JP6169556B2 - Organic electroluminescent device and manufacturing method thereof - Google Patents

Description

    The present invention relates to an organic electroluminescent element (hereinafter sometimes referred to as an organic EL element) that can be effectively used for a surface light source such as a full color display, a backlight, and an illumination light source, and a light source array such as a printer.

  The organic EL element is composed of a light emitting layer or a plurality of organic layers including a light emitting layer and a counter electrode sandwiching the organic layer. In the organic EL element, electrons injected from the cathode and holes injected from the anode are recombined in the organic layer, emitted light from the generated excitons, and other molecules generated by energy transfer from the excitons. It is an element for obtaining light emission using at least one of light emission from the excitons.

  Until now, organic EL elements have been developed with greatly improved brightness and element efficiency by using a laminated structure with separated functions. For example, a two-layer stacked device in which a hole transport layer and a light-emitting / electron transport layer are stacked, a three-layer stacked device in which a hole transport layer, a light-emitting layer, and an electron transport layer are stacked, a hole transport layer, and a light-emitting layer A four-layer stacked element in which a hole blocking layer and an electron transport layer are stacked is often used.

  However, many problems still remain in practical use of organic EL elements, such as improving luminous efficiency and driving durability. In particular, increasing the light emission efficiency can reduce power consumption and is advantageous in terms of driving durability. Therefore, many improvement means have been disclosed so far. However, in general, a light emitting material with high luminous efficiency has a defect of causing luminance deterioration during driving, and a material with excellent driving durability has a defect of low luminance, which improves luminous efficiency and driving durability. It is not easy to achieve both enhancements, and further improvements are being sought.

  For example, an organic EL element having an organic compound layer doped with a metal functioning as a donor (electron donating) dopant at the interface with the cathode is disclosed (for example, see Patent Document 1). According to this configuration, it is said that the energy barrier in electron injection from the cathode to the organic layer is lowered and the driving voltage is reduced.

In addition, a method for manufacturing an organic EL element in which a light emitting layer made of an organic compound is formed by vacuum deposition and then heat-treated at 50 ° C. or higher is disclosed (for example, see Patent Document 2). According to the production method, the organic compound as a luminescent material is in an unstable crystalline state at the stage of vacuum deposition, and is subjected to heat treatment at a temperature of 50 ° C. or higher and lower than the melting point of the organic compound. It is said that it changes to an agglomerated structure, thereby efficiently emitting light at a low voltage and emitting light stably for a long period of time.
JP-A-10-270171 JP-A-5-18264

    An object of the present invention is to provide an organic electroluminescence device having high luminous efficiency, low driving voltage, and excellent durability, and a method for producing the same.

It has been found that the above-mentioned problems of the present invention can be solved by the following means.
<1> A method for producing an organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic layers is at least one kind of alkali metal or alkaline earth. An organic layer containing a metal or a salt thereof, and the alkali metal or alkaline earth at 50 ° C. or higher during or after the formation of the organic layer containing the alkali metal, alkaline earth metal or salt thereof A method for producing an organic electroluminescent device, comprising a heat treatment step of performing a heat treatment at a temperature not higher than a melting point of an organic layer containing a similar metal or a salt thereof.
<2> The organic electroluminescent element according to <1>, wherein the heat treatment step is performed during the formation of the organic layer containing the alkali metal, alkaline earth metal, or salt thereof. Production method.
<3> The organic electroluminescence device according to <1>, wherein the heat treatment step is performed after the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is formed. Method.
<4> A method for producing an organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic layers is at least one kind of alkali metal or alkaline earth. It is an organic layer containing a metal or a salt thereof, and has an energization treatment step of applying an energization treatment during or after the formation of the organic layer containing the alkali metal, alkaline earth metal, or salt thereof A method for producing an organic electroluminescent device, comprising:
<5> The organic electroluminescence element according to <4>, wherein the energization treatment step is performed after the formation of the organic layer containing the alkali metal, alkaline earth metal, or salt thereof. Production method.
<6> The method for producing an organic electroluminescent element according to <4> or <5>, wherein a current density in the energization treatment is 0.1 A / cm ² or less.
<7> The at least one alkali metal, alkaline earth metal, or salt thereof contains at least one selected from the group consisting of Li, Na, K, Ca, and Sr, < The manufacturing method of the organic electroluminescent element in any one of 1>-<6>.
<8> The method for producing an organic electroluminescent element according to <7>, wherein the at least one alkali metal or alkaline earth metal, or a salt thereof contains Li.
<9> The concentration of the alkali metal, alkaline earth metal, or salt thereof in the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is 0.01 relative to the organic material in the organic layer. The method for producing an organic electroluminescent element according to any one of <1> to <8>, wherein the organic electroluminescent element is 10% by mass to 10% by mass.
<10> Any one of <1> to <9>, wherein the organic layer containing the alkali metal, alkaline earth metal, or salt thereof contains at least one electron transporting material. The manufacturing method of the organic electroluminescent element of description.
<11> The method for producing an organic electroluminescent element according to <10>, wherein the electron transporting material is an organic material.
<12> An organic electroluminescent element having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic layers is at least one kind of alkali metal, alkaline earth metal, or An organic layer containing a salt thereof, at least the organic layer containing the alkali metal, alkaline earth metal, or salt thereof contains the alkali metal, alkaline earth metal, or salt thereof at 50 ° C. or higher. An organic electroluminescent element, wherein the organic electroluminescent element is a layer that has been heat-treated at a temperature lower than the melting point of the organic layer.
<13> An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic layers is at least one kind of alkali metal, alkaline earth metal, or Organic electroluminescent device characterized in that it is an organic layer containing a salt thereof, and at least the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is a layer subjected to an energization treatment .
<14> The organic electroluminescent element according to <12> or <13>, wherein the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is an electron transport layer.
<15> The organic electroluminescent element as described in <14>, wherein the electron transport layer contains a phenanthroline derivative as an electron transport material.
<16> A <14> or <15> comprising a second electron transport layer not containing an alkali metal, an alkaline earth metal, or a salt thereof between the electron transport layer and the light emitting layer. The organic electroluminescent element of description.

    ADVANTAGE OF THE INVENTION According to this invention, it has the high luminous efficiency, the low drive voltage, and the organic EL element excellent in durability, and its manufacturing method are provided.

It is the schematic which shows the layer structure of this invention organic EL element. It is the schematic which shows another layer structure of this invention organic EL element.

In the method for producing an organic electroluminescent element of the present invention, at least one of the organic layers including the light emitting layer contains at least one kind of alkali metal, alkaline earth metal, or salt thereof. And a heat treatment step of performing a heat treatment at a temperature of 50 ° C. or more and a melting point or less of the organic layer during or after the formation of the organic layer.
According to another aspect of the method for producing an organic electroluminescent element of the present invention, at least one of the organic layers including the light emitting layer contains at least one alkali metal, alkaline earth metal, or salt thereof. It is an organic layer to be contained, and includes an energization process step of applying an energization process during or after the formation of the organic layer containing the alkali metal, alkaline earth metal, or salt thereof.
According to the heat treatment step or the energization treatment step of the present invention, in the organic layer containing an alkali metal, alkaline earth metal, or salt thereof, the organic material of the layer and the alkali metal, alkaline earth metal, or salt thereof As a result, the carrier density is increased, the electric resistance is decreased, and it is presumed that the driving voltage is decreased, the luminous efficiency is improved, and the driving durability is improved. This effect is completely different from the formation of the microcrystalline aggregate structure of the luminescent material disclosed in JP-A-5-18264.
The effect of the present invention is particularly great when the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is an electron transport layer. Furthermore, a particularly great effect is obtained when the electron transport material of the electron transport layer is a phenanthroline derivative.

Next, the organic electroluminescent element of the present invention will be described in detail.
(Constitution)
In the organic electroluminescent element of the present invention, the organic compound layer is laminated in the order of the light emitting layer and the electron transport layer from the anode side. Further, a hole injection layer may be provided between the anode and the light emitting layer, a hole transport layer may be provided between the hole injection layer and the light emitting layer, and an electron injection layer may be provided between the electron transport layer and the cathode. Furthermore, you may have a charge block layer (an electron block layer, a hole block layer) etc. between the positive hole transport layer and the light emitting layer, or between the light emitting layer and the electron transport layer.
In the present invention, an organic layer containing at least one alkali metal, alkaline earth metal, or salt thereof is preferably an electron transport layer. More preferably, a second electron transport layer not containing an alkali metal, an alkaline earth metal, or a salt thereof is disposed between the electron transport layer and the light emitting layer.

The configuration of the organic compound layer in the organic electroluminescent element of the present invention is preferably an embodiment having at least a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer in order from the anode side. is there. More preferably, in order from the anode side, at least a hole injection layer, a hole transport layer, a light emitting layer, a second electron transport layer, an electron transport layer (sometimes referred to as a first electron transport layer), and an electron injection layer It is the aspect which has. The first electron transport layer is an organic layer containing at least one alkali metal, alkaline earth metal, or salt thereof.
FIG. 1 is a schematic cross-sectional view of a preferred embodiment of the layer structure of the organic EL device of the present invention. On the substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, a first electron transport layer 6, an electron injection layer 7, and a cathode 8 are arranged in this order.
FIG. 2 is a schematic cross-sectional view of another preferred embodiment of the layer structure of the organic EL device of the present invention. On the substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, a second electron transport layer 9, a first electron transport layer 6, an electron injection layer 7, and a cathode 8 are sequentially formed. Be placed.

  Each layer may be divided into a plurality of secondary layers.

  Next, elements constituting the light emitting device of the present invention will be described in detail.

(Method for producing organic compound layer)
In the organic electroluminescent device of the present invention, each layer constituting the organic compound layer is suitable for any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, a printing method, a coating method, an ink jet method, or a spray method. Can be formed.

Each layer constituting the organic compound layer is sequentially formed and laminated on the substrate.
The step of forming the organic compound layer in the present invention includes at least 50 ° C. and below the melting point of the organic layer during or after the formation of the organic layer containing at least one alkali metal, alkaline earth metal, or salt thereof. It has the heat processing process which heat-processes at the temperature of, or the electricity supply process process which performs an electricity supply process, It is characterized by the above-mentioned. The step of performing the heat treatment is a step of forming the organic layer, and may be continuously performed from the initial stage of the film formation until the film formation is completed. Or you may heat-process after forming all the organic layers. The step of applying the energization treatment is preferably performed after all the organic layers and electrodes are formed.

1) Heat treatment step The heating means used in the heat treatment step in the present invention is not particularly limited as long as it heats the organic layer at a desired temperature, and generally known heating means can be used. Specific examples include, for example, a method in which a drum-like or flat plate-like heat medium is brought into contact with the substrate, the substrate is heated, and the organic layer is heated by heat conduction from the substrate, or radiant heat from infrared rays or far infrared rays is used. There are a method of heating indirectly from the surface of the organic layer, a high-frequency heating method, a method of heating by holding in a high-temperature oven, and the like.

As a means for heating during the formation of the organic layer, a substrate heating method is preferable.
As a means for heating after the organic layer is formed, a heating method using infrared rays, far-infrared rays, or the like, or a method of heating the whole formed element in a high-temperature oven can be preferably used.
As the heat treatment step in the present invention, heating is preferably performed during the formation of an organic layer containing an alkali metal, an alkaline earth metal, or a salt thereof by a substrate heating method.
As the heat treatment temperature, a temperature of 50 ° C. or higher and the melting point of the organic layer or lower is used. Preferably, it is 60 ° C. or higher and below the melting point of the organic layer, more preferably 70 ° C. or higher and below the melting point of the organic layer.
Below 50 ° C., sufficient heat treatment effect cannot be obtained even if the heating time is increased. Further, the melting point of the organic layer is not preferable because the organic layer is denatured or the film is broken, and the device performance is not exhibited.
The heat treatment time is arbitrary and can be set by finding appropriate conditions depending on the material of the organic layer.

2) Energizing process The energizing process in the present invention includes a method in which the electrode plate is brought into close contact with the energizing surface, and a method in which both electrodes are energized after forming a pair of electrodes of the organic EL element. Preferably, the electrodes of the organic EL element can be used as they are, and it is preferable to energize the electrodes after forming all the organic layers and electrodes.
The energization process of the present invention uses a region different from the current density region for causing the organic EL element to emit light, and the effect of the present invention cannot be obtained by normal energization for light emission.
Current density in conduction process in the present invention is ^preferably from ^{0.01mA / m 2 ~100mA / m 2} , more preferably ^{0.1mA / m 2 ~50mA / m 2} , 0.1mA / m 2 ~10mA / M ² is more preferable.

(Electron transport layer)
The organic layer containing at least one alkali metal, alkaline earth metal, or salt thereof in the present invention is preferably an electron transport layer.
The electron transport layer is a layer having a function of receiving electrons from the cathode side and transporting them to the anode side, and is disposed between the cathode and the light emitting layer.
Preferably, the electron transport layer in the present invention contains at least one alkali metal, alkaline earth metal, or a salt thereof and an organic electron transport material. Alkali metals, alkaline earth metals, or salts thereof may be used alone or in combination of two or more. An organic electron transport material may be used independently and may use 2 or more types.
More preferably, the electron transport layer of the present invention has at least two layers, and includes a first electron transport layer containing at least one alkali metal, alkaline earth metal, or a salt thereof and an organic electron transport material, A second electron transport layer not containing an alkali metal, an alkaline earth metal, or a salt thereof is provided on the light emitting layer side of the first electron transport layer.
The total thickness of the electron transport layer is preferably 5 nm to 500 nm, more preferably 10 nm to 200 nm, and still more preferably 15 nm to 100 nm.
The thickness of the first electron transport layer is preferably 5 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The thickness of the second electron transport layer is preferably 0.5 nm to 50 nm, more preferably 1 nm to 30 nm, and still more preferably 3 nm to 20 nm.
The thickness of the first electron transport layer is preferably thicker than the thickness of the second electron transport layer, and the ratio of the thickness of the first electron transport layer / the thickness of the second electron transport layer is preferably 1 to 500, and preferably 1.5 to 100 is more preferable, and 2-50 is still more preferable.

1) First electron transport layer The first electron transport layer is a layer containing at least one alkali metal, alkaline earth metal, or a salt thereof and an electron transport material. Preferably, the content of alkali metal, alkaline earth metal, or salt thereof in the first electron transport layer is 0.01% by mass or more and 10% by mass, and more preferably 0.1% by mass or more and 5% by mass. %, More preferably 0.2% by mass or more and 3% by mass.
If the content of alkali metal, alkaline earth metal, or salt thereof is less than 0.01% by mass, a sufficient driving voltage reduction effect cannot be obtained even if heating or energization treatment is performed, which is not preferable.
If the content of alkali metal, alkaline earth metal, or a salt thereof exceeds 10% by mass, the efficiency is lowered, which is not preferable.

-Alkali metals, alkaline earth metals, or their salts-
As the alkali metal, alkaline earth metal, or salt thereof, a metal or salt selected from the group consisting of Li, Na, K, Ca, and Sr is preferable. More preferably, it is Li or its salt.
Here, the salt refers to a complex compound formed by reaction with a Lewis base, and examples thereof include halides, carbonates, sulfates, nitrates, phosphates, acetates, titanates, and silicates. Moreover, when using a salt, the mode which dopes these salts formed from alkali metal (alkaline earth metal) in an organic layer, and the simple substance of the alkali metal (alkaline earth metal) doped in the organic layer is organic. An embodiment in which a complex compound is formed by reacting with a compound in the layer is exemplified.

  -Electron transport material-

  As the electron transport material used for the electron transport layer, an organic electron transport material is preferable. Specifically, a pyridine derivative, a quinoline derivative, a pyrimidine derivative, a pyrazine derivative, a phthalazine derivative, a phenanthroline derivative, a triazine derivative, a triazole derivative, an oxazole derivative. Oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene, etc. Ligand of aromatic ring tetracarboxylic acid anhydride, phthalocyanine derivative, 8-quinolinol derivative metal complex, metal phthalocyanine, benzoxazole or benzothiazole Various metal complexes typified by metal complexes of organic silane derivatives typified by silole, and the like. These electron transport materials may be used alone or in combination of two or more.

  In the present invention, a preferred electron transport material is a phenanthroline derivative. The phenanthroline derivative is preferably a compound represented by the following general formula (ET).

In General Formula (ET), R ₁ represents a hydrogen atom or a substituent, and n represents an integer of 0 to 8. If n is an integer of 2 or more, plural R ₁ may be the same or different.

<Description of Substituent R ₁ >
The substituent represented by R ₁ is not particularly limited and includes, for example, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (cycloalkenyl group). Group, bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group , Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl Oxycarbonylamino Group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, Aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido Groups, boronic acid groups (—B (OH) ₂ ), phosphato groups (—OPO (OH) ₂ ), sulfato groups (—OSO ₃ H), and other known substituents.
More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover.

  An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and the like 1-methyl-2-pyridinio and 1-methyl-2-quinolinio A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, Propoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4- t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy),

A heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, A substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p- Methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy) N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyl Oxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy , P-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, carbon number 6 30 substituted or unsubstituted anilino groups such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), ammonio groups (preferably ammonio groups, substituted or unsubstituted carbon atoms of 1 to 30) Substituted alkyl, aryl, heterocyclic groups substituted with ammonio groups such as trimethylammonio, triethylammonio, diphenylmethylammonio), acylamino groups (preferably formylamino groups, substituted or unsubstituted carbon atoms of 1 to 30) Alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxy Phenylka Rubonylamino),

An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino p- chlorophenoxy carbonyl amino, m-n-octyloxy phenoxy carbonyl amino),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino) , Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio , Ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably carbon A substituted or unsubstituted heterocyclic thio group having a number of 2 to 30, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted group having 0 to 30 carbon atoms) Sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N '-Phenylcarbamoyl) sulfamoyl), sulfo group, Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- Methylphenylsulfinyl),

Alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substitution having 4 to 30 carbon atoms) Or a heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2- Furylcarbonyl), a Over Le oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms,

For example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxy Carbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethyl Carbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, carbon 3 to 30 substituted or unsubstituted heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide groups (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably 2 carbon atoms). To 30 substituted or unsubstituted phosphinyl groups, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy groups (preferably substituted or unsubstituted phosphinyl having 2 to 30 carbon atoms) Ruoxy groups such as diphenoxyphosphinyloxy , Dioctyloxyphosphinyloxy), phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino) A phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group (preferably having 0 to 30 carbon atoms). A substituted or unsubstituted hydrazino group, such as trimethylhydrazino, or a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N-dimethylureido).
R may be a linking group, for example, a linking group formed of C, N, O, S, Si, or Ge, more preferably a linking group comprising an aromatic ring or an aromatic heterocycle. And particularly preferably a linking group comprising a benzene ring, a pyridine ring, a pyrimidine ring, or a triazine ring.

  Next, although the specific example of a compound represented by general formula (ET) is given, this invention is not necessarily limited to these compounds.

2) 2nd electron transport layer The 2nd electron transport layer in this invention is a layer which does not contain an alkali metal, alkaline-earth metal, or those salts substantially. “Substantially not contained” means that the content of the electron transporting layer is within a range in which no difference is recognized from the case where the electron transporting property of the electron transporting layer does not contain these metals or salts.

  The second electron transport layer in the present invention preferably contains an organic electron transport material as an electron transport material, and specifically includes a pyridine derivative, a quinoline derivative, a pyrimidine derivative, a pyrazine derivative, a phthalazine derivative, a phenanthroline derivative, and a triazine. Derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine Derivatives, aromatic ring tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzoates Various metal complexes typified by metal complexes of an azole as a ligand, organic silane derivatives typified by silole, and the like. These electron transport materials may be used alone or in combination of two or more.

(Light emitting layer)
The light emitting layer in the present invention is a layer having a function of receiving holes from the anode, receiving electrons from the cathode, and providing a field for recombination of holes and electrons to emit light when an electric field is applied.
The light emitting layer in the present invention preferably contains at least one light emitting material and a host material.
Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors. Even when there are a plurality of light-emitting layers, each layer of the light-emitting layer preferably contains at least one light-emitting material and a plurality of host materials.

As the light emitting material and host material contained in the light emitting layer in the present invention, light emission from triplet excitons (phosphorescence) can be obtained by combining a fluorescent light emitting material and a host material capable of obtaining light emission (fluorescence) from singlet excitons. A combination of a phosphorescent light emitting material and a host material may be used, and among these, a combination of a phosphorescent light emitting material and a host material is preferable from the viewpoint of light emission efficiency.
The light emitting layer in the present invention can contain two or more kinds of light emitting materials in order to improve the color purity and widen the light emission wavelength region.

<Phosphorescent material>
In general, examples of the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
For example, the transition metal atom is not particularly limited, but preferably includes ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum, more preferably rhenium, iridium, and platinum. More preferred are iridium and platinum.
Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .
Specific ligands are preferably halogen ligands (preferably chlorine ligands), aromatic carbocyclic ligands (eg, cyclopentadienyl anion, benzene anion, or naphthyl anion), Nitrogen-containing heterocyclic ligand (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, or phenanthroline), diketone ligand (eg, acetylacetone), carboxylic acid ligand (eg, acetic acid ligand) , Alcoholate ligands (eg, phenolate ligands), carbon monoxide ligands, isonitrile ligands, and cyano ligands, more preferably nitrogen-containing heterocyclic ligands.
The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  Among these, as specific examples of the light emitting material, for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1 Gazette, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, JP2001-247859, JP2002-117978, JP2002-225352, JP2002-235076 JP, JP-A-2002-170684, EP-121257, JP-A-2002-226495, JP-A-2002-234894, JP-A-2001-247859, JP-A-2001-29 470, JP 2002-173694, JP 2002-203678, JP 2002-203679, JP 2004-357771, JP 2006-256999, etc. Examples of the light emitting material satisfying the relationship (2) are Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex. Eu complex, Tb complex, Gd complex, Dy complex and Ce complex. Particularly preferred are Ir complexes, Pt complexes, and Re complexes. Among them, Ir complexes, Pt complexes, which include at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond, Re complexes are preferred.

<Fluorescent material>
As the fluorescent material, generally, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclohexane Pentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, condensed polycyclic aromatic compounds (anthracene, phenanthroline, pyrene, perylene, rubrene, pentacene, etc.), 8- Various metal complexes represented by quinolinol metal complexes, pyromethene complexes and rare earth complexes, polymers such as polythiophene, polyphenylene, and polyphenylene vinylene Compounds, organic silane, and the like, and their derivatives.

  Among these, specific examples of the light emitting material include the following, but are not limited thereto.

  Among the above, the luminescent material used in the present invention is D-2, D-3, D-4, D-5, D-6, D-7, D-8, D from the viewpoint of luminous efficiency and durability. -9, D-10, D-11, D-12, D-13, D-14, D-15, D-16, D-21, D-22, D-23, or D-24 are preferred, D-2, D-3, D-4, D-5, D-6, D-7, D-8, D-12, D-14, D-15, D-16, D-21, D- 22, D-23, or D-24 is more preferable, and D-21, D-22, D-23, or D-24 is still more preferable.

  The light emitting material in the light emitting layer is preferably contained in an amount of 1% by mass to 50% by mass from the viewpoint of durability and external quantum efficiency with respect to the total mass of the compound generally forming the light emitting layer in the light emitting layer. It is more preferable to contain 2 mass%-40 mass%.

  The thickness of the light emitting layer is not particularly limited, but is usually preferably 1 nm to 500 nm, and more preferably 5 nm to 200 nm from the viewpoint of light emission efficiency. Is more preferable.

(Host material)
As the host material used in the present invention, a hole transporting host material excellent in hole transportability (sometimes referred to as a hole transportable host) and an electron transporting host compound excellent in electron transportability (electron transportability) May be described as a host).

《Hole-transporting host》
Specific examples of the hole-transporting host used in the present invention include the following materials.
Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone , Stilbene, silazane, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, polythiophenes, etc. Conductive polymer oligomers, organic silanes, carbon films, and derivatives thereof.
Preferred are indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, and thiophene derivatives, and more preferred are those having a carbazole group in the molecule. In particular, a compound having a t-butyl substituted carbazole group is preferable.

《Electron transporting host》
The electron transporting host in the light emitting layer used in the present invention preferably has an electron affinity Ea of 2.5 eV or more and 3.5 eV or less from the viewpoint of improving durability and lowering driving voltage. More preferably, it is 0.4 eV or less, and further preferably 2.8 eV or more and 3.3 eV or less. Further, from the viewpoint of improving durability and reducing driving voltage, the ionization potential Ip is preferably 5.7 eV or more and 7.5 eV or less, more preferably 5.8 eV or more and 7.0 eV or less, and 5.9 eV or more. More preferably, it is 6.5 eV or less.

Specific examples of such an electron transporting host include the following materials.
Pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, Fluorine-substituted aromatic compounds, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanines, and derivatives thereof (which may form condensed rings with other rings), metal complexes of 8-quinolinol derivatives, Examples thereof include various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole or benzothiazol as a ligand.

Preferred examples of the electron transporting host include metal complexes, azole derivatives (benzimidazole derivatives, imidazopyridine derivatives, etc.), and azine derivatives (pyridine derivatives, pyrimidine derivatives, triazine derivatives, etc.). To metal complex compounds are preferred. The metal complex compound is more preferably a metal complex having a ligand having at least one nitrogen atom, oxygen atom or sulfur atom coordinated to the metal.
The metal ion in the metal complex is not particularly limited, but is preferably beryllium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion, tin ion, platinum ion, or palladium ion, more preferably beryllium ion, Aluminum ion, gallium ion, zinc ion, platinum ion, or palladium ion, and more preferably aluminum ion, zinc ion, or palladium ion.

  There are various known ligands contained in the metal complex. For example, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, H.C. Examples include the ligands described in Yersin, published in 1987, “Organometallic Chemistry: Fundamentals and Applications”, Sakai Hanafusa, Yamamoto Akio, published in 1982, and the like.

The ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and a monodentate ligand. Alternatively, it may be a bidentate or higher ligand, preferably a bidentate or higher and a hexadentate or lower ligand, or a bidentate or higher and lower 6 or lower ligand and a monodentate mixed ligand. preferable.
Examples of the ligand include an azine ligand (for example, pyridine ligand, bipyridyl ligand, terpyridine ligand, etc.), a hydroxyphenylazole ligand (for example, hydroxyphenylbenzimidazole coordination). And a hydroxyphenyl benzoxazole ligand, a hydroxyphenyl imidazole ligand, a hydroxyphenylimidazopyridine ligand, etc.), an alkoxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom). To 20, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy), aryloxy ligands (preferably 6 to 30 carbon atoms, more preferably 6-20 carbon atoms, particularly preferably 6-12 carbon atoms, for example phenyl Carboxymethyl, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyl oxy, and 4-biphenyloxy and the like.),

Heteroaryloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, and quinolyloxy. ), An alkylthio ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), arylthio ligands (Preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio), heteroarylthio ligand (preferably 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio , 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), a siloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 3 to 25 carbon atoms). Particularly preferably, it has 6 to 20 carbon atoms, and examples thereof include a triphenylsiloxy group, a triethoxysiloxy group, and a triisopropylsiloxy group.), An aromatic hydrocarbon anion ligand (preferably having 6 carbon atoms) To 30, more preferably 6 to 25 carbon atoms, particularly preferably 6 to 20 carbon atoms, such as a phenyl anion, a naphthyl anion, an anthranyl anion, etc.), an aromatic heterocyclic anion ligand (preferably Has 1 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, and particularly preferably 2 to 20 carbon atoms. Pyrrole anion, pyrazole anion, pyrazole anion, triazole anion, oxazole anion, benzoxazole anion, thiazole anion, benzothiazole anion, thiophene anion, benzothiophene anion, etc.), indolenine anion ligand, etc. Preferably a nitrogen-containing heterocyclic ligand, an aryloxy ligand, a heteroaryloxy group, a siloxy ligand, an aromatic hydrocarbon anion ligand, or an aromatic heterocyclic anion ligand, more preferably Is a nitrogen-containing heterocyclic ligand, aryloxy ligand, siloxy ligand, aromatic hydrocarbon anion ligand, or aromatic heterocyclic anion ligand.

  Examples of the metal complex electron transporting host include, for example, JP-A No. 2002-235076, JP-A No. 2004-214179, JP-A No. 2004-221106, JP-A No. 2004-221665, and JP-A No. 2004-221068. And compounds described in JP-A-2004-327313.

  In the light emitting layer of the present invention, it is preferable in terms of color purity, light emission efficiency, and driving durability that the triplet lowest excitation level (T1) of the host material is higher than T1 of the phosphorescent light emitting material.

  Further, the content of the host compound in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass to 95% by mass with respect to the total compound mass forming the light emitting layer. Preferably there is.

(substrate)
As the substrate used in the present invention, the substrate on the side from which light emitted from the light emitting layer is extracted is preferably a substrate that does not scatter or attenuate. Specific examples include zirconia-stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Norbornene resins, and organic materials such as poly (chlorotrifluoroethylene).
For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.
As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.
When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.
The substrate may be cleaned and / or pretreated before and after electrode preparation or before the organic layer is formed. Cleaning can be performed with water, pure water, ion-exchanged water, acid, alkaline water, or an organic solvent, or immersion and ultrasonic cleaning. In addition, pretreatment may be performed for the purpose of decomposing and removing organic substances, the purpose of improving adhesiveness, and the purpose of promoting charge injection from the electrode to the organic layer. As the pretreatment method, UV-ozone treatment, oxygen plasma treatment and the like are preferably used, but are not particularly limited.

(anode)
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is provided as a transparent anode on the light extraction side, and may or may not be transparent on the side opposite to the light extraction side.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is preferable in terms of productivity, high conductivity, transparency, etc., but may be laminated with other materials, auxiliary electrodes, etc. May be provided

The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.
The work function of the anode is not limited as long as the work function can inject holes into the hole injection layer or hole transport layer adjacent to the anode, and is preferably 4.0 eV or more and 6.0 eV or less, and 4.5 eV More preferably, it is 5.8 eV or less.
The work function of the anode can be adjusted to an arbitrary value by UV ozone treatment or oxygen plasma treatment.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element, but it is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

(cathode)
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. Further, when the cathode side is a side from which light is extracted, it is preferably transparent or translucent.

Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, LI, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium and ytterbium. These may be used alone, but from the viewpoint of achieving both stability and electron injecting properties, two or more of them can be co-deposited or laminated to be suitably used in combination.
The work function of the cathode is not particularly limited as long as it is a work function capable of injecting electrons into the adjacent organic layer, preferably 2.5 eV or more and 4.5 eV, more preferably 2.5 eV or more and 4.3 eV or less. is there.

Among these, the material constituting the cathode is preferably an alkali metal or an alkaline earth metal from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability. A laminated structure with a conductive metal oxide may be employed.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).

  The cathode materials are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these publications can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 nm to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 5 nm to 5 μm, and preferably 10 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 nm to 10 nm and further laminating a transparent conductive material such as ITO or IZO.
In the present invention, the anode side can be made opaque (reflective electrode), and the cathode side can be made transparent or translucent to make a top emission type element. It is also possible to make a bottom emission type element by making the anode side transparent and the cathode side opaque (reflection electrode). Further, both the anode and the cathode can be made transparent to be a double-sided emission type.

(Hole injection layer, hole transport layer)
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. The material that can be used for the hole injection layer and the hole transport layer of the present invention is not particularly limited, and may be a low molecular compound, a high molecular compound, or an inorganic material.
Specifically, pyrrole derivatives, carbazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives , Silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, phenylazole, phenylazine A layer containing a metal complex or the like is preferable.
Examples of the inorganic material include silicon oxide, silicon dioxide, germanium oxide, germanium dioxide, germanium oxide silicide, vanadium pentoxide, molybdenum trioxide, aluminum oxide, iron dioxide, iron trioxide and the like.

  An electron-accepting dopant can be contained in the hole injection layer or the hole transport layer of the organic EL device of the present invention. As the electron-accepting dopant introduced into the hole-injecting layer or the hole-transporting layer, an inorganic compound or an organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.

  Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, metal oxides such as vanadium pentoxide, and molybdenum trioxide.

In the case of an organic compound, a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
In addition, JP-A-6-212153, JP-A-11-111463, JP-A-11-251067, JP-A-2000-196140, JP-A-2000-286054, JP-A-2000-315580 JP, JP-A-2001-102175, JP-A-2001-160493, JP-A-2002-252085, JP-A-2002-56985, JP-A-2003-157981, JP-A-2003-217862 JP-A-2003-229278, JP-A-2004-342614, JP-A-2005-72012, JP-A-2005-166637, JP-A-2005-209643, and the like are preferably used. I can do it.

  These electron-accepting dopants may be used alone or in combination of two or more. Although the usage-amount of an electron-accepting dopant changes with kinds of material, it is preferable that it is 0.01 mass%-50 mass% with respect to hole transport layer material, and it is 0.05 mass%-20 mass%. It is further more preferable and it is especially preferable that it is 0.1 mass%-10 mass%.

The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 300 nm, and still more preferably 10 nm to 200 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 500 nm, more preferably 0.5 nm to 300 nm, and still more preferably 1 nm to 200 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .
In the present invention, a hydrocarbon compound such as an adamantane compound that is electrically inactive can be added to the hole transport layer by a method disclosed in JP-A-2005-294249 or the like for the purpose of improving luminous efficiency.
The T1 of the hole injection layer and the hole transport layer is not particularly limited, but the difference between the T1 of the hole transport layer adjacent to the light emitting layer and the T1 of the light emitting layer is within 1 eV for the purpose of suppressing exciton diffusion. Preferably there is.

(Electron injection layer)
The electron injection layer is a layer having a function of receiving electrons from the cathode. There is no limitation in particular as a material which can be used for the electron injection layer of this invention, A low molecular compound or a high molecular compound may be sufficient.
Specifically, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, Metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole as ligands, organosilane derivatives represented by siloles Body, or the like is preferably a layer containing.

The electron injection layer can contain an electron donating dopant. The electron donating dopant introduced into the electron injecting layer only needs to have an electron donating property and a property of reducing an organic compound, and includes alkali metals such as Li, alkaline earth metals such as Mg, and rare earth metals. Transition metals and reducing organic compounds are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
In addition, the materials described in JP-A-6-212153, JP-A-2000-196140, JP-A-2003-68468, JP-A-2003-229278, JP-A-2004-342614, and the like are used. Can be used.

  These electron donating dopants may be used alone or in combination of two or more. The amount of the electron-donating dopant used varies depending on the type of material, but is preferably 0.1% by mass to 30% by mass, and 0.1% by mass to 20% by mass with respect to the electron transport layer material. Is more preferable, and 0.1% by mass to 10% by mass is particularly preferable.

The thickness of the electron injection layer is preferably from 0.1 nm to 200 nm, more preferably from 0.2 nm to 100 nm, and even more preferably from 0.5 nm to 50 nm.
The electron injection layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

(Hole blocking layer)
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
The hole blocking function can be exhibited when the ionization potential of the hole blocking layer is larger than the ionization potential of the light emitting layer or the hole mobility of the hole blocking layer is smaller than the hole mobility of the light emitting layer.
Examples of the compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
In the present invention, an electrically inactive hydrocarbon compound such as an adamantane compound is added to the hole blocking layer by a method disclosed in Japanese Patent Application Laid-Open No. 2005-294248 for the purpose of further improving the light emission efficiency. Can do.
In the present invention, an exciton diffusion blocking layer may be provided between the electron transport layer and the light emitting layer. The exciton diffusion blocking layer can be installed for the purpose of suppressing the exciton from diffusing from the light emitting layer to the adjacent layer and lowering the light emission efficiency. The function can be exhibited by using a T1 of the exciton block layer larger than that of the light emitting layer.

(Electronic block layer)
The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as the organic compound layer adjacent to the light emitting layer on the anode side.
The electron blocking function can be exerted when the electron affinity of the electron blocking layer is smaller than the electron affinity of the light emitting layer or when the electron mobility of the electron blocking layer is smaller than the electron mobility of the light emitting layer.
As examples of the compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
In the present invention, an exciton diffusion blocking layer may be provided between the hole transport layer and the light emitting layer. The exciton diffusion blocking layer can be installed for the purpose of suppressing the exciton from diffusing from the light emitting layer to the adjacent layer and lowering the light emission efficiency. The function can be exhibited by using a T1 of the exciton block layer larger than that of the light emitting layer.

(Protective layer)
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ , TiO ₂ , metal nitrides such as SiN _x , SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ , CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerization, cyclic in the copolymer main chain Examples thereof include a fluorine-containing copolymer having a structure, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

(Sealing)
Furthermore, the organic electroluminescent element of this invention may seal the whole element using a sealing container.
It can also be sealed with an inorganic film such as SiN or SiON. Furthermore, solid sealing can be performed by a method disclosed in Japanese Patent Application Laid-Open No. 2003-203762.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide, and the like. The inert liquid is not particularly limited, and examples thereof include paraffins, liquid paraffins, fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether, chlorinated solvents, and silicone oils. Can be mentioned.

(Drive)
The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Can be obtained.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234585, The driving methods described in Japanese Patent No. 8-24047, Japanese Patent No. 2784615, US Pat. No. 5,828,429, Japanese Patent No. 6023308, and the like can be applied.
The element of the present invention can be heat-treated by a method disclosed in Japanese Patent Application No. 2008-48630 application specification and the like for the purpose of driving it more stably after the element is manufactured. Further, current processing can be performed by a method disclosed in Japanese Patent Application Laid-Open No. Hei 8-185579.
In the case of active driving by TFT, the TFT can use any of amorphous silicon, low-temperature polysilicon, and oxide semiconductor.

The light-emitting element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.
Further, the chromaticity can be further improved by installing a color filter or using a color conversion material.
In addition, light emitting materials of other colors can be added to the element of the present invention to reproduce other colors including white. In this case, the light emitting layer may be a single light emitting layer, a plurality of light emitting layers, or a multi-photon element.
The element of the present invention can reproduce many colors in combination with other pixels in the panel. In that case, three sub-pixels of red, green, and blue may be combined, and which color can be combined can be determined according to the purpose.
The panel driving method can be either active driving or passive driving. Either current driving or voltage driving can be used.

(Use of the present invention)
The organic electroluminescent element of the present invention can be suitably used for a display element, a display, a backlight, an electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, or optical communication.

  Examples of the organic electroluminescence device of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
1. Preparation of organic EL element 1) Preparation of comparative organic EL element 1 A 0.5 mm thick, 2.5 cm square glass substrate was placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. The following layers were deposited on this transparent anode by vacuum deposition. The vapor deposition rate in the examples of the present invention is 0.2 nm / second unless otherwise specified. The deposition rate was measured using a quartz resonator. The film thicknesses described below were also measured using a crystal resonator.

Anode: Indium Tin Oxide (abbreviated as ITO) was deposited on a glass substrate to a thickness of 100 nm.
Hole injection layer: 4,4 ′, 4 ″ -Tris (N- (2-naphthyl) -N-phenyl-amino) -triphenylamine (abbreviated as 2-TNATA) was deposited on ITO to a thickness of 40 nm. .
Hole transport layer: Bis [N- (1-naphthyl) -N-pheny] benzidine (abbreviated as α-NPD) was deposited on the hole injection layer to a thickness of 7 nm.
Second hole transport layer: The hole transport material 1 was deposited on the hole transport layer to a thickness of 3 nm.
Light-emitting layer: abbreviated as tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ) which is a phosphorescent material of 10 mass% with respect to the host material 1 and the host material 1 on the second hole transport layer The light emitting layer doped with) was deposited to a thickness of 30 nm.

First electron transport layer: Bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolate) -aluminum (III) (abbreviated as BAlq) as a first electron transport layer on the light-emitting layer has a thickness of 10 nm. Vapor deposited.
Second electron transport layer: 2,9-dimethyl-4,7-diphenyl-1,10-phenthroline (abbreviated as BCP) was deposited as a second electron transport layer on the first electron transport layer to a thickness of 30 nm.
Electron injection layer: LiF was deposited on the second electron transport layer to a thickness of 1 nm.
Cathode: A patterned mask (a mask having a light emitting area of 2 mm × 2 mm) was placed on the electron injection layer, and metal aluminum was deposited to 100 nm to form a cathode.

The produced laminate was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.).
In this way, a comparative organic EL element 1 was produced.

2) Production of Comparative Organic EL Element 2 An organic EL element produced in the same manner as the production of comparative organic EL element 1 was subjected to heat treatment in an oven at 85 ° C. for 24 hours to produce comparative organic EL element 2. did.

3) Production of Comparative Organic EL Element 3 The organic EL element produced in the same manner as the comparative organic EL element 1 was subjected to energization treatment at a current density of 10 mA / cm ² for 24 hours, and the comparative organic EL element 3 was produced. Was made.

4) Production of comparative organic EL element 4 In production of comparative organic EL element 1, as the second electron transporting layer, BCP was 0.2 nm / second and Li was 30 nm by co-evaporation at a deposition rate of 0.15 nm / min. A comparative organic EL element 4 was produced in the same manner as the production of the comparative organic EL element 1 except that the film was formed.

5) Production of Comparative Organic EL Element 5 The production of the comparative organic EL element 4 was the same as the production of the comparative organic EL element 4 except that Bathphenathhroline (abbreviated as Bphen) was used instead of BCP. Preparation of the comparative organic EL element 5 was produced.

6) Preparation of comparative organic EL element 6 Comparative organic EL element 6 was manufactured in the same manner as comparative organic EL element 5 except that Cs was used instead of Li in the preparation of comparative organic EL element 5. Produced.

7) Preparation of organic EL element 1 of the present invention An organic EL element manufactured in the same manner as the comparative organic EL element 4 was heat-treated in an oven at 85 ° C. for 24 hours, and the organic EL element of the present invention was then prepared. Element 1 was produced.

8) Production of Organic EL Element 2 of the Present Invention An organic EL element produced in the same manner as the production of the comparative organic EL element 4 was subjected to energization treatment at a current density of 10 mA / cm ² for 24 hours. The organic EL element 2 was produced.

9) Preparation of organic EL element 3 of the present invention An organic EL element manufactured in the same manner as the comparative organic EL element 5 was subjected to heat treatment in an oven at 85 ° C. for 24 hours to obtain the organic EL element of the present invention. Element 3 was produced.

10) Production of organic EL element 4 of the present invention An organic EL element produced in the same manner as the production of the comparative organic EL element 5 was subjected to an energization treatment at a current density of 10 mA / cm ² for 24 hours. The organic EL element 4 was produced.

11) Production of organic EL element 5 of the present invention The production of comparative organic EL element 4 was the same as that of comparative organic EL element 4 except that the following platinum complex 1 was used instead of Ir (ppy) ₃ in the production of comparative organic EL element 4. The organic EL device produced as described above was subjected to a heat treatment at 85 ° C. for 24 hours in an oven to produce the organic EL device 5 of the present invention.

12) Production of Organic EL Element 6 of the Present Invention The organic EL element 6 of the present invention was produced by subjecting the comparative organic EL element 6 to heat treatment at 50 ° C. for 72 hours in an oven.

13) Preparation of organic EL element 7 of the present invention In preparation of comparative organic EL element 4, platinum complex 1 was used instead of Ir (ppy) ₃ , and BCP and Li of the second electron transport layer were co-evaporated. At that time, the organic EL element 7 of the present invention was prepared in the same manner as the comparative organic EL element 4 except that the film was formed while heating the glass substrate to about 50 ° C. by infrared rays through the co-evaporation step. did.

2. Performance Evaluation About the obtained organic EL device of the present invention and the comparative organic EL device, the driving voltage, the external quantum efficiency, and the driving durability were examined according to the following.
1) Driving voltage Using a source measure unit 2400 manufactured by Toyo Technica Co., Ltd., a DC voltage was applied to each element to emit light. The voltage when the luminance was 1000 cd / m ² was measured as the driving voltage. The driving voltage of the comparative organic EL element 1 is set to 100, and the relative value is shown.
2) External quantum efficiency Using a source measure unit 2400 manufactured by Toyo Technica Co., Ltd., a direct current voltage was applied to each element to emit light. The brightness was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Based on these numerical values, the external quantum efficiency at a luminance of 1000 cd / m ² was calculated by a luminance conversion method. The external quantum efficiency of the comparative organic EL element 1 is set as 100, and the relative value is shown.
3) driving durability: a luminance half-life each element by applying a DC voltage so that the luminance 1000 cd / ^{m 2,} the luminance was measured the time until 500 cd / ^{m 2} is continuously driven. The relative half-life time of the comparative organic EL element 1 is taken as 100, and the relative value is shown.
The obtained results are shown in Table 1.

From the results shown in Table 1, when the comparative organic EL element 1 in which the electron transporting layer is not doped without heat treatment and energization is used as a reference, the driving durability is improved in the comparative organic EL element 2 in which only the heat treatment is performed without doping. However, the driving voltage has increased and the external quantum efficiency has decreased. In the comparative organic EL element 3 in which only the energization treatment was performed without doping, the driving durability deteriorated, the driving voltage increased, the external quantum efficiency decreased, and the element performance deteriorated.
Although the electron transport layer was doped with Li, the comparative organic EL element 4, element 5 and element 6, which were not subjected to heat treatment or current application treatment, showed a decrease in driving voltage and an improvement in driving durability, but the effect was small. And the external quantum efficiency has fallen.
The organic EL elements 1 to 7 of the present invention in which the electron transport layer is doped with Li and subjected to the heat treatment or the energization treatment can further reduce the driving voltage and improve the driving durability than the comparative organic EL elements 4 and 5. In addition, the external quantum efficiency was greatly improved as compared with the comparative organic EL elements 4 and 5, and the element performance was greatly improved.

Claims (10)

A method for producing an organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic layers is at least one kind of alkali metal, alkaline earth metal, or an organic layer containing the salts thereof, the alkali metal, after deposition of an alkaline earth metal, or an organic layer containing the salts thereof, at a current density of 0.1mA ^/ cm ² ~10mA ^/ cm 2 The manufacturing method of the organic electroluminescent element characterized by having an electricity supply process process which performs an electricity supply process. The at least one kind of alkali metal, alkaline earth metal, or salt thereof contains at least one selected from the group consisting of Li, Na, K, Ca, and Sr. The manufacturing method of the organic electroluminescent element of description. The method of manufacturing an organic electroluminescent element according to claim 2, wherein the at least one alkali metal or alkaline earth metal, or a salt thereof contains Li. The concentration of the alkali metal or alkaline earth metal, or salt thereof in the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is 0.01% by mass to the organic material in the organic layer. It is 10 mass%, The manufacturing method of the organic electroluminescent element of any one of Claims 1-3 characterized by the above-mentioned. The organic layer containing the alkali metal, alkaline earth metal, or salt thereof contains at least one kind of electron transporting material, according to any one of claims 1 to 4. The manufacturing method of the organic electroluminescent element of description. 6. The method of manufacturing an organic electroluminescent element according to claim 5, wherein the electron transporting material is an organic material. An organic electroluminescent element having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic layers is at least one kind of alkali metal, alkaline earth metal, or salt thereof An organic layer containing at least the alkali metal, alkaline earth metal, or salt thereof is 0.1 mA / cm. ² -10 mA / cm ² An organic electroluminescent element characterized by being a layer that has been subjected to an energization treatment at a current density of 5 μm. The organic electroluminescent element according to claim 7, wherein the organic layer containing the alkali metal, alkaline earth metal, or salt thereof is an electron transport layer. The organic electroluminescence device according to claim 8, wherein the electron transport layer contains a phenanthroline derivative as an electron transport material. The second electron transporting layer not containing an alkali metal, an alkaline earth metal, or a salt thereof is provided between the electron transporting layer and the light emitting layer. Organic electroluminescent device.