JPH04332787A - Organic electroluminescent element - Google Patents

Abstract

PURPOSE:To obtain an element having a light emitting layer composed of a compound assuming light emission of specific blue to bluish green and an adhesive layer composed of a metallic complex of 8-hydroxyquinoline (derivative) and capable of improving luminous homogeneity and suppressing deterioration of initial brightness. CONSTITUTION:The objective element having a light emitting layer composed of a compound, expressed by formula I (R<1> to R<4> are H, 1-6C alkyl, 1-6C alkoxy, 7-8C aralkyl, etc.), the formula A-Q-B (A and B are monofunctional group obtained by removing one H from the compound expressed by formula I; Q is bifunctional group cutting a conjugated system) or formula II [A<1> is (substituted) 6-20C arylene or bifunctional aromatic heterocyclic group; A<2> is (substituted) 6-20C aryl or monofunctional aromatic heterocyclic group; R<5> and R<6> are H, (substituted) 6-20C aryl, cyclohexyl, etc.] and assuming light emission of blue, greenish blue to bluish green and an adhesive layer, composed of a metallic complex of 8-hydroxyquinoline (derivative) and having a smaller thickness than that of the light emitting layer.

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device, and more particularly to an organic electroluminescent device that improves the uniformity of light emission and suppresses a decrease in initial brightness.

0001

[Prior Art and Problems to be Solved by the Invention] Electroluminescent elements (EL elements) have the characteristics of being highly visible due to their self-luminescence, being completely solid-state elements, and having excellent impact resistance. Therefore, various devices using inorganic and organic compounds are currently being proposed and attempts are being made to put them into practical use. Among these devices, organic EL devices can significantly reduce the applied voltage, and therefore various materials and devices are being developed. Regarding the structure of the organic EL element, it is known that the basic structure is an anode/emitting layer/cathode, and a hole injection layer and an electron injection layer are provided as necessary to improve the light emission performance. In such a device configuration, the cathode must have sufficient adhesion to the light emitting layer. If this adhesion is not sufficient, the mechanical strength will be reduced, resulting in non-uniform light emission or, in the worst case, non-emissive areas. Furthermore, the load within the light emitting surface becomes uneven,
This becomes a factor that accelerates deterioration and shortens the lifespan, which poses a problem for practical use.

Conventionally, a technique is known in which an electron injection layer or a hole barrier layer is provided between a light emitting layer and a cathode as necessary. In these technologies, especially when providing the latter layer, it is determined by the difference in energy level from the light emitting layer.
Materials must comply with this concept. For example, "a hole blocking layer (hole blocking layer) having a first oxidation potential that is 0.1 V or more higher than the first oxidation potential of the light emitting layer is provided between the light emitting layer and the cathode" (Japanese Unexamined Patent Publication No. 195683/1999). One example is technology. JP-A-2-195683 and JP-A-2-195683
In Publication No. 255788, an 8-hydroxyquinoline derivative is used as a hole blocking layer based on the above concept, but the luminous efficiency in blue is 0.3 (lm・W-1).
This is still low. On the other hand, patent application No. 2-242669
When the material described in the publication and Japanese Patent Application No. 2-279304 is used in the light-emitting layer, it is possible to obtain high-intensity light emission in the blue range, which will be effective in the future for full-color flat panel displays, etc. It can be mentioned as a material. However, when these materials are used to create devices with the above-mentioned configurations such as anode/emissive layer/cathode/anode/hole injection layer/emissive layer/cathode, uneven light emission or non-emissive areas may occur. This has caused problems in terms of device lifespan, microfabrication, etc. for practical application.

0003

[Means for solving the problem] Therefore, the present inventors
While maintaining the characteristics of conventional EL elements, as a result of intensive studies on the degree of adhesion between the emissive layer and the cathode, we found that by providing a layer (adhesive layer) between the emissive layer and the cathode to improve adhesion, the color of the emitted light can be changed. It has been found that an EL element with improved luminous uniformity and luminous efficiency can be obtained without any change.

The present invention was completed based on this knowledge. That is, the present invention provides anode/emitting layer/adhesive layer/
A cathode or an anode/hole injection layer/light emitting layer/adhesive layer/cathode are laminated in this order, and the light emitting layer is represented by the general formula (I).

00
05]

[C4]

(In the formula, R1 to R4 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, a substituted or unsubstituted group having 6 carbon atoms) ~18 aryl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted carbon number 6
-18 aryloxy group and a C1-6 alkoxy group. Here, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or a C 1 to 6 alkyl group.
-6 acyl group, C1-6 acyloxy group, carboxyl group, styryl group, C6-20 arylcarbonyl group, C6-20 aryloxycarbonyl group, C1-6 alkoxycarbonyl group group, vinyl group, anilinocarbonyl group, carbamoyl group, phenyl group, nitro group, hydroxyl group, or halogen. These substituents may be single or multiple. Also, R1 to R4
may be the same or different from each other, R1
and R2 and R3 and R4 may be bonded to mutually substituting groups to form a substituted or unsubstituted saturated five-membered ring or a substituted or unsubstituted saturated six-membered ring. Ar represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and may be singly substituted or multiply substituted, and the bonding site may be any of ortho, para, and meta. However, when Ar is unsubstituted phenylene, R1 to R
4 is an alkoxy group having 1 to 6 carbon atoms, and 7 carbon atoms, respectively.
~8 aralkyl groups, substituted or unsubstituted naphthyl groups, biphenyl groups, cyclohexyl groups, and aryloxy groups. ), general formula (II)

[0007]

[C5]

(wherein, A and B each represent a monovalent group obtained by removing one hydrogen atom from the compound represented by the above general formula (I), and may be the same or different. Q
indicates a divalent group that breaks a conjugated system. ) or general formula (III)

[0009]

[C6]

(In the formula, A1 represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a divalent aromatic heterocyclic group. The bonding position may be ortho, meta, or para. A2 is Represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a monovalent aromatic heterocyclic group.R5
and R6 are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyclohexyl group, a monovalent aromatic heterocyclic group, an alkyl group having 1 to 10 carbon atoms,
It represents an aralkyl group having 7 to 20 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Note that R5 and R6 may be the same or different. Here, the substituent means, in the case of a single substitution,
It is an alkyl group, an aryloxy group, an amino group, or a phenyl group with or without a substituent. Each substituent of R5 may be combined with A1 to form a saturated or unsaturated five- or six-membered ring, and similarly each substituent of R6 may be combined with A2 to form a saturated or unsaturated five- or six-membered ring. A five-membered ring or a six-membered ring may be formed. Moreover, Q represents a divalent group that breaks conjugation. ) and exhibits blue, verdigris, or blue-green luminescence, and the adhesive layer is composed of a metal complex of 8-hydroxyquinoline or its derivative, and its thickness is thinner than the thickness of the luminescent layer. The present invention provides an organic electroluminescent device characterized by the following.

The organic EL device of the present invention is characterized by being laminated in the order of anode/emissive layer/adhesive layer/cathode, or anode/hole injection layer/emissive layer/adhesive layer/cathode as described above. do. As the anode in this EL element, an electrode material made of a metal, alloy, electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and dielectric transparent materials such as CuI, ITO, SnO2, and ZnO. The anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. When emitting light from this electrode, it is desirable that the transmittance be greater than 10%, and the sheet resistance of the electrode is preferably several hundred Ω/□ or less. Furthermore, the film thickness depends on the material, but is usually 10 nm to 1 μm, preferably 10 to 200 nm.
selected within the range.

On the other hand, as a cathode, a cathode with a small work function (
(4 eV or less) metals, alloys, electrically conductive compounds, and mixtures thereof are used as electrode materials. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, Al/(Al2O3), indium, and the like. The cathode can be manufactured by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Further, the sheet resistance of the electrode is preferably several hundred Ω/□ or less, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. In addition, in this EL element, either the anode or the cathode is transparent or semitransparent.
Since the light is transmitted, the light emission efficiency is high and convenient.

Next, the light-emitting layer in the above EL element has the same functions as normal light-emitting layers: (1) injection function (holes can be injected from the anode or hole injection layer when voltage is applied; and the cathode or electron injection layer). It is possible to inject more electrons.),■
Has a transport function (holes and electrons can be moved by the force of an electric field), and a light-emitting function (can provide a field for holes and electrons to recombine and emit light). It is something. The thickness of this layer is not particularly limited and can be selected depending on the situation, preferably 1 nm to 10 μm.
m, particularly preferably from 5 nm to 5 μm. Specific examples of this light-emitting layer include the above general formula (I) and general formula (II).
) or a compound represented by general formula (III).

Here, R1 to R4 in general formula (I)
may be the same or different as mentioned above, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i
-butyl group, sec -butyl group, tert-butyl group, isopentyl group, t-pentyl group, neopentyl group,
isohexyl group), alkoxy groups having 1 to 6 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, etc.),
Aralkyl groups with 7 to 8 carbon atoms (benzyl group, phenethyl group, etc.), aryl groups with 6 to 18 carbon atoms (phenyl group, biphenyl group, naphthyl group, etc.), cyclohexyl groups, aryloxy groups with 6 to 18 carbon atoms ( (phenoxy group, biphenyloxy group, naphthyloxy group, etc.).

[0015] R1 to R4 may also have substituents bonded to them. That is, R1 to R4 each represent a substituent-containing phenyl group, a substituent-containing aralkyl group, a substituent-containing cyclohexyl group, a substituent-containing biphenyl group, and a substituent-containing naphthyl group. Here, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 1 to 6 carbon atoms. group, carbon number 1-6
Acyloxy group, carboxyl group, styryl group, arylcarbonyl group having 6 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms, alkoxycarbonyl group having 1 to 6 carbon atoms, vinyl group, anilinocarbonyl group, carbamoyl group group, phenyl group, nitro group, hydroxyl group, or halogen, and may be multiply substituted. Therefore, for example, substituent-containing aralkyl groups include alkyl group-substituted aralkyl groups (methylbenzyl group, methylphenethyl group, etc.), alkoxy group-substituted aralkyl groups (methoxybenzyl group, ethoxyphenethyl group, etc.), aryloxy group-substituted aralkyl groups ( phenoxybenzyl group, naphthyloxyphenethyl group, etc.), phenyl group-substituted aralkyl group (
(phenylphenethyl group, etc.) The above substituent-containing phenyl group includes alkyl group-substituted phenyl group (tolyl group, dimethylphenyl group, ethylphenyl group, etc.), alkoxy group-substituted phenyl group (methoxyphenyl group, ethoxyphenyl group, etc.), aryloxy group It is a substituted phenyl group (phenoxyphenyl group, naphthyloxyphenyl group, etc.) or a phenyl group substituted with phenyl group (that is, biphenylyl group). In addition, the substituent-containing cyclohexyl group is an alkyl group-substituted cyclohexyl group (methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, etc.), an alkoxy group-substituted cyclohexyl group (methoxycyclohexyl group, ethoxycyclohexyl group, etc.), or an aryloxy group-substituted cyclohexyl group. (phenoxycyclohexyl group, naphthyloxycyclohexyl group), phenyl group-substituted cyclohexyl group (phenylcyclohexyl group). A naphthyl group containing a substituent is an alkyl group-substituted naphthyl group (methylnaphthyl group, dimethylnaphthyl group, etc.)
, alkoxy-substituted naphthyl group (methoxynaphthyl group,
(ethoxynaphthyl group, etc.), aryloxy-substituted naphthyl group (phenoxynaphthyl group, naphthyloxynaphthyl group), or phenyl-substituted naphthyl group. R1
-R4 is preferably an alkyl group having 1 to 6 carbon atoms, an aryloxy group, a phenyl group, a naphthyl group, a biphenyl group, or a cyclohexyl group among those mentioned above. These may be substituted or unsubstituted. Also,
R1 to R4 may be the same or different from each other, and R1 and R2 and R3 and R4 are bonded to mutually substituted groups to form a substituted or unsubstituted 5-membered ring or a substituted or unsubstituted saturated ring. It may also form a six-membered ring.

On the other hand, Ar in the general formula (I) represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and substituted or unsubstituted phenylene group, biphenylene group, p-
Terphenylene group, naphthylene group, terphenylene group,
It is an arylene group such as naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, phenalenediyl group, and may be unsubstituted or substituted. Further, the bonding position of methylidine (=C=CH-) may be at any position such as ortho, meta, para, etc. However, when Ar is unsubstituted phenylene, R1 to R4 are alkoxy groups having 1 to 6 carbon atoms, aralkyl groups having 7 to 8 carbon atoms, substituted or unsubstituted naphthyl groups, biphenyl groups, cyclohexyl groups, or aryloxy groups. It is the chosen one. The substituent is an alkyl group (
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t
-butyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, i-propoxy group,
butyloxy group, i-butyloxy group, sec-butyloxy group, t-butyloxy group, isopentyloxy group, t-pentyloxy group), aryloxy group (phenoxy group, naphthyloxy group, etc.), acyl group (formyl group, acetyloxy group, etc.) group, propionyl group, butyryl group, etc.), acyloxy group, aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, hydroxyl group, carboxyl group, anilinocarbonyl group, carbamoyl group, aryloxycarbonyl group, methoxycarbonyl group, ethoxy These are carbonyl groups, butoxycarbonyl groups, nitro groups, and halogens, and may be singly or multiply substituted. The formula (I
The dimethylidine aromatic compound represented by ) has two methylidine (=C=CH-) units in one molecule,
The geometric isomerism of this methylidine unit allows four combinations: cis-cis, trans-cis, cis-
There are transformers and transformer-transformer combinations. The light-emitting layer of the present invention may be any of these or may be a mixture of geometric isomers. Particularly preferred are all trans-isomers. Further, the above substituents may be bonded together to form a substituted or unsubstituted saturated five-membered ring or six-membered ring.

A and B in the general formula (II) each represent a monovalent group obtained by removing one hydrogen atom from the compound represented by the above general formula (I), and may be the same or different. It is. Here, Q in general formula (II) represents a divalent group that cuts a conjugated system. Here, conjugation is due to the nonpolar nature of π electrons, and includes conjugated double bonds, unpaired electrons, or lone pairs of electrons. Specifically, Q is a divalent group obtained by removing one H atom from a straight chain alkane, for example,

[0018]

[C7]

[0019] etc. The reason for using a divalent group that cuts a conjugated system in this way is that A or B shown above (i.e., the compound of general formula (I)) can be used alone as the organic EL element of the present invention. The organic E of the present invention
This is to ensure that the EL emission color obtained when used as an L element does not change. In other words, this is to prevent the light-emitting layer represented by the general formula (I) or the general formula (II) from becoming shorter in wavelength or longer in wavelength. In addition, it was confirmed that the glass transition temperature (Tg) increases when connecting with a divalent group that cuts the conjugated system, and a uniform pinhole-free microcrystalline or amorphous thin film can be obtained, improving the uniformity of light emission. Improving. Furthermore, since they are bonded with a divalent group that breaks the conjugation system, they have the advantage that EL light emission does not have a longer wavelength and can be easily synthesized or purified.

In addition, A1 in the general formula (III) is an arylene group having 6 to 20 carbon atoms, a divalent aromatic heterocyclic group,
A2 represents an aryl group having 6 to 20 carbon atoms (phenyl group, biphenyl group, naphthyl group, etc.) or a monovalent aromatic heterocyclic group. R5 and R6 each represent a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyclohexyl group, a monovalent aromatic heterocyclic group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, , n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, etc.), carbon number 7 -20 aralkyl group (benzyl group, phenethyl group, etc.) or a C1-C10 alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.). Note that R5 and R6 may be the same or different. here,
In the case of single substitution, the substituent is an alkyl group, an aryloxy group, an amino group, or a phenyl group with or without a substituent. Each substituent of R5 may be combined with A1 to form a saturated or unsaturated five- or six-membered ring, and similarly R6
Each of the substituents may be combined with A2 to form a saturated or unsaturated five- or six-membered ring. Further, Q represents a divalent group that breaks conjugation as described above. Furthermore, in the present invention, the light-emitting layer represented by the above general formula (I), general formula (II), or general formula (III) is a compound that emits blue, green-blue, or blue-green light in CIE chromaticity coordinates. It is necessary. The method for forming the light emitting layer is as follows:
For example, it can be formed by forming a thin film by a known method such as a vapor deposition method, a spin coating method, a casting method, or an LB method, but a molecular deposition film is particularly preferable. Here, the molecular deposited film refers to a thin film formed by depositing the compound from a gas phase state, or a film formed by solidifying the compound from a solution state or liquid phase state, and usually this molecular deposited film can be distinguished from the thin film (molecular cumulative film) formed by the LB method based on differences in aggregated structure, higher-order structure, and functional differences resulting therefrom. In addition, as disclosed in Japanese Patent Application Laid-open No. 59-194393, the light-emitting layer can be formed by dissolving a binder such as a resin and the compound in a solvent to form a solution, and then using a spin coating method or the like. It is possible to form a thin film. The thickness of the light-emitting layer formed in this way is not particularly limited and can be selected depending on the situation, but is preferably 1.
The range is preferably from nm to 10 μm, particularly preferably from 5 nm to 5 μm.

As described above, the light-emitting layer of the present invention has an injection function capable of injecting holes from the anode or the hole injection layer and injecting electrons from the cathode or the electron injection transport layer when an electric field is applied. , injected charges (electrons and holes)
It has a transport function that moves electrons using the force of an electric field, and a light emitting function that provides a field for recombination of electrons and holes, which leads to light emission. Note that there may be a difference in the ease with which holes are injected and the ease with which electrons are injected. Further, although the transport function represented by the mobility of holes and electrons may be different in magnitude, it is preferable to move one or the other.

Next, although the hole injection layer in the present invention is not necessarily necessary for the present device, it is preferable to use it in order to improve the light emitting performance. This hole-injection layer is preferably a material that transports holes to the light-emitting layer at a lower electric field, and furthermore, if the hole mobility is at least 10-6 cm2 volts/cm at an electric field of 104-106 volts/cm. Even more preferred. For example, any material can be selected and used from among those conventionally used as charge injection and transport materials for holes in photoconductive materials and known materials used in hole injection layers of EL devices. .

As the hole injection layer, for example, triazole derivatives (see US Pat. No. 3,112,197, etc.), oxadiazole derivatives (US Pat. No. 3,189, etc.) can be used.
, 447, etc.), imidazole derivatives (see Japanese Patent Publication No. 37-16096, etc.), polyarylalkane derivatives (U.S. Pat. No. 3,615,402, U.S. Pat. No. 3,820,989, etc.), 3,542,
Specification No. 544, Japanese Patent Publication No. 45-555, No. 51
-10983 publication, JP-A-51-93224 publication,
No. 55-17105, No. 56-4148,
No. 55-108667, No. 55-156953, No. 56-36656, etc.), pyrazoline derivatives and pyrazolone derivatives (U.S. Pat. No. 3,180,
Specification No. 729, Specification No. 4,278,746,
JP-A No. 55-88064, JP-A No. 55-88065, JP-A No. 49-105537, JP-A No. 55-5108
Publication No. 6, Publication No. 56-80051, Publication No. 56-881
Publication No. 41, Publication No. 57-45545, Publication No. 54-11
(See Publication No. 2637, Publication No. 55-74546, etc.)
Phenyldiamine derivatives (U.S. Pat. No. 3,615,4
Specification No. 04, Japanese Patent Publication No. 51-10105, No. 4
6-3712, 47-25336, JP-A-54-53435, JP-A-54-110536, JP-A-54-119925, etc.), arylamine derivatives (U.S. Pat. No. 3,567, Specification No. 450, Specification No. 3,180,703, Specification No. 3,240,5
Specification No. 97, Specification No. 3,658,520, Specification No. 4,232,103, Specification No. 4,175,961
Specification of No. 4,012,376, Japanese Patent Publication No. 49-35702, Japanese Patent Publication No. 39-27577,
JP-A-55-144250, JP-A No. 56-11913
Publication No. 2, Publication No. 56-22437, West German Patent No. 1,
110,518, etc.), amino-substituted chalcone derivatives (see U.S. Pat. No. 3,526,501, etc.), oxazole derivatives (U.S. Pat. No. 3,257,
No. 203, etc.), styryl anthracene derivatives (see JP-A-56-46234, etc.)
, fluorenone derivatives (see JP-A-54-110837, etc.), hydrazone derivatives (US Pat. No. 3,717)
, 462 specification, JP-A-54-59143,
No. 55-52063, No. 55-52064, No. 55-46760, No. 55-85495, No. 57-11350, No. 57-148749
No. 2-311591, etc.), stilbene derivatives (JP-A No. 61-210363, No. 6)
No. 1-228451, No. 61-14642,
61-72255, 62-47646, 62-36674, 62-10652, 62-30255, 60-93445, 60-94462, 60-17474
9, No. 60-175052, etc.). Furthermore, as hole injection and transport materials, silazane derivatives (US Pat. No. 4,950,950), polysilane-based materials (JP-A-2-204,996) are used.
, aniline copolymers (Japanese Unexamined Patent Publication No. 2-282263), and conductive polymer oligomers, particularly thiophene oligomers, as disclosed in Japanese Patent Application No. 1-211399.

In the present invention, these compounds can be used as the hole injection layer, but the following porphyrin compounds (described in JP-A No. 63-2956965 etc.) and aromatic tertiary Amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-27033, JP-A-54-58)
No. 445, No. 54-149634, No. 54-
No. 64299, No. 55-79450, No. 55
-144250 publication, 56-119132 publication,
(See Japanese Patent Publication No. 61-295558, Japanese Publication No. 61-98353, Japanese Publication No. 63-295695, etc.), and it is particularly preferable to use the aromatic tertiary amine compound.

Representative examples of the porphyrin compounds include:
Porphine, 1,10,15,20-tetraphenyl-
21H,23H-porphine copper (II), 1,10,1
5,20-tetraphenyl 21H,23H-porphine cuprous(II), 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine, silicon phthalocyanine oxide, aluminum phthalocyanine chloride, phthalocyanine (metal-free) ), dilithium phthalocyanine, copper tetramethyl phthalocyanine, copper phthalocyanine, chromium phthalocyanine, zinc phthalocyanine, lead phthalocyanine, titanium phthalocyanine oxide, magnesium phthalocyanine, copper octamethyl phthalocyanine, etc. Further, as representative examples of the aromatic tertiary amine compound and styrylamine compound, N,N,N',N'-tetraphenyl-4
,4'-diaminophenyl,N,N'-diphenyl-N
, N'-di(3-methylphenyl)-4,4'-diaminobiphenyl (TPDA), 2,2-bis(4-di-p
-tolylaminophenyl)propane, 1,1-bis(4
-di-p-tolylaminophenyl)cyclohexane, N
, N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethyl Amino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N,N'-di(
4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-
Diaminodiphenyl ether, 4,4'-bis(diphenylamino)quadriphenyl, N,N,N-tri(
p-tolyl)amine, 4-(di-p-tolylamino)-
4'-[4(di-p-tolylamino)styryl]stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbenzene, N -phenylcarbazole, aromatic dimethylidine compounds, etc.

[0026] The hole injection layer in the EL element of the present invention is
The above compound can be formed into a film by a known thinning method such as a vacuum evaporation method, a spin coating method, a casting method, or an LB method. The film thickness of this hole injection layer is
Although there is no particular limitation, the thickness is usually 5 nm to 5 μm. This hole injection layer may be composed of a single layer made of one or more of these hole injection transport materials, or may be composed of a stack of hole injection layers made of a compound different from the hole injection layer. It may be something that has been done. Organic EL obtained by the present invention
In the element configuration of the device, it is preferable that a newly added layer (adhesive layer) that improves the adhesion between the emissive layer and the cathode be made of a material that has high adhesion to the emissive layer and the cathode. As a material for such an adhesive layer, a metal complex of 8-hydroxyquinoline or a derivative thereof can be used. Specifically, metal chelate oxinoid compounds that include chelates of oxine (generally 8-quinolinol or 8-hydroxyquinoline). Such compounds exhibit high levels of performance and are easily formed into thin film form. Examples of oxinoid compounds satisfy the following structural formula.

[0027]

[Chemical formula 8]

(In the formula, Mt represents a metal, n is an integer from 1 to 3, and each position of Z is independent, and in order to complete at least two or more fused aromatic rings, (Indicates the necessary atoms.) Here, the metal represented by Mt is
It can be a monovalent, divalent or trivalent metal, for example an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as magnesium or calcium, or an earth metal such as boron or aluminium. be. Any monovalent, divalent, or trivalent metal that is generally known to be a useful chelate compound can be used.

Further, Z represents an atom forming a heterocycle in which one of at least two condensed aromatic rings is azole or azine. Here, if necessary, it is possible to add other different rings to the fused aromatic ring. Also, to avoid adding bulky molecules without functional improvement, the number of atoms denoted by Z is 18.
It is preferable to maintain the following. Further, specific examples of chelated oxinoid compounds include tris(8-
quinolinol)aluminum, bis(8-quinolinol)magnesium, bis(benzo-8-quinolinol)zinc, bis(2-methyl-8-quinolinol)aluminum oxide, tris(8-quinolinol)indium,
Tris(5-methyl-8-quinolinol)aluminum, 8-quinolinollithium, tris(5-chloro-8
-quinolinol) gallium, bis(5-chloro-8-quinolinol)calcium, 5,7-dichloro-8-quinolinol aluminum, tris(5,7-dibromo-8
-hydroxyquinolinol) aluminum, etc. Further, the thickness of the adhesive layer needs to be thinner than the thickness of the light emitting layer, and is preferably 1 to 50 nm, particularly preferably 5 to 30 nm. The reason for limiting the film thickness in this manner is to maintain the emitted light color in the blue range.

[0030] Examples of methods for producing this adhesive layer include a spin coating method, a casting method, and a vapor deposition method. Preferably, the vapor deposition method is preferable as in the case of the light emitting layer and the hole injection layer described above. Here, examples of compounds used in the above-mentioned light-emitting layer are shown below.

[0031]

[Chemical formula 9]

[0032]

[Chemical formula 10]

[0033]

[Chemical formula 11]

[0034]

[Chemical formula 12]

[0035]

[Chemical formula 13]

[0036]

[Chemical formula 14]

[0037]

[Chemical formula 15]

[0038]

[Chemical formula 16]

[0039]

[Chemical formula 17]

[0040]

[Chemical formula 18]

[0041]

[Production method of 4,4'-bis(2,2'-diphenylvinyl)biphenyl]

(2) Production of arylene group-containing phosphorus compound 9.0 g of 4,4'-bis(bromomethyl)biphenyl and 11 g of triethyl phosphite were heated and stirred at a temperature of 140 DEG C. for 6 hours in an oil bath under an argon stream. Thereafter, excess triethyl phosphite and by-produced ethyl bromide were distilled off under reduced pressure. After standing overnight, 9.5 g of white crystals (yield: 8
0%) was obtained. The results of this analysis are as follows. Melting point: 97.0-100.0°C Proton nuclear magnetic resonance [1H-NMR (CDCl3)
Measurement by: δ = 7.3 to 8.4 ppm (m; 8H, biphenylene ring-H) δ = 4.1 ppm (d; 4H, J = 20
Hz (31P- 1H coupling) P-CH2 δ=3.7ppm (q; 8H, ethoxy group methylene-
CH2) δ=1.0ppm (t; 12H, ethoxy group methyl-CH3) From the above results, the above product has the following formula

[0042]

[Chemical formula 19]

It was confirmed that the compound was an arylene group-containing phosphorus compound (phosphonate: Mw=454.5) represented by the following formula.

(2) Preparation of aromatic dimethylidine compound 4.5 g of the phosphonate obtained in Reference Example 1 (2) and 5.5 g of benzophenone were dissolved in 100 ml of dimethyl sulfoxide, and 2.5 g of potassium t-butoxide was dissolved therein.
After adding 2 g of the mixture and stirring at room temperature under an argon atmosphere for 4 hours, it was left to stand overnight. 100 ml of methanol was added to the resulting mixture, and the precipitated crystals were filtered. The filtered product was diluted three times with 100 ml of water, followed by 1 ml of methanol.
The mixture was thoroughly washed three times with 0.00 ml, and column purification was performed to obtain 2.0 g of yellow-orange powder (yield: 26%). The results of this analysis are as follows. Melting point: 204.5-206.5°C Measurement by 1H-NMR (CDCl3): δ = 6.7
~7.3ppm (m; 30H, terminal phenyl ring -H
, central biphenylene and methylidine =C=CH-
) Elemental analysis value: The composition formula C40H30 is as follows. Note that the values in parentheses are theoretical values. C: 94.23% (94.08%) H: 5.8
4% (5.92%)N: 0.00% (
0%) Also, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. νC=C 1520, 1620cm-1 Also, from the mass spectrum, the molecular ion peak of the target object m/
Z=510 was detected. From the above, the above product, pale yellow powder, can be obtained by the following formula:

[0045]

[C20]

4,4'-bis(2,2'-
It was confirmed to be diphenylvinyl)biphenyl.

Reference Example 2 [Production method of 4,4'-bis(2,2'-di(4-t-butylphenyl)vinyl)biphenyl] ■Production of arylene group-containing phosphorus compound Same as Reference Example 1■ . ■Production of aromatic dimethylidine compound 1.8g of the phosphonate obtained in Reference Example 2■ above and 4,
2.4 g of 4'-di-t-butylbenzophenone was dissolved in 100 ml of dimethyl sulfoxide, 1.0 g of potassium t-butoxide was added thereto, the mixture was stirred at room temperature under an argon atmosphere for 4 hours, and then left overnight. did. 100 ml of methanol was added to the resulting mixture, and the precipitated crystals were filtered. The filtered product was thoroughly washed three times with 100 ml of water and then three times with 100 ml of methanol, and column purification was performed to obtain 1.0 g of pale yellow powder.
was obtained (yield 35%). The results of this analysis are as follows. Melting point: 293.0-296.0°C 1H-NMR (CDCl3) δ = 7.0-7.4 ppm (m; 24H, terminal phenyl ring-H, central biphenylene-H) δ = 6.9 ppm (s; 2H , methylidine =C=CH-) δ=1.3ppm (s;36H,t-
Butyl group -C(CH3)3) Elemental analysis value: Compositional formula C56H62 is as follows. Note that the values in parentheses are theoretical values. C: 91.42% (91.50%) H: 8.4
5% (8.50%)N: 0.00% (
0%) Also, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. νC=C 1520, 1610cm-1 Also, from the mass spectrum, the molecular ion peak of the target object m/
Z=734 was detected. From the above, the above product, pale yellow powder, can be obtained by the following formula:

[0048]

[C21]

4,4'-bis(2,2'-
It was confirmed to be di(4-t-butylphenyl)vinyl)biphenyl.

Reference Example 3 [4,4'-bis(2-(4-t-butylphenyl)-
Production method of 2-phenylvinyl)biphenyl] (1) Production of arylene group-containing phosphorus compound Same as Reference Example 1 (2). ■Production of aromatic dimethylidine compound 3.0g of phosphonate obtained in Reference Example 3■ above and 4-
Dissolve 4.1 g of t-butylbenzophenone in 100 ml of dimethyl sulfoxide, and add potassium-
1.5 g of t-butoxide was added, and the mixture was stirred at room temperature for 4 hours under an argon atmosphere, and then left overnight. 100 ml of methanol was added to the resulting mixture, and the precipitated crystals were filtered. The filtered product was mixed with 100 ml of water three times.
Subsequently, the mixture was thoroughly washed three times with 100 ml of methanol, and column purification was performed to obtain 1.8 g of pale yellow powder (yield: 38%). The results of this analysis are as follows. Melting point: 202.0-204.0°C 1H-NMR (CDCl3) δ = 7.0-7.4 ppm (m; 26H, terminal phenyl ring-H, center biphenylene-H) δ = 6.9 ppm (s; 2H , methylidine =C=CH-) δ=1.3ppm (s;18H,t-
Butyl group -C(CH3)3) Elemental analysis value: Compositional formula C48H46 is as follows. Note that the values in parentheses are theoretical values. C: 92.38% (92.56%) H: 7.1
8% (7.44%)N: 0.00% (
0%) Also, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. νC=C 1520, 1610cm-1 Also, from the mass spectrum, the molecular ion peak of the target object m/
Z=622 was detected. From the above, the yellow-orange powder that is the above product can be obtained by the following formula:

[0051]

[C22]

4,4'-bis(2-(4-
It was confirmed to be t-butylphenyl)-2-phenylvinyl)biphenyl.

Reference Example 4 (Production of 4,4'-bis(2,2'-di-p-tolylvinyl)biphenyl) (1) Production of arylene group-containing phosphorus compound Same as Reference Example 1 (2). ■Production of aromatic dimethylidine compound 4.0 g of the phosphonate obtained in Reference Example 4■ above and 4,
5.0 g of 4'-dimethylbenzophenone was dissolved in 60 ml of tetrahydrofuran, 2.0 g of potassium t-butoxide was added, the mixture was stirred under reflux under an argon atmosphere, and then left overnight. After distilling off the solvent of the resulting mixture, 200 ml of methanol was added, and the precipitated crystals were filtered. The filtered product was then diluted three times with 100 ml of water, followed by 3 times with 100 ml of methanol.
After thorough washing twice and recrystallization from benzene, 1.0 g of pale yellow powder was obtained (yield 22%). The melting point of this product was 153-155°C. Also, 1 of this powder
The H-NMR analysis results are as follows. 1H-NMR (CDCl3) δ = 6.3 to 7.3 ppm (m; 26H, aromatic ring -
H and methylidine CH=C-) δ=1.0 to 2.0 ppm (s; 12H, p-tolylmethyl group -CH3) Further, the elemental analysis results are as follows for the composition formula C44H38. Note that the values in parentheses are theoretical values. C: 93.10% (93.24%) H: 7.0
4% (6.76%)N: 0.00% (
0%) Also, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. νC=C 1520, 1610cm-1 Also, from the mass spectrum, the molecular ion peak m of the target object
/Z=566 was detected. From the above, the above product, pale yellow powder, can be obtained by the following formula:

[0054]

[C23]

4,4'-bis(2,2'-
It was confirmed to be di-p-tolylvinyl)biphenyl.

Reference Example 5 [Production of 4,4'-bis(2,2'-di-p-methoxyphenylvinyl)biphenyl] (1) Production of arylene group-containing phosphorus compound Same as in Reference Example 1 (2). ■Production of aromatic dimethylidine compound 3.0 g of the phosphonate obtained in Reference Example 5■ above and 4,
4.8 g of 4'-di-methoxybenzophenone was dissolved in 100 ml of dimethyl sulfoxide, 1.5 g of potassium t-butoxide was added thereto, the mixture was stirred at room temperature under an argon atmosphere for 4 hours, and then left overnight. 100 ml of methanol was added to the resulting mixture, and the precipitated crystals were filtered. The filtered product was thoroughly washed three times with 100 ml of water and then three times with 100 ml of methanol, and purified by column to obtain 1.1 g of yellow-green powder (yield: 26%). The results of this analysis are as follows. Melting point: 218-218.5°C 1H-NMR (CDCl3) δ = 6.7-7.3 ppm (m; 26H, terminal phenyl ring -H, central biphenylene-H, methylidine
=C=CH-) δ=3.8ppm (s; 12H, terminal methoxy-OCH3) Elemental analysis value: The compositional formula C44H38O4 is as follows. Note that the values in parentheses are theoretical values. C: 83.51% (83.78%) H: 5.8
9% (6.07%)N: 0.00% (
0%) Also, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. νC=C 1520, 1620cm-1 Also, from the mass spectrum, the molecular ion peak of the target object m/
Z=630 was detected. From the above, the yellow-green powder that is the above product can be obtained by the following formula:

[0057]

[C24]

4,4'-bis(2,2'-
It was confirmed to be di-p-methoxyphenylvinyl)biphenyl.

Reference Example 6 [Production method of 3,3'-dimethyl-4,4'-bis(2,2'-diphenylvinyl)biphenyl] ■ Production of arylene group-containing phosphorus compound 3,3'-dimethyl-4, 4'-bis(bromomethyl)
12 g of biphenyl and 12 g of triethyl phosphite were heated and stirred at a temperature of 130° C. for 6 hours in an oil bath under an argon stream. Thereafter, excess triethyl phosphite and by-produced ethyl bromide were distilled off under reduced pressure. After standing overnight, the obtained white crystals were recrystallized from benzene-hexane to obtain 15.2 g of white crystals (yield 97%). The results of this analysis are as follows. Melting point: 90.5-91.5°C 1H-NMR (CDCl3) δ = 7.2 ppm (s; 6H, biphenyl ring-H)
δ=3.1ppm (d; 4H, J=20Hz (31
P- 1H coupling) P-CH2) δ=4.0ppm (q; 8H, ethoxy group methylene-
CH2) δ=1.2ppm (t; 12H, ethoxy group methyl-
CH3) δ=2.5ppm (s; 6H, methyl-CH3 of biphenyl ring) From the above results, it was confirmed that the above-mentioned product was an arylene group-containing phosphorus compound (phosphonate) represented by the following formula. .

[0060]

[C25]

■Preparation of aromatic dimethylidine compound 0.75 g of the phosphonate obtained in Reference Example 6■ and 0.6 g of benzophenone were dissolved in 100 ml of dimethyl sulfoxide, and 0.0 ml of potassium t-butoxide was dissolved in this.
．． After adding 35 g of the mixture and stirring at room temperature under an argon atmosphere for 4 hours, it was left to stand overnight. Add 10 methanol to the resulting mixture
0 ml was added and the precipitated crystals were filtered. The filtered product was thoroughly washed three times with 100 ml of water and then three times with 100 ml of methanol, and column purification was performed to obtain 0.45 g of pale yellow powder (yield: 54%). The results of this analysis are as follows. Melting point: 201.8-202.8°C 1H-NMR (CDCl3) δ = 6.9-7.3 ppm (m; 26H, terminal phenyl ring-H, central biphenylene-H) δ = 6.8 ppm (s; 2H , methylidine =C=CH-) δ=2.2ppm (s; 6H, central biphenylene-CH3) Elemental analysis value: Compositional formula C42H34 is as follows. Note that the values in parentheses are theoretical values. C: 93.54% (93.64%) H: 6.2
2% (6.36%)N: 0.00% (
0%) Also, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. νC=C 1520, 1610cm-1 Also, from the mass spectrum, the molecular ion peak of the target object m/
Z=538 was detected. From the above, the above product, pale yellow powder, can be obtained by the following formula:

[0062]

[C26]

3,3'-dimethyl-4,4 represented by
It was confirmed to be '-bis(2,2'-diphenylvinyl)biphenyl.

Reference example 7■

[0065]

[C27]

[0066]

[C28]

11.2 g (0.037 mol) of O,O-diethyldiphenylmethylphosphonate and 4-methyl-
7.2 g (0.036 mol) of 4'-formyl biphenyl was dissolved in anhydrous dimethyl sulfoxide 2 under a stream of argon gas.
00 ml, and 4.1 g (0.036 mol) of potassium t-butoxide was added. Then, after stirring at room temperature for 6 hours, 200 ml of methanol was added, and 8.0 g of white powder was precipitated (yield: 64%).
) was obtained. This compound has a melting point of 128.0-129.0
It was ℃. 1H-NMR of the product is as follows. 1H-NMR (CDCl3) δ = 6.8 to 7.4 ppm (m; 19H, aromatic ring -
H and methylidine -CH=C=) δ=2.3ppm (s; 3H, methyl group -CH3)

[0068]■

[0069]

[C29]

6.5 g of the compound obtained in Reference Example 7■ above
(0.018 mol) and N-bromosuccinimide3.
5g (0.019 mol) and 0.7g benzoyl peroxide
was suspended in 150 ml of carbon tetrachloride and heated to an external temperature of 10
The mixture was stirred vigorously at 0°C. After stirring under reflux for 4 hours, the solvent was distilled off to obtain 10 g of pale yellow powder. This was purified by silica gel column (solvent: methylene chloride) to obtain 5.3 g of white powder (yield: 70%). The melting point of this compound was 127.0-128.0°C. Product 1H-
NMR is as follows. 1H-NMR (CDCl3) δ=7.6-6.9ppm (m; 19H, aromatic ring -
H and methylidine-CH=C=) δ=4.5ppm (s;2H, bromomethyl-CH2
Br)

0071]■

[0072]

[C30]

5.3 g of the compound obtained in Reference Example 7■ above
(0.0125 mol) to triethyl phosphite 13.0
g (0.079 mol) was added thereto, and the mixture was heated and stirred at 110° C. for 6 hours under an argon gas atmosphere. After standing overnight, excess triethyl phosphite was distilled off under reduced pressure to obtain a yellow paste compound. This was purified by silica gel column (solvent:
Initially, methylene chloride was used, and then the ratio was changed to methylene chloride:acetone=1:1 (volume ratio). ) to obtain 6.0 g (quantitative) of pale yellow powder. The melting point of this compound is 62~
The temperature was 64°C. Moreover, the 1H-NMR of this compound is as follows. 1H-NMR (CDCl3) δ = 7.0 to 7.4 ppm (m; 18H, aromatic ring -
H) δ = 6.9 ppm (s; 1H, methylidine-C
H=C= ) δ=4.0ppm (q; 4H, ethoxy group -CH
2-)δ=3.1ppm (d;2H,-CH2-
P J = 16Hz) δ = 1.3ppm (t; 6H
, ethoxy group -CH3)■

3.8 g (0.009 g) of the phosphonate obtained in Reference Example 5■ above
3 mol) was suspended in 150 ml of dimethyl sulfoxide under an argon gas flow, and the above-mentioned Reference Example 7
2.0g of the compound (diketone) obtained in (0.004
9 mol) and 1.2 g (0.9 mol) of potassium t-butoxide.
010 mol) was added. The solution presented a reddish-brown suspension and was stirred at room temperature for 6 hours. After standing overnight and distilling off the solvent,
Pour 700 ml of methanol into the reaction mixture,
The precipitated pale yellow powder was collected by filtration. This was applied to a silica gel column (solvent: CH2Cl2, diameter 40 mm x length 230 m).
m) to obtain 0.9 (yield 20%) amorphous crystals. According to DSC measurement, the Tg of this item is 91.7
It was ℃. The melting point of this compound is 203.0-2
The temperature was 04.0°C. Moreover, 1H-NMR of the product was as follows. 1H-NMR (CDCl3) δ=6.8-7.9ppm (m; 56H, aromatic ring and methylidine-CH=C=) δ=2.5ppm (s,6H, methyl group-CH3)
Moreover, only the molecular ion peak m/Z=1062 of the target object was detected from the direct mass spectrum (MS). Furthermore,
The elemental analysis results are as follows with a compositional formula of C82H62O. Note that the values in parentheses are theoretical values. C: 92.31% (92.62%) H: 5.41% (5.88%) N: 0.0
0% (0%) In addition, the infrared (IR) absorption spectrum (KBr tablet method) is as follows. From the fact that νC=C 1520, 1610 cm-1 or more, the above compound has the following formula

[0075]

[Chemical formula 31]

It was confirmed that it was a compound represented by the following formula.

Example 1 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol and further for 5 minutes in pure water, and then UV ozone cleaning was performed for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition device (manufactured by Japan Vacuum Technology Co., Ltd.) and placed in a molybdenum resistance heating boat.
,N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (TPD) (200 mg) was added to another molybdenum boat. -bis(2,2'-diphenylvinyl)
Biphenyl (DPVBi, ionization energy: 5.9
200 mg of eV) was added, and the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa. After that, the said boat with TPD is 215～
Heating to 220℃, TPD deposition rate 0.1-0.3
A hole injection layer having a thickness of 60 nm was formed by vapor deposition on a transparent support substrate at a rate of nm/s. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, DPVBi was deposited in a 40 nm layer as a light emitting layer on the hole injection layer from another boat. The deposition conditions are a boat temperature of 24
The deposition rate was 0.1 to 0.3 nm/s at 0° C., and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, 200 mg of tris(8-quinolinol)aluminum (Alq3, ionization energy: 5.6 eV) was placed in a molybdenum boat and the boat was placed in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. After that, the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa, and the boat containing Alq3 was heated to 230°C.
Alq3 was deposited to a thickness of 20 nm at a deposition rate of 0.01 to 0.03 nm/s. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by the resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 2 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (
4,4'-bis(4-t-butylphenylvinyl) in another molybdenum boat.
Biphenyl (DTBPPVBi, ionization energy: 5
．． 9eV) and put 200mg of it in the vacuum chamber to 1x10-4P.
The pressure was reduced to a. After that, the said boat containing TPD was 21
Heating to 5-220℃, TPD deposition rate 0.1-0
．． Deposited on a transparent support substrate at 3 nm/s to a film thickness of 60 nm.
A hole injection layer of m was formed into a film. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, DTBPVBi was deposited in a 40 nm layer as a light emitting layer on the hole injection layer from another boat. The deposition conditions were a boat temperature of 330° C., a deposition rate of 0.1 to 0.3 nm/s, and a substrate temperature of room temperature. This was removed from the vacuum chamber, a stainless steel mask was placed on top of the luminescent layer,
It was fixed on the substrate holder again. Next, tris(8-quinolinol) aluminum (Alq3) was added to the molybdenum boat.
) was placed in a vacuum chamber. moreover,
Magnesium ribbon 1 on a molybdenum resistance heating boat
Then, 500 mg of silver wire was placed in another tungsten basket and vapor deposited. After that, vacuum chamber 1x
After reducing the pressure to 10-4 Pa, the boat containing Alq3 was heated to 230°C to reduce the Alq3 to 0.01-0.
A thickness of 20 nm was deposited at a deposition rate of 0.3 nm/s. moreover,
At the same time, silver was deposited at a rate of 0.1 nm/s by resistance heating, and magnesium was deposited from the other molybdenum boat at a rate of 0.1 nm/s.
．． Deposition started at a deposition rate of 4 nm/s. Under the above conditions, a mixed metal electrode of magnesium and silver was placed on the light emitting layer for 150 nm.
m layers were deposited to form a counter electrode.

Example 3 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (
200 mg of 4,4'-bis[2-(4-t-butylphenyl)] was added to another molybdenum boat.
-2-biphenylvinyl]biphenyl (TBPVBi,
200 mg of ionization energy: 5.85 eV) was added, and the pressure of the vacuum chamber was reduced to 1×10 −4 Pa. Then T.P.
The boat containing D is heated to 215-220°C, and T
PD was deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm/s to form a hole injection layer with a thickness of 60 nm. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, a 40 nm thick layer of TBPVBi was deposited as a light emitting layer on the hole injection layer from another boat. The deposition conditions are a boat temperature of 280°C and a deposition rate of 0.1~
0.3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, 200 mg of tris(8-quinolinol)aluminum (Alq3) was placed in a molybdenum boat and the boat was placed in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. Then, after reducing the pressure in the vacuum chamber to 1 x 10-4 Pa,
A boat containing lq3 is heated to 230℃, and Alq
3 for 20n at a deposition rate of 0.01-0.03nm/s.
m was deposited. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by the resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 4 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (
4,4'-bis(2,2-di-p-trivinyl)biphenyl (DTVBi, ionization energy: 5.85) in another molybdenum boat.
200 mg of eV) was added, and the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa. After that, the said boat with TPD is 215～
Heating to 220℃, TPD deposition rate 0.1-0.3
A hole injection layer having a thickness of 60 nm was formed by vapor deposition on a transparent support substrate at a rate of nm/s. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, DTVBi was placed on the hole injection layer from another boat as a light emitting layer for 40 minutes.
A layered film with a thickness of nm thick was deposited. The deposition conditions were a boat temperature of 275° C., a deposition rate of 0.1 to 0.3 nm/s, and a substrate temperature of room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, Tris (8-
quinolinol) aluminum (Alq3) 200
mg and installed it in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 m of silver wire was placed in a different tungsten basket.
g was deposited. After that, the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa, and the boat containing Alq3 was heated to 230°C.
Alq3 is heated to 0.01-0.03 nm/s.
A thickness of 20 nm was deposited at a deposition rate of . Furthermore, 0.1n of silver
Magnesium was simultaneously deposited at 1.4 nm/s from the other molybdenum boat by resistance heating at a deposition rate of m/s.
Deposition started at a deposition rate of . A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 5 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (
200 mg of 4,4'-bis(2,2-di-p-methoxyphenylvinyl)biphenyl (DMVBi, ionization energy: 5.85 eV) was placed in another molybdenum boat, and the vacuum chamber was heated to 1. ×1
The pressure was reduced to 0-4 Pa. Thereafter, the boat containing TPD was heated to 215 to 220°C, and TPD was deposited at a evaporation rate of 0.
．． A hole injection layer having a thickness of 60 nm was formed by vapor deposition on a transparent support substrate at a rate of 1 to 0.3 nm/s. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, DMVBi was placed on top of the hole injection layer from another boat.
A 40 nm layer was deposited as a light emitting layer. The deposition conditions were a boat temperature of 320°C and a deposition rate of 0.1 to 0.3 nm/s.
, the substrate temperature was room temperature. Take this out of the vacuum chamber,
A stainless steel mask was placed on top of the light emitting layer, and the mask was fixed to the substrate holder again. Next, tris(8-quinolinol) aluminum (Al) was added to the molybdenum boat.
q3) was placed in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. Thereafter, the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa, and the boat containing Alq3 was heated to 230°C to reduce the Alq3 to 0.01
20 nm was deposited at a deposition rate of ~0.03 nm/s. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by a resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. Under the above conditions, place a mixed metal electrode of magnesium and silver on the light emitting layer.
A 50 nm layer was deposited to form a counter electrode.

Example 6 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (
TPD) and 200 mg of 3,3'-dimethyl-4,4'-bis(2,2-diphenylvinyl)biphenyl (DMDPVBi, ionization energy: 5.85 eV) in a different molybdenum boat and placed in a vacuum chamber. The pressure was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, DMDPVBi was deposited in a 40 nm layer as a light emitting layer on the hole injection layer from another boat. The deposition conditions are a boat temperature of 305℃ and a deposition rate of 0.1~
0.3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, 200 mg of tris(8-quinolinol)aluminum (Alq3) was placed in a molybdenum boat and the boat was placed in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. Then, after reducing the pressure in the vacuum chamber to 1 x 10-4 Pa,
A boat containing lq3 is heated to 230℃, and Alq
3 for 20n at a deposition rate of 0.01-0.03nm/s.
m was deposited. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by the resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 7 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (
200 mg of TPD) was added to another molybdenum boat, and 200 mg of the compound obtained in Reference Example 7■ ((DPVTPVBi
)2 E, ionization energy: 5.8eV) to 200
mg, and the vacuum chamber was depressurized to 1 x 10-4 Pa. Thereafter, the boat containing TPD was heated to 215 to 220°C, and TPD was deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, a 40 nm thick layer of (DPVTPVBi)2E was deposited as a light emitting layer on the hole injection layer from another boat. The deposition conditions are boat temperature 2.
The deposition rate was 0.1 to 0.3 nm/s at 25° C., and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed again to the substrate holder. Next, tris(8-quinolinol) aluminum (Alq3) was added to the molybdenum boat.
200mg of was added and vapor deposited in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. After that, the vacuum chamber was
After reducing the pressure to 4 Pa, the boat containing Alq3 was heated to 230°C to reduce the Alq3 to 0.01-0.03
A thickness of 20 nm was deposited at a deposition rate of nm/s. Furthermore, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by a resistance heating method.
1.4 magnesium from the other molybdenum boat
Deposition started at a deposition rate of nm/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 8 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, bis(8-hydroxyquinolinol) was added to the molybdenum boat.
200 mg of magnesium (Mg(Ox)2: ionization energy: 5.55 eV) was placed and deposited in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. Then, after reducing the pressure in the vacuum chamber to 1 x 10-4 Pa, Mg(Ox
)2 was heated to 410℃, and Mg(O
x) 2 at a deposition rate of 0.01 to 0.03 nm/s
A thickness of 0 nm was deposited. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by the resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 9 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215 to 220°C, and TPD was deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed again to the substrate holder. Next, bis(8-hydroxyquinolinol) was added to the molybdenum boat.
200 mg of copper (Cuq2: ionization energy 5.45 eV) was placed and deposited in a vacuum chamber. Furthermore, 1g of magnesium ribbon was placed in a molybdenum resistance heating boat, and 5g of silver wire was placed in another tungsten basket.
00mg was deposited. After that, the vacuum chamber was
After reducing the pressure to Pa, the boat containing Cuq2 was
Heat to 80℃ and add Cuq2 to 0.05-0.1 nm.
A thickness of 20 nm was deposited at a deposition rate of /s. Furthermore, silver was added to 0.
1.4 nm of magnesium was simultaneously deposited from the other molybdenum boat by resistance heating at a deposition rate of 1 nm/s.
The deposition started at a deposition rate of /s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 10 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, bis(8-hydroxyquinolinol) was added to the molybdenum boat.
200 mg of lead (Pbq2: ionization energy 5.45 eV) was placed and deposited in a vacuum chamber. Furthermore, 1g of magnesium ribbon was placed in a molybdenum resistance heating boat, and 5g of silver wire was placed in another tungsten basket.
00mg was added and vapor deposited. After that, the vacuum chamber was
After reducing the pressure to Pa, the boat containing Pbq2 was
Heat to 90℃ and add 0.01 to 0.03n of Pbq2.
A thickness of 20 nm was deposited at a deposition rate of m/s. Furthermore, silver is 0
．． 1.4n of magnesium was simultaneously deposited from the other molybdenum boat by resistance heating at a deposition rate of 1nm/s.
Deposition started at a deposition rate of m/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 11 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, tris(8-hydroxyquinolinol) gallium (Gaq3: ionization energy 5.5e) was placed in a molybdenum boat.
200 mg of V) was added and deposited in a vacuum chamber. moreover,
Magnesium ribbon 1 on a molybdenum resistance heating boat
Then, 500 mg of silver wire was placed in another tungsten basket and vapor deposited. After that, the vacuum chamber was
After reducing the pressure to 10-4 Pa, the boat containing Gaq3 was heated to 290℃, and the Gaq3 was reduced to 0.01 to 0.
．． A thickness of 20 nm was deposited at a deposition rate of 0.3 nm/s. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by a resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. Under the above conditions, a mixed metal electrode of magnesium and silver was placed on the light emitting layer for 150 m
nm layer was deposited to form a counter electrode.

Example 12 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, tris(8-hydroxyquinolinol) indium (Inq3: ionization energy 5.
200 mg of 5 eV) was added and deposited in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. After that, the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa, and the boat containing Inq3 was heated to 315°C, and the Inq3 was
A thickness of 20 nm was deposited at a deposition rate of 0.03 nm/s. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by the resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. Under the above conditions, a mixed metal electrode of magnesium and silver was placed on the light emitting layer for 15 minutes.
A 0 nm layer was deposited to form a counter electrode.

Example 13 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, 200 mg of tris(2-methyl-8-hydroxyquinolinol)aluminum (Al(mq)3: ionization energy 5.55 eV) was placed in a molybdenum boat and deposited in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. After that, the pressure in the vacuum chamber was reduced to 1 x 10-4 Pa, and the boat containing Al(mq)3 was heated to 300°C, and the Al(mq)3 was heated at 0.01 to 0.03 nm/s.
A thickness of 20 nm was deposited at a deposition rate of . Furthermore, 0.1n of silver
Magnesium was simultaneously deposited at 1.4 nm/s from the other molybdenum boat by resistance heating at a deposition rate of m/s.
Deposition started at a deposition rate of . A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Example 14 IT was placed on a 25 mm x 75 mm x 1.1 mm glass substrate.
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm by vapor deposition. This substrate was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, further in pure water for 5 minutes, and then UV ozone cleaning for 10 minutes using an apparatus manufactured by Samco International Laboratories Co., Ltd. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Japan Vacuum Technology Co., Ltd.), and then placed in a molybdenum resistance heating boat.
Add 200 mg of N'-bis(3-methylphenyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (TPD) and add 4,4' to another molybdenum boat. -bis(2,2'-diphenylvinyl)
200 mg of biphenyl (DPVBi) was added and the pressure in the vacuum chamber was reduced to 1×10 −4 Pa. Thereafter, the boat containing TPD was heated to 215-220°C, and TPD was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1-0.3 nm/s to form a hole injection layer with a thickness of 60 nm. Ta. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, place it on top of the hole injection layer from another boat (D
PVBi) was deposited in a 40 nm layer as a light emitting layer. The deposition conditions were a boat temperature of 240°C and a deposition rate of 0.1-0.
3 nm/s, and the substrate temperature was room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, 200 mg of tris(2-methyl-8-hydroxyquinolinol)indium (In(mq)3: ionization energy 5.5 eV) was placed in a molybdenum boat and deposited in a vacuum chamber. Furthermore, 1 g of magnesium ribbon was placed in a resistance heating boat made of molybdenum, and 500 mg of silver wire was placed in a different tungsten basket for vapor deposition. Then, after reducing the pressure in the vacuum chamber to 1 x 10-4 Pa, In(mq)
3.Heat the boat containing In(mq
)3 at a deposition rate of 0.01 to 0.03 nm/s.
nm was deposited. Further, silver was simultaneously deposited at a deposition rate of 0.1 nm/s by the resistance heating method, and magnesium was started to be deposited from the other molybdenum boat at a deposition rate of 1.4 nm/s. A mixed metal electrode of magnesium and silver was deposited to a thickness of 150 nm on the light emitting layer under the above conditions to serve as a counter electrode.

Comparative Examples 1 to 8 The samples were once taken out of the vacuum layer and placed in the vacuum layer together with magnesium and silver boats, respectively, and a mixed metal electrode of magnesium and silver was deposited under the same conditions as in Example 1, except that An EL device was produced in the same manner as in Example 1.

Comparative Example 9 An EL device was produced in the same manner as in Example 2, except that the light emitting layer was 30 nm thick and the adhesive layer was 30 nm thick. The initial characteristics were as shown in Table 1.

[0093]

[Table 1]

Uniformity: The device was made to emit light with a brightness of 100 cd·m-2, and a luminance meter (CS-100, Minolta camera (
(manufactured by Co., Ltd.) to observe the light emitting surface and evaluate it as follows. ×: There is a non-luminous area with a diameter of 10 μm or more or color unevenness in the observation area. ○: Uniform light emission in the observation area (no light-emitting area with a diameter of 10 μm or more or no color unevenness). Efficiency: Shows the conversion efficiency when the element emits light at a brightness of 100 cd·m-2. After this evaluation, the devices were exposed to I
With TO as the anode and the metal electrode as the cathode, the DC electric field is set to 0V/
cm to 1.3×106 V/cm 4.2×104
Aging was performed while applying voltage at intervals of V/cm for 2 seconds and measuring voltage-current characteristics. Furthermore, in nitrogen,
Aging was performed for 10 minutes from an initial brightness of 100 cd·m −2 . The thus treated element was driven under direct current in nitrogen, and was allowed to emit light continuously for 24 hours at an initial brightness of 100 cd·m<-2 >. After this, evaluation was performed using a luminance meter in the same manner as above. In the examples, all emit light uniformly, whereas
In Comparative Examples 1 to 8, the non-luminescent region expanded, and in Comparative Example 9, color unevenness increased. The luminance at this time is shown in Table 2.

[0095]

[Table 2]

As shown above, the examples have device configurations as claimed in the present invention, the comparative examples have device configurations without the adhesive layer, and the examples with the same numbers have the same luminescent materials. be. It can be seen from the device configuration of the example that the luminous efficiency is improved and deterioration is suppressed while maintaining blue light emission. Further, when comparing Example 2 and Comparative Example 9, it can be seen that in order to maintain blue light emission, it is efficient to make the thickness of the adhesive layer thinner than the thickness of the light emitting layer.

[0097]

[Effects of the Invention] According to the organic EL device of the present invention, it is possible to improve the in-plane uniformity of light emission, and at the same time, it is possible to suppress a decrease in initial brightness. Therefore, fine processing of the device is possible. , improved yield, and even longer life. Therefore, the organic EL device of the present invention is expected to be effectively used as various light emitting materials.

Claims (1)

[Claims] [Claim 1] Anode/light-emitting layer/adhesive layer/cathode, or anode/hole injection layer/light-emitting layer/adhesive layer/cathode are laminated in this order, and the light-emitting layer has the general formula (I) [Formula 1] (In the formula, R1 to R4 are each hydrogen atom, carbon number 1
-6 alkyl group, alkoxy group having 1 to 6 carbon atoms, aralkyl group having 7 to 8 carbon atoms, substituted or unsubstituted aryl group having 6 to 18 carbon atoms, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted represents an aryloxy group having 6 to 18 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Here, the substituent is an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
6 alkoxy group, aralkyl group having 7 to 8 carbon atoms, aryloxy group having 6 to 18 carbon atoms, acyl group having 1 to 6 carbon atoms, acyloxy group having 1 to 6 carbon atoms, carboxyl group,
styryl group, arylcarbonyl group having 6 to 20 carbon atoms,
It represents an aryloxycarbonyl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a vinyl group, an anilinocarbonyl group, a carbamoyl group, a phenyl group, a nitro group, a hydroxyl group, or a halogen. These substituents may be single or plural. Further, R1 to R4 may be the same or different from each other, and R1 and R2 and R3 and R4 are bonded to the groups substituting each other,
A substituted or unsubstituted saturated five-membered ring or a substituted or unsubstituted saturated six-membered ring may be formed. Ar represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and may be singly substituted or multiply substituted, and the bonding site may be any of ortho, para, and meta. However, A
When r is unsubstituted phenylene, R1 to R4 are each selected from an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, a substituted or unsubstituted naphthyl group, a biphenyl group, a cyclohexyl group, and an aryloxy group. It is something that was given. ), general formula (II) [Formula 2] (wherein A and B each represent a monovalent group obtained by removing one hydrogen atom from the compound represented by the above general formula (I),
They may be the same or different. Further, Q represents a divalent group that breaks the conjugated system. ) or general formula (III) [Formula 3] (wherein A1 is substituted or unsubstituted carbon number 6-20
represents an arylene group or a divalent aromatic heterocyclic group. The bonding position may be ortho, meta, or para. A2
represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a monovalent aromatic heterocyclic group. R5 and R6 are each a hydrogen atom, a substituted or unsubstituted carbon number of 6 to
20 aryl group, cyclohexyl group, monovalent aromatic heterocyclic group, alkyl group having 1 to 10 carbon atoms, 7 to 2 carbon atoms
0 aralkyl group or an alkoxy group having 1 to 10 carbon atoms. Note that R5 and R6 may be the same or different. Here, in the case of single substitution, the substituent is an alkyl group, an aryloxy group, an amino group, or a phenyl group with or without a substituent. Each substituent of R5 may be combined with A1 to form a saturated or unsaturated five- or six-membered ring, and similarly each substituent of R6 may be combined with A2 to form a saturated or unsaturated ring. A five-membered ring or a six-membered ring may be formed. Moreover, Q represents a divalent group that breaks conjugation. ) and exhibits blue, verdigris, or blue-green luminescence, and the adhesive layer is composed of a metal complex of 8-hydroxyquinoline or its derivative, and its thickness is thinner than the thickness of the luminescent layer. An organic electroluminescent device characterized by: 0001