 10%
  • the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness is usually selected within the range of 10 to 1000 nm, preferably within the range of 10 to 200 nm.
  • cathode 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 to 5 ⁇ m, preferably in the range of 50 to 200 nm.
  • the emission luminance is improved, which is convenient.
  • a transparent or translucent cathode can be manufactured by forming the above metal on the cathode with a film thickness in the range of 1 to 20 nm and then forming the conductive transparent material mentioned in the description of the anode thereon.
  • an element in which both the anode and the cathode are transmissive can be manufactured.
  • 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. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent.
  • the transparent support substrate that can be used include glass, quartz, and a transparent resin film.
  • a particularly preferable support 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 (TAC), cellulose acetate butyrate, and cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, 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 (
  • the surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • Relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / (m 2 ⁇ 24 h) or less, and oxygen measured by a method according to JIS K 7126-1987.
  • a high barrier film having a permeability of 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ MPa) or less and a water vapor permeability of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material for forming the barrier 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 can be used.
  • the method for forming the barrier film is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or 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, ceramic substrates, and the like.
  • the emission efficiency (external extraction quantum efficiency) of the organic EL device of the present invention 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.
  • 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.
  • a thin film made of a desired electrode material for example, an anode material, is formed on a suitable substrate so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 10 to 200 nm, thereby producing an anode.
  • a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, or a cathode buffer layer, which is an element material, is formed thereon.
  • the cathode and the electron transport layer adjacent to the cathode are applied and formed by a wet method.
  • Wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but precise thin films can be formed.
  • a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable. Different film forming methods may be applied for each layer.
  • 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.
  • 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 DMF and DMSO
  • a dispersion method it can be dispersed by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.
  • a thin film made of a cathode material is formed thereon so as to have a thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a desired organic EL device can be obtained by providing a cathode. .
  • the cathode, cathode buffer layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in the reverse order.
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage in the range of 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • the production of the organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.
  • ⁇ Sealing> As a sealing means used for this invention, the method of adhere
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like.
  • 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, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the element can be thinned.
  • the polymer film has an oxygen permeability of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ MPa) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992.
  • the measured water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat
  • hot melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
  • the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • the method for forming these films is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, 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, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil
  • a vacuum is also possible.
  • a hygroscopic compound can also be enclosed inside.
  • hygroscopic compound examples 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.
  • 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.
  • sulfates, metal halides and perchloric acids are preferably anhydrous salts.
  • a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film.
  • the 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.
  • An organic EL element emits light inside a layer having a refractive index higher than that of air (with a refractive index within a range of 1.7 to 2.1), and light of about 15% to 20% of light generated in the light emitting layer. It is generally said that it can only be taken out. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light undergoes total reflection between the light and the light, and the light is guided through the transparent electrode or the light emitting layer.
  • a method of improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate and preventing total reflection at the transparent substrate and the air interface (US Pat. No. 4,774,435), A method for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No.
  • these methods can be used in combination with the organic EL device of the present invention.
  • a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, a transparent electrode A method of forming a diffraction grating between any of the layers 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 in the range of 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.
  • This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction.
  • Bragg diffraction such as first-order diffraction and second-order diffraction.
  • light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode). I want to take it out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any interlayer or medium (in the transparent substrate or in 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 in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface.
  • a specific direction for example, the device light emitting surface.
  • a quadrangular pyramid having a side of 30 ⁇ m and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably within a range of 10 to 100 ⁇ m. If one side is 10 ⁇ m or more, the screen color does not change, and if it is 100 ⁇ m or less, the demand for thinning can be satisfied.
  • the condensing sheet it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.
  • the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the 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, It can use effectively for the use as a backlight of a liquid crystal display device, and an illumination light source especially.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation.
  • 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 Optics Co., Ltd.) is applied to the CIE chromaticity coordinates.
  • the display device of the present invention comprises the organic EL element of the present invention.
  • the display device of the present invention may be single color or multicolor, but here, the multicolor display device will be described.
  • a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by a vapor deposition method, a cast method, a spin coat method, an inkjet method, a printing method, or the like.
  • the method is not limited, but is preferably a vapor deposition method, an inkjet method, a spin coating method, or a printing method.
  • the configuration of the organic EL element included in the display device is selected from the above-described configuration examples of the organic EL element as necessary.
  • the manufacturing method of an organic EL element is as having shown in the one aspect
  • a DC voltage When a DC voltage is applied to the obtained multicolor display device, light emission can be observed by applying a voltage in the range of 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc.
  • the present invention is not limited to these examples.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
  • the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal.
  • the image information is sequentially emitted to scan the image and display the image information on the display unit A.
  • FIG. 2 is a schematic diagram of the display unit A.
  • the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on the substrate.
  • the main members of the display unit A will be described below.
  • the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
  • the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)
  • the pixel 3 When the scanning signal is applied from the scanning line 5, the pixel 3 receives the image data signal from the data line 6 and emits light according to the received image data.
  • a full color display can be achieved by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
  • FIG. 3 is a schematic diagram of a pixel.
  • the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5
  • the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on.
  • the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues.
  • the driving transistor 12 When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
  • the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. It is carried out.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good.
  • the potential of the capacitor 13 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 4 is a schematic view of a passive matrix display device.
  • a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
  • the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.
  • the lighting device of the present invention has the said organic EL element.
  • the organic EL element of the present invention may be used as an organic EL element having a resonator structure.
  • the purpose of use of the organic EL element having such a resonator structure is as follows.
  • the light source of a machine, the light source of an optical communication processing machine, the light source of an optical sensor, etc. are mentioned, However It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • the organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device.
  • a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc.
  • the thing containing the light emission maximum wavelength may be used.
  • a combination of light emitting materials for obtaining a plurality of light emission colors is a combination of a plurality of materials that emit light by phosphorescence, a light emitting material that emits light by phosphorescence, and light emitted from the light emitting material as excitation light. Any combination with a dye material may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light emitting dopants may be mixed.
  • an electrode film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, etc. Will also improve.
  • the elements themselves are luminescent white.
  • luminescent material used for a light emitting layer For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.
  • CF color filter
  • the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 ⁇ m is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material.
  • LC0629B is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and an illumination device as shown in FIGS. Can be formed.
  • FIG. 5 shows a schematic view of a lighting device, and the organic EL element 101 of the present invention is covered with a sealing substrate 110 and a glass cover 102 (note that the sealing operation with the glass cover is performed by the organic EL element 101).
  • a sealing substrate 110 and a glass cover 102 note that the sealing operation with the glass cover is performed by the organic EL element 101.
  • FIG. 6 shows a cross-sectional view of the lighting device.
  • 102 is a glass cover
  • 105 is a cathode
  • 106 is an organic EL layer
  • 107 is a glass substrate with a transparent electrode
  • 110 is a sealing substrate
  • 111 is an adhesive. Indicates.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • Example 1 Production of HOD (Hall Only Device) 1-1 >> A transparent support substrate provided with an ITO transparent electrode by patterning an ITO (indium tin oxide) 100 nm film-formed substrate (NH-Techno Glass NA-45) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode. After production, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. On this transparent support substrate, H.P. C. A solution obtained by diluting Stark PEDOT-PSS (CLEVIOS P VP AI 4083) to 70% with pure water was formed by spin coating, then dried at 200 ° C. for 1 hour, and a first hole having a thickness of 30 nm was formed. A transport layer was provided.
  • ITO indium tin oxide
  • NH-Techno Glass NA-45 NH-Techno Glass NA-45
  • each material described later was packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate provided with the first hole transport layer described above in a vacuum vapor deposition apparatus.
  • ⁇ -NPD was deposited to a thickness of 20 nm at a deposition rate of 0.1 nm / second to provide a second hole transport layer.
  • HS-2 was co-deposited at a deposition rate of 0.1 nm / second and D-26 was deposited at a deposition rate of 0.02 nm / second, and 30 nm was deposited to provide a light emitting layer.
  • ⁇ -NPD was deposited to a thickness of 20 nm at a deposition rate of 0.1 nm / second to form an electron blocking layer, and then 110 nm of aluminum was deposited as a cathode to prepare HOD1-1.
  • HOD Hap Only Device
  • a transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • H.P. C A solution obtained by diluting Stark PEDOT-PSS (CLEVIOS P VP AI 4083) to 70% with pure water was formed by spin coating, then dried at 200 ° C. for 1 hour, and a first hole having a thickness of 30 nm was formed.
  • a transport layer was provided.
  • a 0.5 mass% OHT-1 dichlorobenzene solution was prepared, and a film was formed by a spin coating method (600 rpm, 30 seconds). Then, it dried at 100 degreeC for 30 minutes in nitrogen atmosphere, and provided the 2nd hole transport layer with a film thickness of 20 nm.
  • the glass substrate provided with the second hole transport layer is set in a vacuum deposition apparatus, and a light emitting layer, an electron blocking layer, and a cathode are formed by a vacuum deposition method in the same manner as the production of HOD1-1. Was made.
  • HOD1-2 to 1-3 and 1-5 to 1-31 Production of HOD1-2 to 1-3 and 1-5 to 1-31 >> In the preparation of HOD1-1, HOD1-2 to 1-3 were similarly performed except that the hole transport material of the second hole transport layer, the host compound and the dopant compound of the light emitting layer were changed as shown in Table 1. Was made. Further, in HOD1-4, HOD1-5 to 1-31 were similarly performed except that the hole transport material of the second hole transport layer, the host compound and the dopant compound of the light emitting layer were changed as shown in Table 1. Was made.
  • the above illumination device was produced, and the external extraction quantum efficiency (%) when a constant current of 2.5 mA / cm 2 was applied at 23 ° C. in a dry nitrogen gas atmosphere. ) was measured, and the luminous efficiency was expressed as a relative value with the external extraction quantum efficiency of the organic EL element 1-1 being 100.
  • a spectral radiance meter CS-1000 manufactured by Konica Minolta Optics was used.
  • Table 3 shows the evaluation results.
  • HOD1-22 and 1-23 and organic EL elements 1-22 and 1-23 were evaluated in the same manner as HOD1-1, and the relative value with the current density amount of HOD1-22 being 100 was expressed as the current amount.
  • the organic EL elements 1-22 and 1-23 were evaluated in the same manner as the organic EL element 1-1, and the luminous efficiency was expressed as a relative value with the external extraction quantum efficiency of the organic EL element 1-22 being 100. Table 4 shows the evaluation results.
  • Evaluation of HOD1-24 and 1-25 and organic EL elements 1-24 and 1-25 was carried out in the same manner as HOD1-1, and the relative value with the current density amount of HOD1-24 as 100 was expressed as a current amount.
  • the organic EL elements 1-24 and 1-25 were evaluated in the same manner as the organic EL element 1-1, and the light emission efficiency was expressed as a relative value where the external extraction quantum efficiency of the organic EL element 1-24 was 100. The evaluation results are shown in Table 5.
  • HOD1-26 and 1-27 and Organic EL Elements 1-26 and 1-27 were evaluated in the same manner as HOD1-1, and a relative value with the current density amount of HOD1-26 as 100 was expressed as a current amount.
  • the organic EL elements 1-26 and 1-27 were evaluated in the same manner as the organic EL element 1-1, and the light emission efficiency was expressed as a relative value where the external extraction quantum efficiency of the organic EL element 1-26 was 100. The evaluation results are shown in Table 6.
  • HOD1-28 and 1-29 and Organic EL Elements 1-28 and 1-29 were evaluated in the same manner as HOD1-1, and the relative value with the current density amount of HOD1-28 as 100 was expressed as a current amount.
  • the organic EL elements 1-28 and 1-29 were evaluated in the same manner as the organic EL element 1-1, and the light emission efficiency was expressed as a relative value where the external extraction quantum efficiency of the organic EL element 1-28 was 100. Table 7 shows the evaluation results.
  • HOD1-30 and 1-31 were evaluated in the same manner as HOD1-1, and a relative value with the current density amount of HOD1-30 as 100 was expressed as a current amount.
  • the organic EL elements 1-30 and 1-31 were evaluated in the same manner as the organic EL element 1-1, and the light emission efficiency was expressed as a relative value where the external extraction quantum efficiency of the organic EL element 1-30 was 100. The evaluation results are shown in Table 8.
  • the light emitting layer contains a blue phosphorescent organometallic complex (blue phosphorescent dopant) coordinated with a ligand represented by the general formula (1), and the anode and the light emitting layer HOD (Hole Only Device) containing an aromatic oligoamine compound having 4 or more nitrogen atoms in the molecule in the second hole transport layer, which is at least one layer between, has a clear improvement in carrier injection property. Is recognized.
  • the organic EL elements 1-1 to 1-14 which are organic EL elements using the conventional blue phosphorescent dopants D-26 and D-46, the effect of improving the luminous efficiency was not recognized. This is because the hole transport capability of the dopant itself is higher than that of the blue phosphorescent organometallic complex coordinated by the ligand represented by the general formula (1) of the present invention, and thus the carrier density and charge This is probably because the impact of improved transportability was relatively small. On the other hand, when the blue phosphorescent organometallic complex of the present invention is used in the light emitting layer, the effect expected by the present invention is apparent.
  • Example 2 Preparation of organic EL elements 2-1 to 2-4 >>
  • Organic EL elements 2-1 to 2-4 were produced in the same manner except that ⁇ 26 was changed as shown in Table 9.
  • ⁇ Luminescent life> When driving at a constant current of 2.5 mA / cm 2 in a dry nitrogen gas atmosphere at 23 ° C., the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured. Is expressed as a relative value with the lifetime of light emission of the organic EL element 2-1 being 100.
  • a spectral radiance meter CS-1000 manufactured by Konica Minolta Optics
  • Table 13 shows the evaluation results.
  • Table 14 shows the evaluation results.
  • Table 15 shows the evaluation results.
  • Table 16 shows the evaluation results.
  • the light-emitting layer contains a blue phosphorescent organometallic complex coordinated with the ligand represented by the general formula (1), and the second positive electrode located between the anode and the light-emitting layer.
  • the organic EL device containing an aromatic triarylamine compound as an aromatic oligoamine compound having a pore transport layer having 4 or more nitrogen atoms in the molecule has a low driving voltage and an improved emission lifetime. The effect is obvious. Further, it is clear that the change in driving voltage is further suppressed by containing a fluorine compound such as FP-1.
  • Example 3 Preparation of organic EL elements 3-1 to 3-4 >>
  • Organic EL elements 3-1 to 3-4 were produced in the same manner except that ⁇ 26 was changed as shown in Table 17.
  • the second positive electrode containing the blue phosphorescent organometallic complex coordinated with the ligand represented by the general formula (1) and located between the anode and the light emitting layer is shown.
  • the organic EL device containing OHT-12 having an average number of repetitions of 28, which is a triarylamine polymer, as an aromatic oligoamine compound having 4 or more nitrogen atoms in the molecule in the pore transport layer, is driven in any case.
  • the emission lifetime is improved and the effect is clear.
  • the drive voltage change is further suppressed by containing a fluorine compound such as FP-1.
  • Example 4 Preparation of organic EL elements 4-1 to 4-4 >>
  • Organic EL elements 4-1 to 4-4 were produced in the same manner except that ⁇ 26 was changed as shown in Table 25.
  • the first positive electrode containing the blue phosphorescent organometallic complex coordinated with the ligand represented by the general formula (1) and located between the anode and the light emitting layer is shown.
  • An organic EL device containing OHT-3 having an average number of repetitions of 16 as an aromatic oligoamine compound having 4 or more nitrogen atoms in the molecule in the hole transport layer or the second hole transport layer is driven in any case.
  • the voltage is low and the light emission lifetime is improved, and the effect is clear.
  • the change in driving voltage is further suppressed by containing the fluorine compound such as FP-1 or FP-2 in the first hole transport layer or the second hole transport layer. .
  • Example 5 Preparation of organic EL element 5-1 >> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • 10 mg of OHT-4 was dissolved in 2 ml of toluene, and a film was formed by spin coating (1000 rpm, 30 seconds). After the film formation, the crosslinking reaction was advanced by heating in the atmosphere at 230 ° C. for 3 hours to form a crosslinked aromatic triarylamine network polymer (film thickness 30 nm, first hole transport layer).
  • each material described later was packed in a molybdenum or tungsten vapor deposition boat, and set together with the glass substrate provided with the first hole transport layer described above in a vacuum vapor deposition apparatus.
  • OHT-3 was deposited to a thickness of 20 nm at a deposition rate of 0.1 nm / second to provide a second hole transport layer.
  • each material to be described later was packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate provided with the second hole transport layer described above in a vacuum vapor deposition apparatus.
  • HS-2 was co-deposited at a deposition rate of 0.1 nm / sec and D-46 was co-deposited at a deposition rate of 0.02 nm / sec.
  • Alq 3 was deposited at 30 nm at a deposition rate of 0.1 nm / second, 1 nm of lithium fluoride was deposited as an electron transport layer and an electron injection layer, and 110 nm of aluminum was deposited as a cathode, thereby producing an organic EL device 5-1.
  • ⁇ Preparation of organic EL element 5-3 A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • a 0.5 mass% OHT-3 toluene solution was prepared, and a film was formed by a spin coating method (1000 rpm, 30 seconds). Then, it dried at 100 degreeC for 30 minute (s) in nitrogen atmosphere, and provided the 2nd hole transport layer with a film thickness of 20 nm. Furthermore, each material to be described later was packed in a molybdenum or tungsten vapor deposition boat and set together with the glass substrate provided with the second hole transport layer described above in a vacuum vapor deposition apparatus.
  • HS-2 was co-deposited at a deposition rate of 0.1 nm / sec and DP-5 was co-deposited at a deposition rate of 0.02 nm / sec.
  • Alq 3 was deposited at a deposition rate of 0.1 nm / second to 30 nm, lithium fluoride was deposited at 1 nm as an electron transport layer and an electron injection layer, and aluminum was deposited at 110 nm as a cathode to produce an organic EL device 5-3.
  • Organic EL elements 5-5 to 5-8 are shown in Table 34.
  • Organic EL elements 5-5 to 5-8 were produced in the same manner except that the changes were made as described above.
  • the first light emitting layer contains a blue phosphorescent organometallic complex coordinated with a ligand represented by the general formula (1), and is located between the anode and the light emitting layer.
  • the hole transport layer or the second hole transport layer contains OHT-4 or OHT-3 having an average number of repeats of 19 as a crosslinked aromatic triarylamine network polymer having 4 or more nitrogen atoms in the molecule
  • the driving voltage is low and the light emission life is long.
  • an organic EL device containing a fluorine-containing compound (FP-2) as a P-type dopant in the first hole transport layer and an organic EL device containing a fluorine compound (FP-1) in the second hole transport layer In either case, the driving voltage is low and the light emission lifetime is improved, and the effect is clear. Further, it is clear that the change in driving voltage is further suppressed by containing a fluorine compound such as FP-1 or FP-2.
  • Example 6 Preparation of organic EL elements 6-1 to 6-4 >> Table 41 shows the first hole transport layer material OHT-4, the second hole transport layer material OHT-3, and the dopant compound D-46 of the light emitting layer in the production of the organic EL element 5-1 of Example 5.
  • Organic EL elements 6-1 to 6-4 were produced in the same manner except for the above changes.
  • the first positive electrode containing the blue phosphorescent organometallic complex in which the ligand represented by the general formula (1) is coordinated and between the anode and the light emitting layer is shown.
  • Contains nitrogen-containing condensed heterocyclic derivatives (OHT-18, OHT-19) or OHT-3, which are aromatic oligoamine compounds having 4 or more nitrogen atoms in the molecule in the hole transport layer or the second hole transport layer In any case, the driving voltage is low and the emission lifetime is improved in any case, and the effect is clear. Furthermore, it is clear that the drive voltage change is further suppressed by containing a fluorine compound such as FP-1.
  • Example 7 Preparation of organic EL elements 7-1 to 7-4 >> Table 49 shows the first hole transport layer material OHT-4, the second hole transport layer material OHT-3, and the dopant compound D-46 of the light emitting layer in the manufacture of the organic EL element 5-1 of Example 5.
  • Organic EL elements 7-1 to 7-4 were produced in the same manner except for the above changes.
  • Organic EL elements 7-5 to 7-8 were fabricated in the same manner except that the above was changed as shown in Table 50.
  • the first positive electrode containing the blue phosphorescent organometallic complex coordinated with the ligand represented by the general formula (1) and between the anode and the light emitting layer is shown.
  • Organic containing OHT-23 or OHT-26 with an average repeating number of 10 as a carbazole derivative as an aromatic oligoamine compound having four or more nitrogen atoms in the molecule in the hole transport layer or the second hole transport layer In any case, the EL device has a low driving voltage and an improved light emission lifetime, and the effect is clear. Further, it is clear that the change in driving voltage is further suppressed by containing a fluorine compound such as FP-1 or FP-2.
  • Example 8 Provide of full-color display device> (Blue light emitting organic EL device) The organic EL element 2-3 produced in Example 2 was used.
  • FIG. 2 shows only a schematic view of the display portion A of the produced display device.
  • the display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (a light emitting color is a red region pixel, a green region pixel, Blue region pixels, etc.).
  • a light emitting color is a red region pixel, a green region pixel, Blue region pixels, etc.
  • Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material.
  • the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern, and are connected to the pixels 3 at the orthogonal positions (details are not shown).
  • the plurality of pixels 3 are driven by an active matrix system in which an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor are provided.
  • an image data signal is received from the data line 6, and light is emitted in accordance with the received image data.
  • a full color display device was produced by juxtaposing the red, green, and blue pixels 3 appropriately.
  • the produced organic EL element showed blue, green, and red light emission by applying a voltage to each electrode, and was found to be usable as a full-color display device.
  • Example 9 Similarly, except that DP-1 of the organic EL element 2-3 produced in Example 2 was changed to a ternary mixture of DP-1, D-3, and D-10, a white light-emitting organic EL element 2- 3W was produced. The obtained organic EL element 2-3W was covered with a glass case on the non-light emitting surface to obtain a lighting device.
  • the illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.
  • a blue light emitting organic EL element As the organic EL element, a blue light emitting organic EL element, a green light emitting organic EL element, and a red light emitting organic EL element can be arranged in a pattern to produce a full color display device. Further, in addition to the blue phosphorescent organic metal complex, a white light emitting organic EL element can be produced by containing a combination of dopants having different emission colors. It can be used as a backlight for display devices.

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Abstract

La présente invention se rapporte à un élément électroluminescent organique qui présente une longue durée de vie, une faible tension d'entraînement et une efficacité d'émission élevée, montre une excellente stabilité temporelle et convient pour une production à l'aide d'un procédé par voie humide. La présente invention se rapporte également à un dispositif d'éclairage et à un dispositif d'affichage pourvus dudit élément électroluminescent organique. Cet élément électroluminescent organique dans lequel une pluralité de couches organiques qui comprennent au moins une couche électroluminescente, sont intercalées entre une électrode positive et une électrode négative, est caractérisé en ce que la couche électroluminescente contient un complexe métallique organique électroluminescent phosphorescent, un ligand représenté par la formule générale (1) étant coordonné, au moins une couche étant disposée entre l'électrode positive et la couche électroluminescente et ladite couche contenant un composé oligoamine aromatique qui comprend au moins quatre atomes d'azote dans une molécule.
PCT/JP2012/071377 2011-08-26 2012-08-24 Élément électroluminescent organique, dispositif d'éclairage et dispositif d'affichage WO2013031662A1 (fr)

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