JP2009070954A - Organic thin film light emitting element, display device, electronic apparatus, and manufacturing method of organic thin film light emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic thin film light emitting element capable of efficiently emitting light rays. <P>SOLUTION: The organic thin film light emitting element includes a substrate, a first electrode formed on the substrate and functioning as a cathode, a first metal oxide film formed on the first electrode, a metal compound film formed on the first metal oxide film, an organic compound film formed on the metal compound film, a second metal oxide film formed on the organic compound film, and a second electrode formed on the second metal oxide film and functioning as an anode, wherein at least either of the substrate and first electrode, and the second electrode has optical transparency, and the metal compound film contains alkali metal or alkali earth metal. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an organic thin film light emitting element, a display device, an electronic device, and a method for manufacturing an organic thin film light emitting element.

As described in the latter patent document 2, the light-emitting elements described in the following patent documents 1 and 2 are not sealed, that is, means for avoiding exposure to the atmosphere. Without being taken, light can be emitted by recombining holes injected from the anode and electrons injected from the cathode in the organic compound layer.

Japanese Patent Laid-Open No. 10-12377 JP 2007-53286 A

However, in the conventional light emitting device described above, holes injected from the anode pass through the organic compound layer, thereby reducing the concentration of holes in the organic compound layer, and as a result, the organic compound layer Since the force for attracting electrons to the surface is reduced, there is a problem that recombination of holes and electrons in the organic compound is not efficiently performed, that is, light cannot be efficiently emitted.

  The present invention is realized by the following application examples in order to solve the above-described problems.

[Application Example 1]
The organic thin film light emitting device of Application Example 1 is
A substrate,
A first electrode formed on the substrate and functioning as a cathode;
A first metal oxide film formed on the first electrode;
A metal compound film formed on the first metal oxide film;
An organic compound film formed on the metal compound film;
A second metal oxide film formed on the organic compound film;
A second electrode functioning as an anode formed on the second metal oxide film, wherein at least one of the substrate and the first electrode or the second electrode is light transmissive. Said second electrode having
The metal compound film contains an alkali metal or an alkaline earth metal.

According to the organic thin film light emitting device of Application Example 1, the metal compound layer is injected from the second electrode functioning as an anode, and blocks holes that have passed through the second metal layer and the organic compound layer, Increase the concentration of holes in the organic compound layer. As a result, the force for drawing electrons into the organic compound layer through the cathode, the first metal oxide layer, and the metal compound layer can be increased. As a result, the holes and electrons in the organic compound layer can be converted into holes. Recombination can be performed more efficiently than before, that is, light can be emitted more efficiently than before.

[Application Example 2]
The organic thin film light emitting device of Application Example 2 is
A substrate,
A first electrode formed on the substrate and functioning as a cathode;
A metal compound film formed on the first electrode;
An organic compound film formed on the metal compound film;
A metal oxide film formed on the organic compound film;
A second electrode functioning as an anode, formed on the metal oxide film, wherein at least one of the substrate and the first electrode, or the second electrode has optical transparency. A second electrode,
The metal compound film contains an alkali metal or an alkaline earth metal.

According to the organic thin film light emitting device of Application Example 2, although it has a metal compound layer as in Application Example 1, unlike Application Example 1, it is a metal oxide film for transporting electrons (first metal oxidation of Application Example 1). It is equivalent to a material film (for example, titanium oxide capable of high photocatalytic activity) and does not have the metal oxide film that needs to be manufactured at a high temperature. Thereby, although the organic thin film light emitting element of Application Example 2 is inferior to the organic thin film light emitting element of Application Example 1, it becomes possible to emit light with higher efficiency than the conventional light emitting element, and the organic thin film of Application Example 1 It can be manufactured at a lower temperature than the light emitting device, and can emit light with better atmospheric storage stability than the organic thin film light emitting device of Application Example 1, that is, the organic thin film of Application Example 1. Light can be emitted for a longer time than a light emitting element.

[Application Example 3]
The organic thin film light emitting device of Application Example 3 is the organic thin film light emitting device of Application Examples 1 and 2,
The alkali metal or alkaline earth metal contains at least one of cesium carbonate, cesium oxide, and cesium hydroxide.

According to the organic thin film light emitting device of Application Example 3, the alkali metal or alkaline earth metal is
By containing at least one of cesium carbonate, cesium oxide, and cesium hydroxide, the holes injected from the second electrode functioning as the anode are effectively blocked. Can be improved.

[Application Example 4]
The organic thin film light emitting device of Application Example 4 is the organic thin film light emitting device of Application Example 1,
The first metal oxide film contains titanium.

According to the organic thin film light-emitting element of Application Example 4, when the first metal oxide film contains titanium, electrons injected from the first electrode functioning as a cathode can be efficiently transferred to the organic compound film. Since it is transported, it becomes possible to emit light with high efficiency.

[Application Example 5]
The organic thin film light emitting device of Application Example 5 is the organic thin film light emitting device of Application Example 1,
The second metal oxide film contains molybdenum or vanadium.

[Application Example 6]
The organic thin film light emitting device of Application Example 6 is the organic thin film light emitting device of Application Example 2,
The metal oxide film contains molybdenum or vanadium.

According to the organic thin film light emitting elements of Application Examples 5 and 6, the second metal oxide film and the metal oxide film are
By containing molybdenum or vanadium, holes injected from the second electrode are efficiently transported to the organic compound film, so that light can be emitted with high efficiency.

[Application Example 7]
The organic thin film light emitting device of Application Example 7 is the organic thin film light emitting device of Application Examples 1 and 2,
The organic compound film includes an organic substance having a benzothiadiazole skeleton.

According to the organic thin film light emitting device of Application Example 7, since the organic compound film contains an organic substance having a benzothiadiazole skeleton, holes are efficiently transported to the second metal oxide film. Light can be emitted with high efficiency.

[Application Example 8]
The organic thin film light emitting device of Application Example 8 is the organic thin film light emitting device of Application Example 7,
The organic compound film is a polymer material.

According to the organic thin film light emitting element of Application Example 8, since the organic compound film is a polymer material, the light emission efficiency can be further increased.

[Application Example 9]
The display device of Application Example 9 includes the organic thin film light emitting elements of Application Examples 1 to 8.

According to the display device of Application Example 9, by providing the organic thin film light emitting element of Application Example 1 to Application Example 8, it is possible to display with higher luminous efficiency than in the past.

[Application Example 10]
The electronic device of Application Example 10 includes the display device of Application Example 9.

According to the electronic device of the application example 10, by including the display device of the application example 9, it is possible to provide the function of the electronic device with high displayability.

[Application Example 11]
The manufacturing method of the organic thin film light emitting device of Application Example 11 is as follows:
Forming a first electrode functioning as a cathode on a substrate;
Forming a first metal oxide film on the first electrode;
Forming a metal compound film on the first metal oxide film;
Forming an organic compound film on the metal compound film;
Forming a second metal oxide film on the organic compound film;
A second electrode functioning as an anode on the second metal oxide film, wherein at least one of the substrate and the first electrode or the second electrode is light-transmissive. Forming a second electrode,
The step of forming the metal compound film includes a first step of forming a compound containing alkali metal or alkaline earth metal, and a step of exposing the formed compound containing alkali metal or alkaline earth metal to the atmosphere. It consists of two steps.

According to the manufacturing method of the organic thin film light emitting element of Application Example 11, the following light emitting element, that is, the metal compound layer is injected from the second electrode functioning as the anode, and the second metal layer and the organic The ability to increase the concentration of holes in the organic compound layer by blocking holes that have passed through the compound layer, and to draw electrons into the organic compound layer through the cathode, the first metal oxide layer, and the metal compound layer As a result, it is possible to recombine holes and electrons in the organic compound layer more efficiently than before, that is, to emit light more efficiently than before. The light emitting element which can be manufactured can be manufactured.

[Application Example 12]
The manufacturing method of the organic thin film light emitting element of Application Example 12
Forming a first electrode functioning as a cathode on a substrate;
Forming a metal compound film on the first electrode;
Forming an organic compound film on the metal compound film;
Forming a metal oxide film on the organic compound film;
A second electrode that functions as an anode on the metal oxide film, wherein at least one of the substrate and the first electrode, or the second electrode is light transmissive. Forming a step,
The step of forming the metal compound film includes a first step of forming a compound containing alkali metal or alkaline earth metal, and a step of exposing the formed compound containing alkali metal or alkaline earth metal to the atmosphere. It consists of two steps.

According to the manufacturing method of the organic thin film light emitting element of application example 12, although it has the metal compound layer as in application example 11, unlike the application example 11, the metal oxide film for transporting electrons (the first of application example 11) An organic thin film light emitting device that does not have the metal oxide film, in other words, the organic thin film of Application Example 11. Although it is inferior to a light emitting element, it can emit light with higher efficiency than a conventional light emitting element, and can emit light with better atmospheric storage stability than the organic thin film light emitting element of Application Example 11, that is, application The organic thin film light emitting element capable of emitting light for a longer time than the organic thin film light emitting element of Example 11 can be manufactured at a temperature lower than the temperature at which the organic thin film light emitting element of Application Example 11 is manufactured.

[Application Example 13]
The manufacturing method of the organic thin film light emitting element of Application Example 13 is the manufacturing method of the organic thin film light emitting element of Application Examples 11 and 12,
In the first step, at least one of cesium carbonate, cesium oxide, and cesium hydroxide is used as the compound containing the alkali metal or alkaline earth metal.

According to the method for manufacturing an organic thin film light emitting element of Application Example 13, the first step uses at least one of cesium carbonate, cesium oxide, and cesium hydroxide as the alkali metal or alkaline earth metal. An organic thin film light emitting device that efficiently blocks holes injected from the second electrode functioning as an anode can be produced.

[Application Example 14]
The manufacturing method of the organic thin film light emitting element of Application Example 14 is the manufacturing method of the organic thin film light emitting element of Application Examples 11 and 12,
In the first step, the compound containing the alkali metal or alkaline earth metal is formed by vacuum deposition.

[Application Example 15]
The manufacturing method of the organic thin film light emitting element of Application Example 15 is the manufacturing method of the organic thin film light emitting element of Application Examples 11 and 12,
In the second step, the compound containing the alkali metal or alkaline earth metal is oxidized.

[Application Example 16]
The manufacturing method of the organic thin film light emitting element of application example 16 is a manufacturing method of the organic thin film light emitting element of application examples 11 and 12,
In the second step, the compound containing the alkali metal or alkaline earth metal is reacted with water.

[Application Example 17]
The manufacturing method of the organic thin film light emitting element of Application Example 17 is the manufacturing method of the organic thin film light emitting element of Application Examples 11 and 12,
In the second step, the compound containing the alkali metal or alkaline earth metal is exposed to an environment recognized as substantially 300 K, 1 atm, and 20% oxygen partial pressure.

Hereinafter, an organic thin film light emitting element, a display device, and an electronic apparatus according to embodiments will be described with reference to the drawings.

<Light emitting element>
FIG. 1 is a view schematically showing a longitudinal section of an embodiment of a light emitting device of the embodiment.

A light-emitting element (electroluminescence element) 1 shown in FIG. 1 includes a substrate 2, a cathode (first electrode) 3 formed on the substrate 2, and an anode (second electrode) 5 facing the cathode 3. Have.
In the light emitting element 1, an organic compound layer 4 is interposed between the cathode 3 and the anode 5 (between a pair of electrodes), and a hole injecting metal compound is further interposed between the organic compound layer 4 and the anode 5. A layer 8 is provided, an electron injecting metal compound layer 6 is provided between the organic compound layer 4 and the cathode 3, and further, between the organic compound layer 4 and the electron injecting metal compound layer 6, after film formation. There is provided a hole blocking metal compound layer 7 prepared by leaving in the atmosphere for a certain period of time.

Here, the sealing structure is not necessary in principle. However, there is no problem even if the sealing structure is used from the viewpoint of maintaining the insulating properties of the electrodes.

The substrate 2 serves as a support for the light-emitting element 1, and is also a support for directly manufacturing the cathode 3 here. The light emitting element 1 is not limited in the light extraction direction, and has a configuration in which light is extracted from the substrate 2 side (bottom emission type) and a configuration in which light is extracted from the anode 5 on the side opposite to the substrate 2 (top There are three possible cases: the emission type) and the case where both are possible (transparent type). In the case of the bottom emission type, each of the substrate 2 and the cathode 3 is substantially transparent (colorless transparent, colored transparent or translucent). In the case of the top emission type, the anode 5 is transparent. The substrate 2, the cathode 3, and the anode 5 are transparent.

Examples of the constituent material of the substrate 2 include resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate, quartz glass, and soda glass. Such glass materials can be used, and one or more of these can be used in combination.

Although the average thickness of such a board | substrate 2 is not specifically limited, It is preferable that it is about 0.1-30 mm, and it is more preferable that it is about 0.1-10 mm.

In the case of the top emission type, the substrate 2 can be either a transparent substrate or an opaque substrate.

As an opaque substrate, for example, a substrate made of a ceramic material such as alumina,
Examples include a substrate formed of an oxide film (insulating film) on the surface of a metal substrate such as stainless steel, a substrate made of a resin material, and the like.

Unlike the normal organic EL element, the cathode 3 in this structure is not subject to the restriction of reducing the work function. In other words, a material having a large work function can be used, which is desirable for obtaining stability in the atmosphere. Other required characteristics are excellent electrical conductivity, and excellent transmissivity in the case of bottom emission type and transparent type. The same applies to the anode 5, and it is desirable to use a material having a large work function, excellent conductivity, and excellent transparency in the case of the top emission type and the transparent type.

The constituent materials of the cathode 3 and the anode 5 are, for example, ITO (indium tin oxide), IZ
O (indium zinc oxide), FTO (fluorine tin oxide), In ₂ O ₃ , SnO ₂ , Sb-containing S
Examples thereof include oxides such as nO ₂ and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing these, and one or more of these can be used in combination.

The average thickness of the cathode 3 is not particularly limited, but is preferably about 10 to 200 nm, and more preferably about 30 to 150 nm. Au, Pt, Ag,
Even when an opaque material such as Cu is used, for example, by setting the average thickness to about 10 to 30 nm, it can be used as a bottom emission type and a transparent type cathode.

On the other hand, the average thickness of the anode 5 is not particularly limited, but is preferably about 10 to 10000 nm, and more preferably about 30 to 50 nm. Au, Pt, Ag, C
Even when an impermeable material such as u is used, it can be used as a top emission type or transparent type anode by setting the average thickness to about 10 to 30 nm, for example.

The organic compound layer 4 is a layer responsible for light emission, and is a layer containing at least a light emitting material. Therefore, the light emitting material and the hole transporting organic material may be mixed or stacked. As a constituent material of the light emitting material, various polymer light emitting materials (polymer materials) and various low molecular light emitting materials (low molecular materials) can be used alone or in combination. In particular, the benzothiadiazole skeleton (
Hereinafter, it is referred to as “BT unit”. It is more preferable that at least one kind of organic material having) is contained. It is also possible not to use the BT unit. In that case, a polymer material and a low-molecular material described later can be used alone or in combination. Organic materials having BT units include poly (dioctylfluorene-alt-benzothiadiazole) (
F8BT), poly (N-dodecyl-2,5, -bis (2′-thienyl) pyrrole-2,1,3-benzothiadiazole) (PPTTB literature: CJBrabec et.al., Adv. Func. Mater. 12,70
9, (2002)), 4,7-diphenyl-benzo [1,2,5] thiadiazole (F1), 4
, 7-Bis-bienyl-4-yl-benzo [1,2,5] thiadiazole (F2), 4,7-
Di (4-methoxy-phenyl) -benzo [1,2,5] thiadiazole (F3), 4,7-bis- (6-methoxy-naphthalen-2-yl) -benzo [1,2,5] thiadiazole ( F4),
4,7-di (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-5-yl) -benzo [1,2,5] thiadiazole (F5), 4,7-di (4- (N, N-dimethylamino) -phenyl) -benzo [1,2,5] thiadiazole (F6) (F1 to F6 Article: Dmitry Aldakov e
t.al., Chem. Mater. 2005, 17, 5238-5241), 4,7-bis [5- (4′-trifluoromethylphenyl) thiophen-2-yl] benzo [1,2,5 Thiadiazole (1)
(See (1) Literature: Takahiro Kono et.al., Chem. Mater. 2007, 19, 1218-1220)
4,7-bis (4-dimethylaminophenyl) -2,1,3-benzothiadiazole (2)
4- (4-dimethylaminophenyl) -7- (4-diphenylaminophenyl) -2,1,
3-benzothiadiazole (3), 4,7-bis (4-diphenylaminophenyl) -2,1
, 3-Benzothiadiazole (4), 4,7-bis {4- [N- (1-naphthyl) -N-phenylamino] phenyl} -2,1,3-benzothiadiazole (5), 4,7-bis {4- [N- (2
-Naphthyl) -N-phenylamino] phenyl} -2,1,3-benzothiadiazole (6),
4,7-bis (4′-diphenylaminophenyl-4-yl) -2,1,3-benzothiadiazole (7), 4,7-bis {5- [4- (diphenylamino) phenyl]- 2-thienyl}-
2,1,3-benzothiadiazole (8), 4,7-bis {2- [4- (diphenylamino) phenyl] ethynyl} -2,1,3-benzothiadiazole (9), 4, 7-bis {2- [4- (diphenylamino) phenyl] ethynyl} -2,1,3-benzothiadiazole (10) ((2) to (10) Article: Shin-ichiro Kato et.al., Chem. Commun., 2004, 23422343)
And its derivatives, and 2,1,3-benzothiadiazole.

When using a BT unit, it can be used by mixing with other organic materials. Specifically, polymer materials (light-emitting materials, electron-transport materials, hole-transport organic materials) or small molecules (light-emitting materials, electron-transport materials, hole-transport organic materials) that function as electronic devices are used. Can be mentioned. It is not limited to these.

Examples of the polymer light-emitting material or electron-transporting material include polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), and poly (alkyl, phenylacetylene) (PAPA). , Poly (para-phenvinylene) (PPV), poly (2,5-dialkoxy-para-phenylenevinylene) (RO-PPV), cyano-substituted-poly (para-phenvinylene) (CN-PPV)
, Poly (2-dimethyloctylsilyl-para-phenylenevinylene) (DMOS-PPV
), Poly (2-methoxy, 5- (2′-ethylhexoxy) -para-phenylenevinylene) (MEH-PPV), polyparaphenylenevinylene compounds such as poly (3-alkylthiophene) (PAT), poly ( Polythiophene compounds such as oxypropylene) triol (POPT), poly (9,9-dialkylfluorene) (PDAF), poly (
Dioctylfluorene-alt-benzothiadiazole) (F8BT), α, ω-bis [
N, N'-di (methylphenyl) aminophenyl] -poly [9,9-bis (2-ethylhexyl) fluorene-2,7-zyl] (PF2 / 6am4), poly (9,9-dioctyl-2, Polyfluorene compounds such as 7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl), poly (para-phenylene) (PPP), poly (1,5-
Polyparaphenylene compounds such as dialkoxy-para-phenylene) (RO-PPP), polycarbazole compounds such as poly (N-vinylcarbazole) (PVK), poly (methylphenylsilane) (PMPS), poly (Naphthylphenylsilane) (PNPS
) And polysilane compounds such as poly (biphenylylphenylsilane) (PBPS).

On the other hand, as a low-molecular light-emitting material or electron-transporting material, for example, 2, 2 ′ is used as a ligand.
-Tricoordinate iridium complexes with bipyridine-4,4'-dicarboxylic acid, factory (2-phenylpyridine) iridium (Ir (ppy) 3), 8-hydroxyquinoline
Aluminum (Alq3), Tris (4-methyl-8quinolinolate) Aluminum (III
) (Almq3), 8-hydroxyquinoline zinc (Znq2), (1,10-phenanthroline) -tris- (4,4,4-trifluoro-1- (2-thienyl) -butane-1,3
-Dionate) Europium (III) (Eu (TTA) 3 (phen)), 2, 3, 7, 8
, 12, 13, 17, 18-octaethyl-21H, 23H-porphine platinum (
II) various metal complexes, distyrylbenzene (DSB), benzene compounds such as diamino distyrylbenzene (DADSB), naphthalene compounds such as naphthalene and nile red, phenanthrene compounds such as phenanthrene, chrysene , Chrysene compounds such as 6-nitrochrysene, perylene, N, N′-bis (2,5-di-t-butylphenyl) -3,4,9,10-perylene-di-carboximide (BPPC) Perylene compounds such as coronene, coronene compounds such as coronene, anthracene compounds such as anthracene and bisstyrylanthracene, pyrene compounds such as pyrene, 4- (di-cyanomethylene) -2-methyl-6 A pyran system such as (para-dimethylaminostyryl) -4H-pyran (DCM) Compound, acridine compound such as acridine, stilbene compound such as stilbene, thiophene compound such as 2,5-dibenzoxazole thiophene, benzoxazole compound such as benzoxazole, benzimidazole such as benzimidazole Compounds, benzothiazole compounds such as 2,2 ′-(para-phenylenedivinylene) -bisbenzothiazole, bistyryl (1,4
-Diphenyl-1,3-butadiene), butadiene compounds such as tetraphenylbutadiene, naphthalimide compounds such as naphthalimide, coumarin compounds such as coumarin, perinone compounds such as perinone, oxadiazole Oxadiazole compounds, aldazine compounds, cyclopentadiene compounds such as 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP), quinacridones such as quinacridone and quinacridone red Compounds, pyridine compounds such as pyrrolopyridine and thiadiazolopyridine, spiro compounds such as 2,2 ′, 7,7′-tetraphenyl-9,9′-spirobifluorene, phthalocyanine (H ₂ Pc) Metallic or non-metallic phthalos such as copper phthalocyanine Nin-based compounds, and the like.

Examples of the polymer hole transporting organic material include polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polythiophene. Examples thereof include alkylthiophene, polyhexylthiophene, poly (p-phenylene vinylene), polytinylene vinylene, pyrene formaldehyde resin, ethyl carbazole formaldehyde resin or derivatives thereof.

Moreover, the said compound can also be used as a mixture with another compound. As an example,
Examples of the mixture containing polythiophene include poly (3,4-ethylenedioxythiophene / styrene sulfonic acid) (PEDOT / PSS).

On the other hand, examples of the low molecular weight hole transporting organic material include 1,1-bis (4-di-para-triaminophenyl) cyclohexane and 1,1′-bis (4-di-para-). Arylcycloalkane compounds such as (tolylaminophenyl) -4-phenyl-cyclohexane, 4,4 ′, 4 ″ -trimethyltriphenylamine, N, N, N ′, N′-tetraphenyl-1,1 ′ -Biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-
Bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (TPD1)
N, N′-diphenyl-N, N′-bis (4-methoxyphenyl) -1,1′-biphenyl-4,4′-diamine (TPD2), N, N, N ′, N′-tetrakis ( 4-methoxyphenyl) -1,1′-biphenyl-4,4′-diamine (TPD3), N, N′-di (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4 , 4′-diamine (α-NPD), N, N, N ′, N′-tetraphenyl-para-phenylenediamine, N, N, N ′, N′-tetra (para-tolyl) ) -Para-phenylenediamine, phenylenediamine compounds such as N, N, N ′, N′-tetra (meta-tolyl) -meta-phenylenediamine (PDA), carbazole, N-isopropylcarbazole, N-phenylcarbazole Carbazo like Le compounds, stilbene, 4-
Stilbene compounds such as di-para-tolylaminostilbene, oxazole compounds such as OxZ, triphenylmethane, triphenylmethane compounds such as m-MTDATA, 1-phenyl-3- (para-dimethylaminophenyl) ) Pyrazoline compounds such as pyrazoline, benzine (cyclohexadiene) compounds, triazole compounds such as triazole, imidazole compounds such as imidazole, 1,3,4-oxadiazole, 2,5-di (4 -Dimethylaminophenyl) -1,3,4, -oxadiazole compounds such as oxadiazole, anthracene, anthracene compounds such as 9- (4-diethylaminostyryl) anthracene, fluorenone, 2,4,7 , -Trinitro-9-fluorenone, 2, Fluorenone compounds such as 7-bis (2-hydroxy-3- (2-chlorophenylcarbamoyl) -1-naphthylazo) fluorenone, aniline compounds such as polyaniline, silane compounds, 1,4-dithioketo-3,6 A pyrrole compound such as diphenyl-pyrrolo- (3,4-c) pyrrolopyrrole, a fluorene compound such as florene, a porphyrin, a porphyrin compound such as metal tetraphenylporphyrin, a quinacridone compound such as quinacridone, Phthalocyanine,
Metallic or metal-free phthalocyanine compounds such as copper phthalocyanine, tetra (t-butyl) copper phthalocyanine, iron phthalocyanine, copper or metal-free naphthalocyanine compounds such as copper naphthalocyanine, vanadyl naphthalocyanine, monochlorogallium naphthalocyanine And benzidine compounds such as N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine and N, N, N ′, N′-tetraphenylbenzidine.

For the formation of the organic compound layer 4, when a polymer material is included, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, Various coating methods such as a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used. In the case of a spin coat method or the like, after coating on the entire surface of the substrate, patterning is performed by photolithography or the like. In addition, in the ink jet printing method or the like, a film can be formed only in a predetermined region by dropping it in a region surrounded by a partition wall.

Examples of the solvent used in this case include nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water,
Inorganic solvents such as carbon disulfide, carbon tetrachloride, ethylene carbonate, methyl ethyl ketone (
MEK), ketone solvents such as acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin, Diethyl ether, diisopropyl ether, 1,2-
Ether solvents such as dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol),
Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, aromatic hydrocarbon solvents such as toluene, xylene, benzene, pyridine, pyrazine, furan, Aromatic heterocyclic compounds such as pyrrole, thiophene and methylpyrrolidone, amides such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), chlorobenzene, dichloromethane, chloroform, 1,2 -Halogen compound solvents such as dichloroethane, ester solvents such as ethyl acetate, methyl acetate, ethyl formate, sulfur compound solvents such as dimethyl sulfoxide (DMSO), sulfolane, acetonitrile, propionitrile,
Examples thereof include nitrile solvents such as acrylonitrile, various organic solvents such as organic acid solvents such as formic acid, acetic acid, trichloroacetic acid and trifluoroacetic acid, or mixed solvents containing these.

Among these, as the solvent, a nonpolar solvent is suitable, for example, an aromatic hydrocarbon solvent such as xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, tetramethylbenzene, pyridine, pyrazine, furan, Examples include aromatic heterocyclic compound solvents such as pyrrole, thiophene, and methylpyrrolidone, and aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane. These can be used alone or in combination.

Note that the following vapor phase film formation method can be used even if the material includes a polymer material as long as the film can be formed without being decomposed.

In the case of a low molecular material, a vapor phase film forming method such as a vacuum evaporation method can be used. In the case of a mixture, a vapor deposition method such as co-evaporation is used. When a good thin film is formed without crystallization or the like by the coating method, the above coating method can also be used. The film thickness of the organic compound layer 4 is not particularly limited, but can be set to an optimum value depending on the type of electronic device.

The average thickness of the organic compound layer 4 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 40 to 100 nm.

The organic compound layer 4 transports holes injected from the hole injecting metal compound layer 8 and is formed by leaving the film from the electron injecting metal compound layer 6 in the atmosphere for a predetermined time after film formation. The electrons are received via the conductive metal compound layer 7. Holes and electrons recombine, and excitons (excitons) are generated by the energy released during the recombination, and energy (fluorescence and phosphorescence) is emitted (emitted) when the excitons return to the ground state. . At this time,
The hole blocking metal compound layer 7 is disposed for the purpose of recombining holes and electrons with higher efficiency and preventing chemical deterioration of the organic compound layer 4 on the electron injecting metal compound layer 6. The

Among these, as a constituent material of the organic compound layer 4, a material mainly composed of a polymer light-emitting material is preferable. A polymer material that can be formed by a liquid phase process can be produced with lower energy without requiring an expensive apparatus.

The electron injecting metal compound layer 6 injects electrons from the cathode 3 and transports them to the organic compound layer 4. A metal oxide constituting such an electron injecting metal compound layer 6 is preferably one having a high energy level of a conduction band, and is not particularly limited. However, titanium oxide (TiO ₂ ), zinc oxide (ZnO), oxide Tungsten (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), iron oxide (Fe ₂ O
₃ ) and the like, and one or more of these can be used in combination.

The film forming method of the electron injecting metal compound layer 6 is not particularly limited,
Chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, laser CVD, etc.
, Vacuum plating, sputtering, ion plating and other dry plating methods, thermal spraying, and liquid phase film forming methods such as electrolytic plating, immersion plating, electroless plating, and other wet plating methods, sol-gel method, MOD method, spraying Printing techniques such as a thermal decomposition method, a doctor blade method using a fine particle dispersion, a spin coating method, an ink jet method, and a screen printing method can be used. In this structure, the spray pyrolysis method was used.

The average thickness of the electron injecting metal compound layer 6 is not particularly limited, but is 1 to 100.
The thickness is preferably about 0 nm, and more preferably about 20 to 200 nm.

The hole blocking metal compound layer 7 blocks a large number of holes injected from the anode 5 into the organic compound layer 4 via the hole injecting metal compound layer 8, and the organic compound layer 4 efficiently generates electrons and electrons. It is what is recombined. The hole blocking metal compound layer 7 is preferably an insulating thin film that exists stably in the atmosphere.

The metal compound constituting the hole blocking metal compound layer 7 is preferably one having a wide energy gap, and is not particularly limited, but alkali metals such as cesium oxide (Cs ₂ O) and calcium oxide (CaO) and alkali Examples include earth metal oxides and other metal oxides, and one or more of these can be used in combination.

Here, since the high stability under the atmosphere is the first condition, the material was produced by leaving it to near the equilibrium state under the atmosphere. The time is 15 minutes or more and less than 24 hours. further,
Here, a carbonic acid compound was used in order to produce a desired thin film more inexpensively and safely. The carbonic acid compound changes to a metal oxide during film formation or in the air after film formation. Furthermore, depending on the metal, it changes to a metal hydroxide. The degree depends on the environment to be left unattended. In other words, the process of leaving the element in the atmosphere and deteriorating has already been taken in during the preparation of the element. Thereby, it is considered that changes in the interface such as voids caused by chemical changes due to moisture and oxygen after the device can be avoided or reduced, leading to a longer lifetime of the device. The film thickness blocks holes,
In addition, since a function for injecting electrons is required, 1 to 50 nm is preferable, and 5 to 30 nm is particularly preferable.

The film forming method of the hole blocking metal compound layer 7 is not particularly limited, and a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, which is a vapor deposition method, Wet plating methods such as vacuum plating, sputtering, ion plating and other dry plating methods, thermal spraying methods, and liquid phase film forming methods such as electrolytic plating, immersion plating, and electroless plating,
Printing techniques such as a sol-gel method, an MOD method, a spray pyrolysis method, a doctor blade method using a fine particle dispersion, a spin coating method, an ink jet method, and a screen printing method can be used. In this structure, a vacuum deposition method was used.

The average thickness of the hole blocking metal compound layer 7 is not particularly limited.
It is preferably about 00 nm, and more preferably about 5 to 20 nm.

The hole injecting metal compound layer 8 injects holes from the anode 5 and transports them to the organic compound layer 4. The metal oxide constituting the hole injecting metal compound layer 8 is preferably a compound having a large work function, and is not particularly limited. For example, vanadium oxide (V ₂ O ₅ ), molybdenum oxide (MoO ₃ ) , Ruthenium oxide (RuO ₂ ), and the like, and one or more of these can be used in combination.

Among these, those containing vanadium oxide or molybdenum oxide as the main component are particularly suitable. By using vanadium oxide or molybdenum oxide as a main material, the hole injecting metal compound layer 8 can be made particularly excellent in the above-described ability.

The film forming method of the hole injecting metal compound layer 8 is not particularly limited,
Chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, laser CVD, etc.
, Vacuum plating, sputtering, ion plating and other dry plating methods, thermal spraying, and liquid phase film forming methods such as electrolytic plating, immersion plating, electroless plating, and other wet plating methods, sol-gel method, MOD method, spraying Printing techniques such as a thermal decomposition method, a doctor blade method using a fine particle dispersion, a spin coating method, an ink jet method, and a screen printing method can be used. In this structure, a vacuum deposition method was used.

The average thickness of the hole injecting metal compound layer 8 is not particularly limited, but is 1 to 100.
The thickness is preferably about 0 nm, and more preferably about 5 to 50 nm.

Although not particularly required in this structure, a sealing material generally used can be used as a constituent material of the sealing structure. For example, Al, Au, Cr, Nb, Ta, Ti or alloys containing these, silicon oxide, various resin materials, and the like can be given.

In summary, a metal compound is provided between the organic compound layer 4 and the cathode 3, and between the organic compound layer 4 and the anode 5, and a block layer is used to keep main carriers, that is, holes, in the organic compound layer 4. It is characterized in that it was prepared by inserting and leaving it in the atmosphere.

The electron injecting metal compound layer 6 between the organic compound layer 4 and the cathode 3 made it possible to use a material having a large work function that is stable to the atmosphere for the cathode 3 itself. Usually, it is necessary to use a material with a low work function for the electron injection for the cathode. By using an already oxidized metal oxide having a high energy level of the conduction band for the electron injection part inside the material. This realizes stable electron injection in the atmosphere. Therefore, the cathode 3 and the metal oxide (electron injecting metal compound layer 6
In this case, sufficient electrical and physical contact with the cathode 3 is necessary.
The structure was arranged. Thereby, a process such as a sufficient temperature can be provided. From this point of view, the metal oxide-based conductive material shown in the following example is used as the cathode 3 and is manufactured by a process including a process of sufficiently making contact with an electrode such as a thermal decomposition method. More preferred. Of course, other methods are possible.

As the hole-injecting metal compound layer 8 between the organic compound layer 4 and the anode 5, a metal compound layer, particularly a metal oxide layer was used here in order to realize a more stable device in the atmosphere. Here, in order to ensure electrical and physical contact between the organic compound layer 4 and the hole injecting metal oxide layer 8,
From the viewpoint of the process, it is more preferable to use a vapor deposition method. Of course, other methods are possible.

In addition, by leaving an alkali metal or alkaline earth metal carbonate compound thin film in the atmosphere as the hole blocking metal compound layer 7 between the organic compound layer 4 and the electron injecting metal compound layer 6, A metal compound thin film that reached equilibrium in the environment was used. Here, stable and efficient light emission under the atmosphere achieved by the above two features has been made more efficient and stable. Specifically, it prevents the excessive holes from escaping to the cathode 3 and improves the physical and electrical contact failure due to oxidation and moisture that are likely to occur at the interface between the organic compound layer 4 and the electron injecting metal compound layer 6. Is.

Due to these three characteristics, electrons are injected into the organic compound layer 4 from the air-stable cathode 3 and holes are also injected from the air-stable anode 5.

"Production method"
Such a light emitting element 1 can be manufactured as follows, for example. Below,
The case where the organic compound layer 4 is composed of a polymer material as a main material will be described as a representative.

[1] First, the substrate 2 is prepared, and the cathode 3 is formed on the substrate 2. The cathode 3 may be, for example, a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, a dry plating method such as vacuum deposition, sputtering, or ion plating, a vapor deposition method such as a thermal spraying method, or an electrolytic plating. It can be formed using a wet plating method such as immersion plating or electroless plating, a liquid phase film forming method such as a sol-gel method or a MOD method, or a metal foil bonding. FTO is difficult to sputtering, and CVD or spray pyrolysis is used.

[2] Next, the electron injecting metal compound layer 6 is formed on the cathode 3. The electron injecting metal compound layer 6 can be formed using, for example, the vapor phase film forming method or the liquid phase film forming method as described above. Among these, the electron injecting metal compound layer 6 is more preferably formed using a spray pyrolysis method of a liquid phase film forming method. According to the spray pyrolysis method, the electron injecting metal compound layer 6
Can be formed more densely and in good contact with the cathode 3, and as a result, the above-described effects become more prominent.

[3] Next, the hole blocking metal compound layer 7 is formed on the electron injecting metal compound layer 6. The hole blocking metal compound layer 7 can be formed using, for example, the vapor phase film formation method or the liquid phase film formation method as described above. Among these, the hole blocking metal compound layer 7 is more preferably formed by a vacuum deposition method which is a simple method. Further, as a manufacturing method, in order to use a metal compound that is in an equilibrium state with the atmosphere, it is left in the atmosphere. The standing time is suitably from about 15 minutes to about 24 hours, and particularly from about 1 hour to about 12 hours. The environment in which the device is left is not particularly limited as long as it is close to the environment in which the device is left in the future. Here, as a safe and inexpensive material, a metal or a metal oxide is not directly used, but a carbonate that is safe and easy to handle even if it is changed is used. As a result, the effects as described above become more remarkable.

[4] Next, a light-emitting polymer material containing a BT unit is formed as the organic compound layer 4 on the upper surface of the hole blocking metal compound layer 7. Of course, it is also possible to mix a hole transporting material therein, and it is also possible to form a laminate in which a light-emitting polymer material is first formed and a hole transporting material is formed thereon. It is also possible to mix a material containing a BT unit.
Here, an example of single-layer film formation is shown. Lamination can be achieved by repeating this.

First, the polymer material constituting the organic compound layer 4 is dissolved in a solvent (liquid medium) to prepare a liquid material. Examples of the solvent include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, ethylene carbonate, and methyl ethyl ketone (MEK).
, Ketone solvents such as acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, methanol, ethanol,
Alcohol solvents such as isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), Anisole, diethylene glycol dimethyl ether (diglyme)
, Ether solvents such as diethylene glycol ethyl ether (carbitol), cellosolv solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, toluene, xylene, benzene, etc. Aromatic hydrocarbon solvents, pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone and other aromatic heterocyclic compounds solvents, N, N-dimethylformamide (D
MF), amide solvents such as N, N-dimethylacetamide (DMA), chlorobenzene,
Halogen compound solvents such as dichloromethane, chloroform, 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate, ethyl formate, dimethyl sulfoxide (DMS
O), sulfur compound solvents such as sulfolane, nitrile solvents such as acetonitrile, propionitrile, acrylonitrile, various organic solvents such as organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, or these And a mixed solvent containing.

Among these, as the solvent, a nonpolar solvent is suitable, for example, an aromatic hydrocarbon solvent such as xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, tetramethylbenzene, pyridine, pyrazine, furan, Examples include aromatic heterocyclic compound solvents such as pyrrole, thiophene, and methylpyrrolidone, and aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane. These can be used alone or in combination.

Next, this liquid material is supplied onto the electron injecting metal compound layer 6 to form a liquid film.
Examples of the method for supplying the liquid material include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing. Law, flexographic printing method,
Various coating methods such as an offset printing method and an ink jet printing method can be used. According to such a coating method, a liquid film can be formed relatively easily.

Next, the solvent is removed from the liquid film.
[5] Next, the hole injecting metal compound layer 8 is formed on the organic compound layer 4. The hole injecting metal compound layer 8 can be formed using, for example, the vapor phase film forming method or the liquid phase film forming method as described above.

Among these, the hole injecting metal compound layer 8 is more preferably formed by using a vapor phase film forming method. According to the vapor deposition method, the surface of the organic compound layer 4 is cleaned without breaking the surface, and the anode 5
As a result, the effects as described above become more remarkable.

[6] Next, the anode 5 is formed on the hole injecting metal compound layer 8 as a final step. The anode 5 can be formed using, for example, a vacuum deposition method, a sputtering method, a metal foil bonding, or the like. Thus, the manufacture of the light emitting device 1 of the embodiment is completed. If you do
Thereafter, a sealing step may be performed.

(Example)
Next, the light emitting device of the example will be described.

<1. Manufacturing of light emitting device>
Example 1
[1] First, a transparent glass substrate with FTO (substrate 2) having an average thickness of 2.3 mm, which is commercially available from Hartford Glass, USA, was prepared.

[2] Next, the FTO electrode (cathode) 3 was etched with zinc powder and 4N hydrochloric acid to form a pattern.

[3] Next, an average thickness of 100 nm is formed on the FTO electrode 3 by spray pyrolysis.
Titanium oxide (TiO ₂ ) layer (electron-injecting metal compound layer 6) was formed (Journal of Euro
pean Ceramic Society 19, p903 (1999) or Ceramic Trans.109, p473 (2000)). Here, a diisopropoxy / bisacetylacetonato titanium solution and ethanol were mixed at a mass ratio of 1:10, and spray-coated on the FTO electrode 3 described in [2] heated at 450 ° C.

[4] Next, a cesium compound layer having an average thickness of 20 nm was formed on the titanium oxide layer produced by the spray pyrolysis method by a vacuum deposition method. Then, in the atmosphere (25 ° C., 5
0 RH%) for 12 hours. As a result, a hole blocking metal compound 7 that can contain a cesium carbonate, a cesium oxide layer, and cesium hydroxide was formed.

[5] Next, polyfluorene derivative ADS133YE manufactured by ADS was dissolved in xylene at 1.0 wt%, and spin coating method (1000r) was applied on the hole blocking metal compound 7.
pm) and then dried. The drying conditions for the liquid material were atmospheric and room temperature. Thus, the organic compound layer 4 is completed.

[6] The manufacturing process of the hole injecting metal compound layer 8 and the manufacturing process of the anode 5 are performed in a vacuum vapor deposition machine. Here, a molybdenum oxide (MoO ₃ ) layer (hole-injecting metal compound layer 8) was vapor-deposited on the organic compound layer 4 with an average thickness of 5 nm.

  In the continuous process of [7], gold (Au) (anode 5) was vapor-deposited with an average thickness of 40 nm.

(Example 2)
Step [3] is omitted. Other than that, the light-emitting element 1 was fabricated in the same manner as in Example 1.
As is clear from a comparison between FIG. 1 showing the light-emitting element 1 of Example 1 and FIG. 2 showing the light-emitting element 1 of Example 2, the light-emitting element 1 of Example 2 includes the electron-injecting metal compound layer 6. It is a light emitting element in which only (shown in FIG. 1) does not exist.

(Comparative Example 1)
As Comparative Example 1, that is, as a conventional light emitting device, a light emitting device similar to that of Example 1 was manufactured except that the step [4] was omitted. That is, the light emitting device of Comparative Example 1 is a light emitting device without only the electron injecting metal compound layer 6.

<2. Evaluation>
For the light emitting devices manufactured in each of the examples and comparative examples, the initial light emission efficiency and the light emission efficiency after being left in the atmosphere for 500 hours were evaluated. The luminous efficiency was evaluated by applying a voltage from 0 V to 6 V with a DC power source, measuring the current value, and measuring the luminance with a luminance meter.

The results are shown in FIGS. 3 and 4, respectively. As shown in FIG. 3, each of the light-emitting elements in each example had a luminous efficiency higher than that of the comparative example (the non-sealed and air-stable light-emitting element reported in JP 2007-53286 A). And it was excellent in luminance. In particular, Example 1 is a dramatic improvement. Also in Example 2, it is higher than that under high voltage, and it can be said that it is a great improvement comprehensively in view of the fact that it does not have a high-temperature process when producing a titanium oxide layer. As the data of Comparative Example 1, the data reported in Japanese Patent Application Laid-Open No. 2007-53286 was used.

More specifically, in Example 1, both the luminous efficiency and the luminance are improved by 10 times or more. This is effectively blocked by the "hole-blocking metal compound layer 7 prepared by leaving in the atmosphere" into which the carriers that have been lost to the other electrode without recombination so far, that is, holes are newly introduced. It is thought that it was used. As a result, although not shown here, the energization life is also improved by about 1.5 to 2 times. The same applies to the second embodiment. In the first place, electron injection is realized at a low voltage from an FTO having a low electron injection capability because the local electric field is generated by the fact that holes are blocked and accumulated by the “hole blocking metal compound layer 7 prepared by leaving in the atmosphere”. It is thought to be drawn in. This facilitates the use of the plastic substrate.

FIG. 4 shows the efficiency after leaving the unsealed elements of the examples and comparative examples in the atmosphere for 500 hours. In Comparative Example 1, light emission could not be confirmed in the range of 0 to 6V. On the other hand, in Examples 1 and 2, light emission could be confirmed although a slight increase in threshold voltage was observed. This confirmed the realization of an unsealed light-emitting element 1 that is air-stable and has high luminous efficiency. Although not shown here, Example 2 using molybdenum oxide as the hole-injecting metal oxide layer 8 obtained the same results as Example 1.

<Display device>
The light emitting element 1 of the above-described embodiment can be used as a light source, for example. Also,
By arranging a plurality of light emitting elements 1 in a matrix, a display device (display device of the embodiment) can be configured.

The driving method of the display device is not particularly limited, and may be either an active matrix method or a passive matrix method.

  Next, an example of a display device to which the display device of the embodiment is applied will be described.

FIG. 5 is a longitudinal sectional view showing an embodiment of a display device to which the display device of the embodiment is applied. The display device 10 shown in FIG. 5 includes a base body 20 and a plurality of light emitting elements 1 provided on the base body 20.

  The base body 20 includes a substrate 21 and a circuit unit 22 formed on the substrate 21.

The circuit unit 22 includes a protective layer 23 made of, for example, a silicon oxide layer formed on the substrate 21, a driving TFT (switching element) 24 formed on the protective layer 23, a first interlayer insulating layer 25, And a second interlayer insulating layer 26.

The driving TFT 24 includes a semiconductor layer 241 made of silicon, a gate insulating layer 242 formed on the semiconductor layer 241, a gate electrode 243 formed on the gate insulating layer 242, a source electrode 244, and a drain electrode 245. have.

On such a circuit portion 22, the light emitting element 1 is provided corresponding to each driving TFT 24. Adjacent light emitting elements 1 include a first partition wall 31 and a second partition wall 3.
It is divided by 2.

In this embodiment, the cathode 3 of each light emitting element 1 and the electron injecting metal oxide layer 6 formed thereon constitute a pixel electrode, and are electrically connected to the drain electrode 245 of each driving TFT 24 by the wiring 27. It is connected. Further, the anode 5 of each light emitting element 1 and the hole injecting metal oxide layer 8 produced thereunder are made common.

The display device 10 may be monochromatic display, and color display is also possible by selecting a light emitting material used for each light emitting element 1. Such a display device 10 (display device of the present invention) can be incorporated into various electronic devices.

"Electronics"
FIG. 6 is a perspective view illustrating a configuration of a mobile (or notebook) personal computer to which the electronic device of the embodiment is applied.

In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.

In the personal computer 1100, the display unit included in the display unit 1106 is configured by the display device 10 described above.

FIG. 7 is a perspective view illustrating a configuration of a mobile phone (including PHS) to which the electronic device of the embodiment is applied.

In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202 and an earpiece 1204.
A mouthpiece 1206 and a display unit are provided. In the mobile phone 1200, the display unit is configured by the display device 10 described above.

FIG. 8 is a perspective view illustrating a configuration of a digital still camera to which the electronic apparatus of the embodiment is applied. In this figure, connection with an external device is also simply shown.

Here, a normal camera sensitizes a silver halide photographic film with a light image of a subject, whereas
The digital still camera 1300 uses a CCD (Charge Coupled Device) to capture an optical image of a subject.
An image pickup signal (image signal) is generated through photoelectric conversion by an image pickup device such as the above.

A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image. Digital still camera 1300
The display unit is composed of the display device 10 described above.

A circuit board 1308 is installed inside the case 1302. This circuit board 130
A memory 8 is provided for storing (storing) the imaging signal. A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).

When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302.
As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer (PC) 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

In addition to the personal computer (mobile personal computer) in FIG. 6, the mobile phone in FIG. 7, and the digital still camera in FIG.
TV, video camera, viewfinder type, monitor direct-view type video tape recorder,
Laptop personal computers, car navigation devices, pagers, electronic notebooks (including those with communication functions), electronic dictionaries, calculators, electronic game devices, word processors, workstations, videophones, security TV monitors, electronic binoculars, POS terminals, Devices equipped with touch panels (for example, cash dispensers and ticket vending machines at financial institutions), medical devices (
For example, electronic thermometer, blood pressure monitor, blood glucose meter, electrocardiogram display device, ultrasonic diagnostic device, endoscope display device), fish detector, various measuring instruments, instruments (eg, vehicle, aircraft, ship instruments) It can be applied to a flight simulator, other various monitors, a projection display device such as a projector, and the like.

As described above, the light-emitting element, the display device, and the electronic apparatus according to the embodiment have been described based on the illustrated embodiment, but the present invention is not limited thereto.

FIG. 3 is a diagram schematically showing a longitudinal section of a light emitting device of Example 1. FIG. 6 is a diagram schematically showing a longitudinal section of a light emitting device of Example 2. It is a graph which shows the result of having evaluated initial luminous efficiency and the brightness | luminance with respect to the non-sealing light emitting element manufactured by each Example and the comparative example 1. FIG. It is a graph which shows the result of having evaluated the luminous efficiency after leaving to air | atmosphere for the unsealed light emitting element manufactured by each Example and the comparative example 1 for 500 hours. It is a longitudinal cross-sectional view which shows embodiment of the display apparatus to which the display apparatus of embodiment is applied. 1 is a perspective view illustrating a configuration of a mobile (or notebook) personal computer to which an electronic device of an embodiment is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of embodiment is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of embodiment is applied.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Light emitting element, 2 ... Board | substrate, 3 ... Cathode, 4 ... Organic compound layer, 5 ... Anode, 6 ... Electron injection metal compound layer, 7 ... Hole block property metal compound layer produced by leaving to air, 8 ... Hole injection metal compound layer, 10 ... display device, 20 ... substrate, 21 ... substrate, 22 ... circuit portion, 2
3 ... protective layer, 24 ... driving TFT, 241 ... semiconductor layer, 242 ... gate insulating layer, 243
... Gate electrode, 244 ... Source electrode, 245 ... Drain electrode, 25 ... First interlayer insulating layer, 2
6 ... 2nd interlayer insulation layer, 27 ... Wiring, 31 ... 1st partition part, 32 ... 2nd partition part, 1100 ... Personal computer 1102 ... Keyboard, 1104 ... Main part, 1106 ... Display unit, 1200 ... Mobile phone, 1202 ... Operation buttons, 1204 ... Earpiece, 1206 ... Mouthpiece, 1300 ... Digital still camera, 1302 ... Case (body), 1304 ...
Light receiving unit, 1306 ... shutter button, 1308 ... circuit board, 1312 ... video signal output terminal, 1314 ... input / output terminal for data communication, 1430 ... TV monitor, 1440 ...
Personal computer.

Claims (17)

A substrate,
A first electrode formed on the substrate and functioning as a cathode;
A first metal oxide film formed on the first electrode;
A metal compound film formed on the first metal oxide film;
An organic compound film formed on the metal compound film;
A second metal oxide film formed on the organic compound film;
A second electrode functioning as an anode formed on the second metal oxide film, wherein at least one of the substrate and the first electrode or the second electrode is light transmissive. Said second electrode having
The organic thin film light-emitting element, wherein the metal compound film contains an alkali metal or an alkaline earth metal. A substrate,
A first electrode formed on the substrate and functioning as a cathode;
A metal compound film formed on the first electrode;
An organic compound film formed on the metal compound film;
A metal oxide film formed on the organic compound film;
A second electrode functioning as an anode, formed on the metal oxide film, wherein at least one of the substrate and the first electrode, or the second electrode has optical transparency. A second electrode,
The organic thin film light-emitting element, wherein the metal compound film contains an alkali metal or an alkaline earth metal. The organic thin film light-emitting element according to claim 1, wherein the alkali metal or alkaline earth metal contains at least one of cesium carbonate, cesium oxide, and cesium hydroxide. The organic thin film light-emitting element according to claim 1, wherein the first metal oxide film contains titanium. 2. The organic thin film light emitting element according to claim 1, wherein the second metal oxide film contains molybdenum or vanadium. 3. The organic thin film light emitting element according to claim 2, wherein the metal oxide film contains molybdenum or vanadium. The organic thin film light-emitting element according to claim 1, wherein the organic compound film contains an organic substance having a benzothiadiazole skeleton. 8. The organic thin film light emitting element according to claim 7, wherein the organic compound film is a polymer material.   A display device comprising the organic thin film light emitting element according to claim 1.   An electronic apparatus comprising the display device according to claim 9. Forming a first electrode functioning as a cathode on a substrate;
Forming a first metal oxide film on the first electrode;
Forming a metal compound film on the first metal oxide film;
Forming an organic compound film on the metal compound film;
Forming a second metal oxide film on the organic compound film;
A second electrode functioning as an anode on the second metal oxide film, wherein at least one of the substrate and the first electrode or the second electrode is light-transmissive. Forming a second electrode,
The step of forming the metal compound film includes a first step of forming a compound containing alkali metal or alkaline earth metal, and a step of exposing the formed compound containing alkali metal or alkaline earth metal to the atmosphere. The manufacturing method of the organic thin film light emitting element characterized by consisting of two processes. Forming a first electrode functioning as a cathode on a substrate;
Forming a metal compound film on the first electrode;
Forming an organic compound film on the metal compound film;
Forming a metal oxide film on the organic compound film;
A second electrode that functions as an anode on the metal oxide film, wherein at least one of the substrate and the first electrode, or the second electrode is light transmissive. Forming a step,
The step of forming the metal compound film includes a first step of forming a compound containing alkali metal or alkaline earth metal, and a step of exposing the formed compound containing alkali metal or alkaline earth metal to the atmosphere. The manufacturing method of the organic thin film light emitting element characterized by consisting of two processes. The organic material according to claim 11 or 12, wherein the first step uses at least one of cesium carbonate, cesium oxide, and cesium hydroxide as the compound containing the alkali metal or alkaline earth metal. Manufacturing method of thin film light emitting element. 13. The method of manufacturing an organic thin film light emitting element according to claim 11, wherein in the first step, the compound containing the alkali metal or alkaline earth metal is formed by vacuum deposition. 13. The method of manufacturing an organic thin film light emitting element according to claim 11, wherein the second step oxidizes the compound containing the alkali metal or alkaline earth metal. 13. The method for producing an organic thin film light-emitting element according to claim 11, wherein the second step comprises reacting the compound containing the alkali metal or alkaline earth metal with water. The second step is characterized in that the alkali metal or alkaline earth metal-containing compound is exposed to an environment that is substantially recognized as being 300 K, 1 atm, and 20% oxygen partial pressure. The manufacturing method of the organic thin film light emitting element of Claim 11, 12 to do.

Images