US20010051284A1

US20010051284A1 - Organic electroluminescent element

Info

Publication number: US20010051284A1
Application number: US09/162,322
Authority: US
Inventors: Hideaki Ueda; Keiichi Furukawa; Yoshihisa Terasaka
Original assignee: Individual
Current assignee: Minolta Co Ltd
Priority date: 1997-09-29
Filing date: 1998-09-28
Publication date: 2001-12-13
Anticipated expiration: 2018-09-28
Also published as: US6395409B2

Abstract

The present invention relates to an organic electroluminescence element comprising an anode, an organic luminous layer, an electron-injection layer and a cathode, in which the electron-injection layer comprises a metal oxide or a metal halide, and a different material therefrom.

Description

This application is based on Japanese Patent Application Nos. Hei 9-264102, Hei 9-267037 and Hei 10-217039, respectively filed in Japan Sep. 29, 1997, Sep. 30, 1997 and Jul. 31, 1998, the contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an organic electroluminescence element.

2. Description of the Prior Art

The organic electroluminescence element emit light in accordance with electric signals and is constituted of an organic compound as a luminous material.

The organic electroluminescence element is basically constituted of an organic luminous layer and a pair of electrodes with the luminous layer sandwiched between the electrodes. Luminescence is a phenomenon in which electrons are injected from one electrode and holes are injected from the other electrode so that the luminous material in the luminous layer is excited to a higher energy level and then the excited luminous material goes down to a ground state to emit extra energy as light.

In addition to the above basic structure, a hole-injection layer for injecting holes is formed on the hole-injection electrode or an electron-injection layer is formed on the electron-injection electrode in order to improve luminous efficiency.

U.S. Pat. No. 3,530,325 discloses an example of electroluminescence elements in which single crystal anthracene is contained as a luminous material. Japanese Patent Laid-Open No. Sho 59-194,393 proposes the combination of a hole-injection layer with an organic luminous layer. Japanese Patent Laid-Open No. Sho 63- 295,695 proposes the combination of an organic hole-injection transporting layer with an organic electron-injection tranporting layer.

Those laminated electroluminescence element has a structure in which an organic fluorescent material, a charge-transporting organic compound (charge-transporting material) and electrodes are laminated. Holes and electrons injected from respective electrode move in the charge-transporting material and are recombined to emit light. An organic pigments which can emit fluorescenct light, such as 8-qunolinol aluminum complex and cumarin, are used as the organic fluorescent material. The electron-transporting material is, for example, exemplified by amino compounds, such as N,N′-di(m-tolyl)N,N′-diphenyl benzidine and 1,1-bis[N,N-di(p-tolyl)aminophenyl]cyclohexane, and 4-(N,N-diphenyl)aminobenzaldehyde-N,N-diphenyl hydrazone. In addition, porphyrin, such as cupper phthalocyanine, is proposed.

By the way, organic electroluminescence element has a high luminous properties. Stability at light-emitting time and preserving stability, however, are not sufficient for the electroluminescence element to be put into practical use. The stability of charge-transporting material is pointed out as one of problems with respect to the light-emitting stability and preserving stability of the element. A layer constituted by an organic material in the electroluminescence element is several tens of nm to several hundred of nm in thickness, being very thin. A voltage applied to the layer in unit of thickness is very high. As heat is emitted at light-emitting time or in electriferous conditions, the charge-transporting material is required to have electrical stability, thermal stability or chemical stability.

Japanese Patent Laid-Open Nos. Hei 2-15,595, Hei 3-37, 994, Hei 4-132, 191 and Hei 5-121, 172 disclose that materials other than aluminum is used as cathode in order to lower light luminescence-starting voltage of an electroluminescence element.

Japanese Patent Laid-Open Nos. Hei 4-132, 189 and Hei 7-268, 317 disclose that a layer constituted of a mixture of an electron transporting material and metal is used as an electron-injection layer.

The handling of the material other than aluminum is difficult in layer-forming conditions and the material is liable to be oxidized. The same problem arises when the mixture of the electron transporting material and metal.

When metal used for formation of an electron-injection layer is oxidized at vapor deposition time, powdery ones are formed. A uniform layer can not be formed. White haze occurs. Metallic layer is not formed. The formed one can not be used as an electrode.

A layer having excellent properties as an electron-injection layer has not been obtained yet as things are.

SUMMARY OF THE INVENTION

The present invention is to provide an electroluminescence element having high luminous strength and displaying stable performance even if used repeatedly.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view illustrating one embodiment of organic electroluminescence elements. [0018]
FIG. 2 is a schematic sectional view illustrating one embodiment of organic electroluminescence elements. [0019]
FIG. 3 is a schematic sectional view illustrating one embodiment of organic electroluminescence elements. [0020]
FIG. 4 is a schematic sectional view illustrating one embodiment of organic electroluminescence elements.[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to an organic electroluminescence element comprising an anode, an organic luminous layer, an electron-injection layer and a cathode, in which the electron-injection layer comprises a metal oxide or a metal halide, and a different material therefrom. [0022]
The electroluminescence element of the present invention has at least a luminous layer and an electron-injection layer between a pair of an anode and a cathode. The present invention is basically characterized in that the electron-injection layer is a composite layer comprising a metal oxide, a metal halide and a different material therefrom. [0023]
The present invention is further explained by referring to FIG. 1. In FIG. 1, the [0024] reference number 1 is an anode. On the anode, a hole-injection transporting layer 2, an organic luminous layer 3, an electron-injection layer 4 and a cathode 5 are laminated in the order.
It is preferred that an electrically conductive substance to be used for an [0025] anode 1 of the organic electroluminescence element has a work function of more than 4 eV. Conductive substances such as carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc, tungsten, silver, tin, gold, etc., and an alloy thereof, tin oxide, indium oxide, antimony oxide, zinc oxide or zirconium oxide are used.
It is preferred that a metal forming a [0026] cathode 5 has a work function of less than 4 eV. Magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, indium and an alloy thereof are used.
In the organic electroluminescence element, it is necessary that at least the [0027] anode 1 or the cathode 5 is a transparent electrode so that emission is observed. In this case, if the transparent electrode is used for the cathode, the transparency is easily deteriorated. Therefore, it is preferred that the transparent electrode is used for the anode.
When the transparent electrode is formed, it may be formed using the above-mentioned conductive substances, by means of vapor deposition, spattering, sol-gel method, or applying resin in which the above conductive substance is dispersed, etc., so that the desired transparency and conductivity are secured. [0028]
The transparent substrate is not specifically limited as long as it has suitable strength, is not affected by heat due to deposition, etc. at the time of preparing an organic electroluminescence element, and is transparent. Examples thereof include glass substrate, transparent resin such as polyethylene, polypropylene, polyethersulfon or polyetherketone. As the transparent electrode formed on the glass substrate, commercially available ITO, NESA, etc., are known. They may also be used. [0029]
FIG. 1 shows a construction with the hole-[0030] injection transporting layer 2 formed on the anode 1. The hole-injection transporting layer 2 can be formed by means of a vapor deposition of a compound, a dip coating or spin coating of the compound.
When the hole-injection transporting layer is formed by a deposition method, the thickness thereof is normally 1 to 200 nm, preferably 5 to 100 nm. When the hole-injection transporting layer is formed by the coating method, the thickness thereof is normally about 5 to 500 nm. The thicker the thickness of the layer, the higher the applied voltage is required, which results in the degradation of luminous efficiency. The deterioration of an electroluminescence element is liable to occur. If the thickness of the layer is smaller, the luminous efficiency is improved, however, the electroluminescence element easily causes breakdown, which shortens its life. [0031]
Examples of the hole-transporting material to be used for the hole-injection transporting layer include known compounds such as N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine, N,N′-diphenyl-N,N′-bis(4-methylphenyl)-1,1′-diphenyl-4,4′-diamine, N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-diphenyl-4,4′-diamine, N,N′-diphenyl-N,N′-bis(2-naphthyl)-1,1′-diphenyl-4,4′-diamine, N,N′-tetra(4-methylphenyl)-1,1′-diphenyl-4,4′-diamine, N,N′-tetra(4-methylphenyl)-1,1′-bis(3-methylphenyl)- 4,4′-diamine, N,N′-diphenyl-N,N′-bis(3-methylphenyl)-4,4′-diamine, N,N′-bis(N-carbazolyl)-1,1′-diphenyl-4,4′-diamine, 4,4′, 4″-tris(N-carbazolyl)triphenylamine, N,N′,N″-triphenyl-N,N′,N″-tris(3-methylphenyl)-1,3,5-tri(4-aminophenyl)benzene, 4,4′,4″-tris[N,N′,N″-triphenyl-N,N′, N″-tris(3-methylphenyl)]triphenylamine and the like. They may be used in a mixture of more than one compounds. [0032]
organic [0033] luminous layer 3 is formed on the hole-injection transporting layer 2. Examples of an organic luminous material to be used for the organic luminous layer 3 include those which are known to the art. For example, epidorisin, 2,5-bis[5,7-di-t-pentyl-2-benzoxazolyl]-thiophene, 2,2′-(1,4-phenylenedivinylene)bisbenzothiazole, 2,2′-(4,4′-biphenylene)bisbenzothiazole, 5-methyl-2-{2-[4-(5-methyl-2-benzoxazolyl)phenyl]vinyl}benzoxazole, 2,5-bis(5-methyl-2-benzoxazolyl)thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, perynone, 1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin, acridine, stilbene, 2-(4-biphenyl)-6-phenylbenzoxazole, aluminum trisoxine, magnesium bisoxine, bis(benzo-8-quinolinol)zinc, bis(2-methyl-8-quinolinol)-aluminum oxide, indium trisoxine, aluminum tris(5-methyloxine), lithium oxine, gallium trisoxine, calcium bis(5-chloroxine), poly(zinc-bis(8-hydroxy-5-quinolinolyl) methane), dilithium epindolision, zinc bisoxine, 1,2-phthaloperynone, 1,2-naphthaloperynone and the like.
Further, conventional fluorescent dyes such as fluorescent coumarine dye, fluorescent perylene dye, fluorescent pyran dye, fluorescent thiopyran dye, fluorescent polymethine dye, fluorescent mecyanin dye, fluorescent imidazole dye, etc. can be used. Among them, chelating oxynoid compounds are particularly preferred. [0034]
The organic luminous layer may be composed of a single layer construction of the above-mentioned luminous substance. It may also be composed of a multi-layer construction in order to adjust the properties such as luminous color or luminous intensity. Further, the luminous layer may be formed with two or more luminous substances or doped with luminous substances. [0035]
When the luminous layer is formed by a deposition method, the thickness thereof is normally 1 to 200 nm, preferably 1 to 100 nm. When the luminous layer is formed by a coating method, the thickness thereof is normally about 5 to 500 nm. The thicker the thickness of the layer, the higher the applied voltage is required, which results in the degradation of luminous efficiency. The deterioration of an electroluminescence element is liable to occur. If the thickness of the layer is smaller, the luminous efficiency is improved, however, the electroluminescence element easily causes breakdown, which shortens its life. [0036]
On the [0037] luminous layer 3, a composite layer comprising a metal oxide, a metal halide and a different material therefrom is formed as the electron-injection layer 4.
It is preferred that metal oxides or metal halides to be mixed in the electron-injection layer have a work function of less than 4.2 eV. As such, magnesium oxide, magnesium fluoride, calcium fluoride, strontium fluoride, yttrium oxide, strontium oxide, yttrium fluoride, lithium fluoride, lithium bromide, lithium oxide, magnesium bromide may be used. Magnesium fluoride, calcium fluoride, lithium fluoride, yttrium fluoride, lithium oxide, magnesium oxide, lithium bromide and yttrium oxide are preferred from the viewpoint of luminous properties and layer-forming properties. [0038]
As the metals to be mixed in the electron-injection layer, aluminum, indium, silver, magnesium, and gold are used. Among those metals, aluminum, indium, silver and gold are preferable each of which has a work function of more than 4.2 eV. [0039]
The different material therefrom to be mixed and contained in the electron-injection layer is a charge-transporting material or a metal. [0040]
The charge-transporting material contained in the electron-[0041] injection layer 4 may be exemplified by nitro-substituted fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxadiazole, triazole, thiadiazole, cumarin, chelated oxynoid compound, and a derivative thereof. Among those, the chelated oxynoid compound are particularly preferred from the viewpoint of heat resistance.
When the organic luminous materials have charge-transporting ability, such the organic luminous materials may be used as an electron-transporting material of the electron-injection layer. In this case, it is preferable that the organic luminous material and the electron transporting material in the electron-injection layer are same. Such material may be exemplified by chelated oxynoid compound, benzoxazole complex, benzothiazole complex. Among those compounds, chelated oxynoid compound is preferable. [0042]
When the electron transporting material is mixed, its mixing ratio to metal oxide or matal halide (electron transporting material:metal oxide and/or metal halide) is 100:1 to 1:1.2, preferably 20:1 to 1:1. [0043]
When metal is mixed, its mixing ratio to metal oxide or metal halide (metal oxide and/or metal halide:metal) is 1:100 to 100:1, preferably 1:20 to 20:1. [0044]
The electron-injection layer may be formed by a vacuum vapor deposition method to have a layer thickness of 0.1 to 20 nm. The thicker the thickness of the layer, the higher the applied voltage is required to emit light, which results in the degradation of luminous efficiency. The deterioration of an electroluminescence element is liable to occur. If the thickness of the layer is smaller, it becomes difficult to form a uniform layer. Defects in the layer are liable to be formed. The luminous efficiency is also deteriorated. The life of electroluminescence element is shortened. The layer thickness of, for example, the electron-injection layer can be measured by means of a layer-thickness measuring apparatus of crystal oscillator type. [0045]
The mixture of a metal oxide, a metal halide and a different material therefrom can be deposited to form a layer by many known methods, such as an electrical resistance heating method, an EB vapor deposition method, an ion plating method and an ionizing vapor deposition method. [0046]
Different constitutions of electroluminescence element are shown in FIG. 2 to FIG. 4. [0047]
In FIG. 2, the [0048] reference number 1 is an anode. On the anode, a hole-injection transporting layer 2, an organic luminous layer 3, an electron transporting layer 6, an electron-injection layer 4 and a cathode 5 are laminated in the order. The above-mentioned electron-injection layer is a composite layer comprising a metal oxide, a metal halide and a different material therefrom.
In FIG. 3, the [0049] reference number 1 is an anode. On the anode, a hole-injection layer 7, a hole-transporting layer 8, an organic luminous layer 3, an electron-transporting layer 6, an electron-injection layer 4 and a cathode 5 are laminated in the order. The above-mentioned electron-injection layer is a composite layer comprising a metal oxide, a metal halide and a different material therefrom.
In FIG. 4, the [0050] reference number 1 is an anode. On the anode, a hole-injection layer 7, a hole-transporting layer 8, an organic luminous layer 3, an electron-injection layer 4, a cathode 5 and a sealing layer 9 are laminated in the order. The above-mentioned electron-injection layer is a composite layer comprising a metal oxide, a metal halide and a different material therefrom.
When the electron-transporting layer is formed as shown in FIG. 2 or FIG. 3, a layer thickness thereof is about 1 to 200 nm, preferably 1 to 100 nm. The same electron-transporting material as described in the elecrton-injection layer may be used as an electron-transporting material. When the luminous material has electron-transporting ability, the electron-transporting [0051] layer 6 may be formed with such a luminous material. In this case, it is preferable that the same material as that used in the electron-transporting layer is used in the luminous layer with the material doped. For example, when the electron-transporting layer may be formed with aluminum trisoxine, it is preferable that the luminous layer is formed with aluminum trisoxine doped with a luminant. The electron-transporting layer may be formed by means of a vapor deposition method, a coating method and other known method in a manner similar to the luminous layer formation.
In the organic electroluminescence element as shown in FIG. 3 or FIG. 4, the hole-injection transporting layer is divided functionally into two layers of the hole-[0052] injection layer 7 and the hole-transporting layer 8. Such the hole-injection layer 7 may be formed with a phthalocyanine compound, an electrically conductive polymer compound, an arylamine compound etc. by a vapor deposition method etc. to have a layer thickness of 1 to 30 nm. The hole-transporting layer 8 may be formed with a benzidine compound, an arylamine compound and a styryl compound etc. by a vapor deposition method etc. to have a layer thickness of 10 to 200 nm.
When the sealing layer [0053] 9 is formed as shown in FIG. 9, silicon oxide, zinc oxide, magnesium fluoride and magnesium oxide etc. are vapor-deposited to form a thin layer having a thickness of 5 to 1000 nm.
In a pair of transparent electrodes (i.e., the [0054] cathode 5 and the anode 1), a suitable leading wire (10) such as nichrome wire, gold wire, copper wire or platinum wire is connected to the electrodes. An organic electroluminescence element emits light by applying appropriate voltage to both electrodes.
When the electron-injection layer is formed of a composite layer comprising a metal oxide, a metal halide and a different material therefrom according to the present invention, electron-injecting properties are improved. It is thought that when its layer is formed to have a thin thickness of 0.1 to 20 nm, the flow of electrons is made smooth under a high electrical field, so that light luminescence-starting voltage necessary for an organic electroluminescence element to emit light may be low and that stable light emission may achieved a long period of time. [0055]
The organic electroluminescence element of the present invention is applicable to various indicator devices or display devices, etc. [0056]
The following are Examples to explain the present invention. Further, the organic electroluminescence element achieves the improvement in luminous efficiency and luminance, and long life. It should not be construed that the present invention is limited to a luminous substance, an auxiliary luminous material, a charge-transporting material, a sensitizer, resin, a material for electrodes, etc., and a method of preparing an element, which are used in Examples below. [0057]

EXAMPLE 1

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm [0058]
A thin layer having a thickness of 60 nm was formed by means of vacuum deposition with aluminum trisoxine serving as an organic luminous layer. [0059]
Lithium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:10 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 5 nm. A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0060]
In this way, an organic electroluminescence element was prepared. [0061]

EXAMPLE 2

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium in oxide. The obtained layer had a thickness of 60 nm [0062]
A thin layer having a thickness of 60 nm was formed by means of vapor deposition with aluminum trisoxine serving as an organic luminous layer. [0063]
Lithium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:10 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0064]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0065]
In this way, an organic electroluminescence element was prepared. [0066]

EXAMPLE 3

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm [0067]
A thin layer having a thickness of 60 nm was formed by means of vapor deposition with aluminum trisoxine serving as an organic luminous layer. [0068]
Lithium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:5 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0069]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0070]
In this way, an organic electroluminescence element was prepared. [0071]

EXAMPLE 4

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm. [0072]
A thin layer having a thickness of 60 nm was formed by means of vapor deposition with aluminum trisoxine serving as an organic luminous layer. [0073]
Lithium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 0.5 nm. [0074]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0075]
In this way, an organic electroluminescence element was prepared. [0076]

Comparative Example 1

An organic electroluminescence element was prepared in a manner similar to Example 1, except that an electron-injection layer was not formed. [0077]

EXAMPLE 5

N,N′-diphenyl-N,N′-bis (1-naphtyl) -1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm [0078]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight serving as an organic luminous layer. [0079]
Aluminum trisoxine was vapor-deposited to form a thin electron transporting layer having a thickness of 45 nm. [0080]
Magnesium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:5 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0081]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0082]
In this way, an organic electroluminescence element was prepared. [0083]

Comparative Example 2

An organic electroluminescence element was prepared in a manner similar to Example 5, except that magnesium was vapor-deposited by means of an electrical resistance heating method to form an electron-injection layer having 2 nm thickness. [0084]

Comparative Example 3

In example 5, magnesium and aluminum trisoxine were co-deposited at a ratio of 1:5 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. Then, a thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. In this way, an organic electroluminescence element was prepared. [0085]

Comparative Example 4

In example 5, an oxadiazole compound (A) represented by the formula below was vapor-deposited by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. Then, a thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. In this way, an organic electroluminescence element was prepared. [0086]

EXAMPLE 6

N,N′-diphenyl-N,N′-bis(1-naphtyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm . [0087]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0088]
Aluminum trisoxine was vapor-deposited to form a thin electron transporting layer having a thickness of 45 nm. [0089]
Yttrium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0090]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0091]
In this way, an organic electroluminescence element was prepared. [0092]

EXAMPLE 7

4,4′,4″-tris[N,N′,N″-triphenyl-N,N′,N″-tris(3-methylphenyl)] triphenylamine was vapor-deposited as a hole-injection layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 15 nm [0093]
N,N′-diphenyl-N,N′-bis(4-methylphenyl)-1,1′-bis(3-methylphenyl)-4,4′-diamine was vapor-deposited as a hole-transporting layer on the hole-injection layer. The obtained layer had a thickness of 45 nm [0094]
A thin layer having a thickness of 30 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0095]
Aluminum trisoxine was vapor-deposited to form a thin electron-transporting layer having a thickness of 30 nm. [0096]
Magnesium fluoride and aluminum trisoxine were co-deposited at a ratio of 1:3 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0097]
A layer having a thickness of 200 nm was formed by means of vapor deposition with Mg and Ag, the atomic ratio of which was 10:1, to give a cathode. [0098]
In this way, an organic electroluminescence element was prepared. [0099]

EXAMPLE 8

N,N′-diphenyl-N,N′-bis(1-naphtyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm. [0100]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0101]
Aluminum trisoxine was vapor-deposited to form a thin electron-transporting layer having a thickness of 45 nm. [0102]
Lithium bromide and aluminum trisoxine were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0103]
A layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0104]
In this way, an organic electroluminescence element was prepared. [0105]

EXAMPLE 9

N,N′-diphenyl-N,N′-bis(1-naphtyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm . [0106]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0107]
Aluminum trisoxine was vapor-deposited to form a thin electron-transporting layer having a thickness of 45 nm. [0108]
Lithium oxide and aluminum trisoxine were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0109]
A layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0110]
In this way, an organic electroluminescence element was prepared. [0111]

EXAMPLE 10

N,N′-diphenyl-N,N′-bis(1-naphtyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm [0112]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0113]
Aluminum trisoxine was vapor-deposited to form a thin electron-transporting layer having a thickness of 45 nm. [0114]
Yttrium oxide and aluminum trisoxine were co-deposited at a ratio of 1:3 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0115]
A layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0116]
In this way, an organic electroluminescence element was prepared. [0117]

Comparative Example 5

An organic electroluminescence element was prepared in a manner similar to Example 7, except that an electron-injection layer was not formed. [0118]

EXAMPLE 11

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm [0119]
A thin layer having a thickness of 60 nm was formed by means of vacuum deposition with aluminum trisoxine serving as an organic luminous layer. [0120]
Lithium fluoride and aluminum were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0121]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0122]
In this way, an organic electroluminescence element was prepared. [0123]

EXAMPLE 12

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′1-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm . [0124]
A thin layer having a thickness of 60 nm was formed by means of vapor deposition with aluminum trisoxine serving as an organic luminous layer. [0125]
Lithium fluoride and aluminum were co-deposited at a ratio of 1:2 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 3 nm. [0126]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0127]
In this way, an organic electroluminescence element was prepared. [0128]

EXAMPLE 13

N,N′-diphenyl-N,N′-bis (3-methylphenyl) -1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm . [0129]
A thin layer having a thickness of 60 nm was formed by means of vapor deposition with aluminum trisoxine serving as an organic luminous layer. [0130]
Lithium fluoride and indium were co-deposited at a ratio of 1:5 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0131]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0132]
In this way, an organic electroluminescence element was prepared. [0133]

EXAMPLE 14

N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 60 nm [0134]
A thin layer having a thickness of 60 nm was formed by means of vapor deposition with aluminum trisoxine serving as an organic luminous layer. [0135]
Magnesium fluoride and aluminum were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0136]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0137]
In this way, an organic electroluminescence element was prepared. [0138]

Comparative Example 6

In example 11, indium was deposited by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0139]
Then, a thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. In this way, an organic electroluminescence element was prepared. [0140]

Comparative Example 7

In example 13, magnesium and aluminum trisoxine were co-deposited at a ratio of 2:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 3 nm. [0141]
Then, a thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0142]
In this way, an organic electroluminescence element was prepared. [0143]

EXAMPLE 15

N,N′-diphenyl-N,N′-bis (1-naphtyl) -1,1′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm [0144]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight serving as an organic luminous layer. [0145]
Aluminum trisoxine was vapor-deposited to form a thin electron transporting layer having a thickness of 45 nm. [0146]
Magnesium fluoride and indium were co-deposited at a ratio of 1:5 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0147]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with indium to give a cathode. [0148]
In this way, an organic electroluminescence element was prepared. [0149]

Comparative Example 8

An organic electroluminescence element was prepared in a manner similar to Example 15, except that an electron-injection layer was not formed. [0150]

Comparative Example 9

In example 15, magnesium fluoride was deposited by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0151]
Then, a thin layer having a thickness of 200 nm was formed by means of vapor deposition with indium to give a cathode. [0152]
In this way, an organic electroluminescence element was prepared. [0153]

EXAMPLE 16

N,N′-diphenyl-N,N′-bis(1-naphtyl)-1,′-diphenyl-4,4′-diamine was vapor-deposited as an organic hole-injection transporting layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 55 nm . [0154]
A thin layer having a thickness of 10 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0155]
Aluminum trisoxine was vapor-deposited to form a thin electron transporting layer having a thickness of 45 nm. [0156]
Yttrium fluoride and aluminum were co-deposited at a ratio of 1:1 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 1 nm. [0157]
A thin layer having a thickness of 200 nm was formed by means of vapor deposition with aluminum to give a cathode. [0158]
In this way, an organic electroluminescence element was prepared. [0159]

EXAMPLE 17

4,4′,4″-tris [N,N′,N″-triphenyl-N,N′, N″-tris (3-methylphenyl)] triphenylamine was vapor-deposited as a hole-injection layer on a glass substrate coated with indium tin oxide. The obtained layer had a thickness of 15 nm. [0160]
N,N′-diphenyl-N,N′-bis (4-methylphenyl)-1,1′-bis (3-methylphenyl)-4,4′-diamine was vapor-deposited as a hole-transporting layer on the hole-injection layer. The obtained layer had a thickness of 45 nm [0161]
A thin layer having a thickness of 30 nm was formed by means of co-deposition with aluminum trisoxine doped with rubrene at 5% by weight as an organic luminous layer. [0162]
An oxadiazole compound represented by the formula (A) below was vapor-deposited to form an electron-transporting layer having a layer thickness of 30 nm. [0163]
Magnesium oxide and indium were co-deposited at a ratio of 1:3 (volume ratio) by means of an electrical resistance heating method to form an electron-injection layer having a layer thickness of 2 nm. [0164]
A layer having a thickness of 200 nm was formed by means of vapor deposition with magnesium to give a cathode. [0165]
In this way, an organic electroluminescence element was prepared. [0166]

Comparative Example 10

An organic electroluminescence element was prepared in a manner similar to Example 17, except that an electron-injection layer was not formed. [0167]

Evaluation

A direct voltage was gradually applied to the organic electroluminescence elements obtained in Examples 1 to 17 and Comparative Examples 1 to 10 with the glass electrode as an anode. Luminescence-starting voltage (V), luminous brightness at 5V (cd/cm[0168] ²), and luminous brightness at 10V (cd/cm²) were measured.
Each electroluminescence element was driven at current density of 5 mA/cm[0169] ²for 5 hours. Then, maintaining ratio of initial output power (%) was measured as follows;
maintaining ratio of initial output power (%)=(output power (mW/cm²)after 5 hours)/(initial output power (mW/cm²))×100

The result are summarized in Table 1 and Table 2.

TABLE 1


	Luminous	Luminous	Maintaining
Luminescence	Brightness	Brightness	Ratio of
Starting	at 5 V	at 10 V	initial output
Voltage (V)	(cd/m²)	(cd/m²)	power (%)

Example 1	3.5	12	410	90
Example 2	3.0	51	5240	95
Example 3	3.0	62	7440	93
Example 4	3.0	82	14530	94
Comparative	9.0	0	20	43
Example 1
Example 5	3.0	70	10160	91
Comparative	4.0	25	3942	77
Example 2
Comparative	3.5	34	4590	80
Example 3
Comparative	8.0	0	50	57
Example 4
Example 6	3.0	80	12940	92
Example 7	3.0	90	14970	93
Example 8	3.5	55	6100	90
Example 9	3.0	75	10350	92
Example 10	3.5	18	1700	89
Comparative	3.5	37	4725	83
Example 5

TABLE 2


	Luminous	Luminous	Maintaining
Luminescence	Brightness	Brightness	Ratio of
Starting	at 5 V	at 10 V	initial output
Voltage (V)	(cd/m²)	(cd/m²)	Power (%)

Example 11	3.0	85	15310	95
Example 12	3.0	71	12440	94
Example 13	3.0	68	11750	94
Example 14	3.0	75	13930	94
Comparative	5.0	2	530	66
Example 6
Comparative	3.5	39	4650	80
Example 7
Example 15	3.0	65	9260	93
Comparative	5.0	1	420	64
Example 8
Comparative	6.0	0	370	65
Example 9
Example 16	3.0	50	7950	92
Example 17	3.5	39	6570	90
Comparative	8.5	0	25	51
Example 10

As is apparent from Tables and 2, and organic electroluminescece element of the present invention can start to emit light at a low voltage and shows good luminous brightness. [0172]
An organic electrouminescence element of the present invention can keep initial-emission for a long preriod of time stably [0173]

Claims

What is claimed is:

1. An organic electroluminescence element comprising an anode, an organic luminous layer, an electron-injection layer comprising a metal oxide or a metal halide, and a different material therefrom and a cathode.

2. The organic electroluminescence element according to

claim 1

, wherein the different material is metal.

3. The organic electroluminescence element according to

claim 2

, wherein the metal has a work function of more than 4.2 eV

4. The organic electroluminescence element according to

claim 2

, wherein a mixing ratio of the metal oxide to the metal halide is 1:100 to 100:1.

5. The organic electroluminescence element according to

claim 2

, wherein a mixing ratio of the metal oxide to the metal halide is 1:20 to 20:1.

6. The organic electroluminescence element according to

claim 1

, wherein the different material is an electron transporting material.

7. The organic electroluminescence element according to

claim 6

, wherein the electron transporting material is an organic compound.

8. The organic electroluminescence element according to

claim 7

, wherein a mixing ratio of the electron transporting material to the metal oxide or matal halide (electron transporting material metal oxide and/or metal halide) is 100:1 to 1:1.2.

9. The organic electroluminescence element according to

claim 7

, wherein a mixing ratio of the electron transporting material to the metal oxide or matal halide (electron transporting material metal oxide and/or metal halide) is 20:1 to 1:1.

10. The organic electroluminescence element according to

claim 1

, wherein the electron-injection layer has a thickness of 0.1 to 20 nm.

11. The organic electroluminescence element according to

claim 1

, wherein the metal oxide or the metal halide to be mixed in the electron-injection layer have a work function of less than 4.2 eV.

12. The electroluminescence element of

claim 1

, in which the metal halide is selected from the group consisting of magnesium fluoride, calcium fluoride, yttrium fluoride, lithium fluoride and lithium bromide.

13. The electroluminescence element of

claim 1

, in which the metal oxide is selected from the group consisting of magnesium oxide, yttrium oxide and lithium oxide.

14. The electroluminescence element of

claim 1

, in which the electron-injection layer is formed by co-deposition of a metal oxide or a metal halide, and a different material therefrom.

15. The electroluminescence element of

claim 1

, in which an electron-transporting layer is formed between the electron-injection layer and the organic luminous layer.

16. The electroluminescence element of

claim 1

, in which the cathode is formed of a metal selected from the group consisting of aluminum, silver and indium.

17. The electroluminescence element of

claim 1

, in which a sealing layer is formed on the cathode.

18. The electroluminescence element of

claim 1

, further comprising a hole-injection transporting layer.

19. The electroluminescence element of

claim 1

, further comprising a hole-injection layer and a hole-transporting layer.

20. The electroluminescence element of

claim 1

, in which the same charge transporting materila is contained in both the electron-injection layer and the luminous layer.