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WO2006100888A1 - Material for organic el device, organic el device, display and illuminating device - Google Patents

Material for organic el device, organic el device, display and illuminating device Download PDF

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Publication number
WO2006100888A1
WO2006100888A1 PCT/JP2006/304062 JP2006304062W WO2006100888A1 WO 2006100888 A1 WO2006100888 A1 WO 2006100888A1 JP 2006304062 W JP2006304062 W JP 2006304062W WO 2006100888 A1 WO2006100888 A1 WO 2006100888A1
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Prior art keywords
group
organic
ring
layer
light
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PCT/JP2006/304062
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French (fr)
Japanese (ja)
Inventor
Noboru Sekine
Tomohiro Oshiyama
Masato Nishizeki
Eisaku Katoh
Original Assignee
Konica Minolta Holdings, Inc.
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Priority to JP2007509174A priority Critical patent/JPWO2006100888A1/en
Publication of WO2006100888A1 publication Critical patent/WO2006100888A1/en

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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • 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
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    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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Definitions

  • the present invention relates to an organic EL element material, and an organic EL element, a display device, and an illumination device using the same.
  • ELD EL display
  • ELD components include inorganic EL elements and organic EL elements.
  • Inorganic EL elements have been used as planar light sources, but a high AC voltage is required to drive the light emitting elements.
  • An organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the light-emitting layer and recombined to generate excitons.
  • it is a thin-film, complete solid-state device with a wide viewing angle and high visibility, so it is attracting attention from the viewpoint of space saving and portability.
  • an organic EL device having an organic light emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of a phosphor is doped therein for example, Japanese Patent Laid-Open No. 63-264692
  • 8 An organic EL device having an organic light emitting layer in which a hydroxyquinoline aluminum complex is a host compound and doped with a quinatalidone dye is known (for example, JP-A-3-255190).
  • the upper limit of internal quantum efficiency is 100 when excited triplets are used.
  • the luminous efficiency is S4 times in principle compared to the case of singlet excitation, and there is a possibility of obtaining almost the same performance as a cold cathode tube. .
  • bidentate ligands and derivatives thereof which are mainly bonded to the central metal through two coordination atoms, such as phenylpyridine, have been used as preferred examples of orthometalated complexes.
  • the light emission brightness and light emission efficiency when these are used as light emitting elements are greatly improved compared to conventional organic EL elements because the emitted light is derived from phosphorescence. It is known that the lifetime is lower than that of conventional organic EL devices.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-181617
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-247859
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-332291
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-332292
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-338588
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-226495
  • Patent Document 7 Japanese Patent Laid-Open No. 2002-234894
  • Patent Document 8 Japanese Unexamined Patent Publication No. 2003-73355
  • Patent Document 9 W ⁇ 2004Z39781 Non-Fret
  • Non-Patent Document 1 Inorganic Chemistry, No. 43, No. 21, pp. 6513-6515 (2004)
  • Non-Patent Document 2 IDW 2004, pages 1425-1426 Disclosure of the invention
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a material for an organic EL element having a high synthesis yield and a high light emission efficiency and a long emission lifetime, an organic EL element using the same, and It is to provide a display device and a lighting device using an EL element.
  • M is a metal atom
  • X, Y, and ⁇ are constituents of ring ⁇ , ring ⁇ , and ring C, respectively, and are a carbon atom or a nitrogen atom, and at least one is a carbon atom.
  • the ring ⁇ , ring ⁇ , and ring C are aromatic hydrocarbon rings, aromatic heterocycles, or heterocycles R to R are substituents, and nl, n2, and n3 are 0 or a positive integer L is auxiliary
  • At least one of the substituents R of the ring B includes a ring A and a ring C;
  • VDW van der Waals volume
  • An organic EL device comprising the organic EL device material according to any one of the above (1) and (2) in one of the constituent layers forming the organic EL device. EL element.
  • the R represents a hydrogen atom or a substituent.
  • a display device comprising the organic EL element according to the item (3) to (5), and the displacement force described in item 4.
  • a lighting device comprising the organic EL element according to item (3) to (5), wherein the organic EL element according to item 1 is provided.
  • At least one of ring A and ring C is a monocyclic nitrogen-containing 5-membered ring, described in (1) or (2) above Material for organic EL devices.
  • At least one of the ring A and the ring C is a heterocyclic ring bonded to the ring B with a nitrogen atom, (1), (2) And (8) Any of the forces described in item 1 for organic EL device materials.
  • Y is a carbon atom
  • the auxiliary ligand L is bonded to the metal M by a carbon atom, a nitrogen atom, or a sulfur atom.
  • the material for an organic EL device according to any one of (1), (2), (8) and (9).
  • Y is a nitrogen atom
  • the auxiliary ligand L is bonded to the metal M through a nitrogen atom, an oxygen atom, or a sulfur atom.
  • the auxiliary ligand L is a dione bonded to the metal M by a nitrogen atom, (1), (2), (8) The material for organic EL elements according to 1 above, wherein any one of (9) and (11) is used.
  • At least one of the auxiliary ligands L is a bidentate ligand.
  • the metal M is Ir, Pt, Rh, Pd, Os or Au, (1), (2) and (8) to (13 The organic EL element material described in item 1 above.
  • the metal complex represented by the general formula (1) is a part of a main chain or a side chain of the polymer (1), (2) and (8) Any of the powers of ⁇ (: 15)
  • a material for an organic EL element having a high synthesis yield and luminous efficiency and a long emission lifetime an organic EL element using the material, a display device using the organic EL element, and a lighting device. That power S.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements.
  • FIG. 2 is a schematic diagram of display unit A.
  • FIG. 3 is an equivalent circuit diagram of a drive circuit constituting a pixel.
  • FIG. 4 is a schematic diagram of a passive matrix display device.
  • FIG. 5 is a schematic diagram of a sealing structure of an organic EL element.
  • FIG. 6 is a schematic diagram of a lighting device including an organic EL element.
  • the organic EL device material of the present invention has a tridentate ligand having three rings, and each ring is directly bonded. Such tridentate ligands have more bonds with the central metal than bidentate ligands such as phenylpyridine, which have been used so far, making it easy to transfer energy between the metal and ligand. Thus, highly efficient light emission is possible, and more stabilization energy associated with complex formation can be obtained.
  • the organic EL device material described in any one of (1) or (2) or (8) to (16) is preferably used. As a result, it was possible to obtain an organic EL device having a high emission efficiency and a long emission lifetime.
  • the tridentate ligand according to the present invention has three ring structures of ring A, ring B, and ring C, and has a substituent that suppresses bidentate coordination.
  • a substituent enables the metal to selectively form a tridentate coordination with a ligand, and a desired metal complex can be obtained with high selectivity.
  • the bonding position and bulkiness of the substituent are not particularly limited as long as bidentate coordination can be suppressed, but in particular, ring B has a substituent of van der Waals volume (VDW) force S45A 3 or more.
  • VDW van der Waals volume
  • it is preferred instrument 45 ⁇ 250A 3 is a more preferable device 45: it forces S more preferably 150A is three.
  • a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group and a silyl group are more preferred, and an alkyl group, a cycloalkyl group, an alkenyl group and a silyl group are more preferred.
  • the tridentate ligand in the present invention has three ring structures, and these are aromatic hydrocarbon rings, aromatic heterocyclic rings or heterocyclic rings, which are 5-membered or 6-membered rings. Is preferred.
  • ring B preferably has a 6-membered ring structure.
  • at least one of ring A or ring C is preferably a nitrogen-containing 5-membered ring structure or a heterocyclic ring bonded to ring B with a nitrogen atom.
  • the tridentate ligand has coordinating atoms X, Y, and ⁇ in ring A, ring B, and ring C, respectively. It became clear that the selection of the auxiliary ligand L has a great influence on the stability and emission characteristics of organic EL devices.
  • the auxiliary ligand L when the ring ⁇ is a carbon atom, the auxiliary ligand L is preferably bonded to the metal ⁇ ⁇ ⁇ ⁇ by a carbon atom, a nitrogen atom, or a sulfur atom.
  • the auxiliary ligand L is preferably bonded to the metal cage by a nitrogen atom, oxygen atom, or sulfur atom.
  • the auxiliary ligand L is preferably an anion bonded to the metal cage with a nitrogen atom.
  • the auxiliary ligand L may be one kind or more, but preferably satisfies the coordination number of the central metal. For this reason, the auxiliary ligand may be monodentate, bidentate or tridentate, or a combination thereof. However, if there are multiple vacant coordination sites, the chelating effect In order to obtain stabilization, it is preferable to use a double-dentate ligand. Further, it is more preferable that the material for the organic EL element has a counter ion but is neutral as a whole.
  • the central metal is not particularly limited as long as it can emit phosphorescence, but is preferably a metal included in Group 8 to 11 in the periodic table: Ir, Pt, Pd, Rh, Pt, Pd or Au is more preferred, with Os or Au being more preferred.
  • the method for producing the organic EL device is not particularly limited, but the metal complex in the present invention, which is preferably wet, is preferably a main chain or a part of a side chain of the polymer chain.
  • the material for an organic EL device of the present invention is preferably used for a light emitting layer among the constituent layers of the organic EL device. It is preferable to be used as a dopant in the light emitting layer for further highly efficient light emission. At this time, by combining with the materials that make up the other organic layers, such as the electron transport layer used, the hole transport layer, and the light-emitting host, it is possible to emit light with higher brightness and higher efficiency, and to further increase the lifetime of the organic EL device Is possible. From this point of view, it is preferable to use the general formula (2) as a light emitting host and / or hole blocking material that preferably uses the compound represented by the general formula (2) in at least one of the organic layers. preferable.
  • the metal complex having a partial structure represented by the general formula (1) of the present invention (hereinafter also referred to as a metal complex represented by the general formula (1)) will be described.
  • the present inventors have replaced a bidentate ligand that has been studied in various fields so far with a metal complex using a tridentate ligand represented by the general formula (1). By using this, it is possible to provide materials for organic EL devices that have a high synthesis yield and light emission efficiency, and that have a significantly improved light emission lifetime. It was.
  • the tridentate ligand in the present invention has three ring structures of ring A, ring B, and ring C directly connected by a carbon atom.
  • ring B has a van der Waals volume (VDW) of 45 A. It preferably has 3 or more substituents. Such bulky substituents allow the metal to selectively tridentate with the ligand and prevent the formation of undesirable bidentate complexes.
  • VDW van der Waals volume
  • VDW Dimension D CD C volume
  • VDW van der Waals
  • Ring A, ring B, and ring C are aromatic hydrocarbon rings, aromatic heterocycles, or heterocycles.
  • the aromatic hydrocarbon rings constituting Ring A, Ring B, and Ring C include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, talycene ring, naphthacene ring, triphenyl ring.
  • the aromatic heterocyclic ring constituting Ring A, Ring B, and Ring C includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole ring.
  • Triazole ring imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, force rubazole ring, canoleporin ring, diaza force And a rubazole ring (representing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom).
  • R to R are substituents, and examples of the substituent include an alkyl group (for example, a methyl group and an ethyl group).
  • Propyl group isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecinole group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.) ), Alkenyl groups (eg, vinyl groups, aryl groups, etc.), alkynyl groups (eg, ethynyl groups, propargyl groups, etc.), aryl groups (eg, phenyl groups, naphthyl groups, etc.), aromatic heterocyclic groups (eg, furyl) Group, phenyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyraduryl group, triazinyl group, imidazolyl group, pyrazolyl group,
  • arylthio group for example, phenylthio group, naphthylthio group, etc.
  • alkoxycarbonyl group for example, methyloxycarbonyl group, ethyloxycarbonyl group, butoxycarbonyl group, Octyloxycarbonyl group, dodecyloxycarbonyl group, etc.
  • aryloxycarbonyl group eg, phenylcarbonyl group, naphthyloxycarbonyl group, etc.
  • sulfamoyl group eg, aminosulfonyl group, methyl
  • Aminosulfonyl group dimethylaminosulfonyl group, butyraminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfony
  • nl, n2, and n3 are 0 or a positive integer, and an integer of 0 to 4 is preferable.
  • the compound represented by the general formula (1) of the present invention is preferably used in at least one of the constituent layers (organic layers) of the organic EL device.
  • one of the constituent layers is a light emitting layer, and it is preferable to use a compound represented by the general formula (1) as a dopant in this light emitting layer.
  • a compound represented by the general formula (1) as a dopant in this light emitting layer.
  • an organic EL device When an organic EL device is produced using the organic EL device material of the present invention, it is preferably used for the light emitting layer in the constituent layers (details will be described later) of the organic EL device. In the light emitting layer, as described above, it is preferably used as a light emitting dopant.
  • the mixing ratio of the light-emitting dopant to the light-emitting host is preferably 0.:! To less than 30 mass%.
  • the luminescent dopant may be a mixture of a plurality of types of compounds.
  • the partner to be mixed may have a different structure, and other metal complexes or phosphorescent dopants or fluorescent dopants having other structures may be used. Good.
  • Luminescent dopants can be broadly divided
  • fluorescent dopants that emit fluorescence
  • phosphorescent dopants that emit phosphorescence
  • fluorescent dopant include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes. And pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • a typical example of the latter is preferably a complex compound containing a metal of group 8 to 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound. Of these, iridium compounds are most preferred.
  • a light-emitting host means the compound with the highest mixing ratio (mass) in a light-emitting layer composed of two or more compounds, and other compounds It is called “Dopan Pantoy compound (also simply called dopant)”.
  • Dopan Pantoy compound also simply called dopant
  • Compound C is a host compound.
  • phosphorescence of the luminescent dopant used in combination is 0-0 bar.
  • a compound containing a blue light-emitting component whose phosphorescence 0-0 band is 480 nm or less is used as a preferred light-emitting dopant
  • a compound having a phosphorescence 0-0 band with a wavelength shorter than that of Preferably, the phosphorescence 0-0 band is 450 nm or less.
  • the light-emitting host according to the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, thiophene.
  • Preferred compounds include those having a basic skeleton such as derivatives, furan derivatives, and oligoarylene compounds, and having the 0_0 band of 450 nm or less.
  • the light emitting host according to 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 (evaporation polymerizable light emitting host). Good.
  • a compound that has a hole transporting ability and an electron transporting ability, prevents an increase in the wavelength of light emission, and has a high Tg (glass transition temperature) is preferable.
  • the organic EL device material is preferably used for the light emitting layer, but in addition to these materials, the above known light emitting host and light emitting dopant may be used in combination.
  • the light emitting layer preferably contains a compound represented by the general formula (2). These compounds are preferably used as a light emitting host in the light emitting layer.
  • Z is an element forming an aromatic heterocyclic ring which may have a substituent.
  • And z represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring which may have a substituent.
  • R represents a group of atoms, and Z represents a divalent linking group or a simple bond.
  • R is a hydrogen atom
  • Examples of the aromatic heterocycle represented by the atomic group of Z and Z include a furan ring, a thiophene ring, and a pyri ring.
  • Quinoxaline ring, quinazoline ring, phthalazine ring, force rubazole ring, carboline ring, diaza force rubazole ring (indicates a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), etc. Is mentioned.
  • the aromatic heterocycle may have a substituent represented by R described later.
  • the aromatic hydrocarbon ring represented by the atomic group of Z includes a benzene ring, a biphenyl ring,
  • the aromatic hydrocarbon ring may have a substituent represented by R described later.
  • Examples of the substituent represented by R include an alkyl group (for example, methyl group, ethyl group, propyl group).
  • substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • Preferred substituents are an alkyl group, a cycloalkyl group, a fluorinated hydrocarbon group, an aryl group, and an aromatic heterocyclic group.
  • the divalent linking group may be a hydrocarbon group such as alkylene, alkenylene, alkynylene, arylene, etc., or may contain a heteroatom, and thiophene _ 2,5-diyl group may be pyrazine. 1 It may be a divalent linking group derived from a compound having an aromatic heterocycle such as a 2,3-diyl group (also referred to as a heteroaromatic compound), or it may be a force lucogen atom such as oxygen or sulfur. It ’s okay. In addition, a hetero atom such as an anolequinolemino group, a dialkylsilane diyl group or a diarylgermandyl group may be linked to meet each other.
  • the simple bond is a bond that directly bonds the connecting substituents together.
  • the ring formed by Z in the general formula (2) is preferably a 6-membered ring.
  • the ring to be formed is preferably a 6-membered ring. Thereby, the luminous efficiency can be further increased. Furthermore, if both Z and Z are 6-membered rings, the luminous efficiency can be further increased.
  • the light emitting layer according to the present invention can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method.
  • the thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 5 nm to 5 m.
  • This light emitting layer may have a single layer structure composed of one or two or more of these light emitting materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
  • this light-emitting layer is made into a solution by dissolving the above light-emitting material in a solvent together with a binder such as a resin, and then spinning it. It can be formed as a thin film by a coating method or the like.
  • the film thickness of the light emitting layer formed in this manner can be appropriately selected depending on the situation where there is no particular limitation, but is usually in the range of 5 nm to 5 ⁇ m.
  • the blocking layer (for example, hole blocking layer, electron blocking layer) according to the present invention will be described.
  • the thickness of the blocking layer according to the present invention is preferably 3 to:! OOnm, more preferably 5 to 30 nm.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons and has a very small ability to transport holes, and blocks holes while transporting electrons. By doing so, the probability of recombination of electrons and holes can be improved.
  • the organic EL device material of the present invention can be preferably used for the hole blocking layer in an adjacent layer adjacent to the light emitting layer, for example, a hole blocking layer, an electron blocking layer and the like.
  • Examples of the hole blocking layer include those disclosed in JP-A-11-204258, JP-A-11204359, and “OLED device and its forefront of industrialization” (November 30, 1998, NTS).
  • the hole blocking (hole blocking) layer described on page 237 of “Issued by the company” can be used as the hole blocking layer according to the present invention.
  • the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer according to the present invention preferably contains the compound represented by the general formula (2).
  • the hole blocking layer according to the present invention preferably contains a boron derivative.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and an extremely small capacity of transporting electrons. The probability of recombination of electrons and holes can be improved by blocking the children. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. [0142] In the present invention, it is preferable to use the organic EL device material of the present invention described above for the adjacent layer adjacent to the light emitting layer, that is, the hole blocking layer and the electron blocking layer. It is preferable to use it for the layer.
  • the hole transport layer includes a 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.
  • hole transport material there are no particular restrictions on the hole transport material. Conventionally, in photoconductive materials, it is commonly used as a hole charge injection / transport material, and used in the hole injection layer and hole transport layer of EL devices. Any known medium force can be selected and used.
  • the hole transport material has either a hole injection or transport or electron barrier property, and may be either an organic or inorganic substance.
  • a hole injection or transport or electron barrier property may be either an organic or inorganic substance.
  • 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, hydrazones
  • stilbene derivatives silazane derivatives
  • aniline copolymers conductive polymer oligomers, particularly thiophene oligomers.
  • Typical examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N r —tetraphenyl _4, 4 ; — diaminophenyl; ⁇ , ⁇ ' — diphenylenole _ ⁇ , ⁇ '— Bis (3-methylphenyl) -1- [1,1'-biphenyl] -1,4-diamine (TPD); 2, 2 _bis (4-di- ⁇ -tolylaminophenyl) propane; 1, 1 _Bis (4_di__trilaminophenyl) cyclohexane; ⁇ , ⁇ , ⁇ ', N r —tetra-p-tolyl-1,4′-diaminobiphenyl; 1,1-bis (4-di-one) p-tolylaminophenyl) 1-4-phenyl mouth hexane; bis (4-dimethylamino-2
  • the hole transport material of the hole transport layer preferably has a fluorescence maximum wavelength of 415 nm or less, and more preferably has a 0-0 band of phosphorescence of 450 nm or less. Also, the hole transport material is preferably high Tg.
  • the hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. That power S.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 to 5000 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • 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 multiple layers.
  • an electron transport material also serving as a hole blocking material used for an electron transport layer adjacent to the light emitting layer on the cathode side is used.
  • the electron transport layer only needs to have a function of transferring electrons injected from the cathode to the light emitting layer, and any material of any conventionally known compound can be selected and used. .
  • electron transport materials examples include heterocyclic tetrafluoride derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, and other heterocyclic tetra Examples thereof include carboxylic acid anhydrides, force-repository imides, fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-dib mouth mode) 8 quinolinol) aluminum, tris (2methyl 8quinolinol) aluminum, tris (5-methyl 8-quinolinol) aluminum, bis (8-quinolinol) zinc (Zn q), etc.
  • Metal complexes replacing Mg, Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials.
  • metal free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • the distyrylvirazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, n-type Si, n- type SiC, etc.
  • Inorganic semiconductors can also be used as electron transport materials.
  • This electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. S can. Although there is no restriction
  • This electron transport layer has a single layer structure composed of one or more of the above materials. It may be made.
  • the injection layer is provided as necessary, and has an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or hole transport layer and between the cathode and the light emitting layer or electron transport layer. May be.
  • the injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of the light emission.
  • the organic EL element and the forefront of industrialization June 30, 1998, NTT) 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “The Company”), the hole injection layer (anode buffer layer) and the electron injection layer (cathode buffer layer). There is.
  • anode buffer layer hole injection layer
  • One layer of phthalocyanine buffer typified by copper phthalocyanine
  • one layer of oxide buffer typified by vanadium oxide
  • one layer of amorphous carbon buffer typified by vanadium oxide
  • one layer of polymer buffer using a conductive polymer such as polyaniline (emeraldine) or polythiophene, etc.
  • 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-917574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide Etc.
  • the buffer layer (injection layer) preferably has a very thin film thickness, although the film thickness is preferably in the range of 0.1 to: OOnm.
  • This injection layer can be formed by thin-filming the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method.
  • the thickness of the injection layer is not particularly limited, but is usually about 5 to 5000 nm.
  • This The injection layer may have a single layer structure composed of one or more of the above materials.
  • 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 Cul, indium tin oxide (ITO), SnO, and ZnO.
  • ITO indium tin oxide
  • SnO indium tin oxide
  • ZnO ZnO.
  • a material such as _ZnO) that is amorphous and capable of producing a transparent conductive film may be used.
  • these electrode materials can be formed into a thin film by vapor deposition or sputtering, and a pattern of the desired shape can be formed by photolithography, or when the pattern accuracy is not so high (100 ⁇ m As described above, a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
  • the film thickness is a force depending on the material. Usually, 10 to 1000 nm, preferably 10 to 200 nm is selected.
  • the cathode according to the present invention 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 is used.
  • an electron injecting metal a material having a low work function (4 eV or less) metal
  • an alloy a material having a low work function (4 eV or less) metal
  • an alloy a material having a low work function (4 eV or less) metal
  • an alloy referred to as an electron injecting metal
  • an alloy an electrically conductive compound
  • a mixture thereof is used as the cathode according to the present invention.
  • electrode materials include sodium, sodium isotropic lithium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al O) mixture, indium, lithium / aluminum mixture, dilute
  • Examples include earth metals.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium Z silver mixture , Magnesium Z aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O) mixture
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as a cathode is several hundred ⁇ . Usually 10 to: 1000 nm, preferably 50 to 200 nm.
  • the anode or the cathode of the organic EL element is transparent or translucent to improve the light emission luminance.
  • substrate also referred to as substrate, substrate, support, etc.
  • the substrate of the organic EL device of the present invention is not particularly limited as long as it is transparent or transparent, and there are no particular restrictions on the type of glass, plastic, etc.
  • Examples of substrates that are preferably used include glass, Examples thereof include quartz and a light-transmitting resin film.
  • a particularly preferred substrate is a resin film that can give flexibility to the organic EL element.
  • Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate ( PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyethersulfone
  • PES polyetherimide
  • polyether ether ketone polyphenylene sulfide
  • PC polycarbonate
  • TAC cellulose triacetate
  • CAP cellulose acetate propionate
  • the surface of the resin film may have an inorganic or organic coating or a hybrid coating of both, and the water vapor permeability is 0.01 g / m 2 'day' atm or less. It is preferred to be a film.
  • the external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 2% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons flowed to the organic EL element ⁇ 100.
  • a hue improving filter such as a color filter may be used in combination.
  • a roughened film such as anti-glare phenol
  • a roughened film may be used in combination in order to reduce unevenness in light emission.
  • an anode Z hole injection layer Z hole transport layer A method for producing an organic EL device composed of / luminescent layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode will be described.
  • a desired electrode material for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm.
  • 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, or an electron transport layer, which is an element material, is formed thereon.
  • the deposition conditions vary due to kinds of materials used, generally baud solved ⁇ temperature 50 to 450 ° C, vacuum degree of 10- 6 ⁇ : 10- 2 Pa Desirably, the deposition rate is 0.01 to 50 nm / second, the substrate temperature is 50 to 300 ° C., and the film thickness is 0.1 nm to 5 / im.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so that the film thickness is 1 ⁇ m or less, preferably in the range of 50 to 200 nm.
  • the desired organic EL device can be obtained by forming the cathode and providing a cathode.
  • the organic EL element is preferably manufactured 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 necessary to consider that the work is performed in a dry inert gas atmosphere.
  • the display device of the present invention will be described.
  • the display device of the present invention may be monochromatic or multicolor, but here, a 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 casting method, a spin coating method, an ink jet method, a printing method, or the like.
  • the method is not limited, but the vapor deposition method, the ink jet method, and the printing method are preferable.
  • a vapor deposition method use a shadow mask, and use a patterning plate.
  • the order of preparation may be reversed, and the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, and the anode may be formed in this order.
  • the multicolor display device can be used as a display device, a display, and various light sources. Full color display is possible by using three types of organic EL elements, blue, red, and green, for display devices and displays.
  • Display devices and displays include TVs, personal computers, mopile devices, AV devices, text broadcast displays, information displays in automobiles, and the like.
  • the driving method when used as a display device for reproducing moving images which may be used as a display device for reproducing still images or moving images, may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light emitting 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 sensors Although a light source etc. are mentioned, it is not limited to this.
  • the lighting device of the present invention will be described.
  • the organic EL element having a resonator structure may be used as an organic EL element having a resonator structure in the organic EL element of the present invention.
  • Examples include, but are not limited to, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, and the like. Further, it may be used for the above application by causing laser oscillation.
  • the organic EL device of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device of a type for projecting an image, a still image or a moving image. It may be used as a type of display device (display) that is directly visible.
  • the driving method may be either a simple matrix (passive matrix) method or an active matrix method.
  • a full color display device can be produced by using two or more organic EL elements of the present invention having different emission colors.
  • FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements.
  • FIG. 2 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 staging 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.
  • the image information is displayed by sequentially emitting light according to the image data signal and displaying the image information.
  • 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, a plurality of pixels 3 and the like on a substrate.
  • the main members of the display unit A will be described below.
  • FIG. 2 shows a case where 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. (The details are not shown).
  • the pixel 3 When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light in accordance with the received image data.
  • Full color display is possible 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.
  • Full-color display can be performed by using organic EL elements of red, green, and blue light emission as organic EL elements 10 in a plurality of pixels and arranging 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 stray 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 driven by the capacitor 13. It is transmitted to the gate of transistor 12.
  • the capacitor 13 is charged according to the potential of the image data signal, and the drive of 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 organic EL element is connected from the power supply line 7 according to the potential of the image data signal applied to the gate. Current is supplied to element 10.
  • the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 holds 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.
  • the organic EL device 10 continues to emit light until it is seen.
  • 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 organic EL element 10 emits light by providing a switching transistor 11 and a driving transistor 12 as active elements for each of the organic EL elements 10 of each of the plurality of pixels.
  • Element 10 is emitting light.
  • 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 a predetermined light emission amount of the binary image data signal. It may be on or off.
  • the potential of the capacitor 13 can be maintained until the next scanning signal is applied, or can be discharged immediately before the next scanning signal is applied.
  • FIG. 4 is a schematic diagram of a display device using a passive matrix method.
  • 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 passive matrix method can reduce the manufacturing cost of an active element in addition to pixel 3.
  • the organic EL material according to the present invention can also 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 mixing colors.
  • the combination of multiple emission colors may include the three maximum emission wavelengths of the three primary colors of blue, green, and blue, and it uses the relationship of complementary colors such as blue and yellow, and blue-green and orange 2 It may be one containing two emission maximum wavelengths.
  • a combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescent or phosphorescent light, and A combination of a dye material that emits light of the light emitting material power as excitation light may be misaligned.
  • the white organic EL element according to the present invention may be combined with a plurality of light emitting dopants. Is preferred.
  • the layer structure of the organic EL device for obtaining a plurality of emission colors includes a method in which a plurality of emission dopants exist in one emission layer, a plurality of emission layers, and each emission layer includes Examples include a method in which dopants having different emission wavelengths are present, and a method in which minute pixels that emit light at different wavelengths are formed in a matrix.
  • patterning may be performed by a metal mask or an ink jet printing method when forming a film, if necessary.
  • patterning only the electrode may be patterned, or the electrode and the light emitting layer may be patterned. However, the entire layer of the element may be patterned.
  • the light emitting material used for the light emitting layer is not particularly limited.
  • the light emitting material according to the present invention is adapted so as to conform to the wavelength range corresponding to the CF (color filter) characteristics. Select a platinum complex or any of the known luminescent materials and combine them to make them white.
  • the white light-emitting organic EL element is used as various types of light sources, lighting devices, home lighting, interior lighting, and a kind of lamp such as an exposure light source. It is also useful for display devices such as backlights for liquid crystal display devices.
  • light sources such as backlights for watches, billboard advertisements, traffic lights, optical storage media, light sources for electronic photocopiers, light sources for optical communication processors, light sources for optical sensors, etc. And a wide range of uses such as general household appliances.
  • this transparent support substrate with ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • This transparent support substrate is fixed to the substrate holder of a commercially available vacuum deposition apparatus, while _NPD, CBP, Ir_ll, BCP, and Alq are placed in five resistance heating boats made of tantalum, respectively. It was attached to the first vacuum chamber.
  • lithium fluoride was placed in a tantalum resistance heating boat, and aluminum was placed in a tungsten resistance heating boat, which were attached to the second vacuum chamber of the vacuum evaporation system.
  • the heating boat containing CBP and the boat containing Ir 11 are independently energized, so that the deposition rate of CBP as the light emitting host and Ir-11 as the light emitting dopant is 100: 6.
  • the light emitting layer was provided by vapor deposition so that the film thickness was adjusted to 30 nm.
  • the heating boat containing BCP was energized and heated, and a hole blocking layer having a thickness of 10 nm was provided at a deposition rate of 0.0 :! to 0.2 nm / sec. Furthermore, the heated boat containing Alq
  • An electron transport layer with a film thickness of 40 nm was provided at a deposition rate of 0 :! to 0.2 nm / sec.
  • Barium oxide 105 a water-absorbing agent, is made of Aldrich's high-purity barium oxide powder with a fluororesin-based semipermeable membrane (Microtex S-NTF8031Q made by Nitto Denko) with adhesive. What was affixed on the sealing can 104 was prepared in advance and used. An ultraviolet curable adhesive 107 was used to bond the sealing can and the organic EL element, and the sealing element was prepared by irradiating an ultraviolet lamp to bond them together.
  • 101 is a glass substrate provided with a transparent electrode
  • 102 is an organic EL layer comprising the hole injection / transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and the like
  • 103 is a cathode.
  • organic EL elements 2 to 16 were produced in the same manner except that the light emitting host, the light emitting dopant and the hole blocking layer were changed.
  • the produced organic EL device was evaluated as follows. The evaluation results are shown in Table 1.
  • the external extraction quantum efficiency (%) was measured when a constant current of 2.5 mA / cm 2 was applied at 23 ° C. in a dry nitrogen gas atmosphere.
  • a spectral radiance meter CS-1000 Konica Minolta Sensing was used for the measurement.
  • the quantum efficiency is expressed as a relative value when the organic EL element 1 is 100.
  • the organic EL device was continuously lit at a constant current of 2.5 mA / cm 2 at room temperature, and the time ( ⁇ 1/9) required to reach 90 % of the initial luminance was measured.
  • a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing was used for the measurement.
  • the light emission lifetime is expressed as a relative value when the organic EL element 1 is 100.
  • the organic EL device using the metal complex according to the present invention for the light-emitting layer is a comparative organic E element.
  • the quantum efficiency is further improved by using the compound represented by 2) in the light-emitting host and the Z or hole blocking layer.
  • the surface resistance of this anode was 10 ⁇ / mouth.
  • a buttered mask (a mask with a light emitting area of 5 mm x 5 mm) is placed on the organic compound layer, and the cathode mask is placed in the vapor deposition system.
  • a cathode was provided by depositing lithium fluoride 0.5 nm as a fur layer and 150 nm of aluminum as a cathode.
  • a light emitting element was manufactured by extending aluminum lead wires from the anode and the cathode, respectively. The light-emitting element was put in a glove box substituted with nitrogen gas, and sealed with a glass sealing container using an ultraviolet curable adhesive (XNR5493, manufactured by Chiba Nagase) to produce an organic EL element.
  • the organic EL element can be produced by coating the material for the L element.
  • the organic EL element 15 of Example 1 was used as a blue light emitting element.
  • the organic EL device 13 of Example 1 was used as a green light emitting device.
  • the organic EL element 14 of Example 1 was used as a red light emitting element.
  • Each of the red, green, and blue light emitting organic EL elements produced above is juxtaposed on the same substrate to produce an active matrix type full-color display device having the configuration shown in FIG. 1, and FIG. Only the schematic view of the display part A of the produced display device is shown.
  • a wiring portion including a plurality of scanning lines 5 and data lines 6 and a plurality of juxtaposed pixels 3 (emission color is a red region pixel, a green region pixel, a blue region pixel, etc.)
  • 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 not shown).
  • the plurality of pixels 3 are driven by a formula that is an organic EL element and an active element corresponding to each emission color, and when a scanning signal is applied from the scanning line 5, the image data is transmitted from the data line 6. A signal is received, and light is emitted according to the received image data.
  • a full-color display device was produced by juxtaposing the red, green, and blue pixels appropriately.
  • the electrode of the transparent support substrate of Example 1 was patterned to 20 mm x 20 mm, and then a single NPD was formed to a thickness of 25 nm as a hole injection / transport layer in the same manner as in Example 1,
  • the heating boat containing the compound 74, the boat containing the compound (1 1 1) and the boat containing the compound (2-10) are energized independently, respectively, A boat containing a compound (1 1 1) and a compound (2-10) were deposited so that the deposition rate was 10 0: 7: 1 and deposited to a thickness of 40 nm. Provided.
  • BCP was deposited to a thickness of 10 nm to provide a hole blocking layer.
  • Alq was deposited at 40 nm to provide an electron transport layer.
  • Example 2 a square perforated mask having substantially the same shape as the transparent electrode made of stainless steel was placed on the electron transport layer, and lithium fluoride 0.5 nm and the cathode were formed as one cathode buffer layer. As a film, 150 nm of aluminum was deposited.
  • FIG. 6 shows a schematic diagram of a flat lamp.
  • Fig. 6 (a) shows a schematic plan view and
  • Fig. 6 (b) shows a schematic cross-sectional view.

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Abstract

Disclosed is a material for organic EL devices which is high in synthesis yield and luminous efficiency while having long emission life. Also disclosed are an organic EL device using such a material, and a display and illuminating device using such an organic EL device. The organic EL material is composed of a metal complex having a partial structure represented by the general formula (1) below, and is characterized by having at least one substituent in a ligand part which suppresses bidentate coordination.

Description

明 細 書  Specification
有機 EL素子用材料、有機 EL素子、表示装置及び照明装置  Materials for organic EL elements, organic EL elements, display devices and lighting devices
技術分野  Technical field
[0001] 本発明は、有機 EL素子用材料、及びこれを用いた有機 EL素子、表示装置及び照 明装置に関する。  The present invention relates to an organic EL element material, and an organic EL element, a display device, and an illumination device using the same.
背景技術  Background art
[0002] 従来、発光型の電子ディスプレイデバイスとして、 ELディスプレイ（以下、 ELDとレヽ う）がある。 ELDの構成要素としては、無機 EL素子や有機 EL素子が挙げられる。無 機 EL素子は平面型光源として使用されてきたが、発光素子を駆動させるためには交 流の高電圧が必要である。有機 EL素子は発光する化合物を含有する発光層が陰極 と陽極で挟んだ構成を有し、発光層に電子及び正孔を注入して、再結合させることに より励起子 (エキシトン)を生成させ、このエキシトンが失活する際の光の放出（蛍光 · 燐光）を利用して発光する素子であり、数 V〜数十 V程度の電圧で発光が可能であり 、さらに自己発光型であるために視野角に富み、視認性が高ぐ薄膜型の完全固体 素子であるために省スペース、携帯性等の観点から注目されてレ、る。  Conventionally, there is an EL display (hereinafter referred to as ELD) as a light-emitting electronic display device. ELD components include inorganic EL elements and organic EL elements. Inorganic EL elements have been used as planar light sources, but a high AC voltage is required to drive the light emitting elements. An organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the light-emitting layer and recombined to generate excitons. This is an element that emits light by using light emission (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts, and is self-luminous. In addition, it is a thin-film, complete solid-state device with a wide viewing angle and high visibility, so it is attracting attention from the viewpoint of space saving and portability.
[0003] し力 ながら、今後の実用化に向けた有機 EL素子においては、さらに低消費電力 で効率よく高輝度に発光する有機 EL素子の開発が望まれている。  [0003] However, for organic EL elements for practical use in the future, it is desired to develop organic EL elements that emit light efficiently and with high luminance with lower power consumption.
[0004] 特許第 3093796号公報では、スチルベン誘導体、ジスチリルァリーレン誘導体ま たはトリススチリルァリーレン誘導体に微量の蛍光体をドープし、発光輝度の向上、有 機 EL素子の長寿命化を達成してレ、る。  [0004] In Japanese Patent No. 3093796, a small amount of phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to improve emission luminance and extend the lifetime of an organic EL device. And les.
[0005] また、 8—ヒドロキシキノリンアルミニウム錯体をホストイ匕合物として、これに微量の蛍 光体をドープした有機発光層を有する有機 EL素子（例えば、特開昭 63— 264692 号公報）、 8—ヒドロキシキノリンアルミニウム錯体をホストイ匕合物として、これにキナタリ ドン系色素をドープした有機発光層を有する有機 EL素子 (例えば、特開平 3— 255 190号公報）等が知られてレ、る。  [0005] Further, an organic EL device having an organic light emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of a phosphor is doped therein (for example, Japanese Patent Laid-Open No. 63-264692), 8 An organic EL device having an organic light emitting layer in which a hydroxyquinoline aluminum complex is a host compound and doped with a quinatalidone dye is known (for example, JP-A-3-255190).
[0006] 以上のように励起一重項からの発光を用いる場合、一重項励起子と三重項励起子 の生成比が 1： 3であるため発光性励起種の生成確率が 25%であり、光の取り出し効 率が約 20%であるため、外部取り出し量子効率 ext)の限界は 5%とされている。 [0006] As described above, when emission from excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, so the generation probability of luminescent excited species is 25%. Extraction effect Since the rate is about 20%, the limit of external extraction quantum efficiency ext) is set to 5%.
[0007] ところが、プリンストン大より励起三重項からの燐光発光を用いる有機 EL素子の報 告（M. A. Baldo et al. , Nature, 395卷， 151〜： 154頁（1998年））力 Sされて以 来、室温で燐光を示す材料の研究が活発になってきている。例えば、 M. A. Baldo et al. , Nature, 403卷， 17号， 750〜753頁（2000年）、また米国特許第 6, 0[0007] However, Princeton University has reported on organic EL devices using phosphorescence from excited triplets (MA Baldo et al., Nature, 395 卷, 151-: 154 (1998)). Recently, research on materials that exhibit phosphorescence at room temperature has become active. For example, M. A. Baldo et al., Nature, 403 卷, 17, 750-753 (2000), and US Pat.
97, 147号明細書等にも開示されている。 No. 97, 147 and the like are also disclosed.
[0008] 励起三重項を使用すると、内部量子効率の上限が 100。/oとなるため、励起一重項 の場合に比べて原理的に発光効率力 S4倍となり、冷陰極管とほぼ同等の性能が得ら れる可能性があることから照明用途としても注目されている。 [0008] The upper limit of internal quantum efficiency is 100 when excited triplets are used. As a result, the luminous efficiency is S4 times in principle compared to the case of singlet excitation, and there is a possibility of obtaining almost the same performance as a cold cathode tube. .
[0009] 例えば、 S. Lamansky et al. , J. Am. Chem. So ， 123卷， 4304頁（2001 年)等においては、多くの化合物がイリジウム錯体系等重金属錯体を中心に合成検 討されている。 [0009] For example, in S. Lamansky et al., J. Am. Chem. So, 123 卷, p. 4304 (2001), many compounds have been synthesized and studied focusing on heavy metal complexes such as iridium complexes. ing.
[0010] また、前述の M. A. Baldo et al. , Nature, 403卷， 17号， 750〜753頁（200 0年）においては、ドーパントとしてトリス（2—フエ二ルビリジン)イリジウムを用いた検 討がされている。  [0010] In addition, in the above-mentioned MA Baldo et al., Nature, 403 卷, 17, 750-753 (2000), a study using tris (2-phenylpyridine) iridium as a dopant was conducted. Has been.
[0011] その他、 M. E. Tompson等は The 10th International  [0011] In addition, M. E. Tompson et al.
Workshop on Inorganic and Organic Electroluminescence (EL 00、 浜松）において、ドーパントとして L Ir (acac)、例えば、 (ppy) Ir (acac)を、また Moo n— Jae Youn. Og, Tetsuo Tsutsui等はやはり The 10th International Wo rkshop on Inorganic and Organic Electroluminescence (EL' 00、浜松) において、ドーパントとして、トリス（2— (p—トリル）ピリジン)イリジウム（Ir (ptpy) )、ト リス（ベンゾ [h]キノリン)イリジウム（Ir (bzq) )等を用いた検討を行っている。なおこれ らの金属錯体は一般にオルトメタル化イリジウム錯体と呼ばれている。  In Workshop on Inorganic and Organic Electroluminescence (EL 00, Hamamatsu), L Ir (acac), for example, (ppy) Ir (acac) as a dopant, and Moon—Jae Youn. Og, Tetsuo Tsutsui, etc. In Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), as dopants, tris (2- (p-tolyl) pyridine) iridium (Ir (ptpy)), tris (benzo [h] quinoline) iridium (Ir (bzq)) etc. are being studied. These metal complexes are generally called orthometalated iridium complexes.
[0012] また、前記 S. Lamansky et al. ， J. Am. Chem. So ， 123卷， 4304頁（20 01年）等においても、各種イリジウム錯体を用いて有機 EL素子化する試みがされて いる。  [0012] In addition, in the above-mentioned S. Lamansky et al., J. Am. Chem. So, 123 頁, p. 4304 (2001), attempts have been made to make organic EL devices using various iridium complexes. Yes.
[0013] また、高い発光効率を得るために、 The 10th International Workshop on Inorganic and Organic Electroluminescence (EL' 00、浜松)では、 Ikai等 はホール輸送性の化合物を燐光性化合物のホストとして用いている。また、 M. E. T ompson等は各種電子輸送性材料を燐光性化合物のホストとして、これらに新規なィ リジゥム錯体をドープして用いている。 [0013] In order to obtain high luminous efficiency, the 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) Uses a hole transporting compound as a host of a phosphorescent compound. In addition, ME Thompson et al. Use various electron transport materials as a host of phosphorescent compounds and dope these with new iridium complexes.
[0014] 中心金属をイリジウムの代わりに白金としたオノレトメタルイ匕錯体も注目されている。こ の種の錯体に関しては、配位子に特徴を持たせた例が多数知られている（例えば、 特許文献:!〜 7参照。）。  [0014] An onoleto metal complex having a central metal platinum instead of iridium is also attracting attention. With regard to this type of complex, there are many known examples in which a ligand is characterized (see, for example, Patent Documents:! To 7).
[0015] 何れの場合も主にフエニルピリジン等、二つの配位原子によって中心金属に結合 する二座配位子及びその誘導体がオルトメタル化錯体の好適な例として用いられて きた。し力 これらを発光素子とした場合の発光輝度や発光効率は、その発光する光 が燐光に由来することから、従来の有機 EL素子に比べ大幅に改良されるものである 力 有機 EL素子の発光寿命については従来の有機 EL素子よりも低いことが知られ ている。  [0015] In any case, bidentate ligands and derivatives thereof, which are mainly bonded to the central metal through two coordination atoms, such as phenylpyridine, have been used as preferred examples of orthometalated complexes. The light emission brightness and light emission efficiency when these are used as light emitting elements are greatly improved compared to conventional organic EL elements because the emitted light is derived from phosphorescence. It is known that the lifetime is lower than that of conventional organic EL devices.
[0016] 近年、三つの配位原子を有する三座配位子を用いた白金錯体及びイリジウム錯体 が報告されている（例えば、特許文献 8、 9及び非特許文献 1、 2参照。）。しかしなが らこれら有機 EL素子の発光特性はいまだ不十分であり、実用化に耐えうる、さらに高 特性なりん光発光材料を用いた有機 EL素子の開発が望まれていた。  [0016] In recent years, platinum complexes and iridium complexes using a tridentate ligand having three coordination atoms have been reported (see, for example, Patent Documents 8 and 9 and Non-Patent Documents 1 and 2). However, the light-emitting properties of these organic EL devices are still insufficient, and there has been a demand for the development of organic EL devices that use high-performance phosphorescent materials that can withstand practical use.
特許文献 1 :特開 2001— 181617号公報  Patent Document 1: Japanese Patent Laid-Open No. 2001-181617
特許文献 2：特開 2001— 247859号公報  Patent Document 2: Japanese Patent Laid-Open No. 2001-247859
特許文献 3 :特開 2002— 332291号公報  Patent Document 3: Japanese Patent Laid-Open No. 2002-332291
特許文献 4 :特開 2002— 332292号公報  Patent Document 4: Japanese Patent Laid-Open No. 2002-332292
特許文献 5 :特開 2002— 338588号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2002-338588
特許文献 6 :特開 2002— 226495号公報  Patent Document 6: Japanese Patent Laid-Open No. 2002-226495
特許文献 7：特開 2002— 234894号公報  Patent Document 7: Japanese Patent Laid-Open No. 2002-234894
特許文献 8 :特開 2003— 73355号公報  Patent Document 8: Japanese Unexamined Patent Publication No. 2003-73355
特許文献 9 :W〇2004Z39781号ノ ンフレット  Patent Document 9: W〇2004Z39781 Non-Fret
非特許文献 1 : Inorganic Chemistry,第 43卷，第 21号， 6513〜6515頁（2004 年）  Non-Patent Document 1: Inorganic Chemistry, No. 43, No. 21, pp. 6513-6515 (2004)
非特許文献 2 : IDW2004. 1425〜1426頁 発明の開示 Non-Patent Document 2: IDW 2004, pages 1425-1426 Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0017] 本発明は、上記課題に鑑みなされたものであり、その目的は、合成収率と発光効率 が高ぐ発光寿命の長い有機 EL素子用材料及びこれを用いた有機 EL素子、該有 機 EL素子を用いた表示装置及び照明装置を提供することである。  [0017] The present invention has been made in view of the above problems, and an object of the present invention is to provide a material for an organic EL element having a high synthesis yield and a high light emission efficiency and a long emission lifetime, an organic EL element using the same, and It is to provide a display device and a lighting device using an EL element.
課題を解決するための手段  Means for solving the problem
[0018] 本発明の上記課題は、以下の構成により達成される。 [0018] The above-described problems of the present invention are achieved by the following configurations.
[0019] (1)下記一般式（1)で表される部分構造を有する金属錯体であって、配位子部分 に二座配位を抑制する置換基を少なくとも一つ有することを特徴とする有機 EL素子 用材料。  [0019] (1) A metal complex having a partial structure represented by the following general formula (1), characterized in that the ligand portion has at least one substituent that suppresses bidentate coordination. Materials for organic EL devices.
[0020] [化 1]  [0020] [Chemical 1]
Figure imgf000006_0001
Figure imgf000006_0001
[0021] (式中、 Mは金属原子であり、 X、 Y、 Ζはそれぞれ環 Α、環 Β、環 Cの構成要素である とともに炭素原子または窒素原子であり、少なくとも一つは炭素原子であって、 Μに 結合している。環 Α、環 Β、環 Cは芳香族炭化水素環、芳香族複素環または複素環 である。 R〜Rは置換基であり、 nl、 n2、 n3は 0または正の整数である。 Lは補助配  [In the formula, M is a metal atom, X, Y, and Ζ are constituents of ring Α, ring Β, and ring C, respectively, and are a carbon atom or a nitrogen atom, and at least one is a carbon atom. The ring Α, ring Β, and ring C are aromatic hydrocarbon rings, aromatic heterocycles, or heterocycles R to R are substituents, and nl, n2, and n3 are 0 or a positive integer L is auxiliary
1 3  13
位子を表し、 mは 1〜3の整数である。 )  Represents a ligand, and m is an integer of 1 to 3. )
(2)前記一般式（1)において、環 Bの置換基 Rの少なくとも一つは、環 A及び環 Cと  (2) In the general formula (1), at least one of the substituents R of the ring B includes a ring A and a ring C;
2  2
結合しない、ファンデルワールス体積 (VDW)力 S45A3以上のアルキル基、シクロア ノレキル基、アルケニル基、アルキニル基、複素環基、アルコキシ基、シクロアルコキシ 基、スノレフィニノレ基、アルキルスルホニル基またはシリル基であることを特徴とする前 記（1)に記載の有機 EL素子用材料。 No bond, van der Waals volume (VDW) force S45A 3 or more alkyl group, cycloanolalkyl group, alkenyl group, alkynyl group, heterocyclic group, alkoxy group, cycloalkoxy group, snorfininore group, alkylsulfonyl group or silyl group Before characterized by The material for an organic EL device according to (1).
[0022] (3)前記（1)または（2)のいずれ力 1項に記載の有機 EL素子用材料を、有機 EL素 子を形成する構成層の一つに含有することを特徴とする有機 EL素子。 [0022] (3) An organic EL device comprising the organic EL device material according to any one of the above (1) and (2) in one of the constituent layers forming the organic EL device. EL element.
[0023] (4)前記構成層の一つが発光層であることを特徴とする前記（3)に記載の有機 EL 素子。 [0023] (4) The organic EL device according to (3), wherein one of the constituent layers is a light emitting layer.
[0024] (5)前記構成層の少なくとも一層に下記一般式 (2)で表される化合物を含有するこ とを特徴とする前記（3)または (4)に記載の有機 EL素子。  [0024] (5) The organic EL device according to (3) or (4), wherein a compound represented by the following general formula (2) is contained in at least one of the constituent layers.
[0025] [化 2] [0025] [Chemical 2]
—般式《2ί —General formula << 2ί
Figure imgf000007_0001
Figure imgf000007_0001
[0026] (式中、 Zは芳香族複素環を形成する原子群を表し、 Zは芳香族複素環または芳香 [0026] (wherein Z represents an atomic group forming an aromatic heterocycle, Z represents an aromatic heterocycle or aromatic
1 2  1 2
族炭化水素環を形成する原子群を表し、 Zは 2価の連結基または単なる結合手を表  Represents a group of atoms that form an aromatic hydrocarbon ring, and Z represents a divalent linking group or a simple bond.
3  Three
す。 Rは水素原子または置換基を表す。 )  The R represents a hydrogen atom or a substituent. )
4  Four
(6)前記（3)〜（5)のレ、ずれ力 4項に記載の有機 EL素子を有することを特徴とする 表示装置。  (6) A display device comprising the organic EL element according to the item (3) to (5), and the displacement force described in item 4.
[0027] (7)前記（3)〜（5)のレ、ずれ力 1項に記載の有機 EL素子を有することを特徴とする 照明装置。  [0027] (7) A lighting device comprising the organic EL element according to item (3) to (5), wherein the organic EL element according to item 1 is provided.
[0028] 又、以下の（8)〜（16)については、前記記一般式（1)で表される部分構造を有す る、二座配位を抑制する置換基を少なくとも一つ配位子部分に有する金属錯体であ る有機 EL素子用材料の好ましレ、態様を示す。  [0028] Regarding the following (8) to (16), at least one substituent having a partial structure represented by the general formula (1) and suppressing bidentate coordination is coordinated. The preferred and mode of materials for organic EL elements that are metal complexes in the child part are shown.
[0029] (8)前記一般式（1)において、環 A及び環 Cの少なくとも 1つは、単環式含窒素 5員 環であることを特徴とする前記（1)または（2)に記載の有機 EL素子用材料。 [0029] (8) In the above general formula (1), at least one of ring A and ring C is a monocyclic nitrogen-containing 5-membered ring, described in (1) or (2) above Material for organic EL devices.
[0030] (9)前記一般式（1)において、環 A及び環 Cの少なくとも 1つは、環 Bと窒素原子で 結合した複素環であることを特徴とする前記（1)、（2)および（8)のいずれ力 1項に記 載の有機 EL素子用材料。 [0031] (10)前記一般式（1)において、 Yは炭素原子であって、かつ、補助配位子 Lは炭 素原子、窒素原子、硫黄原子によって金属 Mに結合していることを特徴とする前記（ 1)、（2)、（8)および（9)のいずれか 1項に記載の有機 EL素子用材料。 [0030] (9) In the general formula (1), at least one of the ring A and the ring C is a heterocyclic ring bonded to the ring B with a nitrogen atom, (1), (2) And (8) Any of the forces described in item 1 for organic EL device materials. [0031] (10) In the general formula (1), Y is a carbon atom, and the auxiliary ligand L is bonded to the metal M by a carbon atom, a nitrogen atom, or a sulfur atom. The material for an organic EL device according to any one of (1), (2), (8) and (9).
[0032] (11)前記一般式（1)において、 Yは窒素原子であって、かつ、補助配位子 Lが、窒 素原子、酸素原子、硫黄原子によって金属 Mに結合していることを特徴とする前記（ 1)、（2)、（8)および（9)のいずれか 1項に記載の有機 EL素子用材料。  (11) In the general formula (1), Y is a nitrogen atom, and the auxiliary ligand L is bonded to the metal M through a nitrogen atom, an oxygen atom, or a sulfur atom. 10. The organic EL device material according to any one of (1), (2), (8) and (9), which is characterized in that
[0033] (12)前記一般式（1)において、補助配位子 Lは窒素原子で金属 Mに結合したァ 二オンであることを特徴とする前記（1)、 （2)、（8)、（9)および（11)のいずれ力、 1項 に記載の有機 EL素子用材料。  [0033] (12) In the general formula (1), the auxiliary ligand L is a dione bonded to the metal M by a nitrogen atom, (1), (2), (8) The material for organic EL elements according to 1 above, wherein any one of (9) and (11) is used.
[0034] (13)前記一般式（1)において、補助配位子 Lの少なくとも一つは、複座の配位子 であることを特徴とする前記（1)、 (2)および（8)〜（12)のいずれ力、 1項に記載の有 機 EL素子用材料。  [0034] (13) In the above general formula (1), at least one of the auxiliary ligands L is a bidentate ligand. (1), (2) and (8) Any of the powers of (12) to the organic EL element material according to item 1.
[0035] (14)前記一般式（1)において、金属 Mが Ir、 Pt、 Rh、 Pd、 Osまたは Auであること を特徴とする前記（1)、 (2)および（8)〜（13)のレ、ずれ力 1項に記載の有機 EL素子 用材料。  [0035] (14) In the general formula (1), the metal M is Ir, Pt, Rh, Pd, Os or Au, (1), (2) and (8) to (13 The organic EL element material described in item 1 above.
[0036] (15)前記一般式（1)において、金属 Mが Pt、 Pdまたは Auであることを特徴とする 前記 14に記載の有機 EL素子用材料。  [0036] (15) The material for an organic EL element as described in 14 above, wherein in the general formula (1), the metal M is Pt, Pd or Au.
[0037] (16)前記一般式（1)で表される金属錯体が、高分子の主鎖または側鎖の一部で あることを特徴とする前記（1)、（2)および（8)〜（： 15)のいずれ力 1項に記載の有機[0037] (16) The metal complex represented by the general formula (1) is a part of a main chain or a side chain of the polymer (1), (2) and (8) Any of the powers of ~ (: 15)
EL素子用材料。 Materials for EL elements.
発明の効果  The invention's effect
[0038] 本発明により、合成収率と発光効率が高ぐ発光寿命の長い有機 EL素子用材料及 びこれを用いた有機 EL素子、該有機 EL素子を用いた表示装置及び照明装置を提 供すること力 Sできる。  [0038] According to the present invention, there are provided a material for an organic EL element having a high synthesis yield and luminous efficiency and a long emission lifetime, an organic EL element using the material, a display device using the organic EL element, and a lighting device. That power S.
図面の簡単な説明  Brief Description of Drawings
[0039] [図 1]有機 EL素子から構成される表示装置の一例を示した模式図である。  FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements.
[図 2]表示部 Aの模式図である。  FIG. 2 is a schematic diagram of display unit A.
[図 3]画素を構成する駆動回路の等価回路図である。 [図 4]パッシブマトリクス方式による表示装置の模式図である。 FIG. 3 is an equivalent circuit diagram of a drive circuit constituting a pixel. FIG. 4 is a schematic diagram of a passive matrix display device.
[図 5]有機 EL素子の封止構造の概略模式図である。  FIG. 5 is a schematic diagram of a sealing structure of an organic EL element.
[図 6]有機 EL素子を具備してなる照明装置の模式図である。  FIG. 6 is a schematic diagram of a lighting device including an organic EL element.
符号の説明  Explanation of symbols
[0040] 1 ディスプレイ [0040] 1 display
3 画素  3 pixels
5 走査線  5 scan lines
6 データ線  6 Data line
7 電源ライン  7 Power line
10 有機 EL素子  10 Organic EL devices
12 駆動トランジスタ 12 Drive transistor
13 コンデンサ  13 Capacitor
A 表示部  A Display section
B 制御部  B Control unit
101 透明電極付きガラス基板  101 Glass substrate with transparent electrode
102 有機 EL層  102 OLED layer
103 陰極  103 cathode
104 ガラス製封止缶  104 glass sealing can
105 酸化バリウム（捕水剤）  105 Barium oxide (water trapping agent)
106 窒素ガス  106 Nitrogen gas
107 紫外線硬化型接着剤  107 UV curable adhesive
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0041] 本発明の有機 EL素子用材料は、 3つの環を有する三座配位子を有し、それぞれの 環は直接結合されていることを特徴とする。このような三座配位子はこれまで用いら れてきたフエニルピリジンのような二座配位子に比べ中心金属との結合手が多いため 金属、配位子間のエネルギー移動が容易になり、高効率な発光が可能になり、さらに は錯体形成に伴うより大きな安定化エネルギーを得ることができる。 [0042] 本発明においては、前記（1)または（2)また、好ましくは（8)〜（16)のいずれか 1 項に記載の有機 EL素子用材料を用い、前記（3)〜（5)のいずれ力 1項に記載の構 成により、発光効率が高ぐ発光寿命の長い有機 EL素子を得ることができた。 [0041] The organic EL device material of the present invention has a tridentate ligand having three rings, and each ring is directly bonded. Such tridentate ligands have more bonds with the central metal than bidentate ligands such as phenylpyridine, which have been used so far, making it easy to transfer energy between the metal and ligand. Thus, highly efficient light emission is possible, and more stabilization energy associated with complex formation can be obtained. [0042] In the present invention, the organic EL device material described in any one of (1) or (2) or (8) to (16) is preferably used. As a result, it was possible to obtain an organic EL device having a high emission efficiency and a long emission lifetime.
[0043] 本発明者等は上記課題について鋭意検討を行った結果、これまで多方面で検討さ れてきた二座配位子に替えて、前記一般式（1)で表されるような三座配位子を用い た金属錯体を用いることで合成収率と発光効率が高ぐしかも発光寿命が大幅に改 善される有機 EL素子用材料を提供できることを見出した。  [0043] As a result of diligent investigations on the above problems, the present inventors have replaced the bidentate ligands that have been studied in various fields so far, as shown in the general formula (1). It has been found that by using a metal complex using a bidentate ligand, it is possible to provide a material for an organic EL device that has a high synthesis yield and luminous efficiency and has a significantly improved luminous lifetime.
[0044] 本発明に係る三座配位子は環 A、環 B、環 Cの三つの環構造を有し、二座配位を 抑制する置換基を有することを特徴とする。こうした置換基によって金属が配位子と 選択的に三座配位が可能になり、所望の金属錯体を選択性よく得ることができる。こ の時、置換基の結合位置及び嵩高さは二座配位を抑制できるものであれば特に限 定されないが、特に環 Bにファンデルワールス体積 (VDW)力 S45A3以上の置換基を 有することが好ましぐ 45〜250A3であることがより好ましぐ 45〜： 150A3であること 力 Sさらに好ましい。また、置換基の種類としてはアルキル基、シクロアルキル基、アル ケニル基、アルキニル基、複素環基、アルコキシ基、シクロアルコキシ基、スルフィニ ル基、アルキルスルホニル基、シリル基が好ましぐアルキル基、シクロアルキル基、 アルケニル基、アルキニル基、アルコキシ基、シリル基がより好ましぐアルキル基、シ クロアルキル基、アルケニル基、シリル基がさらに好ましい。 [0044] The tridentate ligand according to the present invention has three ring structures of ring A, ring B, and ring C, and has a substituent that suppresses bidentate coordination. Such a substituent enables the metal to selectively form a tridentate coordination with a ligand, and a desired metal complex can be obtained with high selectivity. At this time, the bonding position and bulkiness of the substituent are not particularly limited as long as bidentate coordination can be suppressed, but in particular, ring B has a substituent of van der Waals volume (VDW) force S45A 3 or more. it is preferred instrument 45～250A 3 is a more preferable device 45: it forces S more preferably 150A is three. As the types of substituents, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, a sulfinyl group, an alkylsulfonyl group, and an alkyl group, preferably a silyl group, A cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group and a silyl group are more preferred, and an alkyl group, a cycloalkyl group, an alkenyl group and a silyl group are more preferred.
[0045] 本発明における三座配位子は三つの環構造を有するが、これらは芳香族炭化水 素環、芳香族複素環または複素環であって、 5員環もしくは 6員環であることが好まし レ、。特に環 Bは 6員環構造を有することが好ましい。さらには発光波長の調整のため に環 Aまたは環 Cのうち少なくとも一つは含窒素 5員環構造もしくは窒素原子で環 B に結合した複素環であることが好ましレ、。  [0045] The tridentate ligand in the present invention has three ring structures, and these are aromatic hydrocarbon rings, aromatic heterocyclic rings or heterocyclic rings, which are 5-membered or 6-membered rings. Is preferred. In particular, ring B preferably has a 6-membered ring structure. In order to adjust the emission wavelength, at least one of ring A or ring C is preferably a nitrogen-containing 5-membered ring structure or a heterocyclic ring bonded to ring B with a nitrogen atom.
[0046] また本発明者者等の検討によれば、三座配位子は環 A、環 B、環 Cにそれぞれ配 位原子 X、 Y、 Ζを有するが、この配位原子の組み合わせ及び補助配位子 Lの選択は 有機 EL素子の安定性及び発光特性に大きな影響を有することが明らかとなった。具 体的には、前記一般式（1)において、環 Βの Υが炭素原子の場合は、補助配位子 L は炭素原子、窒素原子、硫黄原子によって金属 Μに結合していることが好ましぐ環 Bの Yが窒素原子の場合は、補助配位子 Lは窒素原子、酸素原子、硫黄原子によつ て金属 Μに結合してレ、ることが好ましレ、。 [0046] According to the study by the present inventors, the tridentate ligand has coordinating atoms X, Y, and に in ring A, ring B, and ring C, respectively. It became clear that the selection of the auxiliary ligand L has a great influence on the stability and emission characteristics of organic EL devices. Specifically, in the general formula (1), when the ring Υ is a carbon atom, the auxiliary ligand L is preferably bonded to the metal に よ っ て by a carbon atom, a nitrogen atom, or a sulfur atom. Mashigu ring When Y in B is a nitrogen atom, the auxiliary ligand L is preferably bonded to the metal cage by a nitrogen atom, oxygen atom, or sulfur atom.
[0047] 補助配位子 Lは窒素原子で金属 Μに結合したァニオンであることが好ましい。 [0047] The auxiliary ligand L is preferably an anion bonded to the metal cage with a nitrogen atom.
[0048] 補助配位子 Lは一種類であってもそれ以上であってもよレ、が、中心金属の配位数 を満足することが好ましレ、。このため補助配位子は単座であっても二座あるいは三座 配位子であってもよぐこれらの組み合わせであってもよいが、複数の空き配位座が ある場合にはキレート効果による安定化を得るためにも複座の配位子であることが好 ましレ、。また有機 EL素子用材料は対イオンを有してもょレ、が、全体として中性である ことがさらに好ましい。 [0048] The auxiliary ligand L may be one kind or more, but preferably satisfies the coordination number of the central metal. For this reason, the auxiliary ligand may be monodentate, bidentate or tridentate, or a combination thereof. However, if there are multiple vacant coordination sites, the chelating effect In order to obtain stabilization, it is preferable to use a double-dentate ligand. Further, it is more preferable that the material for the organic EL element has a counter ion but is neutral as a whole.
[0049] また、中心金属としてはリン光発光可能なものであれば特に限定されないが、周期 表において 8〜： 11族に含まれる金属であることが好ましぐ Ir、 Pt、 Pd、 Rh、 Osまた は Auがより好ましぐ Pt、 Pdまたは Auがさらに好ましい。  [0049] The central metal is not particularly limited as long as it can emit phosphorescence, but is preferably a metal included in Group 8 to 11 in the periodic table: Ir, Pt, Pd, Rh, Pt, Pd or Au is more preferred, with Os or Au being more preferred.
[0050] また有機 EL素子の作製法は特に限定されないが、湿式によることが好ましぐ本発 明における金属錯体は高分子鎖の主鎖あるいは側鎖の一部であることが好ましい。  [0050] The method for producing the organic EL device is not particularly limited, but the metal complex in the present invention, which is preferably wet, is preferably a main chain or a part of a side chain of the polymer chain.
[0051] 本発明の有機 EL素子用材料は、有機 EL素子の構成層のうち発光層に用いること が好ましい。さらなる高効率発光のために発光層にドーパントとして用いられることが 好ましレ、。このとき、用いる電子輸送層ゃ正孔輸送層、発光ホスト等、他の有機層を 構成する材料との適切な組み合わせによって、さらなる高輝度、高効率な発光、さら には有機 EL素子の長寿命化が可能である。こうした観点から有機層のうち少なくとも 一層に前記一般式（2)で表される化合物を用いることが好ましぐ発光ホスト及び/ または正孔阻止材料としては前記一般式（2)を用いることがさらに好ましい。  [0051] The material for an organic EL device of the present invention is preferably used for a light emitting layer among the constituent layers of the organic EL device. It is preferable to be used as a dopant in the light emitting layer for further highly efficient light emission. At this time, by combining with the materials that make up the other organic layers, such as the electron transport layer used, the hole transport layer, and the light-emitting host, it is possible to emit light with higher brightness and higher efficiency, and to further increase the lifetime of the organic EL device Is possible. From this point of view, it is preferable to use the general formula (2) as a light emitting host and / or hole blocking material that preferably uses the compound represented by the general formula (2) in at least one of the organic layers. preferable.
[0052] 以下、本発明を詳細に説明する。  [0052] Hereinafter, the present invention will be described in detail.
[0053] 〔一般式（1)で表される金属錯体〕  [Metal complex represented by general formula (1)]
本発明の前記一般式（1)で表される部分構造を有する金属錯体 (以下、一般式（1 )で表される金属錯体ともいう）について説明する。  The metal complex having a partial structure represented by the general formula (1) of the present invention (hereinafter also referred to as a metal complex represented by the general formula (1)) will be described.
[0054] 本発明者等は、これまで多方面で検討されてきた二座配位子に代えて、前記一般 式（1)で表されるような三座配位子を用いた金属錯体を用いることで、合成収率と発 光効率が高ぐしかも発光寿命が大幅に改善される有機 EL素子用材料を提供でき た。 [0054] The present inventors have replaced a bidentate ligand that has been studied in various fields so far with a metal complex using a tridentate ligand represented by the general formula (1). By using this, it is possible to provide materials for organic EL devices that have a high synthesis yield and light emission efficiency, and that have a significantly improved light emission lifetime. It was.
[0055] 本発明における三座配位子は直接炭素原子によって結合された環 A、環 B、環 C の三つの環構造を有し、特に環 Bにファンデルワールス体積 (VDW)が 45 A3以上の 置換基を有することが好ましい。こうした嵩高い置換基によって金属が該配位子と選 択的に三座配位可能になり、望ましくない二座配位錯体の生成を抑止することができ る。 [0055] The tridentate ligand in the present invention has three ring structures of ring A, ring B, and ring C directly connected by a carbon atom. In particular, ring B has a van der Waals volume (VDW) of 45 A. It preferably has 3 or more substituents. Such bulky substituents allow the metal to selectively tridentate with the ligand and prevent the formation of undesirable bidentate complexes.
卜O C  卜 O C
[0056] 置換 卜  [0056] replacement 卜
基のファンデルワー寸O CO Lル寸  Basic van der Waals O O L
σι寸D CD Cス (VDW)体積とは、アクセルリス社製分子シミュレーシ M 〇 C  σι Dimension D CD C volume (VDW) volume means Accelrys molecular simulation M 〇 C
ヨンソフト Cerius2を用いて求め卜寸O LO LO Lられるパラメーターを用いる力 ベンゼン環に置換基 を導入し、 Dreiding Force Fieldを用いて、 MM計算で分子構造を最適化して、 Connoly Surfaceを用いて求めた Volume値と定義する。具体的な置換基のファ ンデルワールス（VDW)体積を下記に示す。  Force using parameters determined by Yonsoft Cerius2 Introducing substituents into the benzene ring, optimizing the molecular structure using MM calculation using Dreiding Force Field, and using Connoly Surface Defined as a Volume value. Specific van der Waals (VDW) volumes of substituents are shown below.
置換基 A3 Substituent A 3
メチル基  Methyl group
ェチル基 42. 6  Ethyl group 42.6
イソプロピル基  Isopropyl group
tert—ブチル基  tert-butyl group
トリメチルシリル基 91. 9  Trimethylsilyl group 91.9
フエニル基  Phenyl group
フエノキシ基
Figure imgf000012_0001
Phenoxy group
Figure imgf000012_0001
メトキシ基  Methoxy group
アミノ基 22. 2  Amino group 22.2
ジメチノレアミノ基  Dimethinoreamino group
ヒドロキシノレ基  Hydroxy group
塩素原子  Chlorine atom
臭素原子  Bromine atom
フッ素原子 13. 3  Fluorine atom 13.3
トリフルォロメチル基  Trifluoromethyl group
環 A、環 B、環 Cは芳香族炭化水素環、芳香族複素環または複素環である。 [0058] 環 A、環 B、環 Cを構成する芳香族炭化水素環としては、ベンゼン環、ビフエニル環 、ナフタレン環、ァズレン環、アントラセン環、フエナントレン環、ピレン環、タリセン環、 ナフタセン環、トリフエ二レン環、 o—テルフエニル環、 m—テルフエニル環、 p—テノレ フエニル環、ァセナフテン環、コロネン環、フルオレン環、フルオラントレン環、ナフタ セン環、ペンタセン環、ペリレン環、ペンタフェン環、ピセン環、ピレン環、ピラントレン 環、アンスラアントレン環等が挙げられる。 Ring A, ring B, and ring C are aromatic hydrocarbon rings, aromatic heterocycles, or heterocycles. [0058] The aromatic hydrocarbon rings constituting Ring A, Ring B, and Ring C include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, talycene ring, naphthacene ring, triphenyl ring. Diene ring, o-terfenyl ring, m-terphenyl ring, p-thenophenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, Examples include a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.
[0059] 環 A、環 B、環 Cを構成する芳香族複素環としては、フラン環、チォフェン環、ピリジ ン環、ピリダジン環、ピリミジン環、ピラジン環、トリアジン環、ベンゾイミダゾール環、ォ キサジァゾール環、トリァゾール環、イミダゾール環、ピラゾール環、チアゾール環、ィ ンドール環、ベンゾイミダゾール環、ベンゾチアゾール環、ベンゾォキサゾール環、キ ノキサリン環、キナゾリン環、フタラジン環、力ルバゾール環、カノレポリン環、ジァザ力 ルバゾール環（カルボリン環を構成する炭化水素環の炭素原子の一つがさらに窒素 原子で置換されてレ、る環を示す）等が挙げられる。  [0059] The aromatic heterocyclic ring constituting Ring A, Ring B, and Ring C includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole ring. , Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, force rubazole ring, canoleporin ring, diaza force And a rubazole ring (representing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom).
[0060] R〜Rは置換基であり、置換基としては、アルキル基（例えば、メチル基、ェチル基  [0060] R to R are substituents, and examples of the substituent include an alkyl group (for example, a methyl group and an ethyl group).
1 3  13
、プロピル基、イソプロピル基、 tert—ブチル基、ペンチル基、へキシル基、ォクチル 基、ドデシル基、トリデシル基、テトラデシノレ基、ペンタデシル基等）、シクロアルキル 基（例えば、シクロペンチル基、シクロへキシル基等）、アルケニル基（例えば、ビニル 基、ァリル基等）、アルキニル基（例えば、ェチニル基、プロパルギル基等）、ァリール 基 (例えば、フエニル基、ナフチル基等）、芳香族複素環基 (例えば、フリル基、チェ ニル基、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジュル基、トリアジニル基、 イミダゾリル基、ピラゾリル基、チアゾリル基、キナゾリニル基、フタラジェル基等）、複 素環基（例えば、ピロリジノレ基、イミダゾリジノレ基、モルホリル基、ォキサゾリジル基等） 、アルコキシル基（例えば、メトキシ基、エトキシ基、プロピルォキシ基、ペンチルォキ シ基、へキシルォキシ基、ォクチルォキシ基、ドデシノレォキシ基等）、シクロアルコキ シル基（例えば、シクロペンチルォキシ基、シクロへキシルォキシ基等）、ァリールォ キシ基 (例えば、フヱノキシ基、ナフチルォキシ基等）、アルキルチオ基 (例えば、メチ ノレチォ基、ェチルチオ基、プロピルチオ基、ペンチルチオ基、へキシルチオ基、オタ チルチオ基、ドデシノレチォ基等）、シクロアルキルチオ基（例えば、シクロペンチルチ ォ基、シクロへキシノレチォ基等）、ァリールチオ基（例えば、フエ二ルチオ基、ナフチ ルチオ基等）、アルコキシカルボニル基（例えば、メチルォキシカルボニル基、ェチル ォキシカルボニル基、ブチルォキシカルボニル基、ォクチルォキシカルボニル基、ド デシルォキシカルボニル基等）、ァリールォキシカルボニル基（例えば、フエ二ルォキ シカルボニル基、ナフチルォキシカルボニル基等）、スルファモイル基（例えば、ァミノ スルホニル基、メチルアミノスルホニル基、ジメチルアミノスルホニル基、ブチルァミノ スルホニル基、へキシルアミノスルホニル基、シクロへキシルアミノスルホニル基、オタ チルアミノスルホニル基、ドデシルアミノスルホニル基、フエニルアミノスルホニル基、 ナフチルアミノスルホニル基、 2_ピリジルアミノスルホニル基等）、ァシル基（例えば、 ァセチル基、ェチルカルボニル基、プロピルカルボニル基、ペンチルカルボニル基、 シクロへキシルカルボニル基、ォクチルカルボニル基、 2 _ェチルへキシルカルボ二 ル基、ドデシルカルボ二ル基、フヱニルカルボニル基、ナフチルカルボニル基、ピリジ ルカルボニル基等）、ァシルォキシ基（例えば、ァセチルォキシ基、ェチルカルボ二 ルォキシ基、ブチルカルボニルォキシ基、ォクチルカルボニルォキシ基、ドデシルカ ルボニルォキシ基、フエニルカルボニルォキシ基等）、アミド基（例えば、メチルカルボ ニルァミノ基、ェチルカルボニルァミノ基、ジメチルカルボニルァミノ基、プロピルカル ボニルァミノ基、ペンチルカルボニルァミノ基、シクロへキシルカルボニルァミノ基、 2 ェチルへキシルカルボニルァミノ基、ォクチルカルボニルァミノ基、ドデシルカルボ ニルァミノ基、フエニルカルボニルァミノ基、ナフチルカルボニルァミノ基等）、カノレバ モイル基（例えば、ァミノカルボニル基、メチルアミノカノレボニル基、ジメチルァミノ力 ルボニル基、プロピルアミノカルボニル基、ペンチルァミノカルボニル基、シクロへキ シルァミノカルボニル基、ォクチルァミノカルボニル基、 2—ェチルへキシルァミノカル ボニル基、ドデシルァミノカルボニル基、フエニルァミノカルボニル基、ナフチルァミノ カルボニル基、 2_ピリジルァミノカルボニル基等）、ウレイド基（例えば、メチルゥレイ ド基、ェチルウレイド基、ペンチルゥレイド基、シクロへキシルウレイド基、ォクチルウレ イド基、ドデシルウレイド基、フエニルウレイド基ナフチルウレイド基、 2 _ピリジノレアミノ ウレイド基等）、スルフィエル基（例えば、メチルスルフィエル基、ェチルスルフィニル 基、ブチルスルフィニル基、シクロへキシルスルフィニル基、 2 _ェチルへキシルスル フィエル基、ドデシルスルフィニル基、フエニルスルフィニル基、ナフチルスルフィニル 基、 2—ピリジルスルフィエル基等）、アルキルスルホニル基（例えば、メチルスルホニ ノレ基、ェチルスルホニル基、ブチルスルホニル基、シクロへキシルスルホニル基、 2— ェチルへキシルスルホニル基、ドデシルスルホニル基等）、ァリールスルホニル基（例 えば、フエニルスルホニル基、ナフチルスルホニル基、 2 _ピリジルスルホニル基等） 、アミノ基（例えば、アミノ基、ェチノレアミノ基、ジメチノレアミノ基、ブチノレアミノ基、シク 口ペンチルァミノ基、 2—ェチルへキシルァミノ基、ドデシルァミノ基、ァニリノ基、ナフ チルァミノ基、 2_ピリジノレアミノ基等）、ハロゲン原子 (例えば、フッ素原子、塩素原 子、臭素原子等）、フッ化炭化水素基 (例えば、フルォロメチル基、トリフルォロメチル 基、ペンタフルォロェチル基、ペンタフルオロフヱニル基等）、シァノ基、ニトロ基、ヒド 口キシル基、メルカプト基、シリル基（例えば、トリメチルシリル基、トリイソプロピルシリ ル基、トリフエニルシリル基、フエ二ルジェチルシリル基等）等が挙げられる。これらの 置換基は上記の置換基によってさらに置換されてレ、てもよレ、。 Propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecinole group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.) ), Alkenyl groups (eg, vinyl groups, aryl groups, etc.), alkynyl groups (eg, ethynyl groups, propargyl groups, etc.), aryl groups (eg, phenyl groups, naphthyl groups, etc.), aromatic heterocyclic groups (eg, furyl) Group, phenyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyraduryl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthalagel group, etc.), bicyclic ring group (for example, pyrrolidinole group, imidazolidinole group) , Morpholyl group, oxazolidyl group, etc.), alkoxyl (For example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecinoleoxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group ( For example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methenoretio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecinoretio group, etc.), cycloalkylthio group (for example, cyclopentylthio group). Group, cyclohexenoretio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butoxycarbonyl group, Octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenylcarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methyl) Aminosulfonyl group, dimethylaminosulfonyl group, butyraminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2 _Pyridylaminosulfonyl group, etc.), acyl groups (eg, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2_ethylhexylcarbonyl group, dodecylcarbocycle group) Diyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group) , Phenylcarbonyloxy groups, etc.), amide groups (eg, methylcarbonylamino groups, ethylcarbonylamino groups, dimethylcarbonylamino groups, propylcarbonylamino groups, pentylcarbonylamino groups, cyclohexylcarbonylamino groups, etc.) A mino group, a 2-ethylhexylcarbonylamino group, an octylcarbonylamino group, a dodecylcarbonylamino group, a phenylcarbonylamino group, a naphthylcarbonylamino group, etc., a canolamoyl group (for example, an aminocarbonyl group, Methylaminocanolonyl group, dimethylamino group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylamino Carbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2_pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, Dode Silureido group, phenylureido group, naphthylureido group, 2_pyridinoreaminoureido group, etc.), sulfiel group (for example, methylsulfiel group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2_ethylhexylsulfurate) Fier group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonanol group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethynoleamino group, Dimethinoreamino group, Butinoreamino group, Cyclic pentylamino group, 2-Ethylhexylamino group, Dodecylamino group, Anilino group, Naphtylamino group, 2_pyridinoleamino group, etc.), Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.) ) Fluorohydrocarbon groups (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyan group, nitro group, hydroxy group, mercapto group, silyl group ( For example, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a phenyljetylsilyl group, and the like. These substituents may be further substituted with the above substituents.
[0061] nl、 n2、 n3は 0または正の整数であり、 0〜4の整数が好ましい。 [0061] nl, n2, and n3 are 0 or a positive integer, and an integer of 0 to 4 is preferable.
[0062] 以下に本発明に好ましく用いられる一般式（1)で表される金属錯体の具体例を挙 げるが、本発明はこれらに限定されない。 [0062] Specific examples of the metal complex represented by the general formula (1) preferably used in the present invention are listed below, but the present invention is not limited thereto.
[0063] [化 3] [0063] [Chemical 3]
[ [ ■] [[]]
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000017_0001
[0065] [化 5] [9^] [9900] [0065] [Chemical 5] [9 ^] [9900]
Figure imgf000018_0001
Figure imgf000018_0001
Z90tO£l900Zdt/L3d 91· 88800T/9001 OAV [Z900] Z90tO £ l900Zdt / L3d 9188800T / 9001 OAV [Z900]
Figure imgf000019_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000020_0001
[0068] これらの化合物は、 D. J. Cardenas, etal. , Organometallics 18, 3337 (199 9)等を参照して合成することができる。  [0068] These compounds can be synthesized with reference to D. J. Cardenas, etal., Organometallics 18, 3337 (199 9) and the like.
[0069] 本発明の一般式（1)で表される化合物は、有機 EL素子の構成層（有機層）の少な くとも一層に用いることが好ましい。さらなる発光効率の向上のために構成層の一つ が発光層であり、この発光層に一般式（1)で表される化合物をドーパントとして用いる ことが好ましい。このとき、用いる電子輸送層ゃ正孔輸送層、発光ホスト等、他の有機 層を構成する材料との適切な組み合わせによって、さらなる高輝度、高効率な発光、 さらには有機 EL素子の長寿命化が可能である。 [0069] The compound represented by the general formula (1) of the present invention is preferably used in at least one of the constituent layers (organic layers) of the organic EL device. In order to further improve the light emission efficiency, one of the constituent layers is a light emitting layer, and it is preferable to use a compound represented by the general formula (1) as a dopant in this light emitting layer. At this time, by using an appropriate combination with the materials constituting the other organic layers, such as the electron transport layer used, the hole transport layer, and the light emitting host, light emission with higher brightness and higher efficiency can be achieved. Furthermore, it is possible to extend the life of organic EL devices.
[0070] 〔有機 EL素子材料の有機 EL素子への適用〕 [0070] [Application of organic EL element materials to organic EL elements]
本発明の有機 EL素子材料を用いて、有機 EL素子を作製する場合、有機 EL素子 の構成層（詳細は後述する）の中で、発光層に用いることが好ましい。また、発光層 中では上記のように、発光ドーパントとして好ましく用いられる。  When an organic EL device is produced using the organic EL device material of the present invention, it is preferably used for the light emitting layer in the constituent layers (details will be described later) of the organic EL device. In the light emitting layer, as described above, it is preferably used as a light emitting dopant.
[0071] (発光ホストと発光ドーパント） [0071] (Luminescent Host and Luminescent Dopant)
発光層中の主成分となるホストイ匕合物である発光ホストに対する発光ドーパントとの 混合比は、好ましくは 0. ：!〜 30質量％未満である。  The mixing ratio of the light-emitting dopant to the light-emitting host, which is a host compound as a main component in the light-emitting layer, is preferably 0.:! To less than 30 mass%.
[0072] ただし、発光ドーパントは複数種の化合物を混合して用いてもよぐ混合する相手 は構造を異にする、その他の金属錯体やその他の構造を有するリン光性ドーパント や蛍光性ドーパントでもよい。 [0072] However, the luminescent dopant may be a mixture of a plurality of types of compounds. The partner to be mixed may have a different structure, and other metal complexes or phosphorescent dopants or fluorescent dopants having other structures may be used. Good.
[0073] ここで、発光ドーパントとして用レ、られる金属錯体と併用してもよいドーパント（リン光 性ドーパント、蛍光性ドーパント等）について述べる。発光ドーパントは、大きく分けて[0073] Here, the dopant (phosphorescent dopant, fluorescent dopant, etc.) that may be used in combination with the metal complex used as the light emitting dopant will be described. Luminescent dopants can be broadly divided
、蛍光を発光する蛍光性ドーパントとリン光を発光するリン光性ドーパントの 2種類が ある。 There are two types: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescence.
[0074] 前者（蛍光性ドーパント）の代表例としては、クマリン系色素、ピラン系色素、シァニ ン系色素、クロコニゥム系色素、スクァリウム系色素、ォキソベンツアントラセン系色素 、フルォレセイン系色素、ローダミン系色素、ピリリウム系色素、ペリレン系色素、スチ ルベン系色素、ポリチォフェン系色素、または希土類錯体系蛍光体等が挙げられる。  [0074] Representative examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes. And pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
[0075] 後者（リン光性ドーパント）の代表例としては、好ましくは元素の周期表で 8〜： 10属 の金属を含有する錯体系化合物であり、さらに好ましくはイリジウム化合物、ォスミゥ ム化合物であり、中でも最も好ましいのはイリジウム化合物である。  [0075] A typical example of the latter (phosphorescent dopant) is preferably a complex compound containing a metal of group 8 to 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound. Of these, iridium compounds are most preferred.
[0076] 具体的には、以下の特許公報に記載されている化合物である。  [0076] Specifically, it is a compound described in the following patent publications.
[0077] 国際公開第 00/70655号パンフレツ卜、特開 2002— 280178号公報、同 2001— 181616号公報、同 2002— 280179号公報、同 2001— 181617号公報、同 2002 — 280180号公報、同 2001— 247859号公報、同 2002— 299060号公報、同 20 01— 313178号公報、同 2002— 302671号公報、同 2001— 345183号公報、同 2002— 324679号公報、国際公開第 02/15645号パンフレット、特開 2002— 33 2291号公報、同 2002— 50484号公報、同 2002— 332292号公報、同 2002— 8 3684号公報、特表 2002— 540572号公報、特開 2002— 117978号公報、同 200 2— 338588号公報、同 2002— 170684号公報、同 2002— 352960号公報、国際 公開第 01/93642号パンフレット、特開 2002— 50483号公報、同 2002— 10047 6号公報、同 2002— 173674号公報、同 2002— 359082号公報、同 2002— 175 884号公報、同 2002— 363552号公報、同 2002— 184582号公報、同 2003— 7 469号公報、特表 2002— 525808号公報、特開 2003— 7471号公報、特表 2002 — 525833号公報、特開 2003— 31366号公報、同 2002— 226495号公報、同 20 02— 234894号公報、同 2002— 235076号公報、同 2002— 241751号公報、同 2001— 319779号公報、同 2001— 319780号公報、同 2002— 62824号公報、 同 2002— 100474号公報、同 2002— 203679号公報、同 2002— 343572号公報 、同 2002— 203678号公報等。 [0077] International Publication No. 00/70655 Pamphlet, JP 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060, 20 01-313178, 2002-302671, 2001-345183, 2002-324679, WO 02/15645, pamphlet , JP 2002-33 No. 2291, No. 2002-50484, No. 2002-332292, No. 2002-8 3684, No. 2002-540572, No. 2002-117978, No. 2002-338588, 2002-170684, 2002-352960, WO 01/93642, JP 2002-50483, 2002-10047 6, 2002-173674, 2002- 359082 Publication No. 2002-175 884 Publication No. 2002-363552 Publication No. 2002-184582 Publication No. 2003-7469 Publication Special Table No. 2002-525808 Publication No. JP 2003-7471 Publication No. Table 2002-525833, JP 2003-31366, 2002-226495, 2002-234894, 2002-235076, 2002-241751, 2001-319779 2001-319780, 2002-62824, 2002-100474, 2002-203679, 2002-343572, 2002-20 No. 3678.
[0078] その具体例の一部を下記に示す。  [0078] Some of the specific examples are shown below.
[0079] [化 8] [0079] [Chemical 8]
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0003
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0003
Figure imgf000024_0001
Figure imgf000024_0001
[0081] [化 10] Pt— 2 [0081] [Chemical 10] Pt— 2
Figure imgf000025_0001
Figure imgf000025_0001
[0082] (発光ホスト） [0082] (Light-emitting host)
発光ホスト（単にホストともいう）とは、 2種以上の化合物で構成される発光層中にて 混合比（質量）の最も多レ、ィ匕合物のことを意味し、それ以外の化合物にっレ、ては「ド 一パントイ匕合物（単に、ドーパントともいう）」という。例えば、発光層を化合物 A、化合 物 Bという 2種で構成し、その混合比が A: B= 10 : 90であれば化合物 Aがドーパント 化合物であり、化合物 Bがホストイ匕合物である。さらに発光層を化合物 A、化合物 B、 化合物 Cの 3種から構成し、その混合比が八：8 :〇= 5 : 10 : 85でぁれば、化合物 A、 化合物 Bがドーパントイ匕合物であり、化合物 Cがホストイ匕合物である。  A light-emitting host (also simply referred to as a host) means the compound with the highest mixing ratio (mass) in a light-emitting layer composed of two or more compounds, and other compounds It is called “Dopan Pantoy compound (also simply called dopant)”. For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if the light emitting layer is composed of three types of compound A, compound B, and compound C, and the mixing ratio is 8: 8: ○ = 5: 10: 85, compound A and compound B are dopant compounds. Compound C is a host compound.
[0083] 本発明に用いられる発光ホストとしては、併用される発光ドーパントのリン光 0— 0バ ンドよりも短波長なリン光 0— 0バンドを持つ化合物が好ましぐ発光ドーパントにその リン光 0— 0バンドが 480nm以下である青色の発光成分を含む化合物を用いる場合 には、発光ホストとしてはリン光 0— 0バンドが 450nm以下であることが好ましい。 [0083] As the luminescent host used in the present invention, phosphorescence of the luminescent dopant used in combination is 0-0 bar. When a compound containing a blue light-emitting component whose phosphorescence 0-0 band is 480 nm or less is used as a preferred light-emitting dopant, a compound having a phosphorescence 0-0 band with a wavelength shorter than that of Preferably, the phosphorescence 0-0 band is 450 nm or less.
[0084] 本発明に係る発光ホストとしては、構造的には特に制限はないが、代表的にはカル バゾール誘導体、トリアリールァミン誘導体、芳香族ボラン誘導体、含窒素複素環化 合物、チォフェン誘導体、フラン誘導体、オリゴァリーレン化合物等の基本骨格を有 し、かつ前記 0_0バンドが 450nm以下の化合物が好ましい化合物として挙げられる 。また、本発明に係る発光ホストは低分子化合物でも、繰り返し単位をもつ高分子化 合物でもよぐビニル基やエポキシ基のような重合性基を有する低分子化合物 (蒸着 重合性発光ホスト）でもいい。  [0084] The light-emitting host according to the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, thiophene. Preferred compounds include those having a basic skeleton such as derivatives, furan derivatives, and oligoarylene compounds, and having the 0_0 band of 450 nm or less. In addition, the light emitting host according to 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 (evaporation polymerizable light emitting host). Good.
[0085] 発光ホストとしては、正孔輸送能、電子輸送能を有しつつ、かつ発光の長波長化を 防ぎ、なおかつ高 Tg (ガラス転移温度）である化合物が好ましレ、。  [0085] As the light-emitting host, a compound that has a hole transporting ability and an electron transporting ability, prevents an increase in the wavelength of light emission, and has a high Tg (glass transition temperature) is preferable.
[0086] 発光ホストの具体例としては、以下の文献に記載されている化合物が好適である。  [0086] As specific examples of the luminescent host, compounds described in the following documents are suitable.
例えば、特開 2001— 257076号公報、同 2002— 308855号公報、同 2001— 313 179号公報、同 2002— 319491号公報、同 2001— 357977号公報、同 2002— 3 34786号公報、同 2002— 8860号公報、同 2002— 334787号公報、同 2002— 1 5871号公報、同 2002— 334788号公報、同 2002— 43056号公報、同 2002— 3 34789号公報、同 2002— 75645号公報、同 2002— 338579号公報、同 2002— 105445号公報、同 2002— 343568号公報、同 2002— 141173号公報、同 2002 — 352957号公報、同 2002— 203683号公報、同 2002— 363227号公報、同 20 For example, JP 2001-257076, 2002-308855, 2001-313 179, 2002-319491, 2001-357977, 2002-3 34786, 2002- 8860, 2002-334787, 2002-1 5871, 2002-334788, 2002-43056, 2002-3 34789, 2002-75645, 2002 -338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 20
02— 231453号公報、同 2003— 3165号公報、同 2002— 234888号公報、同 2002-231453, 2003-3165, 2002-234888, 20
03— 27048号公報、同 2002— 255934号公報、同 2002— 260861号公報、同 2 002— 280183号公報、同 2002— 299060号公報、同 2002— 302516号公報、 同 2002— 305083号公報、同 2002— 305084号公報、同 2002— 308837号公報 等。 03-27048, 2002-255934, 2002-260861, 2002-280183, 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837, etc.
[0087] 次に、代表的な有機 EL素子の構成について述べる。  Next, the configuration of a typical organic EL element will be described.
[0088] 〔有機 EL素子の構成層〕 [0088] [Constitutional layer of organic EL element]
本発明の有機 EL素子の層構成の好ましい具体例を以下に示すが、本発明はこれ らに限定されない。 （1)陽極/発光層/電子輸送層/陰極（2)陽極/正孔輸送層 /発光層/電子輸送層/陰極（3)陽極/正孔輸送層/発光層/正孔阻止層/電 子輸送層/陰極 (4)陽極/正孔輸送層/発光層/正孔阻止層/電子輸送層/陰 極バッファー層/陰極（5)陽極/陽極バッファ一層/正孔輸送層/発光層/正孔 阻止層/電子輸送層/陰極バッファー層/陰極 Preferred specific examples of the layer structure of the organic EL device of the present invention are shown below. It is not limited to it. (1) Anode / light emitting layer / electron transport layer / cathode (2) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / hole blocking layer / electric Child transport layer / cathode (4) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (5) anode / anode buffer layer / hole transport layer / light emitting layer / Hole blocking layer / electron transport layer / cathode buffer layer / cathode
〔発光層〕  [Light emitting layer]
本発明においては、有機 EL素子用材料は発光層に用いることが好ましいが、これ ら以外にも上記のような公知の発光ホストや発光ドーパントを併用してもよい。  In the present invention, the organic EL device material is preferably used for the light emitting layer, but in addition to these materials, the above known light emitting host and light emitting dopant may be used in combination.
[0089] ここで、本発明の効果をさらに向上させる観点から、発光層が前記一般式（2)で表 される化合物を含有することが好ましレ、。これらの化合物は発光層におレ、て発光ホス トとして好ましく用いられる。  [0089] Here, from the viewpoint of further improving the effect of the present invention, the light emitting layer preferably contains a compound represented by the general formula (2). These compounds are preferably used as a light emitting host in the light emitting layer.
[0090] 前記一般式（2)において、 Zは置換基を有してもよい芳香族複素環を形成する原  [0090] In the general formula (2), Z is an element forming an aromatic heterocyclic ring which may have a substituent.
1  1
子群を表し、 zは置換基を有してもよい芳香族複素環または芳香族炭化水素環を形  And z represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring which may have a substituent.
2  2
成する原子群を表し、 Zは 2価の連結基または単なる結合手を表す。 Rは水素原子  Represents a group of atoms, and Z represents a divalent linking group or a simple bond. R is a hydrogen atom
3 4  3 4
または置換基を表す。  Or represents a substituent.
[0091] Z、 Zの原子群から表される芳香族複素環としては、フラン環、チォフェン環、ピリ  [0091] Examples of the aromatic heterocycle represented by the atomic group of Z and Z include a furan ring, a thiophene ring, and a pyri ring.
1 2  1 2
ジン環、ピリダジン環、ピリミジン環、ピラジン環、トリアジン環、ベンゾイミダゾール環、 ォキサジァゾール環、トリァゾール環、イミダゾール環、ピラゾール環、チアゾール環、 インドール環、ベンゾイミダゾール環、ベンゾチアゾール環、ベンゾォキサゾール環、 キノキサリン環、キナゾリン環、フタラジン環、力ルバゾール環、カルボリン環、ジァザ 力ルバゾール環（カルボリン環を構成する炭化水素環の炭素原子の一つがさらに窒 素原子で置換されている環を示す)等が挙げられる。さらに前記芳香族複素環は、後 述する R で表される置換基を有してもよい。  Gin ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring Quinoxaline ring, quinazoline ring, phthalazine ring, force rubazole ring, carboline ring, diaza force rubazole ring (indicates a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), etc. Is mentioned. Further, the aromatic heterocycle may have a substituent represented by R described later.
41  41
[0092] Zの原子群から表される芳香族炭化水素環としては、ベンゼン環、ビフエニル環、  [0092] The aromatic hydrocarbon ring represented by the atomic group of Z includes a benzene ring, a biphenyl ring,
2  2
ナフタレン環、ァズレン環、アントラセン環、フエナントレン環、ピレン環、タリセン環、 ナフタセン環、トリフエ二レン環、 o _テルフエニル環、 m—テルフエニル環、 p _テノレ フエニル環、ァセナフテン環、コロネン環、フルオレン環、フルオラントレン環、ナフタ セン環、ペンタセン環、ペリレン環、ペンタフェン環、ピセン環、ピレン環、ピラントレン 環、アンスラアントレン環等が挙げられる。さらに前記芳香族炭化水素環は、後述す る Rで表される置換基を有してもよい。 Naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, talycene ring, naphthacene ring, triphenylene ring, o _ terphenyl ring, m-terphenyl ring, p _tenolephenyl ring, acenaphthene ring, coronene ring, fluorene ring , Fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene Ring, anthraanthrene ring and the like. Further, the aromatic hydrocarbon ring may have a substituent represented by R described later.
4  Four
Rで表される置換基としては、アルキル基（例えば、メチル基、ェチル基、プロピル Examples of the substituent represented by R include an alkyl group (for example, methyl group, ethyl group, propyl group).
4 Four
基、イソプロピル基、 tert_ブチル基、ペンチル基、へキシル基、ォクチル基、ドデシ ル基、トリデシノレ基、テトラデシノレ基、ペンタデシノレ基等）、シクロアルキル基（例えば 、シクロペンチル基、シクロへキシル基等）、アルケニル基（例えば、ビュル基、ァリノレ 基等）、アルキニル基（例えば、ェチュル基、プロパルギル基等）、ァリール基（例えば 、フエ二ル基、ナフチル基等）、芳香族複素環基 (例えば、フリル基、チェニル基、ピリ ジノレ基、ピリダジニル基、ピリミジニル基、ピラジュル基、トリアジニル基、イミダゾリノレ 基、ピラゾリル基、チアゾリル基、キナゾリニル基、フタラジュル基等）、複素環基 (例 えば、ピロリジル基、イミダゾリジル基、モルホリル基、ォキサゾリジル基等）、アルコキ シル基（例えば、メトキシ基、エトキシ基、プロピルォキシ基、ペンチルォキシ基、へキ シノレォキシ基、ォクチルォキシ基、ドデシノレォキシ基等）、シクロアルコキシノレ基（例 えば、シクロペンチルォキシ基、シクロへキシルォキシ基等）、ァリールォキシ基（例え ば、フエノキシ基、ナフチルォキシ基等）、アルキルチオ基（例えば、メチルチオ基、ェ チルチオ基、プロピルチオ基、ペンチルチオ基、へキシルチオ基、ォクチルチオ基、 ドデシルチオ基等）、シクロアルキルチオ基（例えば、シクロペンチルチオ基、シクロ へキシルチオ基等）、ァリールチオ基 (例えば、フエ二ルチオ基、ナフチルチオ基等） 、アルコキシカルボニル基（例えば、メチルォキシカルボニル基、ェチルォキシカルボ ニル基、ブチルォキシカルボニル基、ォクチルォキシカルボニル基、ドデシルォキシ カルボニル基等）、ァリールォキシカルボニル基（例えば、フエニルォキシカルボニル 基、ナフチルォキシカルボニル基等）、スルファモイル基（例えば、アミノスルホニル基 、メチルアミノスルホニル基、ジメチルアミノスルホニル基、ブチルアミノスルホニル基 、へキシルアミノスルホニル基、シクロへキシルアミノスルホニル基、ォクチルアミノス ノレホニル基、ドデシルアミノスルホニル基、フエニルアミノスルホニル基、ナフチルアミ ノスルホニル基、 2_ピリジルアミノスルホニル基等）、ァシル基（例えば、ァセチル基 、ェチルカルボニル基、プロピルカルボニル基、ペンチルカルボニル基、シクロへキ シルカルボニル基、ォクチルカルボニル基、 2 _ェチルへキシルカルボニル基、ドデ シルカルボニル基、フエニルカルボニル基、ナフチルカルボニル基、ピリジルカルボ ニル基等）、アシノレオキシ基（例えば、ァセチルォキシ基、ェチルカルボニルォキシ 基、ブチルカルボニルォキシ基、ォクチルカルボニルォキシ基、ドデシルカルボニル ォキシ基、フエ二ルカルボニルォキシ基等）、アミド基（例えば、メチルカルボニルアミ ノ基、ェチルカルボニルァミノ基、ジメチルカルボニルァミノ基、プロピルカルボニルァ ミノ基、ペンチルカルボニルァミノ基、シクロへキシルカルボニルァミノ基、 2—ェチノレ へキシルカルボニルァミノ基、ォクチルカルボニルァミノ基、ドデシルカルボニルァミノ 基、フエニルカルボニルァミノ基、ナフチルカルボニルァミノ基等）、力ルバモイル基（ 例えば、ァミノカルボニル基、メチルァミノカルボニル基、ジメチルァミノカルボニル基 、プロピルアミノカルボニル基、ペンチルァミノカルボニル基、シクロへキシルァミノ力 ルボニル基、ォクチルァミノカルボニル基、 2 _ェチルへキシルァミノカルボニル基、 ドデシルァミノカルボニル基、フエニルァミノカルボニル基、ナフチルァミノカルボニル 基、 2—ピリジノレアミノカルボニル基等）、ウレイド基（例えば、メチノレウレイド基、ェチ ルゥレイド基、ペンチルゥレイド基、シクロへキシルウレイド基、ォクチルゥレイド基、ド デシノレウレイド基、フエニルゥレイド基ナフチルウレイド基、 2—ピリジノレアミノウレイド 基等）、スルフィエル基（例えば、メチルスルフィエル基、ェチルスルフィニル基、ブチ ノレスノレフイエノレ基、シクロへキシノレスノレフイエノレ基、 2—ェチノレへキシノレスノレフイエノレ 基、ドデシルスルフィニル基、フエニルスルフィニル基、ナフチルスルフィニル基、 2— ピリジルスルフィニル基等）、アルキルスルホニル基（例えば、メチルスルホニル基、ェ チルスルホニル基、ブチルスルホニル基、シクロへキシルスルホニル基、 2—ェチノレ へキシルスルホニル基、ドデシルスルホニル基等）、ァリールスルホニル基（例えば、 フエニルスルホニル基、ナフチルスルホニル基、 2 _ピリジルスルホニル基等）、ァミノ 基（例えば、アミノ基、ェチルァミノ基、ジメチルァミノ基、ブチルァミノ基、シクロペン チノレアミノ基、 2—ェチルへキシルァミノ基、ドデシルァミノ基、ァニリノ基、ナフチルァ ミノ基、 2_ピリジノレアミノ基等）、ノ、ロゲン原子 (例えば、フッ素原子、塩素原子、臭素 原子等）、フッ化炭化水素基 (例えば、フルォロメチル基、トリフルォロメチル基、ペン タフルォロェチル基、ペンタフルオロフヱニル基等）、シァノ基、ニトロ基、ヒドロキシノレ 基、メルカプト基、シリル基（例えば、トリメチルシリル基、トリイソプロビルシリル基、トリ フエニルシリル基、フエ二ルジェチルシリル基等）等が挙げられる。 Group, isopropyl group, tert_butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecinole group, tetradecinole group, pentadecinole group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.) An alkenyl group (for example, a buyl group, an aranole group, etc.), an alkynyl group (for example, an ethur group, a propargyl group, etc.), an allyl group (for example, a phenyl group, a naphthyl group, etc.), Furyl group, chenyl group, pyridinole group, pyridazinyl group, pyrimidinyl group, pyraduryl group, triazinyl group, imidazolinole group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthaladyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group) Group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (ex. For example, a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexinoreoxy group, an octyloxy group, a dodecinoreoxy group, etc.), a cycloalkoxynole group (for example, a cyclopentyloxy group, a cyclohexyloxy group, etc.), an aryloxy group ( For example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group) , Cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butoxycarbonyl group, The Oxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethyl) Aminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2_pyridylaminosulfonyl group, etc.) A acyl group (eg, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group) De de A silcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, a pyridylcarbonyl group, etc.), an acyloleoxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyl group) Oxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexane) Hexylcarbonylamino groups, 2-ethynole hexylcarbonylamino groups, octylcarbonylamino groups, dodecylcarbonylamino groups, phenylcarbonylamino groups, naphthylcarbonylamino groups, etc.) , Aminocarbonyl group, Tyraminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylamino force carbonyl group, octylaminocarbonyl group, 2_ethylhexylaminocarbonyl group, dodecylamino Carbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridinoreaminocarbonyl group, etc.), ureido group (for example, methenoureido group, ethylureido group, pentylureido group, cyclohexylureido group, Octylureido group, dodecinoureido group, phenylureido group naphthylureido group, 2-pyridinoreaminoureido group, etc., sulfier group (for example, methylsulfifer group, ethylsulfinyl group, butinourenorefinole group, cyclohexene) Xinoles Norefienol group, 2-ethynolehexinolesnorefienol group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group) Butylsulfonyl group, cyclohexylsulfonyl group, 2-ethynolehexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg phenylsulfonyl group, naphthylsulfonyl group, 2_pyridylsulfonyl group, etc.), amino Group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentynoleamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2_pyridinoreamino group, etc.), no, logogen (For example, fluorine atom, chlorine atom, bromine atom), fluorinated hydrocarbon group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, Hydroxyl group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylpropyl group, A phenylsilyl group, a phenyljetylsilyl group, etc.).
[0094] これらの置換基は上記の置換基によってさらに置換されていてもよい。また、これら の置換基は複数が互いに結合して環を形成していてもよい。好ましい置換基としては 、アルキル基、シクロアルキル基、フッ化炭化水素基、ァリール基、芳香族複素環基 である。  [0094] These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring. Preferred substituents are an alkyl group, a cycloalkyl group, a fluorinated hydrocarbon group, an aryl group, and an aromatic heterocyclic group.
[0095] 2価の連結基としては、アルキレン、アルケニレン、アルキニレン、ァリーレン等の炭 化水素基の他、ヘテロ原子を含むものであってもよぐまたチオフヱン _ 2， 5—ジィ ル基ゃピラジン一 2， 3—ジィル基のような芳香族複素環を有する化合物（ヘテロ芳 香族化合物ともいう）に由来する 2価の連結基であってもよいし、酸素や硫黄等の力 ルコゲン原子であってもよレ、。また、ァノレキノレイミノ基、ジアルキルシランジィル基ゃジ ァリールゲルマンジィル基のようなヘテロ原子を会して連結する基でもよい。  [0095] The divalent linking group may be a hydrocarbon group such as alkylene, alkenylene, alkynylene, arylene, etc., or may contain a heteroatom, and thiophene _ 2,5-diyl group may be pyrazine. 1 It may be a divalent linking group derived from a compound having an aromatic heterocycle such as a 2,3-diyl group (also referred to as a heteroaromatic compound), or it may be a force lucogen atom such as oxygen or sulfur. It ’s okay. In addition, a hetero atom such as an anolequinolemino group, a dialkylsilane diyl group or a diarylgermandyl group may be linked to meet each other.
[0096] 単なる結合手とは、連結する置換基同士を直接結合する結合手である。 [0096] The simple bond is a bond that directly bonds the connecting substituents together.
[0097] 本発明においては、前記一般式（2)の Zが形成する環は 6員環であることが好まし [0097] In the present invention, the ring formed by Z in the general formula (2) is preferably a 6-membered ring.
1  1
レ、。これにより、より発光効率を高くすることができる。また、本発明においては、 zが  Les. Thereby, luminous efficiency can be made higher. In the present invention, z is
2 形成する環は 6員環であることが好ましい。これにより、より発光効率を高くすることが できる。さらに Zと Zを共に 6員環とすることで、より一層発光効率と高くすることができ  2 The ring to be formed is preferably a 6-membered ring. Thereby, the luminous efficiency can be further increased. Furthermore, if both Z and Z are 6-membered rings, the luminous efficiency can be further increased.
1 2  1 2
るので好ましい。  Therefore, it is preferable.
[0098] 以下に、本発明に係る一般式（2)で表される化合物の具体例を示すが、本発明は これらに限定されない。  [0098] Specific examples of the compound represented by the general formula (2) according to the present invention are shown below, but the present invention is not limited thereto.
[0099] [化 11] [0099] [Chemical 11]
化 中心骨格 Central skeleton
Figure imgf000031_0001
12] 化合物 .Φ心骨格 A
Figure imgf000031_0001
12] Compound .Φ heart skeleton A
Figure imgf000032_0001
13]
Figure imgf000032_0001
13]
Figure imgf000033_0001
Figure imgf000033_0001
[0102] [化 14] [0102] [Chemical 14]
Figure imgf000034_0001
Figure imgf000034_0001
[0103] [化 15] 化合物 中心骨袼
Figure imgf000035_0001
[0103] [Chemical 15] Compound central urn
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000035_0002
16] 16]
Figure imgf000036_0001
Figure imgf000036_0001
[0105] [化 17] 化合物 中心骨格 A [0105] [Chemical 17] Compound Central skeleton A
Figure imgf000037_0001
Figure imgf000037_0001
18] 18]
Figure imgf000038_0001
Figure imgf000038_0001
[0107] [化 19] [0107] [Chemical 19]
Figure imgf000039_0001
Figure imgf000039_0001
[0108] [化 20] [0108] [Chemical 20]
Figure imgf000040_0001
Figure imgf000040_0001
[0109] [化 21] [0109] [Chemical 21]
ZZ^ [OIIO] ZZ ^ [OIIO]
Figure imgf000041_0001
Figure imgf000041_0001
Z90l70C/900Zdf/X3d 6S 888001/9001； OAV Z90l70C / 900Zdf / X3d 6S 888001/9001; OAV
Figure imgf000042_0001
Figure imgf000042_0001
[0111] [化 23] [0111] [Chemical 23]
Figure imgf000043_0001
Figure imgf000043_0001
[0112] [化 24] [0112] [Chemical 24]
OAV Ġ OAV Ġ
Figure imgf000044_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000045_0001
[0114] [化 26] [0114] [Chemical 26]
Figure imgf000046_0001
Figure imgf000046_0001
[0115] [化 27] [0115] [Chemical 27]
Figure imgf000047_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000048_0001
[0117] [化 29] [0117] [Chemical 29]
Figure imgf000049_0001
Figure imgf000049_0001
[0118] [化 30] [0118] [Chemical 30]
Figure imgf000050_0001
Figure imgf000050_0001
[0119] [化 31] [0119] [Chemical 31]
Figure imgf000051_0001
Figure imgf000051_0001
[0120] [化 32] [0120] [Chemical 32]
Figure imgf000052_0001
Figure imgf000052_0001
[0121] [化 33] [0121] [Chemical 33]
Figure imgf000053_0001
Figure imgf000053_0001
[0122] [化 34] [0122] [Chemical 34]
Figure imgf000054_0001
Figure imgf000054_0001
[0123] [化 35] [0123] [Chemical 35]
Figure imgf000055_0001
Figure imgf000055_0001
[0124] [化 36] [0124] [Chemical 36]
Figure imgf000056_0001
Figure imgf000056_0001
[0125] [化 37]
Figure imgf000057_0001
[0125] [Chemical 37]
Figure imgf000057_0001
147 147
Figure imgf000058_0001
39]
Figure imgf000058_0001
39]
Figure imgf000059_0001
Figure imgf000059_0001
[0128] [化 40] [0128] [Chemical 40]
Figure imgf000060_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000061_0001
[0130] [化 42] [0130] [Chemical 42]
Figure imgf000062_0001
Figure imgf000062_0001
[0132] [化 44] [0132] [Chemical 44]
Figure imgf000063_0001
Figure imgf000063_0001
[0133] [化 45] [0133] [Chemical 45]
Figure imgf000064_0001
Figure imgf000064_0001
Figure imgf000064_0002
Figure imgf000064_0002
本発明に係る発光層は上記化合物を、例えば、真空蒸着法、スピンコート法、キヤ スト法、 LB法等の公知の薄膜化法により製膜して形成することができる。発光層とし ての膜厚は特に制限はないが、通常は 5nm〜5 mの範囲で選ばれる。この発光層 はこれらの発光材料一種または二種以上からなる一層構造であってもよいし、または 同一組成または異種組成の複数層からなる積層構造であってもよい。 [0135] また、この発光層は特開昭 57— 51781号公報に記載されているように、樹脂等の 結着材と共に上記発光材料を溶剤に溶力して溶液とした後、これをスピンコート法等 により薄膜ィ匕して形成することができる。このようにして形成された発光層の膜厚につ いては特に制限はなぐ状況に応じて適宜選択することができるが、通常は 5nm〜5 μ mの範囲である。 The light emitting layer according to the present invention can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 5 nm to 5 m. This light emitting layer may have a single layer structure composed of one or two or more of these light emitting materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. [0135] Further, as described in JP-A-57-51781, this light-emitting layer is made into a solution by dissolving the above light-emitting material in a solvent together with a binder such as a resin, and then spinning it. It can be formed as a thin film by a coating method or the like. The film thickness of the light emitting layer formed in this manner can be appropriately selected depending on the situation where there is no particular limitation, but is usually in the range of 5 nm to 5 μm.
[0136] 〔阻止層（正孔阻止層、電子阻止層）〕  [Blocking layer (hole blocking layer, electron blocking layer)]
本発明に係る阻止層（例えば、正孔阻止層、電子阻止層）について説明する。本発 明に係る阻止層の膜厚としては好ましくは 3〜： !OOnmであり、さらに好ましくは 5〜30 nmである。  The blocking layer (for example, hole blocking layer, electron blocking layer) according to the present invention will be described. The thickness of the blocking layer according to the present invention is preferably 3 to:! OOnm, more preferably 5 to 30 nm.
[0137] (正孔阻止層）  [0137] (Hole blocking layer)
正孔阻止層とは広い意味では電子輸送層の機能を有し、電子を輸送する機能を有 しつつ正孔を輸送する能力が著しく小さい材料からなり、電子を輸送しつつ正孔を阻 止することで電子と正孔の再結合確率を向上させることができる。  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons and has a very small ability to transport holes, and blocks holes while transporting electrons. By doing so, the probability of recombination of electrons and holes can be improved.
[0138] 本発明においては、発光層に隣接する隣接層、例えば、正孔阻止層、電子阻止層 等に、本発明の有機 EL素子用材料を正孔阻止層に好ましく用いることができる。  In the present invention, the organic EL device material of the present invention can be preferably used for the hole blocking layer in an adjacent layer adjacent to the light emitting layer, for example, a hole blocking layer, an electron blocking layer and the like.
[0139] 正孔阻止層としては、例えば、特開平 11— 204258号公報、同 11 204359号公 報、及び「有機 EL素子とその工業化最前線（1998年 11月 30日 ェヌ 'ティー'エス 社発行）」の 237頁等に記載の正孔阻止（ホールブロック）層等を本発明に係る正孔 阻止層として適用可能である。また、後述する電子輸送層の構成を必要に応じて、本 発明に係る正孔阻止層として用いることができる。  [0139] Examples of the hole blocking layer include those disclosed in JP-A-11-204258, JP-A-11204359, and “OLED device and its forefront of industrialization” (November 30, 1998, NTS). The hole blocking (hole blocking) layer described on page 237 of “Issued by the company” can be used as the hole blocking layer according to the present invention. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
[0140] 本発明に係る正孔阻止層は、前記一般式 (2)で表される化合物を含有することが 好ましレ、。また、本発明に係る正孔阻止層には、ボロン誘導体が含まれることが好ま しい。  [0140] The hole blocking layer according to the present invention preferably contains the compound represented by the general formula (2). The hole blocking layer according to the present invention preferably contains a boron derivative.
[0141] (電子阻止層）  [0141] (Electron blocking layer)
一方、電子阻止層とは広い意味では正孔輸送層の機能を有し、正孔を輸送する機 能を有しつつ電子を輸送する能力が著しく小さい材料からなり、正孔を輸送しつつ電 子を阻止することで電子と正孔の再結合確率を向上させることができる。また、後述 する正孔輸送層の構成を必要に応じて電子阻止層として用いることができる。 [0142] また、本発明においては、発光層に隣接する隣接層、即ち正孔阻止層、電子阻止 層に、上記の本発明の有機 EL素子用材料を用いることが好ましぐ特に正孔阻止層 に用いることが好ましい。 On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and an extremely small capacity of transporting electrons. The probability of recombination of electrons and holes can be improved by blocking the children. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. [0142] In the present invention, it is preferable to use the organic EL device material of the present invention described above for the adjacent layer adjacent to the light emitting layer, that is, the hole blocking layer and the electron blocking layer. It is preferable to use it for the layer.
[0143] 〔正孔輸送層〕 [Hole transport layer]
正孔輸送層とは正孔を輸送する機能を有する材料を含み、広い意味で正孔注入 層、電子阻止層も正孔輸送層に含まれる。正孔輸送層は単層または複数層設けるこ とができる。  The hole transport layer includes a 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.
[0144] 正孔輸送材料としては特に制限はなぐ従来、光導伝材料において、正孔の電荷 注入輸送材料として慣用されているものや EL素子の正孔注入層、正孔輸送層に使 用される公知のものの中力 任意のものを選択して用いることができる。  [0144] There are no particular restrictions on the hole transport material. Conventionally, in photoconductive materials, it is commonly used as a hole charge injection / transport material, and used in the hole injection layer and hole transport layer of EL devices. Any known medium force can be selected and used.
[0145] 正孔輸送材料は正孔の注入または輸送、電子の障壁性のいずれかを有するもの であり、有機物、無機物のいずれであってもよレ、。例えば、トリァゾール誘導体、ォキ サジァゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン 誘導体及びピラゾロン誘導体、フエ二レンジァミン誘導体、ァリールァミン誘導体、アミ ノ置換カルコン誘導体、ォキサゾール誘導体、スチリルアントラセン誘導体、フルォレ ノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、ァニリン系共重 合体、また、導電性高分子オリゴマー、特にチォフェンオリゴマー等が挙げられる。  [0145] The hole transport material has either a hole injection or transport or electron barrier property, and may be either an organic or inorganic substance. 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, hydrazones Derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
[0146] 正孔輸送材料としては上記のものを使用することができる力 ポルフィリン化合物、 芳香族第三級ァミン化合物及びスチリルァミン化合物、特に芳香族第三級ァミン化 合物を用いることが好ましい。  [0146] The ability to use the above-mentioned materials as the hole transport material. It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, particularly an aromatic tertiary amine compound.
[0147] 芳香族第三級ァミン化合物及びスチリルァミン化合物の代表例としては、 N, N, N ' , Nr —テトラフエニル _4， 4; —ジァミノフエニル； Ν， Ν' —ジフエ二ノレ _Ν, Ν ' —ビス（3—メチルフエ二ル）一〔1， 1' —ビフエ二ル〕一 4, 一ジァミン（TPD) ; 2, 2 _ビス（4—ジ一 ρ—トリルァミノフエニル）プロパン； 1， 1 _ビス（4 _ジ_ _トリ ルァミノフエニル）シクロへキサン； Ν, Ν, Ν' , Nr —テトラ一 p—トリル一 4， 4' - ジアミノビフエニル； 1， 1—ビス（4—ジ一 p—トリルァミノフエニル）一4—フエ二ルシク 口へキサン；ビス（4 -ジメチルアミノー 2 -メチルフエニル）フエニルメタン；ビス（4 -ジ —p—トリルァミノフエニル）フエニルメタン； N, N' —ジフエ二ノレ一 N， N' —ジ（4— メトキシフエ二ル）一 4, 一ジアミノビフエニル； N, N, , Ν' —テトラフェニル — 4, 4' —ジアミノジフエニルエーテル； 4, 一ビス（ジフエニルァミノ）クオ一ドリフ ェニル； Ν, Ν, Ν—トリ（ρ—トリル）ァミン； 4— (ジ— ρ—トリルァミノ）— —〔4— (ジ _ ρ—トリルァミノ）スチリル〕スチルベン； 4 _ Ν, Ν—ジフヱニルァミノ一（2—ジフヱ二 ルビニル）ベンゼン； 3—メトキシ一 4' _ Ν, Ν—ジフエニルアミノスチルベンゼン； Ν —フヱ二ルカルバゾール、さらには米国特許第 5, 061， 569号明細書に記載されて いる 2個の縮合芳香族炭化水素環を分子内に有するもの、例えば、 4, 一ビス〔Ν - ( 1—ナフチル） _ Ν _フエニルァミノ〕ビフヱニル（NPD)、特開平 4— 308688号 公報に記載されているトリフエニルァミンユニットが 3つスターバースト型に連結された 4, , " —トリス〔1^— (3—メチルフエ二ル）一 Ν—フエニルァミノ〕トリフエニルアミ ン（MTDATA)等が挙げられる。 [0147] Typical examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N r —tetraphenyl _4, 4 ; — diaminophenyl; Ν, Ν' — diphenylenole _Ν, Ν '— Bis (3-methylphenyl) -1- [1,1'-biphenyl] -1,4-diamine (TPD); 2, 2 _bis (4-di-ρ-tolylaminophenyl) propane; 1, 1 _Bis (4_di__trilaminophenyl) cyclohexane; Ν, Ν, Ν ', N r —tetra-p-tolyl-1,4′-diaminobiphenyl; 1,1-bis (4-di-one) p-tolylaminophenyl) 1-4-phenyl mouth hexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N '— Gifu Ninore N, N '— Di (4— Methoxyphenyl) 1,4,1 diaminobiphenyl; N, N,, Ν '—tetraphenyl — 4, 4' —diaminodiphenyl ether; 4, 1 bis (diphenylamino) quadophenyl; Ν, Ν, Ν —Tri (ρ-tolyl) amine; 4— (Di-ρ-tolylamino) — — [4— (Di_ρ-tolylamino) styryl] stilbene; 4 _ Ν, Ν-diphenylamino (2-diphenyl) benzene 3-methoxy-1 4′_Ν, Ν-diphenylaminostilbenzene; Ν-vinylcarbazole, and two condensed aromatics described in US Pat. No. 5,061,569 Having a hydrocarbon ring in the molecule, for example, triphenylamine described in 4,1bis [Ν- (1-naphthyl) _Ν_phenylamino] biphenyl (NPD), JP-A-4-308688 3 units Starverse 4,, "-tris [1 ^-(3-methylphenyl) -l-phenylamino] triphenylamine (MTDATA), etc., linked in a to-type form.
[0148] さらにこれらの材料を高分子鎖に導入した、またはこれらの材料を高分子の主鎖と した高分子材料を用いることもできる。また、 ρ型— Si、 p型— SiC等の無機化合物も 正孔注入材料、正孔輸送材料として使用することができる。また、本発明においては 、正孔輸送層の正孔輸送材料は 415nm以下に蛍光極大波長を有することが好まし く、リン光の 0— 0バンドが 450nm以下であることがさらに好ましい。また、正孔輸送材 料は高 Tgであることが好ましレ、。  [0148] Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials as a polymer main chain can also be used. Inorganic compounds such as ρ-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. In the present invention, the hole transport material of the hole transport layer preferably has a fluorescence maximum wavelength of 415 nm or less, and more preferably has a 0-0 band of phosphorescence of 450 nm or less. Also, the hole transport material is preferably high Tg.
[0149] この正孔輸送層は上記正孔輸送材料を、例えば、真空蒸着法、スピンコート法、キ ヤスト法、インクジェット法、 LB法等の公知の方法により、薄膜化することにより形成す ること力 Sできる。正孔輸送層の膜厚については特に制限はなレ、が、通常は 5〜5000 nm程度である。この正孔輸送層は上記材料の一種または二種以上からなる一層構 造であってもよい。  [0149] The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. That power S. The thickness of the hole transport layer is not particularly limited, but is usually about 5 to 5000 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.
[0150] 〔電子輸送層〕  [0150] [Electron transport layer]
電子輸送層とは電子を輸送する機能を有する材料からなり、広い意味で電子注入 層、正孔阻止層も電子輸送層に含まれる。電子輸送層は単層または複数層を設ける こと力 Sできる。  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 multiple layers.
[0151] 従来、単層の電子輸送層、及び複数層とする場合は発光層に対して陰極側に隣 接する電子輸送層に用レ、られる電子輸送材料 (正孔阻止材料を兼ねる）としては、下 記の材料が知られている。さらに、電子輸送層は陰極より注入された電子を発光層に 伝達する機能を有していればよぐその材料としては従来公知の化合物の中力 任 意のものを選択して用いることができる。 [0151] Conventionally, when a single electron transport layer and a plurality of layers are used, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is used. ,under The following materials are known. Further, the electron transport layer only needs to have a function of transferring electrons injected from the cathode to the light emitting layer, and any material of any conventionally known compound can be selected and used. .
[0152] この電子輸送層に用いられる材料 (以下、電子輸送材料という）の例としては、ニト 口置換フルオレン誘導体、ジフヱ二ルキノン誘導体、チォピランジオキシド誘導体、ナ フタレンペリレン等の複素環テトラカルボン酸無水物、力ノレポジイミド、フレオレニリデ ンメタン誘導体、アントラキノジメタン及びアントロン誘導体、ォキサジァゾール誘導体 等が挙げられる。さらに上記ォキサジァゾール誘導体において、ォキサジァゾール環 の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子吸引基として知られ ているキノキサリン環を有するキノキサリン誘導体も、電子輸送材料として用いること ができる。  [0152] Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetrafluoride derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, and other heterocyclic tetra Examples thereof include carboxylic acid anhydrides, force-repository imides, fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
[0153] さらにこれらの材料を高分子鎖に導入した、またはこれらの材料を高分子の主鎖と した高分子材料を用いることもできる。  [0153] Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials as a polymer main chain can also be used.
[0154] また、 8 キノリノール誘導体の金属錯体、例えば、トリス（8 キノリノール）アルミ二 ゥム（Alq)、トリス（5, 7—ジクロロ一 8—キノリノール）アルミニウム、トリス（5, 7—ジブ 口モー 8 キノリノール）アルミニウム、トリス（2 メチル 8 キノリノール）アルミニゥ ム、トリス（5—メチル 8—キノリノール）アルミニウム、ビス（8—キノリノール）亜鉛（Zn q)等、及びこれらの金属錯体の中心金属が In、 Mg、 Cu、 Ca、 Sn、 Gaまたは Pbに 置き替わった金属錯体も電子輸送材料として用いることができる。その他、メタルフリ 一またはメタルフタロシアニン、またはそれらの末端がアルキル基ゃスルホン酸基等 で置換されているものも、電子輸送材料として好ましく用いることができる。また、発光 層の材料として例示したジスチリルビラジン誘導体も、電子輸送材料として用いること ができるし、正孔注入層、正孔輸送層と同様に、 n型 _ Si、 n型 _ SiC等の無機半導 体も電子輸送材料として用いることができる。 [0154] In addition, metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-dib mouth mode) 8 quinolinol) aluminum, tris (2methyl 8quinolinol) aluminum, tris (5-methyl 8-quinolinol) aluminum, bis (8-quinolinol) zinc (Zn q), etc., and the central metal of these metal complexes is In, Metal complexes replacing Mg, Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials. In addition, metal free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylvirazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, n-type Si, n- type SiC, etc. Inorganic semiconductors can also be used as electron transport materials.
[0155] この電子輸送層は上記電子輸送材料を、例えば、真空蒸着法、スピンコート法、キ ヤスト法、インクジヱット法、 LB法等の公知の方法により、薄膜化することにより形成す ること力 Sできる。電子輸送層の膜厚については特に制限はないが、通常は 5〜5000 nm程度である。この電子輸送層は上記材料の一種または二種以上からなる一層構 造であってもよい。 [0155] This electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. S can. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, it is about 5-5000 nm. This electron transport layer has a single layer structure composed of one or more of the above materials. It may be made.
[0156] 次に、本発明の有機 EL素子の構成層として用いられる、注入層について説明する  Next, an injection layer used as a constituent layer of the organic EL element of the present invention will be described.
[0157] 〔注入層（電子注入層、正孔注入層）〕 [Injection layer (electron injection layer, hole injection layer)]
注入層は必要に応じて設け、電子注入層と正孔注入層があり、上記のごとく陽極と 発光層または正孔輸送層の間、及び陰極と発光層または電子輸送層との間に存在 させてもよい。  The injection layer is provided as necessary, and has an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or hole transport layer and between the cathode and the light emitting layer or electron transport layer. May be.
[0158] 注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる 層のことで、「有機 EL素子とその工業化最前線（1998年 11月 30日 ェヌ 'ティー'ェ ス社発行）」の第 2編第 2章「電極材料」（123〜166頁）に詳細に記載されており、正 孔注入層（陽極バッファ一層）と電子注入層（陰極バッファ一層）とがある。  [0158] The injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of the light emission. “The organic EL element and the forefront of industrialization (November 30, 1998, NTT) 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “The Company”), the hole injection layer (anode buffer layer) and the electron injection layer (cathode buffer layer). There is.
[0159] 陽極バッファ一層（正孔注入層）は、特開平 9— 45479号公報、同 9一 260062号 公報、同 8— 288069号公報等にもその詳細が記載されており、具体例として、銅フ タロシアニンに代表されるフタロシアニンバッファ一層、酸化バナジウムに代表される 酸化物バッファ一層、アモルファスカーボンバッファ一層、ポリア二リン（ェメラルディ ン)やポリチォフェン等の導電性高分子を用いた高分子バッファ一層等が挙げられる  [0159] The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. One layer of phthalocyanine buffer typified by copper phthalocyanine, one layer of oxide buffer typified by vanadium oxide, one layer of amorphous carbon buffer, one layer of polymer buffer using a conductive polymer such as polyaniline (emeraldine) or polythiophene, etc. Can be mentioned
[0160] 陰極バッファ一層（電子注入層）は、特開平 6— 325871号公報、同 9 17574号 公報、同 10— 74586号公報等にもその詳細が記載されており、具体的にはストロン チウムゃアルミニウム等に代表される金属バッファ一層、フッ化リチウムに代表される アルカリ金属化合物バッファ一層、フッ化マグネシウムに代表されるアルカリ土類金 属化合物バッファ一層、酸化アルミニウムに代表される酸化物バッファ一層等が挙げ られる。 [0160] The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-917574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide Etc.
[0161] 上記バッファ一層（注入層）はごく薄い膜であることが望ましぐ素材にもよるがその 膜厚は 0. 1〜： !OOnmの範囲が好ましい。  [0161] The buffer layer (injection layer) preferably has a very thin film thickness, although the film thickness is preferably in the range of 0.1 to: OOnm.
[0162] この注入層は上記材料を、例えば、真空蒸着法、スピンコート法、キャスト法、インク ジェット法、 LB法等の公知の方法により、薄膜ィ匕することにより形成することができる 。注入層の膜厚については特に制限はなレ、が、通常は 5〜5000nm程度である。こ の注入層は上記材料の一種または二種以上からなる一層構造であってもよい。 [0162] This injection layer can be formed by thin-filming the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. The thickness of the injection layer is not particularly limited, but is usually about 5 to 5000 nm. This The injection layer may have a single layer structure composed of one or more of the above materials.
[0163] 〔陽極〕  [0163] [Anode]
本発明の有機 EL素子に係る陽極としては、仕事関数の大きい (4eV以上)金属、 合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用い られる。このような電極物質の具体例としては、 Au等の金属、 Cul、インジウムチンォ キシド（IT〇）、 Sn〇、 ZnO等の導電性透明材料が挙げられる。また、 IDIX〇（In〇  As the anode of the organic EL device of the present invention, 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. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as Cul, indium tin oxide (ITO), SnO, and ZnO. IDIX〇 (In〇
2 2 3 2 2 3
_Zn〇)等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの 電極物質を蒸着やスパッタリング等の方法により薄膜を形成させ、フォトリソグラフィー 法で所望の形状のパターンを形成してもよぐまたはパターン精度をあまり必要としな い場合は（100 μ m以上程度）、上記電極物質の蒸着やスパッタリング時に所望の形 状のマスクを介してパターンを形成してもよい。この陽極より発光を取り出す場合には 、透過率を 10%より大きくすることが望ましぐまた、陽極としてのシート抵抗は数百 Ω /口以下が好ましい。さらに膜厚は材料にもよる力 通常 10〜： 1000nm、好ましくは 10〜200nmの範囲で選ばれる。 A material such as _ZnO) that is amorphous and capable of producing a transparent conductive film may be used. For the anode, these electrode materials can be formed into a thin film by vapor deposition or sputtering, and a pattern of the desired shape can be formed by photolithography, or when the pattern accuracy is not so high (100 μm As described above, a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. In the case of taking out light emission from this anode, it is desirable to have a transmittance of more than 10%, and the sheet resistance as the anode is preferably several hundred Ω / mouth or less. Further, the film thickness is a force depending on the material. Usually, 10 to 1000 nm, preferably 10 to 200 nm is selected.
[0164] 〔陰極〕 [0164] [Cathode]
一方、本発明に係る陰極としては、仕事関数の小さい (4eV以下)金属（電子注入 性金属と称する）、合金、電気伝導性化合物及びこれらの混合物を電極物質とするも のが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム一力リウ ム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物 、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム /酸化アルミニウム (Al O )混合物、インジウム、リチウム/アルミニウム混合物、希  On the other hand, as the cathode according to the present invention, 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 is used. Specific examples of such electrode materials include sodium, sodium isotropic lithium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al O) mixture, indium, lithium / aluminum mixture, dilute
2 3  twenty three
土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の 点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金 属との混合物、例えば、マグネシウム Z銀混合物、マグネシウム Zアルミニウム混合 物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム (Al O )混合  Examples include earth metals. Among these, from the viewpoint of electron injectability and durability against oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium Z silver mixture , Magnesium Z aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O) mixture
2 3 物、リチウム/アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電 極物質を蒸着やスパッタリング等の方法により、薄膜を形成させることにより作製する こと力 sできる。また、陰極としてのシート抵抗は数百 Ω Ζ口以下が好ましぐ膜厚は通 常 10〜： 1000nm、好ましくは 50〜200nmの範囲で選ばれる。なお、発光を透過さ せるため、有機 EL素子の陽極または陰極のいずれか一方力 透明または半透明で あれば発光輝度が向上し好都合である。 2 3 compounds, 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. In addition, the sheet resistance as a cathode is several hundred Ω. Usually 10 to: 1000 nm, preferably 50 to 200 nm. In order to transmit light, it is convenient that either the anode or the cathode of the organic EL element is transparent or translucent to improve the light emission luminance.
[0165] 〔基体 (基板、基材、支持体等ともいう）〕 [Substrate (also referred to as substrate, substrate, support, etc.)]
本発明の有機 EL素子に係る基体としては、ガラス、プラスチック等の種類には特に 限定はなぐまた透明のものであれば特に制限はないが、好ましく用いられる基板と しては、例えば、ガラス、石英、光透過性樹脂フィルムを挙げることができる。特に好 ましい基体は、有機 EL素子にフレキシブル性を与えることが可能な樹脂フィルムであ る。  The substrate of the organic EL device of the present invention is not particularly limited as long as it is transparent or transparent, and there are no particular restrictions on the type of glass, plastic, etc. Examples of substrates that are preferably used include glass, Examples thereof include quartz and a light-transmitting resin film. A particularly preferred substrate is a resin film that can give flexibility to the organic EL element.
[0166] 樹脂フィルムとしては、例えば、ポリエチレンテレフタレート（PET)、ポリエチレンナ フタレート（PEN)、ポリエーテルスルホン（PES)、ポリエーテルイミド、ポリエーテル エーテルケトン、ポリフエ二レンスルフイド、ポリアリレート、ポリイミド、ポリカーボネート (PC)、セルローストリアセテート（TAC)、セルロースアセテートプロピオネート（CAP )等からなるフィルム等が挙げられる。  [0166] Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate ( PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like.
[0167] 樹脂フィルムの表面には、無機物または有機物の被膜またはその両者のハイブリツ ド被膜が形成されていてもよぐ水蒸気透過率が 0. 01g/m2' day' atm以下の高バ リア性フィルムであることが好ましレ、。 [0167] The surface of the resin film may have an inorganic or organic coating or a hybrid coating of both, and the water vapor permeability is 0.01 g / m 2 'day' atm or less. It is preferred to be a film.
[0168] 本発明の有機 EL素子の発光の室温における外部取り出し量子効率は、 1 %以上 であることが好ましぐより好ましくは 2%以上である。ここに、外部取り出し量子効率（ %) =有機 EL素子外部に発光した光子数/有機 EL素子に流した電子数 X 100で ある。  [0168] The external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 2% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons flowed to the organic EL element × 100.
[0169] また、カラーフィルタ一等の色相改良フィルタ一等を併用してもよい。  [0169] Further, a hue improving filter such as a color filter may be used in combination.
[0170] 照明用途で用いる場合には、発光ムラを低減させるために粗面加工したフィルム（ アンチグレアフイノレム等）を併用することもできる。  [0170] When used for illumination, a roughened film (such as anti-glare phenol) may be used in combination in order to reduce unevenness in light emission.
[0171] 多色表示装置として用いる場合は少なくとも 2種類の異なる発光極大波長を有する 有機 EL素子からなるが、有機 EL素子を作製する好適な例を説明する。 [0171] When used as a multicolor display device, it is composed of at least two types of organic EL elements having different light emission maximum wavelengths. A preferred example of producing an organic EL element will be described.
[0172] 〔有機 EL素子の作製方法〕 [Method of manufacturing organic EL element]
本発明の有機 EL素子の作製方法の一例として、陽極 Z正孔注入層 Z正孔輸送層 /発光層/正孔阻止層/電子輸送層/陰極バッファー層/陰極からなる有機 EL 素子の作製法について説明する。 As an example of a method for producing the organic EL device of the present invention, an anode Z hole injection layer Z hole transport layer A method for producing an organic EL device composed of / luminescent layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode will be described.
[0173] まず適当な基体上に所望の電極物質、例えば、陽極用物質からなる薄膜を 1 μ m 以下、好ましくは 10〜200nmの膜厚になるように、蒸着やスパッタリング等の方法に より形成させ、陽極を作製する。次に、この上に素子材料である正孔注入層、正孔輸 送層、発光層、正孔阻止層、電子輸送層等の有機化合物を含有する薄膜を形成さ せる。 [0173] First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably 10 to 200 nm. To produce an anode. Next, 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, or an electron transport layer, which is an element material, is formed thereon.
[0174] この有機化合物を含有する薄膜の薄膜化の方法としては、前記の如くスピンコート 法、キャスト法、インクジェット法、蒸着法、印刷法等があるが、均質な膜が得られや すぐかつピンホールが生成しにくい等の点から、真空蒸着法またはスピンコート法 が特に好ましい。さらに層ごとに異なる製膜法を適用してもよい。製膜に蒸着法を採 用する場合、その蒸着条件は、使用する化合物の種類等により異なるが、一般にボ 一トカ卩熱温度 50〜450°C、真空度 10— 6〜： 10— 2Pa、蒸着速度 0. 01〜50nm/秒、基 板温度— 50〜300°C、膜厚 0. lnm〜5 /i mの範囲で適宜選ぶことが望ましい。 [0174] As described above, there are spin coating method, casting method, ink jet method, vapor deposition method, printing method and the like as a method for thinning the thin film containing the organic compound, but it is easy to obtain a homogeneous film. The vacuum deposition method or the spin coating method is particularly preferable from the viewpoint of difficulty in generating pinholes. Further, different film forming methods may be applied for each layer. If you use the film adopts the deposition, the deposition conditions vary due to kinds of materials used, generally baud solved卩熱temperature 50 to 450 ° C, vacuum degree of 10- 6 ~: 10- 2 Pa Desirably, the deposition rate is 0.01 to 50 nm / second, the substrate temperature is 50 to 300 ° C., and the film thickness is 0.1 nm to 5 / im.
[0175] これらの層の形成後、その上に陰極用物質からなる薄膜を、 1 β m以下好ましくは 5 0〜200nmの範囲の膜厚になるように、例えば、蒸着やスパッタリング等の方法によ り形成させ、陰極を設けることにより、所望の有機 EL素子が得られる。この有機 EL素 子の作製は、一回の真空引きで一貫して正孔注入層から陰極まで作製するのが好ま しいが、途中で取り出して異なる製膜法を施しても構わない。その際、作業を乾燥不 活性ガス雰囲気下で行う等の配慮が必要となる。  [0175] After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so that the film thickness is 1 β m or less, preferably in the range of 50 to 200 nm. The desired organic EL device can be obtained by forming the cathode and providing a cathode. The organic EL element is preferably manufactured 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 necessary to consider that the work is performed in a dry inert gas atmosphere.
[0176] 〔表示装置〕  [Display device]
本発明の表示装置について説明する。  The display device of the present invention will be described.
[0177] 本発明の表示装置は単色でも多色でもよいが、ここでは多色表示装置について説 明する。多色表示装置の場合は発光層形成時のみシャドーマスクを設け、一面に蒸 着法、キャスト法、スピンコート法、インクジェット法、印刷法等で膜を形成できる。  [0177] The display device of the present invention may be monochromatic or multicolor, but here, a multicolor display device will be described. In the case of a multicolor display device, 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 casting method, a spin coating method, an ink jet method, a printing method, or the like.
[0178] 発光層のみパターユングを行う場合その方法に限定はないが、好ましくは蒸着法、 インクジェット法、印刷法である。蒸着法を用いる場合においては、シャドーマスクを 用レ、たパターユングが好ましレ、。 [0179] また作製順序を逆にして、陰極、電子輸送層、正孔阻止層、発光層、正孔輸送層、 陽極の順に作製することも可能である。 [0178] When patterning is performed only on the light emitting layer, the method is not limited, but the vapor deposition method, the ink jet method, and the printing method are preferable. When using a vapor deposition method, use a shadow mask, and use a patterning plate. [0179] Further, the order of preparation may be reversed, and the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, and the anode may be formed in this order.
[0180] このようにして得られた多色表示装置に直流電圧を印加する場合には、陽極を +、 陰極を—の極性として電圧 2〜40V程度を印加すると発光が観測できる。また、逆の 極性で電圧を印加しても電流は流れずに発光は全く生じない。さらに交流電圧を印 加する場合には、陽極が十、陰極が—の状態になったときのみ発光する。なお、印 加する交流の波形は任意でょレ、。  [0180] When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. In addition, even if a voltage is applied with the opposite polarity, no current flows and no light is emitted. In addition, when an AC voltage is applied, light is emitted only when the anode is in the ten state and the cathode is in the negative state. The AC waveform to be applied is arbitrary.
[0181] 多色表示装置は表示デバイス、ディスプレイ、各種発光光源として用いることができ る。表示デバイス、ディスプレイにおいて、青、赤、緑発光の 3種の有機 EL素子を用 レ、ることにより、フルカラーの表示が可能となる。  [0181] The multicolor display device can be used as a display device, a display, and various light sources. Full color display is possible by using three types of organic EL elements, blue, red, and green, for display devices and displays.
[0182] 表示デバイス、ディスプレイとしてはテレビ、パソコン、モパイル機器、 AV機器、文 字放送表示、自動車内の情報表示等が挙げられる。特に静止画像や動画像を再生 する表示装置として使用してもよぐ動画再生用の表示装置として使用する場合の駆 動方式は単純マトリックス（パッシブマトリックス）方式でもアクティブマトリックス方式で もどちらでもよい。  [0182] Display devices and displays include TVs, personal computers, mopile devices, AV devices, text broadcast displays, information displays in automobiles, and the like. In particular, the driving method when used as a display device for reproducing moving images, which may be used as a display device for reproducing still images or moving images, may be either a simple matrix (passive matrix) method or an active matrix method.
[0183] 発光光源としては家庭用照明、車内照明、時計や液晶用のバックライト、看板広告 、信号機、光記憶媒体の光源、電子写真複写機の光源、光通信処理機の光源、光 センサーの光源等が挙げられるがこれに限定するものではない。  [0183] Light emitting 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 sensors Although a light source etc. are mentioned, it is not limited to this.
[0184] 〔照明装置〕  [0184] [Lighting device]
本発明の照明装置について説明する。  The lighting device of the present invention will be described.
[0185] 本発明の有機 EL素子に共振器構造を持たせた有機 EL素子として用いてもよぐこ のような共振器構造を有した有機 EL素子の使用目的としては、光記憶媒体の光源、 電子写真複写機の光源、光通信処理機の光源、光センサーの光源等が挙げられる が、これらに限定されない。またレーザー発振をさせることにより、上記用途に使用し てもよい。  [0185] The organic EL element having a resonator structure may be used as an organic EL element having a resonator structure in the organic EL element of the present invention. Examples include, but are not limited to, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, and the like. Further, it may be used for the above application by causing laser oscillation.
[0186] また、本発明の有機 EL素子は、照明用や露光光源のような一種のランプとして使 用してもよいし、画像を投影するタイプのプロジェクシヨン装置や、静止画像や動画像 を直接視認するタイプの表示装置 (ディスプレイ）として使用してもよい。動画再生用 の表示装置として使用する場合の駆動方式は単純マトリックス (パッシブマトリックス） 方式でもアクティブマトリックス方式でもどちらでもよい。または異なる発光色を有する 本発明の有機 EL素子を 2種以上使用することにより、フルカラー表示装置を作製す ることが可能である。 [0186] Further, the organic EL device of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device of a type for projecting an image, a still image or a moving image. It may be used as a type of display device (display) that is directly visible. For video playback When used as a display device, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full color display device can be produced by using two or more organic EL elements of the present invention having different emission colors.
[0187] 本発明の有機 EL素子から構成される表示装置の一例を図面に基づいて説明する  An example of a display device composed of the organic EL element of the present invention will be described with reference to the drawings.
[0188] 図 1は、有機 EL素子から構成される表示装置の一例を示した模式図である。有機 EL素子の発光により画像情報の表示を行う、例えば、携帯電話等のディスプレイの 模式図である。 [0188] FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. FIG. 2 is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
[0189] ディスプレイ 1は、複数の画素を有する表示部 A、画像情報に基づいて表示部 Aの 画像走查を行う制御部 B等からなる。  [0189] The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image staging of the display unit A based on image information, and the like.
[0190] 制御部 Bは、表示部 Aと電気的に接続され、複数の画素それぞれに外部からの画 像情報に基づいて走査信号と画像データ信号を送り、走査信号により走査線ごとの 画素が画像データ信号に応じて順次発光して画像走査を行って画像情報を表示部[0190] 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. The image information is displayed by sequentially emitting light according to the image data signal and displaying the image information.
Aに表示する。 Display on A.
[0191] 図 2は、表示部 Aの模式図である。 FIG. 2 is a schematic diagram of the display unit A.
[0192] 表示部 Aは基板上に、複数の走査線 5及びデータ線 6を含む配線部と、複数の画 素 3等とを有する。表示部 Aの主要な部材の説明を以下に行う。図 2においては、画 素 3の発光した光が、白矢印方向（下方向）へ取り出される場合を示している。  The display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below. FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
[0193] 配線部の走査線 5及び複数のデータ線 6は、各々導電材料からなり、走査線 5とデ ータ線 6は格子状に直交して、直交する位置で画素 3に接続してレ、る（詳細は図示せ ず)。  [0193] 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. (The details are not shown).
[0194] 画素 3は、走査線 5から走查信号が印加されると、データ線 6から画像データ信号を 受け取り、受け取った画像データに応じて発光する。発光の色が赤領域の画素、緑 領域の画素、青領域の画素を、適宜、同一基板上に並置することによって、フルカラ 一表示が可能となる。  [0194] When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light in accordance with the received image data. Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
[0195] 次に、画素の発光プロセスを説明する。  [0195] Next, the light emission process of the pixel will be described.
[0196] 図 3は、画素の模式図である。 [0197] 画素は、有機 EL素子 10、スイッチングトランジスタ 11、駆動トランジスタ 12、コンデ ンサ 13等を備えている。複数の画素に有機 EL素子 10として、赤色、緑色、青色発 光の有機 EL素子を用い、これらを同一基板上に並置することでフルカラー表示を行 うことができる。 FIG. 3 is a schematic diagram of a pixel. [0197] The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. Full-color display can be performed by using organic EL elements of red, green, and blue light emission as organic EL elements 10 in a plurality of pixels and arranging them on the same substrate.
[0198] 図 3において、制御部 Bからデータ線 6を介してスイッチングトランジスタ 11のドレイ ンに画像データ信号が印加される。そして、制御部 Bから走査線 5を介してスィッチン グトランジスタ 11のゲートに走查信号が印加されると、スイッチングトランジスタ 11の 駆動がオンし、ドレインに印加された画像データ信号がコンデンサ 13と駆動トランジ スタ 12のゲートに伝達される。  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6. When a stray 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 driven by the capacitor 13. It is transmitted to the gate of transistor 12.
[0199] 画像データ信号の伝達により、コンデンサ 13が画像データ信号の電位に応じて充 電されるとともに、駆動トランジスタ 12の駆動がオンする。駆動トランジスタ 12は、ドレ インが電源ライン 7に接続され、ソースが有機 EL素子 10の電極に接続されており、ゲ 一トに印加された画像データ信号の電位に応じて電源ライン 7から有機 EL素子 10に 電流が供給される。  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of 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 organic EL element is connected from the power supply line 7 according to the potential of the image data signal applied to the gate. Current is supplied to element 10.
[0200] 制御部 Bの順次走査により走査信号が次の走査線 5に移ると、スイッチングトランジ スタ 11の駆動がオフする。しかし、スイッチングトランジスタ 11の駆動がオフしてもコン デンサ 13は充電された画像データ信号の電位を保持するので、駆動トランジスタ 12 の駆動はオン状態が保たれて、次の走査信号の印加が行われるまで有機 EL素子 1 0の発光が継続する。順次走査により次に走査信号が印加されたとき、走査信号に 同期した次の画像データ信号の電位に応じて駆動トランジスタ 12が駆動して有機 E L素子 10が発光する。  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 holds 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. The organic EL device 10 continues to emit light until it is seen. When a 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.
[0201] 即ち、有機 EL素子 10の発光は、複数の画素それぞれの有機 EL素子 10に対して 、アクティブ素子であるスイッチングトランジスタ 11と駆動トランジスタ 12を設けて、複 数の画素 3それぞれの有機 EL素子 10の発光を行っている。このような発光方法をァ クティブマトリックス方式と呼んでレ、る。  That is, the organic EL element 10 emits light by providing a switching transistor 11 and a driving transistor 12 as active elements for each of the organic EL elements 10 of each of the plurality of pixels. Element 10 is emitting light. Such a light emitting method is called an active matrix method.
[0202] ここで、有機 EL素子 10の発光は、複数の階調電位を持つ多値の画像データ信号 による複数の階調の発光でもよいし、 2値の画像データ信号による所定の発光量の オン、オフでもよい。 [0203] また、コンデンサ 13の電位の保持は、次の走査信号の印加まで継続して保持して もよレ、し、次の走査信号が印加される直前に放電させてもょレ、。 [0202] Here, 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 a predetermined light emission amount of the binary image data signal. It may be on or off. [0203] Also, the potential of the capacitor 13 can be maintained until the next scanning signal is applied, or can be discharged immediately before the next scanning signal is applied.
[0204] 本発明においては、上述したアクティブマトリックス方式に限らず、走査信号が走査 されたときのみデータ信号に応じて有機 EL素子を発光させるパッシブマトリックス方 式の発光駆動でもよい。 [0204] In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.
[0205] 図 4は、パッシブマトリックス方式による表示装置の模式図である。図 4において、複 数の走査線 5と複数の画像データ線 6が画素 3を挟んで対向して格子状に設けられ ている。 FIG. 4 is a schematic diagram of a display device using a passive matrix method. In FIG. 4, 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.
[0206] 順次走查により走査線 5の走查信号が印加されたとき、印加された走査線 5に接続 している画素 3が画像データ信号に応じて発光する。パッシブマトリックス方式では画 素 3にアクティブ素子がなぐ製造コストの低減が計れる。  [0206] When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal. The passive matrix method can reduce the manufacturing cost of an active element in addition to pixel 3.
[0207] 本発明に係わる有機 EL材料は、また、照明装置として、実質白色の発光を生じる 有機 EL素子に適用できる。複数の発光材料により複数の発光色を同時に発光させ て混色により白色発光を得る。複数の発光色の組み合わせとしては、青色、緑色、青 色の 3原色の 3つの発光極大波長を含有させたものでもよいし、青色と黄色、青緑と 橙色等の補色の関係を利用した 2つの発光極大波長を含有したものでもよい。  [0207] The organic EL material according to the present invention can also 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 mixing colors. The combination of multiple emission colors may include the three maximum emission wavelengths of the three primary colors of blue, green, and blue, and it uses the relationship of complementary colors such as blue and yellow, and blue-green and orange 2 It may be one containing two emission maximum wavelengths.
[0208] また、複数の発光色を得るための発光材料の組み合わせは、複数のリン光または 蛍光を発光する材料 (発光ドーパント）を、複数組み合わせたもの、蛍光またはリン光 を発光する発光材料と、該発光材料力 の光を励起光として発光する色素材料とを 組み合わせたもののレ、ずれでもよレ、が、本発明に係わる白色有機 EL素子にぉレ、て は、発光ドーパントを複数組み合わせる方式が好ましレ、。  [0208] In addition, a combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescent or phosphorescent light, and A combination of a dye material that emits light of the light emitting material power as excitation light may be misaligned. However, the white organic EL element according to the present invention may be combined with a plurality of light emitting dopants. Is preferred.
[0209] 複数の発光色を得るための有機 EL素子の層構成としては、複数の発光ドーパント を、一つの発光層中に複数存在させる方法、複数の発光層を有し、各発光層中に発 光波長の異なるドーパントをそれぞれ存在させる方法、異なる波長に発光する微小 画素をマトリックス状に形成する方法等が挙げられる。  [0209] The layer structure of the organic EL device for obtaining a plurality of emission colors includes a method in which a plurality of emission dopants exist in one emission layer, a plurality of emission layers, and each emission layer includes Examples include a method in which dopants having different emission wavelengths are present, and a method in which minute pixels that emit light at different wavelengths are formed in a matrix.
[0210] 本発明に係わる白色有機 EL素子においては、必要に応じ製膜時にメタルマスクや インクジェットプリンティング法等でパターユングを施してもよレ、。パターユングする場 合は、電極のみをパターユングしてもいいし、電極と発光層をパターユングしてもいい し、素子全層をパターエングしてもいい。 [0210] In the white organic EL device according to the present invention, patterning may be performed by a metal mask or an ink jet printing method when forming a film, if necessary. When patterning, only the electrode may be patterned, or the electrode and the light emitting layer may be patterned. However, the entire layer of the element may be patterned.
[0211] 発光層に用いる発光材料としては特に制限はなぐ例えば、液晶表示素子におけ るバックライトであれば、 CF (カラーフィルター）特性に対応した波長範囲に適合する ように、本発明に係わる白金錯体、また公知の発光材料の中から任意のものを選択 して組み合わせて白色化すればょレ、。  [0211] The light emitting material used for the light emitting layer is not particularly limited. For example, in the case of a backlight in a liquid crystal display element, the light emitting material according to the present invention is adapted so as to conform to the wavelength range corresponding to the CF (color filter) characteristics. Select a platinum complex or any of the known luminescent materials and combine them to make them white.
[0212] このように、白色発光有機 EL素子は、前記表示デバイス、ディスプレイに加えて、 各種発光光源、照明装置として、家庭用照明、車内照明、また、露光光源のような 1 種のランプとして、液晶表示装置のバックライト等、表示装置にも有用に用いられる。  [0212] Thus, in addition to the display device and the display, the white light-emitting organic EL element is used as various types of light sources, lighting devices, home lighting, interior lighting, and a kind of lamp such as an exposure light source. It is also useful for display devices such as backlights for liquid crystal display devices.
[0213] その他、時計等のバックライト、看板広告、信号機、光記憶媒体等の光源、電子写 真複写機の光源、光通信処理機の光源、光センサーの光源等、さらには表示装置を 必要とする一般の家庭用電気器具等広い範囲の用途が挙げられる。  [0213] Other light sources such as backlights for watches, billboard advertisements, traffic lights, optical storage media, light sources for electronic photocopiers, light sources for optical communication processors, light sources for optical sensors, etc. And a wide range of uses such as general household appliances.
実施例  Example
[0214] 以下、実施例により本発明を説明するが、本発明はこれらに限定されない。  [0214] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.
[0215] 実施例 1 [0215] Example 1
〔有機 EL素子 1の作製〕  [Production of organic EL element 1]
陽極としてガラス上に ITOを 150nm成膜した基板 (NHテクノグラス社製: NA— 45 )にパターユングを行った後、この ITO透明電極を設けた透明支持基板を iso プロ ピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、 UVオゾン洗浄を 5分間行 つた。この透明支持基板を、市販の真空蒸着装置の基板ホルダーに固定し、一方、 5つのタンタル製抵抗加熱ボートに、 ひ _NPD、 CBP、 Ir_ l l、 BCP、 Alqをそれ ぞれ入れ、真空蒸着装置 (第 1真空槽）に取付けた。  After patterning a substrate with 150nm ITO film on glass (NH Techno Glass: NA-45) as the anode, this transparent support substrate with ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. This transparent support substrate is fixed to the substrate holder of a commercially available vacuum deposition apparatus, while _NPD, CBP, Ir_ll, BCP, and Alq are placed in five resistance heating boats made of tantalum, respectively. It was attached to the first vacuum chamber.
[0216] さらに、タンタル製抵抗加熱ボートにフッ化リチウムを、タングステン製抵抗加熱ボ ートにアルミニウムをそれぞれ入れ、真空蒸着装置の第 2真空槽に取り付けた。 [0216] Further, lithium fluoride was placed in a tantalum resistance heating boat, and aluminum was placed in a tungsten resistance heating boat, which were attached to the second vacuum chamber of the vacuum evaporation system.
[0217] まず、第 1の真空槽を 4 X 10— 4Paまで減圧した後、 ひ—NPDの入った前記加熱ボ ートに通電して加熱し、蒸着速度 0.：!〜 0. 2nm/秒で透明支持基板に膜厚 25nm の厚さになるように蒸着し、正孔注入/輸送層を設けた。 [0217] First, after the vacuum of the first vacuum chamber to 4 X 10- 4 Pa, and heated by supplying an electric current to the baud preparative containing the shed NPD, deposition rate 0.:!~ 0. 2nm The film was deposited on the transparent support substrate at a film thickness of 25 nm per second, and a hole injection / transport layer was provided.
[0218] さらに、 CBPの入った前記加熱ボートと Ir 11の入ったボートをそれぞれ独立に通 電して発光ホストである CBPと発光ドーパントである Ir— 11の蒸着速度が 100 : 6にな るように調節し膜厚 30nmの厚さになるように蒸着し、発光層を設けた。 [0218] Furthermore, the heating boat containing CBP and the boat containing Ir 11 are independently energized, so that the deposition rate of CBP as the light emitting host and Ir-11 as the light emitting dopant is 100: 6. The light emitting layer was provided by vapor deposition so that the film thickness was adjusted to 30 nm.
[0219] ついで、 BCPの入った前記加熱ボートに通電して加熱し、蒸着速度 0. ：!〜 0. 2n m/秒で厚さ 10nmの正孔阻止層を設けた。さらに、 Alqの入った前記加熱ボートを [0219] Next, the heating boat containing BCP was energized and heated, and a hole blocking layer having a thickness of 10 nm was provided at a deposition rate of 0.0 :! to 0.2 nm / sec. Furthermore, the heated boat containing Alq
3  Three
通電して加熱し、蒸着速度 0.：!〜 0. 2nm/秒で膜厚 40nmの電子輸送層を設けた  An electron transport layer with a film thickness of 40 nm was provided at a deposition rate of 0 :! to 0.2 nm / sec.
[0220] 次に、前記の如く電子輸送層まで製膜した素子を真空のまま第 2真空槽に移した 後、電子輸送層の上にステンレス鋼製の長方形穴あきマスクが配置されるように装置 外部からリモートコントロールして設置した。 [0220] Next, after the element formed up to the electron transport layer as described above is transferred to the second vacuum chamber while being vacuumed, a rectangular perforated mask made of stainless steel is placed on the electron transport layer. Equipment Remotely installed from outside.
[0221] 第 2真空槽を 2 X 10— 4Paまで減圧した後、フッ化リチウム入りのボートに通電して蒸 着速度 0. 01〜0. 02nm/秒で膜厚 0. 5nmの陰極バッファ一層を設け、次いでァ ノレミニゥムの入ったボートに通電して蒸着速度 l〜2nm/秒で膜厚 150nmの陰極を つけた。さらにこの有機 EL素子を大気に接触させることなく窒素雰囲気下のグローブ ボックス（純度 99. 999%以上の高純度窒素ガスで置換したグローブボックス）へ移し 、図 5に示したような内部を窒素で置換した封止構造にして、有機 EL素子 1を作製し た。 [0221] After decompression of the second vacuum chamber up to 2 X 10- 4 Pa, evaporation Chakusokudo 0.01 to 0 by supplying an electric current to the boat of the lithium fluoride-containing. 02nm / sec to a film thickness 0. 5 nm cathode buffer One layer was provided, and then a boat with an anoromiumium was energized, and a cathode having a film thickness of 150 nm was attached at a deposition rate of 1 to 2 nm / second. Furthermore, this organic EL element was transferred to a glove box under nitrogen atmosphere (a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more) without being exposed to the atmosphere, and the interior as shown in Fig. 5 was filled with nitrogen. An organic EL element 1 was fabricated with a substituted sealing structure.
[0222] なお、捕水剤である酸化バリウム 105は、アルドリッチ社製の高純度酸化バリウム粉 末を、粘着剤付きのフッ素樹脂系半透過膜 (ミクロテックス S— NTF8031Q 日東 電工社製)でガラス製封止缶 104に貼り付けたものを予め準備して使用した。封止缶 と有機 EL素子の接着には紫外線硬化型接着剤 107を用い、紫外線ランプを照射す ることで両者を接着し封止素子を作製した。  [0222] Barium oxide 105, a water-absorbing agent, is made of Aldrich's high-purity barium oxide powder with a fluororesin-based semipermeable membrane (Microtex S-NTF8031Q made by Nitto Denko) with adhesive. What was affixed on the sealing can 104 was prepared in advance and used. An ultraviolet curable adhesive 107 was used to bond the sealing can and the organic EL element, and the sealing element was prepared by irradiating an ultraviolet lamp to bond them together.
[0223] 図 5において 101は透明電極を設けたガラス基板、 102が前記正孔注入/輸送層 、発光層、正孔阻止層、電子輸送層等からなる有機 EL層、 103は陰極を示す。  In FIG. 5, 101 is a glass substrate provided with a transparent electrode, 102 is an organic EL layer comprising the hole injection / transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and the like, and 103 is a cathode.
[0224] 〔有機 EL素子 2〜： 16の作製〕  [Organic EL device 2 ~: Fabrication of 16]
有機 EL素子 1の作製において、表 1に記載のように、発光ホスト、発光ドーパント及 び正孔阻止層を変更した以外は同様にして、有機 EL素子 2〜： 16を作製した。  In the production of the organic EL element 1, as described in Table 1, organic EL elements 2 to 16 were produced in the same manner except that the light emitting host, the light emitting dopant and the hole blocking layer were changed.
[0225] [化 46] [0225] [Chem 46]
Figure imgf000079_0001
Figure imgf000079_0001
[0226] 〔有機 EL素子の評価〕  [0226] [Evaluation of organic EL devices]
作製した有機 EL素子について下記のような評価を行った。評価の結果を表 1に示 す。  The produced organic EL device was evaluated as follows. The evaluation results are shown in Table 1.
[0227] (外部取り出し量子効率）  [0227] (External quantum efficiency)
得られた有機 EL素子について、 23°C、乾燥窒素ガス雰囲気下で 2. 5mA/ cm2 定電流を印加した時の外部取り出し量子効率（％)を測定した。測定には分光放射 輝度計 CS— 1000 (コニカミノルタセンシング社製）を用いた。なお、量子効率は有機 EL素子 1を 100とした時の相対値で表した。 With respect to the obtained organic EL device, the external extraction quantum efficiency (%) was measured when a constant current of 2.5 mA / cm 2 was applied at 23 ° C. in a dry nitrogen gas atmosphere. A spectral radiance meter CS-1000 (Konica Minolta Sensing) was used for the measurement. The quantum efficiency is expressed as a relative value when the organic EL element 1 is 100.
[0228] (発光寿命）  [0228] (Luminescence lifetime)
有機 EL素子を室温下、 2. 5mA/cm2の定電流条件下による連続点灯を行レ、、初 期輝度の 90%の輝度になるのに要する時間（ τ 1/9)を測定した。測定には同様に 分光放射輝度計 CS— 1000 (コニカミノルタセンシング社製）を用いた。なお、発光 寿命は有機 EL素子 1を 100とした時の相対値で表した。 The organic EL device was continuously lit at a constant current of 2.5 mA / cm 2 at room temperature, and the time ( τ 1/9) required to reach 90 % of the initial luminance was measured. Similarly, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used for the measurement. The light emission lifetime is expressed as a relative value when the organic EL element 1 is 100.
[0229] [表 1] 有機 EL素子 発光 発光 正孔 外部取り出し発光 [0229] [Table 1] Organic EL element Light emission Light emission Hole External extraction light emission
備考  Remarks
No. ホス卜 ドーパント 阻止層 量子効率 寿命  No. Phosphine dopant blocking layer quantum efficiency lifetime
1 CBP lr-11 BCP 100 100 比較例 1 CBP lr-11 BCP 100 100 Comparative example
2 CBP Pt- 2 BCP 90 74 比較例2 CBP Pt- 2 BCP 90 74 Comparative example
3 CBP ( 1 一 1 ) BCP 118 122 本発明3 CBP (1 1 1) BCP 118 122 The present invention
4 CBP ( 1 一 11) BCP 116 131 本発明4 CBP (1 1 11) BCP 116 131 The present invention
5 CBP ( 2 -10) 74 125 120 本発明5 CBP (2 -10) 74 125 120 The present invention
6 CBP ( 2 -11) BCP 121 124 本発明6 CBP (2-11) BCP 121 124 The present invention
7 CBP (3 - 7 ) BCP 116 119 本発明 7 CBP (3-7) BCP 116 119 The present invention
寸  Size
8 CBP ( ω3 -10) BCP 117 114 本発明 8 CBP (ω3 -10) BCP 117 114 The present invention
9 CBP ω 38 122 129 本発明9 CBP ω 38 122 129 The present invention
10 CBP ( 5 - 1 ) BCP 119 120 本発明10 CBP (5-1) BCP 119 120 The present invention
11 CBP ( 5 - 5) BCP 120 127 本発明11 CBP (5-5) BCP 120 127 The present invention
12 74 ( 1 - 6) 74 127 130 本発明12 74 (1-6) 74 127 130 The present invention
13 74 (4 - 1 ) 74 126 128 本発明13 74 (4-1) 74 126 128 The present invention
14 74 BCP 129 133 本発明14 74 BCP 129 133 The present invention
15 74 74 137 138 本発明15 74 74 137 138 The present invention
16 74 ( 5 - 4) 38 134 144 本発明16 74 (5-4) 38 134 144 The present invention
17 74 74 141 139 本発明 17 74 74 141 139 The present invention
[0230] 表 1から、本発明に係る金属錯体を発光層に用いた有機 EL素子は、比較の有機 E[0230] From Table 1, the organic EL device using the metal complex according to the present invention for the light-emitting layer is a comparative organic E element.
L素子に比べ、発光効率が高ぐ発光寿命が長いことが明らかである。また、一般式（It is clear that the light emission efficiency is high and the light emission lifetime is long as compared with the L element. The general formula (
2)で表される化合物を発光ホスト及び Zまたは正孔阻止層に用いることで、さらに量 子効率が向上することが分かる。 It can be seen that the quantum efficiency is further improved by using the compound represented by 2) in the light-emitting host and the Z or hole blocking layer.
[0231] 実施例 2  [0231] Example 2
〔塗布による白色有機 EL素子の作製〕  [Production of white organic EL elements by coating]
25mm X 25mm XO.5mmのガラス支持基板上に直流電源を用レ、、スパッタ法に てインジウム錫酸化物（ITO、インジウム/錫 = 95/5モル比）の陽極を形成した (厚 み 200nm)。この陽極の表面抵抗は 10 Ω /口であった。これにポリビニルカルバゾ ール (正孔輸送性バインダーポリマー） /(3— 12)/(4— 11)/(4— 3)/2— (4— ビフエ二リル）ー5 （4 t ブチルフエニル）ー1, 3， 4ーォキサジァゾール（電子輸 送材） =200/2/3/2/50 (質量比）を調製、溶解したジクロロエタン溶液をスピン コ一タ一で塗布し、 lOOnmの発光層を得た。この有機化合物層の上にバタ一ニング したマスク（発光面積が 5mm X 5mmとなるマスク）を設置し、蒸着装置内で陰極バッ ファー層としてフッ化リチウム 0. 5nm及び陰極としてアルミニウム 150nmを蒸着して 陰極を設けた。陽極、陰極よりそれぞれアルミニウムのリード線を出して発光素子を 作製した。該発光素子を窒素ガスで置換したグローブボックス内に入れ、ガラス製の 封止容器で紫外線硬化型接着剤 (長瀬チバ製、 XNR5493)を用いて封止して有機 EL素子を作製した。 A direct current power supply was used on a glass support substrate of 25mm X 25mm XO.5mm, and an anode of indium tin oxide (ITO, indium / tin = 95/5 molar ratio) was formed by sputtering (thickness 200nm) . The surface resistance of this anode was 10 Ω / mouth. Polyvinylcarbazole (hole transporting binder polymer) / (3-12) / (4-11) / (4-3) / 2— (4-biphenylyl) -5 (4 t butylphenyl) -1,3,4-Oxadiazole (electron transport material) = 200/2/3/2/50 (mass ratio) prepared, dissolved dichloroethane solution was applied with a spin coater, lOOnm The light emitting layer was obtained. A buttered mask (a mask with a light emitting area of 5 mm x 5 mm) is placed on the organic compound layer, and the cathode mask is placed in the vapor deposition system. A cathode was provided by depositing lithium fluoride 0.5 nm as a fur layer and 150 nm of aluminum as a cathode. A light emitting element was manufactured by extending aluminum lead wires from the anode and the cathode, respectively. The light-emitting element was put in a glove box substituted with nitrogen gas, and sealed with a glass sealing container using an ultraviolet curable adhesive (XNR5493, manufactured by Chiba Nagase) to produce an organic EL element.
[0232] この有機 EL素子に通電したところほぼ白色の光が得られ、本発明における有機 E [0232] When this organic EL element was energized, almost white light was obtained.
L素子用材料は塗布による有機 EL素子の作製が可能であることが分かった。 It was found that the organic EL element can be produced by coating the material for the L element.
[0233] 実施例 3 [0233] Example 3
〔フルカラー表示装置の作製〕  [Production of full-color display device]
(青色発光素子の作製）  (Production of blue light-emitting elements)
実施例 1の有機 EL素子 15を青色発光素子として用いた。  The organic EL element 15 of Example 1 was used as a blue light emitting element.
[0234] (緑色発光素子の作製） [0234] (Production of green light-emitting element)
実施例 1の有機 EL素子 13を緑色発光素子として用いた。  The organic EL device 13 of Example 1 was used as a green light emitting device.
[0235] (赤色発光素子の作製） [0235] (Production of red light-emitting element)
実施例 1の有機 EL素子 14を赤色発光素子として用いた。  The organic EL element 14 of Example 1 was used as a red light emitting element.
[0236] 上記で作製した、各々赤色、緑色、青色発光有機 EL素子を同一基板上に並置し、 図 1に記載のような形態を有するアクティブマトリクス方式フルカラー表示装置を作製 し、図 2には、作製した前記表示装置の表示部 Aの模式図のみを示した。即ち、同一 基板上に、複数の走査線 5及びデータ線 6を含む配線部と、並置した複数の画素 3 ( 発光の色が赤領域の画素、緑領域の画素、青領域の画素等）とを有し、配線部の走 查線 5及び複数のデータ線 6はそれぞれ導電材料からなり、走査線 5とデータ線 6は 格子状に直交して、直交する位置で画素 3に接続している（詳細は図示せず)。前記 複数画素 3は、それぞれの発光色に対応した有機 EL素子、アクティブ素子であるス 式で駆動されており、走査線 5から走查信号が印加されると、データ線 6から画像デ ータ信号を受け取り、受け取った画像データに応じて発光する。このように各赤、緑、 青の画素を適宜、並置することによって、フルカラー表示装置を作製した。 [0236] Each of the red, green, and blue light emitting organic EL elements produced above is juxtaposed on the same substrate to produce an active matrix type full-color display device having the configuration shown in FIG. 1, and FIG. Only the schematic view of the display part A of the produced display device is shown. That is, on the same substrate, a wiring portion including a plurality of scanning lines 5 and data lines 6 and a plurality of juxtaposed pixels 3 (emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) 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 not shown). The plurality of pixels 3 are driven by a formula that is an organic EL element and an active element corresponding to each emission color, and when a scanning signal is applied from the scanning line 5, the image data is transmitted from the data line 6. A signal is received, and light is emitted according to the received image data. Thus, a full-color display device was produced by juxtaposing the red, green, and blue pixels appropriately.
[0237] このフルカラー表示装置を駆動することにより、輝度が高ぐ高耐久性を有し、かつ 、鮮明なフルカラー動画表示が得られることが分かった。 [0237] By driving this full-color display device, the luminance is high and the durability is high. It was found that a clear full-color moving image display can be obtained.
[0238] 実施例 4  [0238] Example 4
〔白色発光素子及び白色照明装置の作製〕  [Production of white light-emitting element and white illumination device]
実施例 1の透明支持基板の電極を 20mm X 20mmにパターユングし、その上に実 施例 1と同様に正孔注入/輸送層としてひ一NPDを 25nmの厚さで製膜し、さらに、 化合物 74の入った前記加熱ボートと、化合物（1一 1)の入ったボート及び化合物（2 - 10)の入ったボートをそれぞれ独立に通電して発光ホストである化合物 74と発光ド 一パントである化合物（1一 1)の入ったボート及び化合物（2— 10)の蒸着速度が 10 0 : 7 : 1になるように調整し膜厚 40nmの厚さになるように蒸着し、発光層を設けた。  The electrode of the transparent support substrate of Example 1 was patterned to 20 mm x 20 mm, and then a single NPD was formed to a thickness of 25 nm as a hole injection / transport layer in the same manner as in Example 1, The heating boat containing the compound 74, the boat containing the compound (1 1 1) and the boat containing the compound (2-10) are energized independently, respectively, A boat containing a compound (1 1 1) and a compound (2-10) were deposited so that the deposition rate was 10 0: 7: 1 and deposited to a thickness of 40 nm. Provided.
[0239] ついで、 BCPを 10nm製膜して正孔阻止層を設けた。さらに、 Alqを 40nmで製膜 し電子輸送層を設けた。 [0239] Next, BCP was deposited to a thickness of 10 nm to provide a hole blocking layer. In addition, Alq was deposited at 40 nm to provide an electron transport layer.
[0240] 次に、実施例 1と同様に、電子輸送層の上にステンレス鋼製の透明電極とほぼ同じ 形状の正方形穴あきマスクを設置し、陰極バッファ一層としてフッ化リチウム 0. 5nm 及び陰極としてアルミニウム 150nmを蒸着製膜した。 [0240] Next, as in Example 1, a square perforated mask having substantially the same shape as the transparent electrode made of stainless steel was placed on the electron transport layer, and lithium fluoride 0.5 nm and the cathode were formed as one cathode buffer layer. As a film, 150 nm of aluminum was deposited.
[0241] この素子を実施例 1と同様な方法及び同様な構造の封止缶を具備させ、平面ラン プを作製した。図 6に平面ランプの模式図を示した。図 6 (a)に平面模式を図 6 (b)に 断面模式図を示す。 [0241] This element was equipped with a sealing can having the same method and the same structure as in Example 1 to produce a planar lamp. Figure 6 shows a schematic diagram of a flat lamp. Fig. 6 (a) shows a schematic plan view and Fig. 6 (b) shows a schematic cross-sectional view.
[0242] この平面ランプに通電したところほぼ白色の光が得られ、照明装置として使用でき ることが分かった。  [0242] When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Claims

請求の範囲 The scope of the claims
下記一般式（1)で表される部分構造を有する金属錯体であって、配位子部分に二座 配位を抑制する置換基を少なくとも一つ有することを特徴とする有機 EL素子用材料  A material for an organic EL device, which is a metal complex having a partial structure represented by the following general formula (1), wherein the ligand portion has at least one substituent that suppresses bidentate coordination.
'般却》 'General Rejection'
Figure imgf000083_0001
Figure imgf000083_0001
(式中、 Mは金属原子であり、 X、 Y、 Ζはそれぞれ環 Α、環 Β、環 Cの構成要素である とともに炭素原子または窒素原子であり、少なくとも一つは炭素原子であって、 Μに 結合している。環 Α、環 Β、環 Cは芳香族炭化水素環、芳香族複素環または複素環 である。 R〜Rは置換基であり、 nl、 n2、 n3は 0または正の整数である。 Lは補助配  (In the formula, M is a metal atom, X, Y, and Ζ are constituents of ring Α, ring Β, and ring C, respectively, and are carbon atoms or nitrogen atoms, and at least one is a carbon atom, Ring Α, ring Β, and ring C are aromatic hydrocarbon rings, aromatic heterocycles or heterocycles R to R are substituents, and nl, n2, and n3 are 0 or positive L is an auxiliary arrangement
1 3  13
位子を表し、 mは 1〜3の整数である。 )  Represents a ligand, and m is an integer of 1 to 3. )
[2] 前記一般式（1)において、環 Bの置換基 Rの少なくとも一つは、環 A及び環 Cと結合 [2] In the general formula (1), at least one of the substituents R of ring B is bonded to ring A and ring C.
2  2
しない、ファンデルワールス体積（VDW)が 45A3以上のアルキル基、シクロアルキル 基、アルケニル基、アルキニル基、複素環基、アルコキシ基、シクロアルコキシ基、ス ノレフィニノレ基、アルキルスルホニル基またはシリル基であることを特徴とする請求の範 囲第 1項に記載の有機 EL素子用材料。 No, van der Waals volume (VDW) is 45A 3 or higher alkyl group, cycloalkyl group, alkenyl group, alkynyl group, heterocyclic group, alkoxy group, cycloalkoxy group, snowfininore group, alkylsulfonyl group or silyl group 2. The material for an organic EL device according to claim 1, wherein the material is an organic EL device material.
[3] 請求の範囲 1または 2に記載の有機 EL素子用材料を、有機 EL素子を形成する構成 層の一つに含有することを特徴とする有機 EL素子。  [3] An organic EL device comprising the organic EL device material according to claim 1 or 2 in one of the constituent layers forming the organic EL device.
[4] 前記構成層の一つが発光層であることを特徴とする請求の範囲第 3項に記載の有機 EL素子。  4. The organic EL device according to claim 3, wherein one of the constituent layers is a light emitting layer.
[5] 前記構成層の少なくとも一層に下記一般式 (2)で表される化合物を含有することを特 徴とする請求の範囲第 3または第 4項に記載の有機 EL素子。 [5] The compound represented by the following general formula (2) is contained in at least one of the constituent layers. 5. The organic EL device according to claim 3 or 4, wherein
[化 2] —般式 ί  [Chemical 2] — General formula ί
Figure imgf000084_0001
Figure imgf000084_0001
(式中、 Zは芳香族複素環を形成する原子群を表し、 Zは芳香族複素環または芳香 (In the formula, Z represents an atomic group forming an aromatic heterocycle, Z is an aromatic heterocycle or aromatic
1 2  1 2
族炭化水素環を形成する原子群を表し、 Zは 2価の連結基または単なる結合手を表  Represents a group of atoms that form an aromatic hydrocarbon ring, and Z represents a divalent linking group or a simple bond.
3  Three
す。 Rは水素原子または置換基を表す。 )  The R represents a hydrogen atom or a substituent. )
4  Four
[6] 請求の範囲第 3 5項のいずれか 1項に記載の有機 EL素子を有することを特徴とす る表示装置。  [6] A display device comprising the organic EL element according to any one of claims 35 to 35.
[7] 請求の範囲第 3 5項のいずれか 1項に記載の有機 EL素子を有することを特徴とす る照明装置。  [7] An illuminating device comprising the organic EL element according to any one of claims 35.
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