JP3988915B2 - Transition metal complex, light emitting device material comprising the same, and light emitting device - Google Patents

Transition metal complex, light emitting device material comprising the same, and light emitting device Download PDF

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JP3988915B2
JP3988915B2 JP2001033684A JP2001033684A JP3988915B2 JP 3988915 B2 JP3988915 B2 JP 3988915B2 JP 2001033684 A JP2001033684 A JP 2001033684A JP 2001033684 A JP2001033684 A JP 2001033684A JP 3988915 B2 JP3988915 B2 JP 3988915B2
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light emitting
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carbon atoms
light
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JP2002235076A (en
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達也 五十嵐
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富士フイルム株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a light-emitting element that emits light by converting electric energy into light, and in particular, a display element, a display, a backlight, an electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, and an optical communication device. The present invention relates to a light-emitting element that can be suitably used for the above. Furthermore, the present invention relates to a light emitting device material used for the light emitting device and a novel transition metal complex that can be used as the light emitting device material.
[0002]
[Prior art]
Research and development related to various display devices are actively conducted today, and organic electroluminescence (EL) devices are attracting attention because they can emit light with high luminance at a low voltage. For example, a light emitting device having an organic thin film formed by vapor deposition of an organic compound is known (Applied Physics Letters, 51, 913, 1987). This light-emitting device has a structure in which an electron transport material (tris (8-hydroxyquinolinato) aluminum complex (Alq)) and a hole transport material (amine compound) are laminated, which is significantly larger than conventional single-layer devices. Shows improved emission characteristics.
[0003]
Ortho metalated iridium complexes (Ir (ppy)Three: Green light-emitting devices with improved light-emitting properties by utilizing light emission from Tris-Ortho-Metalated Complex of Iridium (III) with 2-Phenylpyridine (Applied Physics Letters, 75, 4 (1999) ). This device has achieved an external quantum yield of 8%, which exceeds the external quantum yield of 5%, which was said to be the limit of conventional devices, but improvements are required in terms of emission luminance, durability, and emission color. ing.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a light-emitting element material that can be used for obtaining a light-emitting element that can emit light with high brightness and has excellent durability, a light-emitting element using the same, and a light-emitting element material that can be used as a medical application It is to provide a novel transition metal complex that can be applied to fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, color filter dyes, color conversion filters, optical recording materials and the like.
[0005]
[Means for Solving the Problems]
As a result of diligent research in view of the above object, the present inventor has found that a light-emitting element using a transition metal complex having a specific structure as a material for a light-emitting element can emit light with high brightness and has excellent durability. Discovered and came up with the present invention.
[0006]
The light emitting device material of the present invention is characterized by comprising a transition metal complex containing an isonitrile ligand and a transition metal selected from the group consisting of iridium, ruthenium and rhodium.
[0007]
The transition metal complex is preferably represented by the following general formula (2).
[Chemical 3]
In the general formula (2), M is iridium, ruthenium or rhodium, Rtwenty oneRepresents a substituent, Ltwenty oneRepresents a ligand and Xtwenty oneRepresents a counter ion. n21 represents an integer of 0 to 5, n22 represents an integer of 1 to 6, and n23 represents an integer of 0 to 3.
[0008]
The light-emitting element of the present invention has a light-emitting layer or a plurality of organic compound layers including a light-emitting layer between a pair of electrodes, and at least one of the light-emitting layer or the plurality of organic compound layers contains the light-emitting element material. It is characterized by that. The layer containing the light emitting element material is particularly preferably formed by a coating process.
[0009]
The transition metal complex of the present invention is represented by the following general formula (1).
[Formula 4]
In general formula (1), M is iridium, ruthenium or rhodium, R11, R12And R13Each represents a substituent, n11 and n12 each represent an integer of 0 to 4;11Represents a monovalent ligand. This transition metal complex can be used as a material for a light emitting device, and can also be applied to medical use, fluorescent whitening agent, photographic material, UV absorbing material, laser dye, dye for color filter, color conversion filter, optical recording material and the like.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
[1] Material for light emitting device
The light emitting device material of the present invention comprises a transition metal complex containing an isonitrile ligand and a transition metal. The transition metal complex may contain a plurality of transition metal atoms, that is, a so-called binuclear complex. In this case, the plurality of transition metal atoms may be the same or different. At least one of the transition metals is selected from the group consisting of iridium, ruthenium and rhodium, but may contain other metal ions simultaneously. The transition metal atom is preferably iridium or ruthenium, more preferably iridium.
[0011]
The transition metal complex used in the present invention may have other ligands in addition to the isonitrile ligand. Other ligands are not particularly limited, for example, “Photochemistry and Photophysics of Coordination Compounds” by H. Yersin, Springer-Verlag (1987), “Organic Metal Chemistry: Fundamentals and Applications”, Yuka The ligands described in Bososha (1982) etc. can be used. Among them, halogen ligands (chlorine ligands, etc.), nitrogen-containing heterocyclic ligands (bipyridyl ligands, phenanthroline ligands, phenylpyridine ligands, etc.), diketone ligands, nitrile ligands Ligands, CO ligands, phosphorus ligands (phosphine ligands, phosphite ligands, phosphinin ligands, etc.), and carboxylic acid ligands (acetic acid ligands, etc.) preferable.
[0012]
The transition metal complex may contain a plurality of types of ligands, but preferably contains 1 to 3 types, more preferably 1 or 2 types of ligands.
[0013]
The transition metal complex may be a neutral complex or an ionic complex having a counter ion. The counter ion is not particularly limited, and preferably an alkali metal ion, alkaline earth metal ion, halogen ion, perchlorate ion, PF6Ion, ammonium ion (tetramethylammonium ion, etc.), borate ion or phosphonium ion, more preferably perchlorate ion or PF6Ion. The transition metal complex is preferably a neutral metal complex.
[0014]
The transition metal complex used in the present invention is preferably represented by the following general formula (2), more preferably represented by the following general formula (1).
[0015]
[Chemical formula 5]
[0016]
[Chemical 6]
[0017]
Hereinafter, the general formula (2) will be described. In the general formula (2), M is iridium, ruthenium or rhodium, Rtwenty oneIs R described later11The preferred range is also the same. Ltwenty oneRepresents a ligand, and examples of the ligand include those shown as examples of “other ligands” other than the isonitrile ligand. Ltwenty oneIs preferably a halogen ligand (chlorine ligand, etc.), a nitrogen-containing heterocyclic ligand (bipyridyl-type ligand, phenanthroline-type ligand, phenylpyridine-type ligand, etc.), diketone ligand, nitrile Ligand, CO ligand, phosphorus ligand (phosphine ligand, phosphite ligand, phosphinin ligand, etc.), or carboxylic acid ligand (acetic acid ligand, etc.) It is. Xtwenty oneRepresents a counter ion. Counter ion Xtwenty oneIs not particularly limited, but preferably alkali metal ions, alkaline earth metal ions, halogen ions, perchlorate ions, PF6Ion, ammonium ion (tetramethylammonium ion, etc.), borate ion or phosphonium ion, more preferably perchlorate ion or PF6Ion.
[0018]
n21 represents an integer of 0 to 5, and is preferably an integer of 1 to 3. When n21 is 2 or more, multiple Ltwenty oneMay be the same or different. n22 represents an integer of 1 to 6, and preferably an integer of 1 to 4. When n22 is 2 or more, the plurality of isonitrile ligands may be the same or different. n23 represents an integer of 0 to 3, and is preferably 0 or 1. When n23 is 2 or 3, multiple Xtwenty oneMay be the same or different. n21, n22 and n23 are preferably a combination such that the transition metal complex used as the light emitting device material of the present invention becomes a neutral complex.
[0019]
The general formula (1) will be described below. In general formula (1), M is iridium, ruthenium or rhodium, R11, R12And R13Each represents a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, t -Butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms) Particularly preferably, it has 2 to 10 carbon atoms, such as vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc., alkynyl group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms). Particularly preferably, it has 2 to 10 carbon atoms, for example, propargyl group, 3-pentynyl group, etc., aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 6 carbon atoms). 12 and examples A phenyl group, a p-methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, etc.), an amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 carbon atoms). For example, an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a ditolylamino group, etc., an alkoxy group (preferably having a carbon number of 1-30, more preferably a carbon number) 1 to 20, particularly preferably 1 to 10 carbon atoms, such as methoxy group, ethoxy group, butoxy group, 2-ethylhexyloxy group, etc., aryloxy group (preferably 6 to 30 carbon atoms, more preferably carbon 6-20, particularly preferably 6-12 carbon atoms, such as phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, etc.), heteroary An oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy group, pyrazyloxy group, pyrimidyloxy group, quinolyloxy group, etc.), acyl group ( Preferably it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), alkoxycarbonyl group (preferably carbon 2-30, more preferably 2-20 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, etc., aryloxycarbonyl group (preferably 7-30 carbon atoms, more Preferably it has 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl group, etc.), acyloxy group (preferably Alternatively, it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, an acetoxy group, a benzoyloxy group, etc., an acylamino group (preferably 2 to 30 carbon atoms, more Preferably it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino group, benzoylamino group, etc., alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, more preferably 2 to 2 carbon atoms). 20, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, etc., an aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 carbon atoms). -12, for example, phenyloxycarbonylamino group, etc., sulfonylamino group (preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferred) Or having 1 to 12 carbon atoms, for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 0 carbon atoms). For example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, for example, carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably C1-C12, for example, a methylthio group, an ethylthio group, etc.), an arylthio group (preferably C6-C30) More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio group, etc., heteroarylthio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, for example, pyridylthio group, 2-benzimidazolylthio group, 2-benzoxazolylthio group, 2-benzthiazolylthio group, etc., sulfonyl group (preferably having 1 to 30 carbon atoms, More preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, mesyl group, tosyl group, etc., sulfinyl group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, especially Preferably it has 1 to 12 carbon atoms, for example, methanesulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 carbon atom). For example, ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms). , For example, diethylphosphoric acid amide group, phenylphosphoric acid amide group), hydroxy group, mercapto group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro Group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, nitrogen atom, oxygen atom, sulfur atom, etc. as hetero atoms And may be an aliphatic heterocyclic group or a heteroaryl group, such as imidazolyl group, pyridyl group, quinolyl group, furyl group, Nyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, Particularly preferably, it has 3 to 24 carbon atoms, for example, trimethylsilyl group, triphenylsilyl group, etc., phosphino group (preferably 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, for example, dimethylphosphino group, And diphenylphosphino group). These substituents may be further substituted, or the substituents may be bonded to form a ring structure.
[0020]
R11Is preferably an alkyl group or an aryl group. R11Is L11To form a chelate ligand. R12And R13Are preferably an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, a fluorine atom or a substituted amino group, and more preferably an alkyl group or a fluorine atom.
[0021]
L11Represents a monovalent ligand, preferably a halogen ligand, a sulfonic acid ligand, a carboxylic acid ligand, an alkoxy ligand or a nitrile ligand. N11 and n12 each represents an integer of 0 to 4.
[0022]
The transition metal complex used in the present invention preferably has a low molecular weight, but may be a so-called oligomer or polymer having a repeating unit. In the case of an oligomer or polymer, examples thereof include a high molecular weight compound in which the residue represented by the general formula (1) is bonded to the polymer main chain (for example, a phenylpyridine ligand in the general formula (1), R11Or L11Is a high molecular weight compound having a main chain with a skeleton represented by the general formula (1) (for example, a phenylpyridine ligand in the general formula (1), R11Or L11Is a high molecular weight compound contained in the polymer main chain), and the mass average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 100000, and particularly preferably 3000 to 100,000. Here, the polymer may be a homopolymer or a copolymer with another monomer, and if it is a copolymer, it may be a random copolymer or a block copolymer. .
[0023]
The light emitting device material of the present invention comprising a transition metal complex may function as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., and has a plurality of functions. Also good. The light emitting device material of the present invention is preferably used as a light emitting material or a charge transport material. Hereinafter, although the specific example of the transition metal complex used by this invention is shown, they do not limit this invention.
[0024]
[Chemical 7]
[0025]
[Chemical 8]
[0026]
[Chemical 9]
[0027]
The transition metal complex used in the present invention can be synthesized by various methods. For example, a ligand or a dissociated product thereof and a transition metal compound can be obtained by mixing at room temperature or lower or while heating. In the case of heating, in addition to normal heating, a method of heating with microwaves is also effective. If necessary, a solvent (halogen solvent, alcohol solvent, ether solvent, water, etc.) or a base (may be an inorganic base or an organic base, such as sodium methoxide, t-butoxy potassium, Triethylamine, potassium carbonate, etc.) may be used.
[0028]
[2] Light emitting device
The light-emitting element of the present invention has a light-emitting layer or a plurality of organic compound layers including a light-emitting layer between a pair of electrodes (anode and cathode). At least one layer of the light emitting layer or the plurality of organic compound layers contains the above-described light emitting element material of the present invention. There are no particular restrictions on the light emitting device system, driving method, usage pattern, etc. of the present invention, but the light emitting device material of the present invention is preferably used as a light emitting material or a charge transport material. As a typical light emitting element, an organic EL (electroluminescence) element can be given.
[0029]
The method for forming the layer containing the light emitting device material of the present invention is not particularly limited, and methods such as resistance heating vapor deposition, electron beam, sputtering, molecular lamination, coating, ink jet, printing, transfer, etc. Can be used. Of these, the resistance heating vapor deposition method and the coating method are preferable in terms of device characteristics and production. The layer containing the light emitting element material is particularly preferably formed by a coating process.
[0030]
The light emitting device of the present invention may include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer and the like in addition to the light emitting layer, and each of these layers has other functions. It may be a thing. As described above, the light emitting device material of the present invention may be contained in any of these layers, and is preferably contained in the light emitting layer or the charge transport layer. Hereinafter, each layer will be described in detail.
[0031]
(A) Anode
The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like. As a material for forming the anode, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4 eV or more is preferably used. Specific examples include metals (gold, silver, chromium, nickel, etc.), conductive metal oxides (tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), etc.), these metals and conductive metal oxides. A mixture or laminate of the above, an inorganic conductive material (copper iodide, copper sulfide, etc.), an organic conductive material (polyaniline, polythiophene, polypyrrole, etc.) and a laminate of these with ITO. The anode is preferably made of a conductive metal oxide, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.
[0032]
The method for forming the anode may be appropriately selected according to the material used. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), an indium tin oxide dispersion A method such as coating can be used. By performing a treatment such as cleaning on the anode, the driving voltage of the light emitting element can be lowered or the light emission efficiency can be increased. For example, in the case of an anode made of ITO, UV-ozone treatment, plasma treatment, etc. are effective. The sheet resistance of the anode is preferably several hundred Ω / □ or less. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably 10 nm to 5 μm, more preferably 50 nm to 1 μm, and particularly preferably 100 to 500 nm.
[0033]
The anode is usually formed on a substrate made of soda lime glass, non-alkali glass, transparent resin or the like. In the case of a glass substrate, it is preferable to use an alkali-free glass in order to reduce ions eluted from the glass. When a soda lime glass substrate is used, it is preferable to previously form a barrier coat such as silica on the surface thereof. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but in the case of a glass substrate, it is usually 0.2 mm or more, preferably 0.7 mm or more.
[0034]
(B) Cathode
The cathode supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like. As the material of the cathode, metals, alloys, metal halides, metal oxides, electrically conductive compounds, mixtures thereof, and the like can be used. Adhesion with adjacent layers such as a light emitting layer, ionization potential, and stability It may be selected in consideration of the above. Specific examples include alkali metals (Li, Na, K, etc.) and their fluorides and oxides, alkaline earth metals (Mg, Ca, etc.) and their fluorides and oxides, gold, silver, lead, aluminum, sodium And alloys and mixed metals containing potassium, alloys and mixed metals containing lithium and aluminum, alloys and mixed metals containing magnesium and silver, rare earth metals (indium, ytterbium, etc.), mixtures thereof and the like. The cathode is preferably made of a material having a work function of 4 eV or less, and more preferably made of aluminum, an alloy or mixed metal containing lithium and aluminum, or an alloy or mixed metal containing magnesium and silver.
[0035]
The cathode may have a single layer structure made of the above materials or a laminated structure including layers made of the above materials. For example, a laminated structure of aluminum / lithium fluoride, aluminum / lithium oxide or the like is preferable. The cathode can be formed by an electron beam method, a sputtering method, a resistance heating vapor deposition method, a coating method, or the like. In the case of the vapor deposition method, the material can be vapor-deposited alone, or two or more materials can be vapor-deposited simultaneously. When the alloy electrode is formed, a plurality of metals can be formed by simultaneous vapor deposition, or a previously prepared alloy may be vapor deposited. The sheet resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably 10 nm to 5 μm, more preferably 50 nm to 1 μm, and particularly preferably 100 nm to 1 μm.
[0036]
(C) Hole injection layer and hole transport layer
The material used for the hole injection layer and the hole transport layer has one of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking electrons injected from the cathode. If it is. Specific examples thereof include carbazole, triazole, oxazole, oxadiazole, imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic first Tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, conductive polymer oligomers such as thiophene oligomers and polythiophenes, organic Examples thereof include silane, derivatives thereof, carbon films, and light emitting device materials of the present invention.
[0037]
The hole injection layer and the hole transport layer may have a single layer structure made of one or more of the above materials, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions. As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the above materials are dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method, etc.), An ink jet method, a printing method, a transfer method, or the like is used. In the case of the coating method, a coating solution may be prepared by dissolving or dispersing the above materials together with a resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone. , Polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, polyvinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin Silicon resin or the like can be used. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 to 500 nm.
[0038]
(D) Light emitting layer
When an electric field is applied to the light emitting element, holes injected from the anode, hole injection layer or hole transport layer in the light emitting layer recombine with electrons injected from the cathode, electron injection layer or electron transport layer, Emits light. The material forming the light-emitting layer has the function of receiving holes from the anode, etc. when an electric field is applied, the function of receiving electrons from the cathode, etc., the function of moving charges, and the function of emitting light by providing a field for recombination of holes and electrons. There is no particular limitation as long as it can form a layer having s. The material of the light emitting layer may emit light from either singlet excitons or triplet excitons, such as benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, Phthalimide, coumarin, perylene, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, metal complexes (8-quinolinol) Derivative metal complexes, rare earth complexes, etc.), polymer light-emitting materials (polythiophene, polyphenylene, polyphenylene vinylene, etc.), organic silanes, derivatives thereof, and light-emitting device materials of the present invention are used. It can be.
[0039]
The formation method of the light emitting layer is not particularly limited. Resistance heating vapor deposition method, electron beam method, sputtering method, molecular lamination method, coating method (spin coating method, casting method, dip coating method, etc.), inkjet method, printing method, LB Method, transfer method and the like can be used. Of these, the resistance heating vapor deposition method and the coating method are preferable. The thickness of the light emitting layer is not particularly limited, and is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 to 500 nm.
[0040]
(E) Electron injection layer and electron transport layer
As long as the material forming the electron injection layer and the electron transport layer has any one of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking holes injected from the anode Good. Specific examples include aromatic rings such as triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, naphthalene and perylene. Tetracarboxylic anhydrides, phthalocyanines, metal complexes (metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as a ligand), organic silanes, derivatives thereof, Examples include materials for light emitting elements.
[0041]
The electron injection layer and the electron transport layer may have a single layer structure made of one or more of the above materials, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions. The electron injection layer and electron transport layer can be formed by vacuum deposition, LB, coating by dissolving or dispersing the above materials in a solvent (spin coating, casting, dip coating, etc.), inkjet method The printing method, the transfer method, etc. are used. In the case of the coating method, the above material may be dissolved or dispersed together with the resin component to prepare a coating solution. As this resin component, the thing similar to the case of the positive hole injection layer and positive hole transport layer which were mentioned above can be used. The film thickness of the electron injection layer and the electron transport layer is not particularly limited, and is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 to 500 nm.
[0042]
(F) Protective layer
The protective layer has a function of preventing substances that promote device deterioration such as moisture and oxygen from entering the device. Materials for the protective layer include metals (In, Sn, Pb, Au, Cu, Ag, Al, Ti, Ni, etc.), metal oxides (MgO, SiO, SiO)2, Al2OThree, GeO, NiO, CaO, BaO, Fe2OThree, Y2OThree, TiO2Etc.), metal fluoride (MgF2, LiF, AlFThree, CaF2Etc.), nitride (SiN, SiNxOyEtc.), polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least A copolymer obtained by copolymerizing a monomer mixture containing one kind of comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, and a water absorption of 0.1% or less Can be used.
[0043]
The method for forming the protective layer is not particularly limited, and vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ion plating) Method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method, etc. can be applied.
[0044]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to them.
[0045]
Comparative Example 1
40 mg poly (N-vinylcarbazole), 12 mg PBD (2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole), and 1 mg of the following compound A Was dissolved in 2.5 ml of dichloroethane, and the obtained solution was spin coated (1500 rpm, 20 sec) on the washed substrate to form an organic layer. The film thickness of the obtained organic layer was 98 nm. Next, a mask patterned so as to have a light emitting area of 4 mm × 5 mm is placed on the obtained organic layer, and magnesium and silver (magnesium: silver = 10: 1 (molar ratio)) are co-deposited by 50 nm in the vapor deposition apparatus. Further, 50 nm of silver was vapor-deposited to produce a light emitting device of Comparative Example 1. The obtained light emitting element was made to emit light by applying a DC constant voltage using “source measure unit 2400 type” manufactured by Toyo Technica, and the luminance was measured using “luminance meter BM-8” manufactured by Topcon Corporation. As a result, green light emission is obtained, and the maximum brightness is 3300cd / m2The minimum drive voltage (the minimum drive voltage at which light emission can be obtained) was 11V. When the light emitting device was left in the atmosphere for one day and measured again, the maximum luminance was 410 cd / m.2Met.
[0046]
[Chemical Formula 10]
[0047]
Example 1
A transition metal complex (1-2) was synthesized as follows.
Embedded image
3.5 g 2- (4-fluorophenyl) -pyridine and 5 g KThreeIrCl6To the mixture, 50 ml of 2-methoxyethanol and 30 ml of water were added and stirred under reflux. After stirring for 6 hours, the mixture was cooled to room temperature, and the precipitated yellow solid was filtered off to obtain 3.4 g of compound a. Subsequently, 20 ml of chloroform was added to 0.2 g of compound a, and 0.06 ml of t-C was further added.FourH9NC was added. The solution was stirred at reflux for 4 hours and cooled to room temperature. This was purified by silica gel column chromatography (developing solvent: chloroform) and then recrystallized from a chloroform / hexane system to obtain 0.1 g of a transition metal complex (1-2). Formation of complex (1-2) was confirmed by FAB-MS spectrum (posi 655, 620, 572, 535).
[0048]
A light emitting device of Example 1 was prepared in the same manner as Comparative Example 1 except that the transition metal complex (1-2) obtained as described above was used in place of Compound A. As a result of measuring the light emission luminance of the obtained light emitting element in the same manner as in Comparative Example 1, blue-green light emission was obtained, and the maximum luminance was 3500 cd / m.2The minimum drive voltage was 10V. When the light emitting element was left in the atmosphere for one day and measured again, the maximum luminance was 3000 cd / m.2Met.
[0049]
Example 2
A transition metal complex (1-23) was used in place of compound A, and a light-emitting device was produced in the same manner as in Comparative Example 1. As a result, a red light-emitting device with high luminance and high durability could be obtained.
[0050]
Example 3
A light-emitting device was prepared in the same manner as in Comparative Example 1 using a mixture of transition metal complexes (1-1) and (1-25) in place of 1 mg of compound A. Blue light emission with high luminance and durability was obtained. An element was obtained.
[0051]
Example 4
The cleaned ITO substrate is put into a vapor deposition system, and TPD (N, N'-diphenyl-N, N'-di (m-tolyl) -benzidine) is vapor-deposited to 40 nm, and the following compound B and transition metal complex (1 -2) was co-evaporated at a ratio of 9 to 1 (mass ratio) at 20 nm, and further, the following azole compound C was evaporated at 40 nm to form an organic thin film. Next, a mask patterned to have a light emission area of 4 mm x 5 mm is placed on the obtained organic thin film, and magnesium and silver (magnesium: silver = 10: 1 (mass ratio)) are co-deposited with 50 nm in the vapor deposition system. Further, 50 nm of silver was vapor-deposited to produce the light emitting device of Example 4. As a result of measuring the light emission luminance of the obtained light emitting element in the same manner as in Comparative Example 1, blue-green light emission was obtained, and the maximum luminance was 2400 cd / m.2Met.
[0052]
Embedded image
[0053]
【The invention's effect】
As described above in detail, the light-emitting element using the light-emitting element material of the present invention can emit light with high luminance and has excellent durability. Various light emission colors can be obtained by appropriately selecting the light-emitting element material. Is possible. Therefore, the light-emitting element of the present invention can be suitably used for display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communication devices, and the like. In addition, the transition metal complex forming the light emitting device material of the present invention is applied to medical use, fluorescent brightener, photographic material, UV absorbing material, laser dye, dye for color filter, color conversion filter, optical recording material, etc. Is possible.

Claims (5)

  1. A material for a light-emitting element, comprising a transition metal complex containing an isonitrile ligand and a transition metal selected from the group consisting of iridium, ruthenium and rhodium.
  2. The light emitting device material according to claim 1, wherein the transition metal complex is represented by the following general formula (2).
    In the general formula (2), M represents iridium, ruthenium or rhodium, R 21 represents a substituent, L 21 represents a ligand, and X 21 represents a counter ion. n21 represents an integer of 0 to 5, n22 represents an integer of 1 to 6, and n23 represents an integer of 0 to 3.
  3. 3. The light emitting device according to claim 1, wherein at least one of the light emitting layer or the plurality of organic compound layers is a light emitting device having a light emitting layer or a plurality of organic compound layers including a light emitting layer between a pair of electrodes. A light-emitting element containing a material for use.
  4. 4. The light emitting element according to claim 3, wherein the layer containing the light emitting element material is a layer formed by a coating process.
  5. A transition metal complex represented by the following general formula (1):
    In the general formula (1), M is iridium, ruthenium or rhodium, R 11 , R 12 and R 13 each represent a substituent, n11 and n12 each represent an integer of 0 to 4, and L 11 is monovalent. Represents a ligand.
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