JP2000150152A - Organic electroluminescence display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize luminescence less in deterioration, higher in reliability, higher in brightness, and higher in efficiency, by forming a hole injection zone or an electron injection zone over the whole area of a multi-color luminescent layer having a plurality of patterned color-developing zones of an organic electroluminescent element. SOLUTION: A display device is obtained by gathering together organic electroluminescent elements each made up by forming an organic compound thin film 3 comprising a hole injection zone 5, a multi-color luminescent layer 6, and an electron injection zone 7, between a positive electrode 2 and a negative electrode 4 provided on a glass substrate 1. The multi-color luminescent layer 6 comprises a plurality of patterned luminescent areas, preferably three areas of a blue luminescent area, a green luminescent area, and a red or orange luminescent area, and preferably contains an aromatic tertiary amine compound. Further, a hole injection zone 5 or an electron injection zone 7 is formed over the whole area of the multi-color luminescent layers 6, and the structure thus simplified improves stability for repeated use.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-brightness, high-definition, multicolor organic electroluminescence (EL) display device.

[0002]

2. Description of the Related Art An EL device using an organic compound is
Promising applications as inexpensive large-area, full-color display elements of the solid-state emission type are promising, and many developments have been made. In general, an organic EL device includes a light-emitting layer or a plurality of layers of organic compound thin films including a light-emitting layer, and a pair of counter electrodes sandwiching the layer. When an electric field is applied between the two electrodes, electrons are injected from the cathode side and holes are injected from the anode side toward the organic layer from the electrodes. The injected electrons and holes are transported toward the counter electrode, respectively.
Furthermore, electrons and holes meet and combine in the light emitting layer,
Organic compound molecules involved in light emission in the layer are excited by energy. When the electron energy level of the excited molecule returns from the conduction band to the valence band, the phenomenon of releasing the corresponding energy is observed as light emission.

[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). This method uses a metal chelate complex for a light emitting layer and an amine compound for a hole injection layer to obtain high-luminance green light emission, and a luminance of several thousand at a DC voltage of 6 to 7 V.
(Cd / m ² ) and a maximum luminous efficiency of 1.5 (lm / W), which is close to the practical range.

[0004] However, organic EL devices up to now have improved luminous intensity due to the improved structure, but do not yet have sufficient luminous brightness. In addition, there is a major problem that the stability upon repeated use is poor. This is because, for example, a metal chelate complex such as a tris (8-hydroxyquinolinato) aluminum complex is chemically unstable during electroluminescence, has poor adhesion to a cathode, and is greatly deteriorated by short-time light emission. I was For the above reasons, for the development of an organic EL device having high luminous brightness and luminous efficiency and excellent stability in repeated use, it is desired to develop a material having excellent ability and durability. ing.

[0005] As the light-emitting material, metal complex-based materials up to now,
A wide variety of organic fluorescent dyes, condensed polycyclic aromatics, styryls, aromatic tertiary amines, etc. have been developed. Since the current-voltage characteristics and the like are different, it is very complicated and time-consuming to create a multicolor light-emitting element by combining them in terms of material selection, film thickness, and adjustment of the production conditions. there were.

In order to improve the brightness, efficiency and life of the organic EL element and to change the emission color, in particular, a small amount of an organic fluorescent dye is added to a light-emitting layer made of a material having good film-forming properties, so-called doping. Approaches are often taken. However, in this method, it is necessary to use two (or more) kinds of materials for forming the light emitting layer and pattern the layer to be formed, so that there is a high possibility that the formation is further complicated.

Furthermore, for each multicolor light emitting layer,
If the optimal hole injection material or electron injection material is selected to make the electrical characteristics uniform, the layers made of these materials must be patterned according to the light emitting layer. And the cathode may directly contact with each other to cause a short circuit. As described above, according to the conventional method, the element creation is complicated and time-consuming, and there is a possibility that a problem may occur in the created element.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a high-definition multi-color light emitting organic EL capable of emitting light with high luminance and high efficiency, having little deterioration of light emission, and having high reliability. Display device. As a result of extensive studies by the present inventors, when the hole injection zone and / or the electron injection zone are formed in common over the entire device assembly regardless of the patterning of each light emitting layer, the stability in repeated use is excellent, The inventors have found that the structure of the element and the drive circuit can be simplified, and have accomplished the present invention.

[0009]

According to the present invention, a hole injection zone and a multicolor emission layer, a hole injection zone and a multicolor emission layer and an electron injection zone, or a multicolor emission layer and an electron zone are provided between an anode and a cathode. In a display device consisting of a collection of organic electroluminescent elements formed by forming an organic compound thin film comprising an injection zone,
The organic electroluminescence, wherein the multicolor light-emitting layer has a plurality of patterned coloring regions, and the hole injection zone or the electron injection zone is formed over the entire surface of the multicolor light-emitting layer. It relates to a display device. Further, the present invention provides a multicolor light-emitting layer, a blue color region,
The present invention relates to the organic electroluminescent display device formed of three regions of a green coloring region and a red or orange coloring region.

[0010] The present invention also relates to the above organic electroluminescent display device, wherein one layer in the hole injection zone is a layer containing any of an aromatic tertiary amine compound, a phthalocyanine compound and a hexaoxytriphenylene compound. The present invention also relates to the organic electroluminescent display device, wherein one layer in the electron injection zone is a layer containing a metal complex compound or a nitrogen-containing 5-membered aromatic ring compound. In addition, the present invention relates to the above organic electroluminescent display device, wherein all the coloring regions of the multicolor light emitting layer are layers containing an aromatic tertiary amine compound.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An organic EL device is a device in which one or more organic compound thin films are formed between an anode and a cathode. In the case of an organic EL device, although there are some electrical restrictions during driving, particularly a problem with the electrical resistance of the device, and some restrictions in terms of the preparation device and the drive circuit, basically, a small element to a large area element It is possible to produce elements of any size and two-dimensional shape. However, when used as a backlight or a planar light source, one large-area monochromatic element may be created. However, in order to display arbitrary characters, figures, and even images, one by one A device consisting of a set of elements corresponding to small pixels must be created. Further, when expressing two or more colors, particularly when creating a full-color display device, elements forming pixels corresponding to each color must be divided, and patterning (coloring) is performed at the time of creation. There is a need.

According to the present invention, the materials used for the hole injection zone and / or the electron injection zone are made common, and the layers are formed on the entire surface of the device assembly without patterning the light emitting layer, thereby simplifying the operation. Can solve the problem at the time of driving.

The multilayer organic EL device includes (anode / hole injection zone / light emitting layer / cathode), (anode / light emitting layer / electron injection zone / cathode), (anode / hole injection zone / light emitting layer / electron). This is an element having a multilayer structure such as (injection zone / cathode). Further, each of the hole injection zone, the light emitting layer, and the electron injection zone may be formed by a layer structure of two or more layers. In that case, in the case of a hole injection zone, a layer for injecting holes from the electrode is a first hole injection layer or simply a hole injection layer, which receives holes from the hole injection layer and transports them through the layer, The layer that injects holes into the light emitting layer is called a second hole injection layer or a hole transport layer. Similarly, in the case of the electron injection zone, the layer that injects electrons from the electrode is the first electron injection layer or simply the electron injection layer, the layer that receives electrons from the electron injection layer, transports them through the layer, and injects electrons into the light emitting layer. Is called a second electron injection layer or an electron transport layer. Each of these layers including the light emitting layer is selected and used according to various factors such as energy level, heat resistance, adhesion with the organic layer or the electrode, as well as the charge injecting / transporting properties and the light emitting properties of the material itself. .

The hole injecting material has the ability to transport holes, has the effect of injecting holes from the anode, and has an excellent hole injecting effect on the light emitting layer or the light emitting material. Compounds that prevent excitons from migrating to an electron injection zone or an electron injection material and have excellent thin film forming ability can be used. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone,
Tetrahydroimidazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene, hexaalkoxytriphenylene, hexaaryloxytriphenylene, hexaacyloxytriphenylene, benzidine triphenylamine, styrylamine triphenylamine, diamine triphenylamine, etc. , Their derivatives, and polymer materials such as polyvinyl carbazole, polysilane, and conductive polymers, but are not limited thereto.

Among the hole injection materials that can be used in the organic EL device of the present invention, more effective hole injection materials are aromatic tertiary amine compounds, phthalocyanine compounds or hexaoxytriphenylene compounds. Specific examples of the aromatic tertiary amine compound include triphenylamine, tolylamine, tolylphenylamine,
N, N'-diphenyl-N, N'-di-m-tolyl-
4,4'-biphenyldiamine, N, N, N ', N'-
Tetra (p-tolyl) -p-phenylenediamine, N,
N, N ′, N′-tetra-p-tolyl-4,4′-biphenyldiamine, N, N′-diphenyl-N, N′-di (1-naphthyl) -4,4′-biphenyldiamine,
N, N'-di (4-n-butylphenyl) -N, N'-
Di-p-tolyl-9,10-phenanthylenediamine,
4,4 ′, 4 ″ -tris (N-phenyl-Nm-tolylamino) triphenylamine, 1,1-bis [4-
(Di-p-tolylamino) phenyl] cyclohexane and the like, or oligomers or polymers having an aromatic tertiary amine skeleton, but are not limited thereto.

Specific examples of the phthalocyanine (Pc) compound include H ₂ Pc, CuPc, CoPc, NiPc, Z
nPc, PdPc, FePc, MnPc, ClAlP
c, ClGaPc, ClInPc, ClSnPc, Cl
₂ SiPc, (HO) AlPc, (HO) GaPc, V
OPc, TiOPc, MoOPc, GaPc-O-Ga
Examples include, but are not limited to, phthalocyanine derivatives such as Pc and naphthalocyanine derivatives.

Specific examples of the hexaoxytriphenylene compound include hexaalkoxytriphenylenes such as hexamethoxytriphenylene, hexaethoxytriphenylene, hexahexyloxytriphenylene, hexabenzyloxytriphenylene, trimethylenedioxytriphenylene, and triethylenedioxytriphenylene; Examples include, but are not limited to, hexaaryloxytriphenylenes such as phenoxytriphenylene, hexanaphthyloxytriphenylene, hexabiphenylyloxytriphenylene, triphenylenedioxytriphenylene, hexaacetoxytriphenylene, hexabenzoyloxytriphenylene, and the like. Not something. less than,
Table 1 specifically shows typical examples of the hole injection material.

[0018]

[Table 1]

[0019]

[0020]

[0021]

The electron injecting material has the ability to transport electrons, has the effect of injecting holes from the cathode, and has an excellent effect of injecting electrons into the light emitting layer or the light emitting material. Compounds that prevent migration to the hole injection zone and have excellent thin film forming ability can be mentioned. For example, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole,
Triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane,
Examples include, but are not limited to, anthrones and derivatives thereof. In addition, sensitization can be performed by adding an electron accepting substance to the hole injecting material and adding an electron donating substance to the electron injecting material.

In the organic EL device of the present invention, a more effective electron injecting material is a metal complex compound or a nitrogen-containing five-membered ring compound. Specifically, as the metal complex compound, lithium 8-hydroxyquinolinato, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese , Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium , Bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-
Methyl-8-hydroxyquinolinato) chlorogallium, bis (2-methyl-8-hydroxyquinolinate)
(O-cresolate) gallium, bis (2-methyl-8)
-Hydroxyquinolinato) (1-naphtholate) aluminum, bis (2-methyl-8-hydroxyquinolinato) (2-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinato) phenolate gallium, μ-oxo-bis [di (2-methyl-8-hydroxyquinolinato) gallium], bis [o- (2-benzoxazolyl) phenolate] zinc, bis [o- (2-
Benzothiazolyl) phenolate] zinc, bis [o-
(2-benzotriazolyl) phenolate] zinc and the like, but are not limited thereto.

As the nitrogen-containing five-membered ring compound, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-diphenyloxazole, 1,4-bis [2- (4-methyl-5-phenyloxazolyl)] benzene, 2,5-diphenylthiazole, 2,5-diphenyl-1, 3,4-oxadiazole, 2- (pt
tert-butylphenyl) -5-p-biphenylyl-
1,3,4-oxadiazole, 2,5-di (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyl-1,3,4- Oxadiazolyl)] benzene, 4,4'-bis [2- (5-phenyl-
1,3,4-oxadiazolyl)] biphenyl, 2-
(P-tert-butylphenyl) -5-p-biphenylyl-1,3,4-thiadiazole, 2,5-di (1-
Naphthyl) -1,3,4-thiadiazole, 1,4-bis [2- (5-phenyl-1,3,4-thiadiazolyl)] benzene, 3- (p-tert-butylphenyl) -5-p- Biphenylyl-4-phenyl-1,2,2
4-triazole, 3,5-di (1-naphthyl) -4-
Examples include, but are not limited to, m-tolyl-1,2,4-triazole, 1,4-bis [3- (4,5-diphenyl-1,2,4-triazolyl)] benzene. . Table 2 below shows typical examples of the electron injection material.

[0025]

[Table 2]

[0026]

In the present invention, when an aromatic tertiary amine compound is used in the light emitting layer, holes are more easily injected and transported than electrons, so that injection and transport of holes into the electron injection layer are prevented. It is more effective to use a material with a strong ability to do so. As these materials, gallium complex compounds and nitrogen-containing five-membered ring compounds among the above-mentioned materials are preferable.

In the case of the luminescent material used in the present invention, a sufficient effect can be obtained even if only the luminescent layer is provided between the anode and the cathode. However, in order to increase the luminous brightness and efficiency or to prolong the lifetime. In addition, a new layer can be provided on one or both of the electrodes by using a hole injection material or an electron injection material on the electrode side to form a multilayer structure. With such a configuration, the injection efficiency of holes and electrons is increased, and the holes and electrons injected into the device reach the counter electrode without recombination, or are caused by recombination. Excitons can be prevented from escaping to the electrode. Further, it is possible to prevent a decrease in luminance and life due to quenching.

In the present invention, the apparatus configuration is simplified,
For ease of fabrication, each light-emitting layer may be formed from a single light-emitting material, but if necessary, in addition to the material of the present invention, further known light-emitting materials, hole-injecting materials, Electron injection materials can also be used. If necessary, a combination of a light emitting material, a doping material, a hole injection material, and an electron injection material can be used. In addition, by selecting a doping material, light emission luminance and light emission efficiency can be improved.

The light emitting material or doping material in the present invention includes anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthalopylene, perinone, phthaloperinone, naphthaloperinone,
Diphenylbutadiene, tetraphenylbutadiene, coumarin compounds, oxadiazole compounds, aldazine, bisbenzooxazoline, bisstyryl compounds,
Pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, triphenylamine, benzidine triphenylamine, styrylamine triphenylamine, diamine triamine Phenylaminepyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compounds, porphyrin metal complexes, phthalocyanine complexes, rare earth metal complexes, quinacridone, rubrene, rubicene and dye lasers and fluorescent dyes for laser brightening, etc. It is not limited.

Specific examples of materials effective as a light emitting material or a doping material include tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-
Hydroxyquinolinato) aluminum, tris (8-
Hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc,
Bis (2-methyl-8-hydroxyquinolinato) chlorogallium, bis (2-methyl-8-hydroxyquinolinate) (o-cresolate) gallium, bis (2-methyl-8-hydroxyquinolinate) ( 1-naphtholate) aluminum, bis (2-methyl-8-hydroxyquinolinato) (2-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinato) phenolategallium, μ-oxo-bis [di (2-methyl-8
-Hydroxyquinolinato) gallium], bis [o-
Metal complex compounds such as (2′-benzoxazolyl) phenolate] zinc, bis [o- (2-benzothiazolyl) phenolate] zinc, bis [o- (2-benzotriazolyl) phenolate] zinc, N, N , N ', N'-
Aromatic amine compounds such as tetrakis [p- (α, α-dimethylbenzyl) phenyl] -9,10-anthracenediamine and 9,10-bis [4- (di-p-tolylamino) phenyl] anthracene; 4′-bis (β, β-diphenylvinyl) biphenyl, 4,4′-
Bis [β- (N-ethyl-3-carbazolyl) vinyl]
Bistyryl compounds such as biphenyl and 4,4'-bis [p- (diphenylamino) styryl] biphenyl, perylene, perylenetetracarboxylic diimide derivative, 3- (2'-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6) , 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), neil red, diphenylanthracene and its derivatives, quinacridone and its derivatives, rubrene and its derivatives, rubicene and Derivatives and the like, but are not limited to these.

In the present invention, a more effective light emitting material or doping material includes an aromatic tertiary amine compound. Aromatic tertiary amine compounds can be obtained by changing the chemical structure to have a fluorescent color of any color in the visible region from blue to red. By using this in organic EL devices, , And can emit all luminescent colors. The aromatic or aromatic ring in the present invention may contain a hetero atom other than a carbon atom, and the presence of the hetero ring can greatly change the color. Further, the aromatic tertiary amine compound of the present invention is formed by forming a bond between groups bonded to a nitrogen atom,
Those forming a nitrogen-containing ring are also included. The aromatic tertiary amine compound of the present invention has at least one aromatic ring directly bonded to a nitrogen atom, and the rest may be a non-aromatic group such as an alkyl group. All of the three groups to be bonded are preferably aromatic rings.

The following are specific examples of the aromatic tertiary amine compound of the present invention. 9- [4- (diphenylamino) phenyl] anthracene, N, N-di-m
-Tolyl-9-phenanthreneamine, 4,4'-bis [p- (diphenylamino) styryl] biphenyl, bis [2- {p- (diphenylamino) styryl} phenyl] ether, 9,10-bis [4- (Di-p-tolylamino) phenyl] anthracene, 3,6-bis [4-
(Di-m-tolylamino) phenyl] phenanthrene,
Benzobis [2- {4- (diphenylamino) phenyl}] thiazole, 1,4-bis (N-phenyl-3-
Carbazolyl) benzene, 4,4′-di (N-carbazolyl) biphenyl, 3,5-bis [4- (N-acridonyl) phenyl] -4-phenyl-1,2,4-triazole, 4,4′- Bis [β- (N-ethyl-3-carbazolyl) vinyl] biphenyl, 1,2-bis [1-
{4- (phenyl-m-tolylamino)} naphthyl] ethylene, 1,2-bis [9- {10- (di-p-tolylamino)} anthryl] ethylene, N, N, N ', N'
-Tetra-p-biphenylyl-1,4-naphthalenediamine, N, N, N ', N'-tetra-p-tolyl-2,
6-naphthalenediamine, N, N, N ', N'-tetrakis (p-phenoxyphenyl) -2,7-phenanthylenediamine, N, N'-dimethylphenyl-N, N'
-Di (4-n-butylphenyl) -9,10-phenanthylenediamine, N, N, N ', N'-tetrakis [p
-(Α, α-dimethylbenzyl) phenyl] -9,10
-Anthracenediamine, N, N, N ', N'-tetra-p-tolyl-3,9-perylenediamine, N, N,
N ', N'-tetra-p-tolyl-5,12-rubicenediamine, 3,7-bis (di-p-tolylamino) dibenzothiophene sulfone, 5,6,11,12-tetrakis [4-didiene (P-benzylphenyl) aminodiphenyl] naphthacene, 3,4,9,10-tetrakis (diphenylamino) perylene, 2,3,6,7,10,1
Examples include, but are not limited to, 1-hexakis (di-p-tolylamino) triphenylene.

The electron injecting material, the light emitting material, and the hole injecting material are used in appropriate combinations. However, when an aromatic tertiary amine is used in all the coloring regions of the multicolor emitting layer,
A common material can be used as the electron injection material or the light emitting material regardless of the coloring region. Conventionally, electron injection materials and hole injection materials have been selected and patterned according to the color-forming region, but if they are common, they can be formed over the entire surface without patterning. Become.

As the conductive material used for the anode of the organic EL device, a material having a work function of more than 4 eV is suitable. Specifically, carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten ,Silver,
Metals such as gold, platinum and palladium and their alloys;
Metal oxides such as tin oxide, indium oxide, and zinc oxide used for the TO substrate and the NESA substrate, and composites thereof, and organic conductive resins such as polythiophene and polypyrrole are used.

As the conductive material used for the cathode, 4
Suitable are those having a work function lower than eV, such as, but not limited to, magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, and alloys thereof. . Alloys include magnesium / silver,
Representative examples include magnesium / indium and lithium / aluminum, but are not limited thereto. The ratio of the alloy is controlled by the temperature, atmosphere, degree of vacuum, and the like of the evaporation source, and is selected to be an appropriate ratio. Also L
Metal fluorides having a low work function such as iF and MgF ₂ can also be used as a cathode in a thin film between an organic layer and a conductive material such as a metal. 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 devices is sufficiently transparent in the 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 using the above-described conductive material so as to secure a predetermined translucency by a method such as vapor deposition or sputtering. 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 transparency, but, for example, a glass substrate, a polyethylene plate, a polyethylene terephthalate plate, a polyether sulfone plate, A transparent resin such as a polypropylene plate can be used.

The respective layers of the organic EL device according to the present invention are formed by a dry film forming method such as vacuum evaporation, sputtering, plasma, ion plating, spin coating, or the like.
Any of wet film forming methods such as dipping and flow coating can be applied. The film thickness is not particularly limited, but needs to be set to an appropriate film 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. The thickness of each ordinary organic layer is 1 nm
To 10 μm is suitable, but 5 nm to 1 μm
Is preferable. Further, the range is preferably from 10 nm to 200 nm. The thickness of the entire organic layer is also preferably 1 μm or less, but 1 μm
There are also things that can go beyond.

In the case of the wet film forming method, the material forming each layer is made of ethanol, chloroform, tetrahydrofuran,
The thin film is formed by dissolving or dispersing in a suitable solvent such as dioxane, and any solvent may be used. In any of the organic compound thin film layers, an appropriate resin or additive may be used for improving film forming properties and preventing pinholes in the film. Examples of usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, and poly-
Examples thereof include photoconductive resins such as N-vinylcarbazole and polysilane, and conductive resins such as polythiophene, polypyrrole, and polyphenylenevinylene. However,
In the case of the compound of the present invention, since the compound is highly amorphous, a good film can be formed without mixing a resin. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

In the organic EL device of the present invention, inorganic oxides, sulfides, nitrides, fluorides and low-molecular organic compounds are formed on the surface of the device in order to improve stability against temperature, humidity, atmosphere and the like. Alternatively, it is also possible to provide a protective layer made of a thin film of resin, cover the device with a case made of metal, glass or resin filled with an inert gas, or protect the entire device with silicon oil, resin or the like.

In the present invention, it is necessary to pattern the light-emitting layer. Therefore, in the present technology, the light-emitting layer is preferably formed by dry film formation such as vacuum evaporation. When the hole injection layer and the electron injection layer are formed over the entire surface of the device without patterning, either a dry type or a wet type may be used, but in order to optimize each light emitting portion, either the hole injection layer or the electron injection layer is used. In the case of patterning, dry film formation is preferred. In addition, when a film is formed on a patterned layer, it is necessary to prevent the underlying layer from being destroyed. Therefore, a dry film formation is more preferable.

In order to drive the organic EL display device,
It is necessary that each pixel can be turned on and off arbitrarily. The driving method and configuration for that are as follows. The static drive includes one common electrode and a segment electrode connected to each pixel, and addresses an arbitrary pixel by selectively inputting an electric signal to each segment electrode. It is used for display of fixed symbols and areas, seven segments (figure of eight), and small dot matrix display devices, and performs simple symbol display and segment display.

As shown in FIG. 1, the matrix-driven device has a striped electrode structure in the x-axis and y-axis directions. Here, the electrodes in the x-axis direction (horizontal direction) are called row electrodes or row electrodes, and the electrodes in the y-axis direction (vertical direction) are called column electrodes or column electrodes. The screen display sequentially selects a row electrode (or a column electrode) and inputs an electric signal (data) for display to a column electrode (or a row electrode) in synchronization with the selection to address an arbitrary pixel and form an image. I do. Sequential selection is called scanning, and the pixels arranged on the scanning electrodes are activated according to the signal input to the data electrode in synchronization with the selection of the scanning electrodes, and the time when other scanning electrodes are selected, that is, non- All are inactive during the selection time. This driving method is called simple matrix driving or passive matrix driving. When an organic EL display device is driven in a passive matrix, power consumption and driving voltage can be reduced, so that a cathode is often used as a scanning electrode and an anode is often used as a data electrode. This is because, in general, the current flowing through the anode having a high resistance can be made small, and the current flowing through the cathode having a low resistance can be made larger than that of the anode.

In the case of a display device driven by passive matrix, an operation (light emission) state is caused by a half-selected state by a voltage applied to non-selected pixels other than the selected pixel. This is called crosstalk, and what arises from the half-selected state is suppressed by circuit design. However, in the case of an organic EL element,
A leak current may also occur, and to prevent this, it is necessary to improve the rectification characteristics of the element.

In the passive matrix driving, a non-operation state is generated by scanning, so that the actual operation time is very short. In a general display device, it is lit only for a few hundredth of the time. For this reason, the instantaneous luminance at the time of lighting of each element needs to be extremely high, and the driving voltage needs to be increased accordingly. This becomes more remarkable as a high-definition and large-scale display device is manufactured, so that the required characteristics of materials and conditions in circuit design become severe. An active matrix is a method for avoiding this. This is a method in which a switching element is provided for each pixel arranged on a matrix of scanning electrodes and data electrodes, and driving is performed.The operating state can be maintained during a scanning cycle, and a bright screen is obtained because the entire panel is continuously driven. can get. Generally, p-Si
And the like.

In order to obtain a high-definition display device, the size of a pixel is at least several hundreds of μm, so that a corresponding level of patterning is required. As for the patterning of the organic layer, particularly the light emitting layer, there is a method of performing etching after film formation, but generally, it is difficult to perform fine etching, and the accuracy of the pixel depends on the electrode.
Patterning is performed using a mask or the like during film formation. In the case of a general film forming method in which an anode, an organic layer, and a cathode are formed in this order, patterning of ITO, which is usually used as an anode, is performed by using a mask at the time of film formation, or by using a leak current of an element. SiO ₂ to prevent short circuit,
An oxide such as Al ₂ O ₃ or AlN, a nitride, an organic insulating material, or the like may be further patterned after the ITO film is formed, but usually, a photopolymer is applied to the ITO film formed on the entire surface. It exposed patterned using a photomask, developed, carried out by etching with an acid such as HCl-Fe ₂ O ₃ aqueous solution or aqua regia.

As for the cathode patterning, there is a method of performing patterning at the time of film formation using a mask, or performing etching after film formation. However, in order to reliably produce high-definition pixels, several tens of pixels are required to be formed on a substrate in advance. There is a method in which a reverse-tapered partition (called a cathode partition) in the order of μm is provided, and the cathode partition is automatically patterned using the cathode partition as a shadow mask. A cathode partition is provided so as to be orthogonal to the previously patterned anode. A cathode having a predetermined shape is patterned by sequentially depositing an organic compound and a cathode metal. By this process, the adjacent cathode lines are electrically insulated in the order of several tens of μm by the cathode barrier. The negatively tapered cathode partition is formed, for example, by applying a negative type photopolymer by a spin coating method, and exposing and developing using a photomask. The gap between the dots of the display is determined by the width of the cathode partition, but can be up to several μm,
A high-definition display device can be realized.

In the present invention, multi-color display,
Since the purpose is preferably to express a full-color image, at least the light-emitting layer needs to be separately coated with at least two types, preferably three types of materials. As the patterning, there is a line pattern as shown in FIG.
In addition, for example, a dot pattern may be used, and other patterns may be used as long as the pixels are arranged adjacent to each other and there is no particular difficulty in selecting the pixels during driving. These patterning is most reliably performed at the time of film formation using a metal mask such as SUS or other ferrous alloys or non-ferrous metals or alloys thereof. At this time, masks corresponding to the respective materials may be prepared and exchanged one after another. However, since the pattern of each color is usually the same, each pattern can be created by shifting the same mask. However, when the pattern is different because the size and arrangement of pixels are different for each color, it is necessary to prepare respective masks.

In the present invention, when a display device of a simple area color in which each display color is fixed is formed, only that portion may be separately painted using a mask or the like. In order to express an arbitrary image, it is necessary to provide a dot matrix display device including elements of two or more colors. When formed from two-color elements, an intermediate color between the two colors can be output by adjusting the luminance of adjacent elements. In particular, when blue and yellow or orange elements are arranged, white can be obtained as an intermediate color. In the case of three-color elements, more various colors can be expressed as intermediate colors. Especially CRT and full color L
By arranging three colors of red (R), green (G), and blue (B) like a CD, a full-color organic EL display device capable of expressing any color including white can be manufactured. At this time, the wavelength showing the maximum intensity is 380 to 490 nm for blue, 490 to 570 nm for green, and 570 to 780 n for red or orange.
m is preferably within the range, but is not always limited by the intensity and the shape of the spectrum. In addition, a color filter or a filter that emits fluorescence may be used in combination in order to produce a full-color display device with further excellent color tone.

In the multi-color organic EL display device, it is preferable that the rectification, the light emission threshold voltage, the current-luminance-voltage characteristics, etc. of the respective colors are substantially the same in consideration of the element configuration and the driving device. Aromatic tertiary amine compounds have very similar properties, and can be used in red, green, and blue.
It is suitable as the material of the present invention. However, since each color is independent of the element, a material other than the aromatic tertiary amine may be used, and if there is an appropriate material having similar characteristics or if the structure is somewhat complicated, If it is desired to obtain the best properties with a better material, it may be better to use a material other than the aromatic tertiary amine compound. Also,
Although it is preferable that each light emitting layer is not doped in order to make the formation as simple as possible, doping is often performed for adjusting colors and characteristics. Further, the thickness of each light emitting layer is preferably as close as possible in consideration of the overall configuration, but the thickness may be largely changed in order to further equalize various characteristics of each color element. Further, by changing the area of each color element, characteristics, particularly luminance, can be made uniform.

In a multi-color organic EL display device, since the pixels are minute, leakage of current and short-circuit often cause element defects and crosstalk.
In the present invention, the hole injection zone and the electron injection zone are made common, and are formed on the entire surface of the element assembly, so that the organic layer serving as an insulating layer has a certain thickness at the step formed by etching the anode. Also, by preventing direct contact between the anode and the cathode caused by slight displacement of patterning, it is possible to prevent occurrence of leakage current and short circuit. The layers in the hole injection zone and the electron injection zone to be shared are one of them.
Although layers may be used, it is preferable to use a plurality of layers in common, and furthermore, unless various characteristics are significantly different between the respective color elements,
It is preferable that all the layers except the light emitting layer be common from the viewpoint of simplification of device fabrication. FIGS. 2 and 3 are schematic diagrams showing a case in which one hole injection layer and one electron injection layer are provided, and both are formed on the entire surface. In the present invention, when an aromatic tertiary amine compound having similar characteristics is used for each light emitting material, it is easy to make all injection layer layers common. However, in order to make the characteristics of the respective color elements closer to each other with emphasis on the design of the driving device system, even if the injection material is the same, the film thickness may be changed or the material may be changed for each color element.

As described above, by using the organic EL device according to the present invention, it is possible to improve the organic EL device such as the luminous efficiency and the maximum luminous brightness. In addition, this device is extremely stable against heat and current, and furthermore, can obtain practically usable light emission luminance at a low driving voltage,
Deterioration, which was a major problem up to now, could be significantly reduced. In addition, because some organic layers are common,
The structure of the device and the drive circuit could be simplified.

The multicolor light-emitting organic EL device of the present invention can be used as a thin flat multicolor or full-color display, such as a display panel of instruments, a marker lamp, a monitor screen of a portable information terminal and a computer, and a wall-mounted television. Applications that can replace current color liquid crystal displays and the like are considered, and their industrial value is very large.

[0054]

The present invention will be described in more detail with reference to the following examples. Example 1 N, N′-diphenyl-N, N ′ was placed on a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm.
-Di (1-naphthyl) -4,4'-biphenyldiamine was vacuum-deposited on the entire surface to obtain a hole injection layer having a thickness of 50 nm. Next, as blue, N, N′-dimethylphenyl-N,
N'-di (4-n-butylphenyl) -9,10-phenanthylenediamine, 3,7-bis (di-p-
Tolylamino) dibenzothiophene sulfone and 3,4,9,10-tetrakis (diphenylamino) perylene as red using a mask having a line width of 1 mm, and 40 n each at equal intervals in a direction orthogonal to the ITO line pattern.
m was vacuum-deposited to obtain a light-emitting layer for each color. Further, bis (2-methyl-8-hydroxyquinolinato) phenolate gallium was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. Add magnesium and silver 10:
Using a mask having a line width of 1 mm, an electrode having a thickness of 150 nm is formed directly above the light emitting layer of each color using the alloy mixed in Step 1. Each color element is 1 mm × 1 mm and a dot matrix of 20 × 3 (color) × 16. Was obtained. Each color element emits light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and has a maximum luminance of 1200 (c
d / m ² ) of white light could be obtained.

Example 2 N, N, N ', N'-tetra-p was placed on a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm.
-Tolyl-4,4'-biphenyldiamine dissolved in methylene chloride and spin-coated to a thickness of 50 n
m of the hole injection layer was obtained. Next, 9,10-bis [4- (di-p-tolylamino) phenyl] anthracene is 50 nm for blue and 1,2-bis [1- {4- (phenyl-m-tolylamino)} naphthyl] ethylene for green. 3
0 nm, red as 5,6,11,12-tetrakis [4
-{Di (p-benzylphenyl) amino} phenyl] naphthacene was vacuum-deposited at 40 nm intervals at a regular interval in a direction perpendicular to the ITO line pattern using a mask having a line width of 1 mm to obtain each color light emitting layer. . In addition, Tris (8
-Hydroxyquinolinato) aluminum was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. An electrode having a thickness of 100 nm is formed directly on each color light emitting layer using a mask having a line width of 1 mm using an alloy obtained by mixing aluminum and lithium at a ratio of 50: 1.
An organic EL display device of 1 mm and a dot matrix of 20 × 3 (color) × 16 was obtained. Each color element has a DC voltage of 5V
Showed a light emission of 100 (cd / m ² ) or more, and white light with a maximum luminance of 1500 (cd / m ² ) could be obtained by matrix driving.

Example 3 CuPc was vacuum-deposited on the entire surface of a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm.
A first hole injection layer having a thickness of 30 nm was obtained. Then, ITO
Using a mask having a line width of 1 mm orthogonal to the pattern of (1), N, N′-diphenyl-N,
N'-di (1-naphthyl) -4,4'-biphenyldiamine was 40 nm, and N, N'-diphenyl-N, N'-di-m-tolyl-4,4'- Biphenyldiamine was 50 nm, and 1,1-
Bis [4- (di-p-tolylamino) phenyl] cyclohexane was vacuum-deposited in 30 nm increments to obtain a second hole injection layer. Next, 4,4′-bis (β, β-diphenylvinyl) biphenyl as blue, tris (8-hydroxyquinolinato) aluminum as green, N, N, red as red.
N ′, N′-tetra-p-tolyl-5,12-rubicenediamine is vacuum-deposited by 40 nm on each of the patterned hole injection layers using a mask having a line width of 1 mm to emit light of each color. Layer obtained. Further, 3- (p-tert-butylphenyl) -5-p-biphenylyl-4-phenyl-1,2,4-triazole was added to the blue element portion at 10 nm, and bis (2-methyl-8-hydroxyquinolinate) was further added. ) 40 nm of phenolate aluminum
Μ-oxo-bis [di (2-methyl-
8-hydroxyquinolinato) gallium] at 30 nm,
Bis [o- (2-benzothiazolyl)
[Phenolate] zinc was vacuum-deposited by 50 nm each to obtain an electron injection layer. On top of that, add magnesium and indium
An electrode having a thickness of 200 nm is formed directly on each color light emitting layer using a mask having a line width of 1 mm with an alloy mixed at 0: 1, and each color element is 1 mm × 1 mm and 20 × 3 (color) × 1.
Thus, an organic EL display device having a dot matrix of 6 was obtained. Each color element emits light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and has a maximum luminance of 160 by matrix driving.
0 (cd / m ² ) white light could be obtained.

Example 4 A compound (H-4) shown in Table 1 was dissolved in methylene chloride on a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm, and a film thickness of 5 was obtained by spin coating.
A hole injection layer of 0 nm was obtained. Next, bis [2-
{P- (Diphenylamino) styryl} phenyl] ether is 30 nm, 3,7-bis (di-p-tolylamino) dibenzothiophene sulfone is 40 nm for green, and 1,2-bis [9- {10- (di -P-Tolylamino) {anthryl] ethylene was vacuum-deposited at a uniform interval of 40 nm in a direction perpendicular to the line pattern of the ITO using a mask having a line width of 1 mm to obtain each color light emitting layer. Further, 4,4′-bis [2- (5-phenyl-1,3,4-oxadiazolyl)] biphenyl was vacuum-deposited on the entire surface to obtain a second electron injection layer having a thickness of 20 nm. Next, bis (2-methyl-8-hydroxyquinolinate) (p-cyanophenolate) gallium was vacuum-deposited on the entire surface to obtain a first electron injection layer having a thickness of 30 nm. An electrode having a thickness of 150 nm is formed directly on each color light-emitting layer using an alloy in which magnesium and silver are mixed at a ratio of 10: 1 using a mask having a line width of 1 mm.
An organic EL display device of m × 1 mm and a dot matrix of 20 × 3 (color) × 16 was obtained. Each color element emitted light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and white light with a maximum luminance of 1300 (cd / m ² ) was obtained by matrix driving.

Example 5 2,3,6,7,10,11-hexaethoxytriphenylene was vacuum-deposited over the entire surface of a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm to form a 70 nm-thick film. A hole injection layer was obtained. Next, N as blue
N, N ′, N′-tetrakis (p-phenoxyphenyl) -2,7-phenanthylenediamine, tris (8-hydroxyquinolinato) aluminum as green and N,
N'-dimethylquinacridone in a weight ratio of 100: 1,
Tris (8-hydroxyquinolinato) aluminum and 4- (dicyanomethylene) -2-methyl-6 as orange
-(P-dimethylaminostyryl) -4H-pyran (D
CM) was vacuum-deposited at a weight ratio of 100: 5 using a mask having a line width of 1 mm and at a uniform interval of 50 nm in a direction orthogonal to the line pattern of the ITO, thereby obtaining a light emitting layer of each color. Further, bis (2-methyl-8-hydroxyquinolinato) (1-naphtholate) gallium was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 40 nm. An electrode having a thickness of 150 nm is formed directly on each color light emitting layer using a mask having a line width of 1 mm using an alloy in which magnesium and aluminum are mixed at a ratio of 10: 1.
An organic EL display device of m × 1 mm and a dot matrix of 20 × 3 (color) × 16 was obtained. Each color element emitted light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and white light with a maximum luminance of 1100 (cd / m ² ) was obtained by matrix driving.

Example 6 N, N, N ', N'-tetra-p was placed on a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm.
-Tolyl-2,6-naphthalenediamine was vacuum-deposited on the entire surface to obtain a hole injection layer having a thickness of 50 nm. Next, as blue, N, N, N ', N'-tetra-p-biphenylyl-
1,4-naphthalenediamine, N, N, as orange
N ', N'-tetra-p-tolyl-3,9-perylenediamine is masked with a line width of 1 mm and 50 n each at equal intervals in a direction orthogonal to the line pattern of ITO.
m was vacuum-deposited to obtain a light-emitting layer for each color. Further, bis (2-methyl-8-hydroxyquinolinato) phenolate gallium was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. Add magnesium and silver 10:
An electrode having a film thickness of 150 nm is formed directly above the light emitting layer of each color using a mask having a line width of 1 mm with the alloy mixed in Step 1. Each color element is 1 mm × 1 mm and a dot matrix of 30 × 2 (color) × 16 Was obtained. Each color element emits light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and has a maximum luminance of 2200 (c) by matrix driving.
d / m ² ) of white light could be obtained.

Example 7 4,4 ′, 4 ″ -tris (N-phenyl-Nm-tolylamino) triphenylamine was vacuum-coated on a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm. Vapor deposition was performed to obtain a first hole injection layer having a thickness of 40 nm, and N, N′-diphenyl-N, N′-di (1-naphthyl) -4,4′-biphenyldiamine was applied to the entire surface under vacuum. The second hole injection layer having a thickness of 10 nm was obtained by vapor deposition, and then N, N, N ′, N′-tetra-p- as blue.
Phenyl-1,4-naphthalenediamine, N, as green
N, N ′, N′-tetrakis [p- (α, α-dimethylbenzyl) phenyl] -9,10-anthracenediamine, 1,2-bis [9- {10- (di-p-methoxyphenyl) as red [Amino] {anthryl] ethylene was vacuum-deposited at a uniform interval of 40 nm each in a direction perpendicular to the line pattern of the ITO using a mask having a line width of 1 mm to obtain a light emitting layer of each color. Further, bis (2-methyl-
8-Hydroxyquinolinato) (p-cyanophenolate) gallium was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 40 nm. Add magnesium and silver 10:
Using a mask having a line width of 1 mm, an electrode having a thickness of 150 nm is formed directly above the light emitting layer of each color using the alloy mixed in Step 1. Each color element is 1 mm × 1 mm and a dot matrix of 20 × 3 (color) × 16. Was obtained. Each color element emits light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and has a maximum luminance of 2000 (c
d / m ² ) of white light could be obtained.

Example 8 2,3,6,7,10,11-hexaphenoxytriphenylene was vacuum-deposited on the entire surface of a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm.
A hole injection layer having a thickness of 60 nm was obtained. Next, as blue 4,
4'-bis ([beta], [beta] -diphenylvinyl) biphenyl and 4,4'-bis [[beta]-(N-ethyl-3-carbazolyl) vinyl] biphenyl in a weight ratio of 100: 3 and tris (8- (Hydroxyquinolinato) aluminum and N, N, N ', N'-tetra-p-tolyl-9,1
0-anthracenediamine in a weight ratio of 100: 5, as red, N, N, N ′, N′-tetra-p-tolyl-3,
9-perylenediamine and 3,4,9,10-tetrakis (di-p-tolylamino) perylene in a weight ratio of 100: 1 using a mask with a line width of 1 mm in a direction perpendicular to the ITO line pattern. 40nm each at intervals
Each layer was vacuum deposited to obtain a light emitting layer of each color. Further, tris (8-hydroxyquinolinato) aluminum was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. An electrode having a thickness of 150 nm is formed on the light emitting layer of each color using a mask having a line width of 1 mm using an alloy in which aluminum and lithium are mixed at a ratio of 50: 1.
An organic EL display device of × 1 mm and a dot matrix of 20 × 3 (color) × 16 was obtained. Each color element has a DC voltage of 5
At V, light emission was 100 (cd / m ² ) or more, and white light with a maximum luminance of 1800 (cd / m ² ) was obtained by matrix driving.

Example 9 H ₂ Pc was vacuum-deposited on the entire surface of a glass plate with an ITO electrode patterned to a cleaned line width of 1 mm.
A first hole injection layer having a thickness of 30 nm was obtained. Then, 2,
3,6,7,10,11-hexamethoxytriphenylene was vacuum-deposited on the entire surface to obtain a 50 nm-thick second hole injection layer. Next, bis [o- (2-benzoxazolyl) phenolate] zinc and 9,10-bis [4-
(Di-p-tolylamino) phenyl] anthracene
At a weight ratio of 00: 2, N, N'-diphenyl-N, N'-di (1-naphthyl) -4,4'-biphenyldiamine and rubrene were converted to orange at a weight ratio of 100: 5 and a line width of 1 mm. Each mask was vacuum-deposited at a regular interval of 40 nm in a direction orthogonal to the line pattern of ITO to obtain a light emitting layer of each color. Further, bis [o- (2-benzotriazolyl) phenolate] zinc was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. On top of that, an alloy of magnesium and silver mixed at a ratio of 10: 1 has a line width of 1: 1.
using a 150 mm mask, a film thickness of 150 n
m electrodes, each color element is 1 mm × 1 mm, 3
An organic EL display having a dot matrix of 0 × 2 (color) × 16 was obtained. Each color element is 100 (c) at a DC voltage of 5 V.
d / m ² ) or more, and white light with a maximum luminance of 1900 (cd / m ² ) was obtained by matrix driving.

Example 10 An organic EL display device was prepared in the same manner as in Example 1 except that the compound (H-5) shown in Table 1 was used as a hole injection material and the compound (E-9) shown in Table 2 was used as an electron injection material. Created.

Example 11 Bis (2-methyl-8-hydroxyquinolinato) (p-phenylphenolato) aluminum and perylene were deposited in a co-deposition layer at a weight ratio of 100: 2 on the blue light emitting layer, and tris ( 8-hydroxyquinolinato) aluminum and 3- (2'-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6) in a co-evaporation layer at a weight ratio of 100: 3, and tris (8-hydroxyquinolinate) in a red light emitting layer. Compound (E-12) shown in Table 2 as a co-evaporation layer having a weight ratio of aluminum and Neil Red of 100: 1 and a second electron injection layer.
An organic EL display device was prepared in the same manner as in Example 4 except for using.

Example 12 The same procedures as in Example 6 were carried out except that the compound (H-6) shown in Table 1 was used as the hole injecting material and tris (5-phenyl-8-hydroxyquinolinato) aluminum was used as the electron injecting material. An organic EL display device was created.

As described above, in each of the display devices of Examples 10 to 12, each color element has a DC voltage of 5 V and 100 (cd /
m ² ) or more, and white light with a maximum luminance of 1000 (cd / m ² ) or more could be obtained by matrix driving.

Example 13 An IT patterned to a cleaned line width of 0.3 mm
On a glass plate with an O electrode, N, N, N ', N'-tetra-p-tolyl-4,4'-biphenyldiamine is dissolved in methylene chloride, and a film thickness of 5 is formed by spin coating.
A hole injection layer of 0 nm was obtained. N, N'-diphenyl-
N, N'-di (1-naphthyl) -4,4'-biphenyldiamine was vacuum-deposited on the entire surface to obtain a hole injection layer having a thickness of 50 nm. Next, 9,10-bis [4- (di-p-tolylamino) phenyl] anthracene as blue and N, N, N ', N'-tetrakis [p- (α, α-dimethylbenzyl) phenyl] as green. -9,10-anthracenediamine, 1,2-bis [9- @ 10- (di-
Using a mask having a line width of 0.3 mm, p-methoxyphenylamino) {anthryl] ethylene was vacuum-deposited at a uniform interval of 40 nm directly above the ITO line pattern to obtain a light emitting layer of each color. Further, bis (2-methyl-
8-Hydroxyquinolinato) (1-naphtholate) gallium was vacuum-deposited on the entire surface to obtain a 30 nm-thick electron injection layer. An electrode having a thickness of 150 nm was formed thereon in a direction perpendicular to each light emitting layer using a mask having a line width of 1 mm using an alloy in which magnesium and silver were mixed at a ratio of 10: 1.
Each color element is 0.3 mm x 1 mm, 60 x 3 (color) x 1
Thus, an organic EL display device having a dot matrix of 6 was obtained. Each color element emits light of 100 (cd / m ² ) or more at a DC voltage of 5 V, and has a maximum luminance of 170 by matrix driving.
0 (cd / m ² ) white light could be obtained.

Example 14 An IT patterned to a cleaned line width of 0.3 mm
2,3,6,7,10,11 on glass plate with O electrode
-Hexamethoxytriphenylene was vacuum-deposited on the entire surface to obtain a 70-nm-thick hole injection layer. Next, N, N, N ', N'-tetrakis [p- (α, α-dimethylbenzyl) phenyl] -1,4-naphthalenediamine as blue and benzobis [2- {4- (diphenylamino) as green] Phenyl}] thiazole, red as 3,4,9,1
0-tetrakis (diphenylamino) perylene was vacuum-deposited at a regular interval of 40 nm each directly above the ITO line pattern using a 0.3 mm line width mask,
A light emitting layer of each color was obtained. Further, bis [o- (2-benzothiazolyl) phenolate] zinc was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. On top of this, an alloy of magnesium and indium mixed at a ratio of 10: 1 has a line width of 1: 1.
An electrode having a thickness of 150 nm was formed in a direction orthogonal to the light emitting layers of each color using a mask having a size of 0.3 mm × 0.3 mm ×
An organic EL display device of 1 mm and a dot matrix of 60 × 3 (color) × 16 was obtained. Each color element has a DC voltage of 5V
Showed a light emission of 100 (cd / m ² ) or more, and white light with a maximum luminance of 1500 (cd / m ² ) could be obtained by matrix driving.

Example 15 An IT patterned to a cleaned line width of 0.3 mm
In the direction perpendicular to the ITO line pattern on the glass plate with O electrodes, the substrate is 0.3 mm using photopolymer.
A cathode partition exposed at the line was provided. Next, the compound (H-13) shown in Table 1 was vacuum-deposited on the entire surface to form a film having a thickness of 4.
A first hole injection layer of 0 nm was obtained. Next, the compound (H-5) shown in Table 1 was vacuum-deposited on the entire surface to obtain a second hole injection layer having a thickness of 10 nm. On top of that, N, N, N ',
N'-tetra-p-biphenylyl-1,4-naphthalenediamine, N, N, N ', N'-tetra-p- as green
Phenoxyphenyl-9,10-anthracenediamine, red as 3,4,9,10-tetrakis (di-p-
Tolylamino) perylene was vacuum-deposited at a uniform interval of 40 nm using a mask having a line width of 0.3 mm in parallel with the pattern formed by the cathode barrier ribs to obtain light emitting layers of each color. Further, the compound (E-3) shown in Table 2 was vacuum-deposited on the entire surface to obtain an electron injection layer having a thickness of 30 nm. On top of that, an alloy of magnesium and silver mixed at a ratio of 10: 1 to a thickness of 150 n.
m electrodes are formed and each color element is 0.3 mm x 0.3 m
m, an organic EL display device having a dot matrix of 80 × 3 (color) × 64 was obtained. Each color element is 1 at DC voltage 5V.
It emitted light of 00 (cd / m ² ) or more, and white light with a maximum luminance of 500 (cd / m ² ) was obtained by matrix driving.

The organic EL device of the present invention achieves improvement of luminous efficiency and luminous brightness, long life and simplification of the configuration and drive circuit. The luminescent material, doping material, and hole injection used together are used. The material, the electron injection material, the sensitizer, the resin, the electrode material, and the like, and the element manufacturing method are not limited.

[0071]

The organic EL device having the structure of the present invention has high luminous efficiency and high luminance compared with the prior art, has a long life, and is a multicolor light emitting organic EL device which is easy to manufacture and drive. I got it. As described above, with the organic EL device formed by the device configuration of the present invention, a multicolor light emitting organic EL device having high luminance, high luminous efficiency, and long life can be easily manufactured.

[0072]

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an RGB matrix structure of a known multicolor light emitting EL display device. FIG. 2 is a schematic cross-sectional view of the multi-color light emitting organic EL display device of the present invention, as viewed from the vertical direction of the RGB line, showing the laminated structure of each layer. FIG. 3 is a diagram illustrating a stacked configuration of each layer of the multicolor light emitting organic EL display device of the present invention.
It is the schematic diagram of the cross section seen from the line lateral direction. 1 to 3
Is a schematic diagram for explaining the configuration of each layer and the process of film formation, and does not represent the actual stacked state of elements after film formation.

[0000]

[Explanation of symbols]

 1: Glass substrate 2: Anode (row electrode) 3: Organic layer 4: Cathode (column electrode) 5: Hole injection zone 6: Multicolor emission layer 7: Electron injection zone

FIG. 1 is a schematic view of a known multicolor light emitting EL display device.

FIG. 2 is a schematic cross-sectional view of a multicolor light-emitting organic EL display device according to the present invention in a longitudinal direction.

FIG. 3 is a schematic cross-sectional view of a multicolor light emitting organic EL display device according to the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05B 33/22 H05B 33/22 D

Claims (5)

[Claims] 1. An organic compound thin film comprising a hole injection zone and a multicolor emission layer, a hole injection zone and a multicolor emission layer and an electron injection zone, or a multicolor emission layer and an electron injection zone between an anode and a cathode. In a display device comprising a set of formed organic electroluminescent elements, the multicolor light-emitting layer has a plurality of patterned coloring regions, and the hole injection zone or the electron injection zone is An organic electroluminescent display device formed over the entire surface of the light emitting layer. 2. The organic electroluminescent display device according to claim 1, wherein the multicolor light emitting layer is formed of three regions of a blue coloring region, a green coloring region, and a red or orange coloring region. 3. The organic electroluminescent display according to claim 1, wherein one layer in the hole injection zone is a layer containing any of an aromatic tertiary amine compound, a phthalocyanine compound and a hexaoxytriphenylene compound. apparatus. 4. The organic electroluminescent display according to claim 1, wherein one layer in the electron injection zone is a layer containing a metal complex compound or a nitrogen-containing 5-membered aromatic ring compound. 5. The organic electroluminescent display device according to claim 1, wherein all of the coloring regions of the multicolor light emitting layer are layers containing an aromatic tertiary amine compound.