JPH10340785A - Organic electroluminescence element material and organic electroluminescence element using the same - Google Patents

Abstract

(57) [Problem] To provide a highly reliable electroluminescent element material and an organic electroluminescent element with high luminance, high luminous efficiency, little degradation of luminescence and high reliability. SOLUTION: An organic electroluminescence device material represented by the general formula [1] and an organic electroluminescence device using the same. General formula [1] [Wherein R ^{1 to} R ¹⁴ represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cycloalkyl group, an aryl group, and a heterocyclic group. , An amino group, an alkylamino group, or an arylamino group. Further, adjacent groups of R ^{1 to} R ¹⁴ may be bonded to each other to form a new ring. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence (EL) device used for a flat light source and a display.

[0002]

2. Description of the Related Art An EL device using an organic substance is expected to be used as an inexpensive, large-area, full-color display device of a solid light emitting type, and many developments have been made. Generally EL
Is composed of a light-emitting layer and a pair of opposed electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, the electrons are recombined with holes in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to the valence band.

[0003] Conventional organic EL devices have a higher driving voltage and lower luminous brightness and luminous efficiency than inorganic EL devices.
In addition, the characteristic deterioration was remarkable, and it had not been put to practical use.
2. Description of the Related Art In recent years, an organic EL in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less is laminated.
Devices have been reported and are of interest (see Applied Physics Letters, vol. 51, p. 913, 1987). In this method, the metal chelate complex is converted into a phosphor layer,
High brightness green light emission is obtained by using an amine compound for the hole injection layer, and the brightness is 100 c at a DC voltage of 6 to 7 V.
d / m ² and maximum luminous efficiency of 1.5 lm / W,
Has performance close to the practical range. However, organic EL devices up to now have improved light emission intensity due to the improved structure, but do not yet have sufficient light emission luminance.
In addition, there is a major problem that the stability upon repeated use is poor.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an organic compound having high luminous efficiency and excellent stability when used repeatedly.
L element. As a result of intensive studies by the present inventors,
The present invention has been found that the organic EL device using at least one layer of the organic EL device material of the compound represented by the general formula [1] has high luminous efficiency and excellent stability upon repeated use.

That is, the present invention relates to an organic electroluminescent device material represented by the following general formula [1]. General formula [1]

Embedded image [Wherein R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group,
A substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted cycloalkyl group, It represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group. Also, R ^1-
Adjacent groups of R ¹⁴ may be bonded to each other to form a new ring. ]

Further, the present invention relates to an organic electroluminescent device comprising a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein at least one layer is a layer containing the above-mentioned organic electroluminescent device material. It is an electroluminescent element.

Further, the present invention relates to an organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein the light emitting layer is a layer containing the above organic electroluminescent device material. It is an electroluminescent element.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

In the compound of the present invention represented by the general formula [1], R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group. Substituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group,
Substituted or unsubstituted arylthio group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted amino group, substituted or unsubstituted alkylamino group Represents a substituted or unsubstituted arylamino group.

Specific examples of the halogen atom represented by R ^{1 to} R ^{14 in} the compound represented by the general formula [1] in the present invention include chlorine, bromine, iodine and fluorine, and specific examples of the alkyl group include methyl. Group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, and the like. Specific examples of cycloalkyl include , A cyclopentane ring and a cyclohexane ring.

Specific examples of the alkoxy group represented by R ^{1 to} R ^{14 in} the compound represented by the general formula [1] in the present invention include a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group and a trichloromethoxy group. , Trifluoroethoxy group, pentafluoropropoxy group, 2,2,3,3-
Tetrafluoropropoxy group, 1,1,1,3,3,3
-Hexafluoro-2-propoxy group, 6- (perfluoroethyl) hexyloxy group, and the like. Specific examples of the aryloxy group include a phenoxy group, a p-nitrophenoxy group, a p-tert-butylphenoxy group, -Fluorophenoxy group, pentafluorophenyl group, 3-
And a trifluoromethylphenoxy group.

Specific examples of the alkylthio group represented by R ^{1 to} R ^{14 in} the compound represented by the general formula [1] in the present invention include a methylthio group, an ethylthio group, a tert-butylthio group,
Examples include a hexylthio group, an octylthio group and a trifluoromethylthio group. Specific examples of the arylthio group include a phenylthio group, a p-nitrophenylthio group, and a p-tert.
-Butylphenylthio, 3-fluorophenylthio, pentafluorophenylthio, 3-trifluoromethylphenylthio, and the like.

In the present invention, the aryl group represented by R ^{1 to} R ^{14 in} the compound represented by the general formula [1] is a phenyl group,
There are a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group, and the like.As the heterocyclic group, a pyrrole group, a pyrroline group, a pyrazole group, a pyrazoline group, an imidazole group, a triazole group, pyridine Group, pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, purine group, quinoline group, isoquinoline group, sinoline group, quinoxaline group, benzoquinoline group, fluorenone group, carbazole group, oxazole group, oxadiazole group, Thiazole group, thiadiazole group, triazole group, imidazole group, benzoxazole group, benzothiazole group, benzotriazole group, benzimidazole group, bisbenzooxazole group, bisbenzothiazole group, bisbenzimidazole , Anthrone group, dibenzofuran group, a dibenzothiophene group, anthraquinone group, acridone group, a phenothiazine group, a pyrrolidine group, dioxane group, a morpholine group.

Specific examples of the amino group represented by R ^{1 to} R ¹⁴ of the compound represented by the general formula [1] in the present invention include an amino group, a bis (acetoxymethyl) amino group, a bis (acetoxyethyl) amino group, Examples thereof include a bisacetoxypropyl) amino group and a bis (acetoxybutyl) amino group. Specific examples of the alkylamino group include an ethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a benzylamino group and a dibenzylamino group. There are, as specific examples of the arylamino group, a phenylamino group,
There are a (3-methylphenyl) amino group, a (4-methylphenyl) amino group and the like. Specific examples of the phenylamino group include a phenylamino group, a phenylmethylamino group, a diphenylamino group, and bis (3-methylphenyl) An amino group, a bis (4-methylphenyl) amino group, a naphthylphenylamino group, a bis [4- (α, α′-dimethylbenzyl) phenyl] amino group, and the like.

The adjacent groups R ^{1 to} R ¹⁴ are bonded to each other to form a saturated or unsaturated ring such as a phenyl ring, a naphthyl ring, an anthryl ring, a pyrenyl ring, a carbazole ring, a benzopyranyl ring and a cyclohexyl ring. May be formed.

The alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, cycloalkyl group, aryl group, heterocyclic group, amino group, alkylamino group represented by R ^{1 to} R ¹⁴ in the present invention. Representative examples of the group which may be substituted with an arylamino group include the following substituents.

The halogen atom includes chlorine, bromine, iodine and fluorine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a ter
t-butyl group, pentyl group, hexyl group, heptyl group,
There are an octyl group, a stearyl group, a trichloromethyl group and the like. As the cycloalkyl, a cyclopentane ring, a cyclohexane ring, a 1,3-cyclohexadienyl group, a 2-
Examples thereof include a cyclopenten-1-yl group and a 2,4-cyclopentadiene-1-ylenyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, a trifluoroethoxy group, a pentafluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group. , 1,1,1,3,3,3-hexafluoro-2-propoxy group, 6- (perfluoroethyl) hexyloxy group and the like.
Phenoxy group, p-nitrophenoxy group, p-tert
-Butylphenoxy group, 3-fluorophenoxy group, pentafluorophenyl group, 3-trifluoromethylphenoxy group and the like.

The alkylthio group includes a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a trifluoromethylthio group and the like, and the arylthio groups include a phenylthio group, a p-nitrophenylthio group, Examples include a p-tert-butylphenylthio group, a 3-fluorophenylthio group, a pentafluorophenylthio group, and a 3-trifluoromethylphenylthio group.

Examples of the aryl group include phenyl, biphenyl, terphenyl, naphthyl, anthryl,
There are a phenanthryl group, a fluorenyl group, a pyrenyl group, and the like, and examples of the heterocyclic group include a pyrrole group, a pyrroline group, a pyrazole group, a pyrazoline group, an imidazole group, a triazole group, a pyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, and a triazine group. , Indole, purine, quinoline, isoquinoline, sinoline, quinoxaline, benzoquinoline, fluorenone, carbazole, oxazole, oxadiazole, thiazole, thiadiazole, triazole, imidazole, benzo Oxazole group, benzothiazole group, benzotriazole group, benzimidazole group, bisbenzooxazole group, bisbenzothiazole group, bisbenzimidazole group, anthrone group, dibenzofuran group, dibenzothiophene group Anthraquinone group, acridone group, a phenothiazine group, a pyrrolidine group, dioxane group,
There is a morpholine group and the like.

Examples of the amino group include an amino group, a bis (acetoxymethyl) amino group, a bis (acetoxyethyl) amino group, a bisacetoxypropyl) amino group and a bis (acetoxybutyl) amino group. There are an ethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a benzylamino group and a dibenzylamino group.
Phenylamino group, (3-methylphenyl) amino group,
(4-methylphenyl) amino group and the like. Examples of the phenylamino group include a phenylamino group, a phenylmethylamino group, a diphenylamino group, a bis (3-methylphenyl) amino group, and a bis (4-methylphenyl) amino group. ,
A naphthylphenylamino group and a bis [4- (α, α′-dimethylbenzyl) phenyl] amino group.

In the present invention, the compound represented by the general formula [1] can be prepared by heating a 9-fluorenone derivative in the presence of magnesium (Chem. Ber., Vol. 123, No. 1).
981, p. 1990), a method for obtaining from 9-thiofluorenone derivatives (Chem. Ber., 95, 19).
10 page, 1962). Hereinafter, typical examples of the compound of the present invention are specifically illustrated in Table 1, but the present invention is not limited to the following typical examples.

[0022]

[Table 1]

[0023]

[0024]

[0025]

[0026]

[0027]

The organic EL device is a device in which a single or multilayer organic thin film is formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between an anode and a cathode. The light-emitting layer contains a light-emitting material and may further contain a hole-injection material or an electron-injection material for transporting holes injected from an anode or electrons injected from a cathode to the light-emitting material. The multilayer type is (anode / hole injection layer / light emitting layer /
There is an organic EL device having a multilayer structure of (cathode), (anode / light-emitting layer / electron injection layer / cathode), and (anode / hole injection layer / light-emitting layer / electron injection layer / cathode). General formula [1] of the present invention
Are compounds having strong fluorescence in a solid state and excellent in electroluminescence, and thus can be used in a light emitting layer as a light emitting material. Further, by doping the compound of the general formula [1] as a doping material in the light emitting layer at an optimum ratio in the light emitting layer, it is possible to select a high light emitting efficiency and an optimum light emitting wavelength. Further, since the compound of the general formula [1] can transport carriers such as holes or electrons, the organic EL
It can also be used for the hole injection layer or the electron injection layer of the device.

By using a compound of the general formula [1] as a doping material (guest material) as a host material of the light emitting layer, an organic EL device having high emission luminance can be obtained.
The compound of the general formula [1] is desirably contained in the light emitting layer in a range of 0.001% by weight to 50% by weight relative to the host material, and more preferably 0.01% by weight to 1% by weight.
A range of 0% by weight is effective.

In the light emitting layer, in addition to the light emitting material and the doping material, a hole injection material or an electron injection material can be used if necessary.

When the organic EL element has a multilayer structure, it is possible to prevent a decrease in luminance and life due to quenching. If necessary, a combination of two or more kinds of light emitting materials, doping materials, hole injecting materials for injecting carriers, and electron injecting materials can also be used. Also,
The hole injection layer, the light-emitting layer, and the electron injection layer may each be formed in a layer structure of two or more layers, and an element structure in which holes or electrons are efficiently injected from the electrode and transported in the layer is selected. You.

The conductive material used for the anode of the organic EL device preferably has a work function of more than 4 eV, and is preferably carbon, aluminum, vanadium, iron, cobalt, or the like.
Nickel, tungsten, silver, gold, platinum, palladium and the like and alloys thereof, ITO substrate, metal oxide such as tin oxide and indium oxide called NESA substrate, and organic conductive resin such as polythiophene and polypyrrole are used. . The conductive material used for the cathode is preferably one having a work function of less than 4 eV, such as magnesium, calcium, tin, lead, titanium, yttrium,
Lithium, ruthenium, manganese and the like and alloys thereof are used, but not limited thereto. The anode and the cathode may be formed by two or more layers if necessary.

In the organic EL device, it is desirable that at least one of the organic EL devices is sufficiently transparent in an emission wavelength region of the device in order to emit light efficiently. Further, it is desirable that the substrate is also transparent. The transparent electrode is set so as to secure a predetermined translucency by a method such as vapor deposition or sputtering using the above conductive material. The electrode on the light emitting surface desirably has a light transmittance of 10% or more. The substrate is not limited as long as it has mechanical and thermal strength and is transparent, but examples thereof include a transparent resin such as a glass substrate, a polyethylene plate, a polyether sulfone plate, and a polypropylene plate. .

Each layer of the organic EL device according to the present invention can be formed by any of dry film forming methods such as vacuum evaporation and sputtering and wet film forming methods such as spin coating and dipping. The thickness is not particularly limited, but each layer needs to be set to an appropriate thickness. If the film thickness is too large, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too small, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. Normal thickness is 5nm to 10μ
The range of m is suitable, but the range of 10 nm to 0.2 μm is more preferable.

In the case of the wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent such as chloroform, tetrahydrofuran, dioxane or the like to form a thin film.
The solvent may be any. In any of the thin films, a suitable resin or additive may be used to improve film forming properties, prevent pinholes in the film, and the like. Examples of such a resin include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and poly-N-.
Examples include photoconductive resins such as vinyl carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

Examples of the host material usable in combination with the general formula [1] include quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, triazole, imidazole, oxazole and oxadiazole. , Stilbene, butadiene, benzidine triphenylamine, styrylamine triphenylamine, diamine triphenylamine fluorenone, diaminoanthracene triphenylamine, diaminophenanthrene triphenylamine, anthraquinodimethane, diphenoquinone,
Thiadiazole, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, triphenylene, anthrone and derivatives thereof,
And a conductive polymer material such as polyvinyl carbazole and polysilane. The specific examples are shown in Table 2 below, but the present invention is not limited to the following representative examples.

[0037]

[Table 2]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

The emission color can be changed by using a further doping material together with the general formula [1]. Doping materials used with the general formula [1] include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone,
Phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole ,
Examples include, but are not limited to, pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, and derivatives thereof.

The hole injecting material has the ability to inject holes, has an excellent hole injecting effect on the light emitting layer or the light emitting material, and has an electron injecting layer or electron of excitons generated in the light emitting layer. Compounds that prevent migration to the injection material and have excellent thin film forming ability are mentioned. Specifically, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, poly Arylalkane, stilbene, butadiene,
Benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine and the like, and derivatives thereof, and polyvinyl carbazole,
Although there are polymer materials such as polysilane and conductive polymer,
It is not limited to these.

The electron injecting material has a capability of injecting electrons, has an excellent electron injecting effect on the light emitting layer or the light emitting material, and has a hole injecting layer or hole injecting of excitons generated in the light emitting layer. Compounds that prevent transfer to a material and have excellent thin film forming ability are exemplified. For example, quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxadiazole, thiadiazole, tetrazole, perylenetetracarbon Acid, fluorenylidenemethane, anthraquinodimethane,
Examples include, but are not limited to, anthrones and derivatives thereof. Alternatively, an electron accepting substance may be added to the hole injecting material, and an electron donating substance may be added to the electron injecting material for sensitization.

In order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device or silicon oil is sealed to protect the entire device. It is also possible.

[0055]

EXAMPLES Synthesis of compound (1) 30 g of 9-fluorenone and 10 g of magnesium were stirred in 100 g of biphenyl under reflux for 51 hours. Thereafter, toluene was poured, and undissolved substances were collected by filtration. The collected solid was dissolved in heated nitrobenzene, and the undissolved magnesium was removed by filtration, followed by cooling, followed by precipitation of the solid. The obtained solid was purified by sublimation to obtain 5.6 g of compound (1). Elemental analysis, molecular weight analysis, infrared absorption spectrum, and NMR spectrum confirmed that it was compound (1). Synthesis method of compound (2) 1 g of compound (1) and 0.5 g of aluminum chloride were dispersed in 200 ml of carbon disulfide. Thereafter, 0.75 ml of tert-butyl chloride was added dropwise over 15 minutes, and the mixture was stirred under reflux for 6 hours. After the completion of the reaction, a solid was deposited upon cooling. Compound (2) by sublimation purification of solid
0.5 g was obtained. Elemental analysis, molecular weight analysis, infrared absorption spectrum, and NMR spectrum confirmed that it was compound (2). Synthesis method of compound (3) 1.0 g of compound (1) was dissolved in 100 ml of nitrobenzene. 1.3 ml of nitric acid was added dropwise to the nitrobenzene solution, and after the generation of heat had subsided, the mixture was stirred for 2 hours. Thereafter, when ethanol was poured, a solid precipitated. The obtained solid was purified by sublimation to obtain 0.3 g of compound (3). Elemental analysis, molecular weight analysis, infrared absorption spectrum, N
It was confirmed to be Compound (3) by MR spectrum. Method for synthesizing compound (5) 1.2 g of compound (3) and 35 g of sodium sulfate were added to water 25
The mixture was dispersed in a mixed solvent of 200 ml of ethanol and 200 ml of ethanol, and stirred for 6 hours under reflux. Thereafter, ethanol and water were removed by evaporation to obtain a solid. The obtained solid was extracted with THF and pyridine, and after removing the solvent, 0.8 g of compound (5) was obtained. The compound (5) was analyzed by elemental analysis, molecular weight analysis, infrared absorption spectrum and NMR spectrum.
Was confirmed.

Example 1 N, N '-(3) was placed on a cleaned glass plate with ITO electrodes.
-Methylphenyl) -N, N'-diphenyl-1,1-
Biphenyl-4,4-diamine (TPD) was vacuum-deposited to obtain a hole injection layer having a thickness of 20 nm. Next, the compound (1) was deposited to form a light-emitting layer having a thickness of 40 nm, and a tris (8-hydroxyquinoline) aluminum complex was deposited to obtain an electron-injecting layer having a thickness of 30 nm. On top of that, an alloy of magnesium and silver mixed at a ratio of 10: 1 with a film thickness of 100 n
m electrodes were formed to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 130 cd / m ² and a maximum light emission luminance of 12000 cd / m at a DC voltage of 5 V.
Light emission with a luminous efficiency of 1.8 lm / W at ^2.5 and 5 V was obtained. Next, as a result of a life test in which the device was continuously lit at a current density of 3 mA / cm ² , luminescence of １ ／ or more of the initial luminance was maintained for 10000 hours or more.

Examples 2 to 7 Organic EL devices were prepared in the same manner as in Example 1 except that the compounds shown in Table 3 were used instead of the compound (1) in the light emitting layer. This device exhibited the emission characteristics shown in Table 3.

[0058]

[Table 3]

Example 8 A compound (15) was vacuum-deposited on a washed glass plate with an ITO electrode to form a 100 nm-thick light-emitting layer, on which an alloy obtained by mixing magnesium and silver at a ratio of 10: 1 was used. An electrode having a thickness of 150 nm was formed to obtain an organic EL device. The light emitting layer and the cathode were deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This element has a DC voltage of 5
At 50 V, the emission luminance is 50 cd / m ² , and the maximum emission luminance is 1200 c.
Light emission with a luminous efficiency of 0.7 lm / W at d / m ² and 5 V was obtained. Next, at a current density of 3 mA / cm ² , as a result of a life test in which the device was continuously emitted, 1 / l of the initial luminance was obtained.
Two or more light emissions were maintained for 5000 hours or more.

Example 9 A compound (7) was deposited on a washed glass plate with an ITO electrode to form a hole injection layer having a thickness of 80 nm, and then a tris (8-hydroxyquinoline) aluminum complex was deposited. A light emitting layer having a thickness of 20 nm was obtained. On top of that, an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to a thickness of 100 nm.
Was formed to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 40 cd / m ² at a DC voltage of 5 V, a maximum light emission luminance of 8000 cd / m ² ,
Light emission with a luminous efficiency of 0.8 lm / W at V was obtained. Next, as a result of a life test in which the device was continuously caused to emit light at a current density of 3 mA / cm ² , light emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.

Example 10 TPD was deposited on a washed glass plate with an ITO electrode to form a hole injection layer having a thickness of 50 nm, and then tris (8-hydroxyquinoline) aluminum complex was deposited. A 20 nm light emitting layer was obtained. The compound (18) is vapor-deposited to form an electron injection layer having a thickness of 60 nm, and an alloy obtained by mixing magnesium and silver at a ratio of 10: 1 to a thickness of 100 nm.
An organic EL device was obtained by forming an electrode having a thickness of 10 nm. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 40 cd / m ² at a DC voltage of 5 V and a maximum light emission luminance of 7000 cd / m ² .
Light emission with a light emission efficiency of 0.6 lm / W at m ² and 5 V was obtained. Next, as a result of a life test in which the device was continuously caused to emit light at a current density of 3 mA / cm ² , light emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.

Example 11 N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine and the compound (13) were deposited in a weight ratio of 100: 1 to form a film having a thickness of 30.
As a result, a hole injection layer having a thickness of nm was obtained. Next, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to a film thickness of 5 mm.
A light emitting layer of 0 nm was obtained. An electrode having a thickness of 150 nm was formed thereon with an alloy of magnesium and silver mixed at a ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the cathode
Vapor deposition was performed at a substrate temperature of room temperature in a vacuum of 0 ^-6 Torr. This element emits light at a luminance of 120 cd /
m ² , a maximum emission luminance of 17000 cd / m ² , and a light emission with a luminous efficiency of 1.6 lm / W at 5 V was obtained. Then 3mA
As a result of a life test in which the device was continuously lit at a current density of / cm ² , luminescence having a luminance of 以上 or more of the initial luminance was 100%.
It was kept for more than 0 hours.

Example 12 N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1 ′ was placed on a washed glass plate with an ITO electrode.
-Biphenyl-4,4'-diamine was vacuum-deposited to obtain a 20-nm-thick hole injection layer. Next, N, N'-
(4-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine and compound (1) were deposited at a weight ratio of 100: 1 to form a film having a thickness of 40.
A light emitting layer having a thickness of 10 nm was formed, and a tris (8-hydroxyquinoline) aluminum complex was deposited thereon to obtain an electron injection layer having a thickness of 10 nm. An electrode having a thickness of 100 nm is formed thereon by using an alloy in which magnesium and silver are mixed at a ratio of 10: 1.
An L element was obtained. The hole injection layer and the light emitting layer are 10 ^-6 Torr
The film was deposited under the condition of room temperature and substrate temperature in a vacuum of r. This device emitted light with a luminance of 350 cd / m ² at a DC voltage of 5 V, a maximum luminance of 54000 cd / m ² , and a luminous efficiency of 4.0 lm / W at 5 V. Next, 3 mA / cm ²
As a result of a life test in which the device was continuously lit at a current density of, light emission of １ ／ or more of the initial luminance was maintained for 10000 hours or more.

Examples 13 to 23 Organic EL devices were produced in the same manner as in Example 12, except that the compounds shown in Table 4 were used in place of the compound (1) in the light emitting layer. This device exhibited the emission characteristics shown in Table 4.

[0065]

[Table 4]

Example 24 N, N ′ — (4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a thickness of 30 nm. Next, tris (8-hydroxyquinoline) as a host compound
The aluminum complex and the compound (1) as a doping compound are deposited at a weight ratio of 50: 1 to form a film having a thickness of 30 n.
m was formed, and [2-
(4-tert-butylphenyl) -5- (biphenyl) -1,3,4-oxadiazole] with a thickness of 20 nm
Was obtained. And one more magnesium and silver
An electrode having a thickness of 150 nm was formed from an alloy mixed at 0: 1 to obtain an organic EL device. The hole injection layer, the light emitting layer, the electron injection layer and the cathode were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 330 cd / m ² at a DC voltage of 5 V and a maximum light emission luminance of 53000 cd.
/ M ² , light emission efficiency of 4.3 lm / W at 5 V was obtained. Next, at a current density of 3 mA / cm ² , as a result of a life test in which the device was continuously illuminated, it was found that half of the initial luminance was obtained.
The above light emission was maintained for 10,000 hours or more.

Examples 25 to 34 In the light emitting layer, as a host compound and a doping compound,
An organic EL device was produced in the same manner as in Example 24, except that the compound shown in. Was used. This device exhibited the emission characteristics shown in Table 5.

[0068]

[Table 5]

Example 35 On a washed glass plate with an ITO electrode, 4, 4 ′, 4 ″
-Tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine was vacuum deposited to a film thickness of 40
As a result, a hole injection layer having a thickness of nm was obtained. Then, 4,4′-bis [N
-(1-Naphthyl) -N-phenylamino] biphenyl was vacuum-deposited to obtain a 10-nm-thick second hole injection layer. Further, 9,9-bis (N,
N-bis (3-tolyl) -4-aminophenyl) fluorene and compound (1) as a doping compound are mixed in 10
Evaporation was performed at a weight ratio of 0: 1 to form a light-emitting layer having a thickness of 30 nm. Further, bis (2-methyl-8-hydroxyquinolinato) (1-phenolate) gallium complex was vacuum-deposited to form a light-emitting layer having a thickness of 30 nm. An electron injection layer was formed, and an aluminum and lithium alloy mixed at a ratio of 25: 1 was formed on the electron injection layer.
An 50 nm electrode was formed to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This element has a DC voltage of 5
The emission luminance is 260 (cd / m ² ) at V, and the maximum emission luminance is 64
000 (cd / m ² ) and luminous efficiency of 5.8 (lm / W) were obtained.

Examples 36 to 46 In the light emitting layer, as a host compound and a doping compound,
An organic EL device was produced in the same manner as in Example 35 except that the compound shown in the above was used. This device exhibited the emission characteristics shown in Table 6.

[0071]

[Table 6]

Example 47 N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine is dissolved in chloroform, and the film thickness is 30 by spin coating.
As a result, a hole injection layer having a thickness of nm was obtained. Next, the compound (21) was vapor-deposited to form a light-emitting layer having a thickness of 40 nm.
A methyl-8-hydroxyquinolinato) (1-phenolate) gallium complex was vacuum-deposited to obtain an electron injection layer having a thickness of 30 nm. An electrode having a thickness of 100 nm is formed thereon by using an alloy in which magnesium and silver are mixed at a ratio of 10: 1.
An L element was obtained. The light emitting layer and the electron injection layer were deposited under the same conditions as in Example 1. This device has a light emission luminance of 90 cd / m ² and a maximum light emission luminance of 22000 cd / m at a DC voltage of 5 V.
Light emission with a luminous efficiency of 2.3 lm / W at ^2.5 and 5 V was obtained. Next, as a result of a life test in which the device was continuously caused to emit light at a current density of 3 mA / cm ² , light emission of 1/2 or more of the initial luminance was maintained for 5000 hours or more.

Example 48 A compound (1) was placed on a washed glass plate with an ITO electrode.
4), tris (8-hydroxyquinoline) aluminum
Complex, TPD, polycarbonate resin (PC-A)
Dissolved in tetrahydrofuran in a weight ratio of 3: 2: 3: 8
100nm light emission by spin coating
Layer obtained. Further, magnesium and silver were mixed at a ratio of 10: 1.
An electrode with a thickness of 150 nm is formed from the alloy
Got a child. This element emits 14 cd light at a DC voltage of 5 V.
/ M^Two, Maximum light emission luminance 2300 cd / m ^TwoAt 5V
Light emission with a light emission efficiency of 0.7 lm / W was obtained. Then 3mA
/ Cm^TwoThe device was continuously lit at a current density of
As a result of the life test, 300 or more luminescence of initial luminance was 300
It was kept for more than 0 hours.

Example 49 4,4′-Bis [N- (1-naphthyl) -N-phenylamino] biphenyl was vacuum-deposited on a washed glass plate with an ITO electrode, and a hole having a thickness of 40 nm was injected. Layer obtained. Further, N, N, N ', N'-[4- (α, α'-
Dimethylbenzyl) phenyl] -anthranyl-9,1
0-diamine and compound (14) are vacuum-deposited to a film thickness of 50.
A light emitting layer having a thickness of 40 nm was formed by vacuum evaporation of a tris (8-hydroxyquinolinato) aluminum complex.
An electron injection layer having a thickness of 150 nm was formed, and an electrode having a thickness of 150 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a luminance of 15 at a DC voltage of 5 V.
00 (cd / m ² ), maximum emission luminance 49000 (cd / m ² )
m ² ) and luminous efficiency of 4.2 (lm / W).

The organic EL device of the present invention achieves improvement in luminous efficiency, luminous brightness and long life, and is used together with a luminescent material, a doping material, a hole injection material, an electron injection material, and a sensitizer. It does not limit the agent, resin, electrode material and the like, and the element manufacturing method.

[0076]

According to the present invention, it is possible to obtain an organic EL device having higher luminous efficiency, higher luminance and longer life than the conventional one.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshio Enoda 2-3-13-1 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd.

Claims (3)

[Claims] 1. An organic electroluminescent device material represented by the following general formula [1]. General formula [1] [Wherein R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, Or an unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group,
Substituted or unsubstituted arylthio group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted amino group, substituted or unsubstituted alkylamino group Represents a substituted or unsubstituted arylamino group. Further, adjacent groups of R ^{1 to} R ¹⁴ may be bonded to each other to form a new ring. ] 2. An organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein at least one layer is a layer containing the organic electroluminescence device material according to claim 1. Luminescent element. 3. An organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein the light emitting layer is a layer containing the organic electroluminescent device material according to claim 1. Luminescent element.