JP2001035668A - Organic electroluminescence element and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance brightness, lengthen life, lower driving voltage, and enhance efficiency by including a specific compound in the form of single or mixture in an organic luminescent band and a hole injection band constituted together with a cathode, and using an anode irradiation-treated with ultraviolet rays in a specified wavelength range. SOLUTION: An oxygen ratio on the surface is increased with oxygen radicals produced by irradiation of ultraviolet rays having a wavelength of 100-200 nm to an anode made of an oxide conductor haying a work function of 4 eV or higher; and photoelectric effect to an anode material, an interface between the anode and a hole injection band containing a compound represented by the formula is varied, adhesion is increased, and element characteristics are enhanced. In the formula, Ar1 and Ar2 represent 5-42C allylene group, Ar3-Ar7 represent 6-20C aryl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group or heteocyclic group, aralkyl group, an aryloxy group, an alkoxycarbonyl group, and a carboxyl group, and they are a substituted group or a non-substituted group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device (organic EL device), and more particularly, to a high-efficiency organic EL device capable of high luminance, long life and low voltage driving, and a method of manufacturing the same.

[0002]

2. Description of the Related Art An organic EL element is a self-luminous element utilizing the principle that a fluorescent substance emits light by the recombination energy of holes injected from an anode and electrons injected from a cathode when an electric field is applied. is there. Eastman Kodak C.I. W. Tang et al. Report on low-voltage driven organic EL devices using stacked devices (CWTang, SAVanSlyke, Applied Physics Lett.)
ers, Vol. 51, p. 913, 1987), research on organic EL devices using organic materials as constituent materials has been actively conducted. Tang et al. Use tris (8-hydroxyquinolinol aluminum) for the electron injecting and transporting light-emitting layer and use a triphenyldiamine derivative for the hole injecting and transporting layer. Advantages of the stacked structure include increasing the efficiency of injecting holes into the light emitting layer and increasing the efficiency of generating excitons generated by recombination by blocking electrons injected from the cathode. As in this example, the element structure of the organic EL element includes a hole transport (injection) layer,
Two-layer type of electron injecting and transporting light emitting layer or hole transporting (injection)
A three-layer type including a layer, an electron injection / transport light emitting layer, and an electron transport (injection) layer is well known. In such a laminated structure element, in order to increase the recombination efficiency of injected holes and electrons, the element structure and the forming method are devised.

The hole injecting and transporting materials used in these devices are 4,4 ', 4 "which are starburst molecules.
-Tris (3-methylphenylphenylamino) triphenylamine or N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl]-
Triphenylamine derivatives such as 4,4′-diamine and aromatic diamine derivatives are well known (for example, JP-A-8-20771, JP-A-8-40995, JP-A-8-40997, JP-A-8-54
No. 3397, JP-A-8-87122, etc.).

[0004] Oxadiazole derivatives, triazole derivatives and the like are well known as electron injecting and transporting materials.

A chelate complex typified by a tris (8-quinolinolato) aluminum complex is known as an electron injecting and transporting luminescent material, and the efficiency can be improved by adding a small amount of a fluorescent dye to this luminescent material. Are known. These fluorescent dyes include coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives, oxadiazole derivatives, porphyrin derivatives, phenoxazone dyes, rhodamine dyes,
Acridine-based dyes and the like are known, and it has been reported that their emission colors can emit light in the visible region from blue to red, and the realization of a color display device is expected (for example, see Japanese Unexamined Patent Application Publication No. -239655, JP-A-7-
138561, JP-A-3-200289, etc.).

[0006] However, although the organic EL device having three or more layers has high luminous efficiency, the driving voltage is increased due to the barrier against the injection of each charge and the increase in the overall film thickness. Also,
In the case of using the conventional electron injecting and transporting light emitting layer, there is a disadvantage that the operating voltage is further increased due to a high hole injection barrier to the light emitting layer.

[0007] In order to improve the performance of the organic EL device, the device manufacturing method has been improved. For example, it has been reported that a plasma surface treatment of an ITO film as an anode lowers a light emission starting voltage. (For example, Proceedings of the 44th Joint Lecture on Applied Physics, Spring 1997, p.
1148, 29a-NK-3). As another treatment method for the ITO film, a method of irradiating an excimer UV lamp has been reported, but no improvement in luminous efficiency has been found (Japanese Patent Laid-Open No. Hei 10-261484).

[0008]

Recently, an organic EL device having a high luminance and a long life has been disclosed or reported, but it is not necessarily sufficient. Therefore, there is a strong demand for the development of a material exhibiting high performance and a device manufacturing method for maximizing the performance. An object of the present invention is to provide a high-efficiency organic EL device capable of high luminance, long life and low voltage driving.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, at least the anode,
In an organic EL device including a hole injection zone, an organic emission zone, and a cathode containing a compound of the general formula [1] described below, a conventional anode is used which has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm. It has been found that the device emits light with a higher luminance at a lower voltage than the device, achieves a high luminous efficiency, and has a longer luminescent life in continuous driving.

That is, the present invention has at least an anode, a hole injection zone, an organic light emitting zone, and a cathode as constituent elements, and a layer forming the hole injection zone has the following general formula [1]:
In the method for producing an organic EL device containing the material represented by (1) alone or as a mixture, a method for producing an organic EL device, comprising using an anode that has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm, and the method described above. An organic EL device is shown.

Embedded image (Where, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted arylene group having a carbon number of 5 to 42, Ar ₃ ~
Ar ₇ is independently a substituted or unsubstituted carbon number of 6 to 2
0 is an aryl group. Here, the substituent includes a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group. Group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxycarbonyl group, Or a carboxyl group is mentioned. )

Further, the present invention has at least an anode, a hole injection zone, an organic light emitting zone, and a cathode as constituent elements, and a layer forming the hole injection zone is made of a material represented by the general formula [1] alone or In the method for producing an organic EL device containing the mixture, a work function of the oxide conductor having a work function of 4 ev or more is used as the anode, and an anode that has been subjected to ultraviolet irradiation at a wavelength of 100 nm to 200 nm is used. A manufacturing method and an organic EL device manufactured by the above method.

Further, the present invention has at least an anode, a hole injection zone, an organic emission zone, an electron injection zone, and a cathode as constituent elements, and the layer forming the hole injection zone is represented by the general formula [1]. In a method for manufacturing an organic EL device containing the material alone or as a mixture, a wavelength of 100 nm to 200 nm is used.
A method for producing an organic EL device, comprising using an anode that has been subjected to an ultraviolet irradiation treatment of nm, and an organic EL device produced by the above method.

Further, the present invention has at least an anode, a hole injection zone, an organic light emitting zone, an electron injection zone, and a cathode as constituent elements, and a layer forming the hole injection zone is represented by the general formula [1]. In a method for producing an organic EL device containing the material alone or as a mixture, the work function as an anode is 4
ev or more, using an oxide conductor having a wavelength of 100 nm or more.
A method for producing an organic EL device, comprising using an anode that has been subjected to a 200 nm ultraviolet irradiation treatment, and an organic EL device produced by the above method.

Further, the present invention has at least an anode, a hole injection zone, an organic light emitting zone, and a cathode as constituent elements, and the layer forming the hole injection zone is made of a material represented by the general formula [1] alone or In the method for producing an organic EL device containing the mixture as a mixture, the layer forming the organic light-emitting band contains the material represented by the following general formula [2] alone or as a mixture;
A method for producing an organic EL device, comprising using an anode that has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm, and an organic EL device produced by the above method.

Embedded image (However, Ar ₈ is a substituted or unsubstituted arylene group having 5 to 42 carbon atoms, and Ar _{9 to} Ar ₁₂ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
Here, as the substituent, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group,
Examples thereof include a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, and a carboxyl group. )

Further, the present invention has at least an anode, a hole injection zone, an organic light emitting zone, and a cathode as constituents, and the layer forming the hole injection zone is made of a material represented by the general formula [1] alone or In the method for producing an organic EL device containing a mixture, the oxide conductor having a work function of 4 ev or more is used as the anode, and the layer forming the emission band contains the material represented by the general formula [2] alone or as a mixture. A method for producing an organic EL element, comprising using an anode which has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm,
And an organic EL device manufactured by the method described above.

Further, the present invention has at least an anode, a hole injection zone, an organic light emitting zone, an electron injection zone, and a cathode as constituent elements, and a layer forming the hole injection zone is represented by the general formula [1]. In the method for producing an organic EL device containing the material alone or as a mixture, the layer forming the emission band contains the material represented by the general formula [2] alone or as a mixture, and is subjected to an ultraviolet irradiation treatment at a wavelength of 100 nm to 200 nm. A method for manufacturing an organic EL device using an anode, and an organic EL device manufactured by the above method.

Further, the present invention has at least an anode, a hole injection zone, an organic emission zone, an electron injection zone, and a cathode as constituent elements, and a layer forming the hole injection zone is represented by the general formula [1]. In a method for producing an organic EL device containing the material alone or as a mixture, the work function as an anode is 4
ev or more, and the layer forming the emission band contains the material represented by the general formula [2] alone or as a mixture, and uses an anode that has been subjected to ultraviolet irradiation at a wavelength of 100 nm to 200 nm. Organic EL characterized by:
Device manufacturing method and organic EL manufactured by the above method
Element.

In the present invention, at least the anode, the general formula [1]
In an organic EL device comprising a hole injection zone, an organic emission zone, and a cathode containing the compound of
It is characterized by using an anode that has been subjected to an ultraviolet irradiation treatment of m to 200 nm.

The ultraviolet irradiation lamp used in the present invention may be any lamp which emits light having a wavelength of 100 nm to 200 nm and has an irradiation intensity of 1 mW / cm ² or more. Specific examples include an excimer UV lamp, an excimer laser, and a deuterium lamp, but are not limited thereto.

The wavelength used in the present invention is from 100 nm to 20 nm.
It is known that ultraviolet light of 0 nm is absorbed by atmospheric oxygen (R. Kingslake, Applied Optics and Optical Engineering I, Academic Press New York and London (Applied Optics)
and Optical Engineering I, AcademicPress, New York
and London), 1965, p. 131), and the oxygen ratio on the anode surface increases due to the oxygen radicals generated thereby and the photoelectric effect on the anode material, and the interface between the organic thin film layer forming the emission band and the anode changes. By doing so, the device emits light with higher luminance at a lower voltage than the conventional device, suppresses a decrease in luminous efficiency, and further prolongs the luminous life during continuous driving. In addition, the performance of the organic EL element is also improved because the surface of the anode is cleaned by the generated oxygen radicals and the adhesion to the organic thin film is increased.

The wavelength of 100 nm to 2 for the anode of the present invention
A further effect can be obtained by applying a 00 nm ultraviolet irradiation treatment in advance by performing a wet cleaning method, ozone cleaning, or plasma irradiation treatment with oxygen or the like in advance.

The anode of the organic thin film EL element plays a role of injecting holes into the emission band, and it is effective that the anode has a work function of 4 eV or more, preferably 4.5 eV or more. As the anode material used in the present invention, an oxide conductor is preferable. As a specific example, indium tin oxide alloy (ITO), tin oxide (NESA), tin antimony oxide alloy (ATO), zinc oxide, zinc aluminum alloy (AZO), and the like can be applied.

Further, as the cathode, a material having a small work function is desirable for the purpose of injecting electrons into the emission band or the electron injection band. The cathode material is not particularly limited, but specifically, indium, aluminum, magnesium, a magnesium-indium alloy, a magnesium-aluminum alloy, an aluminum-lithium alloy, an aluminum-scandium-lithium alloy, a magnesium-silver alloy, or the like can be used.

The hole injection zone used in the present invention is a compound having a structure represented by the general formula [1]. In the general formula [1], the compound used for Ar ₁ and Ar ₂ represents a substituted or unsubstituted arylene group having 5 to 42 carbon atoms. Examples of such compounds include phenyl, naphthyl, anthranyl, perylenylene, 1: 2 benzopenenylene, 1: 2: 7: 8 dibenzopenenylene, 1: 2: 11: 12. Dibenzopenylenelenylene group,
Teryleneylene group, pentasenylene group, biphenylene group,
4,4 ′-(1,1′-biphenyl) ylene group, 4,
4 ′-(1,1′-phenylnaphthyl) ylene group, binaphthalenylene group, 4,4 ′-(1,1′-binaphthyl)
Irene group, 4,10 ′-(1,9′-naphthyl anthryl) ylene group, bisanthrenylene group, 10,10′-
(9,9′-bisanthryl) ylene group and aromatic hydrocarbon such as phenanthrene, pyrene, terphenyl or condensed polycyclic hydrocarbon, carbazole, pyrrole, thiophene, furan, imidazole, pyrazole, isothiazole, isoxazole, Pyridine, pyrazine, pyrimidine, pyridazine, furan, thianthrene, isobenzofuran, phenoxazine, indolizine, indole, isoindole, 1H-indazole, purine,
Quinoline, isoquinoline, phthalazine, naphthyridine,
Quinoxaline, quinazoline, cinnoline, pteridine,
Carbazole, β-carbazoline, phenanthridine,
Heterocyclic compounds such as acridine, perimidine, phenanthroline, phenazine, phenothiazine, and phenoxazine or condensed heterocyclic compounds, divalent groups in which two hydrogen atoms have been removed, and derivatives thereof. Ar _{3 to} Ar
₇ is independently substituted or unsubstituted carbon number 6-20
Is an aryl group. Examples of such compounds include:
Examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a naphthacenyl group and a pyrenyl group.

The organic luminescent band used in the present invention is a compound having a structure represented by the general formula [2]. In the general formula [2], the compound used for Ar ₈ represents a substituted or unsubstituted arylene group having 5 to 42 carbon atoms. Examples of such compounds include naphthyl, anthranyl, perylenylene, 1: 2 benzopenenylene,
1: 2: 7: 8 dibenzopenylenelenylene group, 1: 2: 1
1:12 dibenzopenylenelenylene group, terryleneylene group, pentasenylene group, bisanthryleneylene group, 10,10 ′
-(9,9'-bisanthryl) ylene group, 4,4'-
(1,1′-binaphthyl) ylene group, 4,10′-
A (1,9′-naphthylanthryl) ylene group, a divalent group represented by the general formula [3],

Embedded image (However, Ar _{13 to} Ar ₁₅ are each a naphthyl group or an anthranyl group.) And phenanthrene, pyrene,
Aromatic hydrocarbons such as terphenyl or condensed polycyclic hydrocarbons, carbazole, pyrrole, thiophene, furan, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, furazan, thianthrene, isobenzofuran,
Phenoxazine, indolizine, indole, isoindole, 1H-indazole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline,
Quinazoline, cinnoline, pteridine, carbazole,
Examples of the heterocyclic compound such as β-carbazoline, phenanthridine, acridine, perimidine, phenanthroline, phenazine, phenothiazine, and phenoxazine, or a divalent group obtained by removing two hydrogen atoms from a fused heterocyclic compound, and derivatives thereof. Ar _{9 to} Ar ₁₂ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Examples of such compounds include phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pyrenyl and the like.

Here, examples of the substituent include halogen atoms such as fluorine, chlorine, bromine and iodine.

Examples of the substituted or unsubstituted alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, and t-butyl.
Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl, 1,2-dihydroxy Ethyl group,
1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-
Chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group,
2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group,
1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3
-Tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl Group, 1,
2,3-triiodopropyl group, aminomethyl group, 1-
Aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group,
1,2,3-triaminopropyl group, cyanomethyl group,
1-cyanoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricia Propyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl, 1,2-dinitroethyl, 1,3
-Dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group and the like.

Examples of the substituted or unsubstituted alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butanedienyl, 1
-Methylvinyl group, styryl group, 4-methylstyryl group, 4-diphenylaminostyryl group, 4-di-p-tolylaminostyryl group, 4-di-m-tolylaminostyryl group, 2,2-diphenylvinyl group A 1,2-diphenylvinyl group, a 1-methylallyl group, a 1,1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 2-phenylallyl group, a 3-phenylallyl group,
3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group, 3-phenyl-1
-Butenyl group and the like.

Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a 4-methylcyclohexyl group.

The substituted or unsubstituted alkoxy group is --OY
And examples of Y include methyl, ethyl, propyl, isopropyl, n-butyl, and s.
-Butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2
-Hydroxyethyl group, 2-hydroxyisobutyl group,
1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl Group, 2
-Chloroisobutyl group, 1,2-dichloroethyl group,
1,3-dichloroisopropyl group, 2,3-dichloro-
t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 3-diiodoisopropyl group, 2,3-
Diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 3-diaminoisopropyl group, 2,
3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group,
-Cyanoethyl group, 2-cyanoisobutyl group, 1,2-
Dicyanoethyl group, 1,3-dicyanoisopropyl group,
2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group,
1,2-dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2,3
-A trinitropropyl group and the like.

Examples of the substituted or unsubstituted aromatic hydrocarbon group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, and 1-phenanthryl. , 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9
-Phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-
Pyrenyl group, 4-pyrenyl group, 2-biphenylyl group,
3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl Group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p-
(2-phenylpropyl) phenyl group, 3-methyl-2
-Naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenylyl group, 4 ″ -t-butyl-p-terphenyl-4-yl group and the like. .

Examples of the substituted or unsubstituted aromatic heterocyclic group include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridinyl, 3-pyridinyl, and 4-pyridinyl. , 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1
-Isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuranyl, 3 -Benzofuranyl group, 4-benzofuranyl group, 5
-Benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzo Furanyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl Group, 3-isoquinolyl group, 4-isoquinolyl group, 5-
Isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5
-Quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-
Phenanthridinyl group, 4-phenanthridinyl group, 6
-Phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1 , 7-phenanthroline-2-yl group, 1,7-phenanthroline-3
-Yl group, 1,7-phenanthrolin-4-yl group,
1,7-phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl group Group, 1,7-phenanthrolin-10-yl group, 1,8
-Phenanthroline-2-yl group, 1,8-phenanthrolin-3-yl group, 1,8-phenanthroline-4-
Yl group, 1,8-phenanthrolin-5-yl group, 1,
8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthroline-9
-Yl group, 1,8-phenanthrolin-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group, 1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl Group, 1,9-phenanthrolin-6-yl group, 1,9-
Phenanthroline-7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-
An yl group, a 1,10-phenanthrolin-2-yl group,
1,10-phenanthrolin-3-yl group, 1,10-
Phenanthroline-4-yl group, 1,10-phenanthrolin-5-yl group, 2,9-phenanthroline-1-
Yl group, 2,9-phenanthrolin-3-yl group, 2,
9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2,9-phenanthroline-6
-Yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl Group, 2,8-phenanthrolin-4-yl group, 2,8-
Phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group, 2,8-phenanthrolin-9-yl group, 2, 8
-Phenanthroline-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthroline-3
-Yl group, 2,7-phenanthrolin-4-yl group,
2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group, 2,7-phenanthrolin-9-yl group Group, 2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, -Phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group,
4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrole- 3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group,
3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-
t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl Group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4-t-butyl- And 3-indolyl groups.

Examples of the substituted or unsubstituted aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, α -Naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-
α-naphthylisopropyl group, β-naphthylmethyl group,
1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-
Pyrrolyl) ethyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromo Benzyl group, o
-Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-amino Benzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p
-Cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group and the like.

A substituted or unsubstituted aryloxy group is represented by-
OZ, examples of Z include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl,
-Phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-
Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group A p-terphenyl-2-yl group,
m-terphenyl-4-yl group, m-terphenyl-3
-Yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3
-Methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenylyl group, 4 ″ -t-butyl-p-terphenyl-
4-yl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-indolyl group, 3-indolyl group, 4
-Indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2 -Furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5
-Benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzo Furanyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl Group, 3-isoquinolyl group, 4-isoquinolyl group, 5-
Isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5
-Quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 1-phenanthridinyl group,
2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9- Phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthroline-2-yl Group, 1,7-phenanthrolin-3-yl group, 1,7-
Phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthroline-8-yl group, 1, 7
-Phenanthroline-9-yl group, 1,7-phenanthrolin-10-yl group, 1,8-phenanthroline-2
-Yl group, 1,8-phenanthrolin-3-yl group,
1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group, 1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group Group, 1,8-phenanthrolin-9-yl group, 1,8-
Phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group, 1,9-phenanthroline-3-
Yl group, 1,9-phenanthrolin-4-yl group, 1,
9-phenanthrolin-5-yl group, 1,9-phenanthrolin-6-yl group, 1,9-phenanthroline-7
-Yl group, 1,9-phenanthroline-8-yl group,
1,9-phenanthrolin-10-yl group, 1,10-
Phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group, 1,10-phenanthroline-4
-Yl group, 1,10-phenanthrolin-5-yl group,
2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group, 2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group Group, 2,9-phenanthrolin-6-yl group, 2,9-
Phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline-10-
Yl group, 2,8-phenanthrolin-1-yl group, 2,
8-phenanthrolin-3-yl group, 2,8-phenanthrolin-4-yl group, 2,8-phenanthroline-5
-Yl group, 2,8-phenanthrolin-6-yl group,
2,8-phenanthrolin-7-yl group, 2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl Group, 2,7-phenanthrolin-3-yl group, 2,7-
Phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group, 2, 7
-Phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group , 4-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl Group, 3-flazanyl group, 2-thienyl group, 3-
Thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl
Yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrole-5-yl Yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-
Indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-
A butyl-3-indolyl group, a 4-t-butyl-3-indolyl group and the like can be mentioned.

A substituted or unsubstituted alkoxycarbonyl group is represented by --COOY, and examples of Y include methyl, ethyl, propyl, isopropyl, n-butyl, and s.
-Butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2
-Hydroxyethyl group, 2-hydroxyisobutyl group,
1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl Group, 2
-Chloroisobutyl group, 1,2-dichloroethyl group,
1,3-dichloroisopropyl group, 2,3-dichloro-
t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 3-diiodoisopropyl group, 2,3-
Diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 3-diaminoisopropyl group, 2,
3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group,
-Cyanoethyl group, 2-cyanoisobutyl group, 1,2-
Dicyanoethyl group, 1,3-dicyanoisopropyl group,
2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group,
1,2-dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2,3
-A trinitropropyl group and the like.

The following are examples of compounds used in the layer forming the hole injection zone in the present invention, but the present invention is not limited to these unless it exceeds the gist thereof.

[0037]

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Examples of the compounds used in the layer forming the emission band in the present invention will be shown below, but the present invention is not limited to these unless it exceeds the gist.

[0039]

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The device structure of the organic EL device according to the present invention is a structure in which two or more organic layers are stacked between electrodes. As shown in FIGS. 1 and 2, the anode 2 and the hole injection zone 3 are formed. , A light-emitting zone 4, a cathode 5, an anode 2, a hole injection zone 3, a light-emitting zone 4, an electron injection zone 6, and a cathode 5 (in FIG. 1, reference numeral 1 denotes a substrate). The aforementioned compound is
It is used for an organic layer forming a light-emitting band, and it is also possible to form a light-emitting band by doping another hole injecting and transporting material, a light emitting material, and an electron injecting and transporting material.

The electron injecting and transporting material used in the present invention is not particularly limited, and any compound which is generally used as an electron injecting and transporting material may be used. For example, 2-
(4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole [01], bis {2- (4-t-butylphenyl) -1,3,4-oxa Oxadiazole derivatives such as diazole｝ -m-phenylene [02], triazole derivatives ([03],
[04] and the like.

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Also, quinolinol-based metal complexes represented by the general formulas [4], [5] and [6] can be mentioned.

Embedded image (Where Q represents a substituted or unsubstituted hydroxyquinoline derivative, a substituted or unsubstituted benzoquinoline derivative,
M represents a metal atom, and n represents its valence. )

Embedded image (Where Q represents a substituted or unsubstituted hydroxyquinoline derivative, a substituted or unsubstituted benzoquinoline derivative,
L represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, an aryl group which may contain a substituted or unsubstituted nitrogen atom, M represents a metal atom,
n represents its valence. )

Embedded image (Where Q represents a substituted or unsubstituted hydroxyquinoline derivative, a substituted or unsubstituted benzoquinoline derivative,
M represents a metal atom, and n represents its valence. )

Specific examples of the general formula [4] include [05] to
The compound of [10] is mentioned.

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Similarly, specific examples of the general formula [5] include the following compounds [11] to [16].

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Further, specific examples of the general formula [6] include the following [17] to [19].

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Further, the same effect as in the case of using the electron injecting and transporting material may be obtained by doping the light emitting material with a metal having a small work function without using the electron injecting and transporting material. The metal to be doped is not particularly limited, and examples thereof include lithium, magnesium, aluminum, and the like that constitute a cathode.

The method for forming each layer of the organic EL device of the present invention is not particularly limited, and a conventionally known method such as a vacuum deposition method or a spin coating method can be used. The organic thin film layer containing the compound represented by the general formula [1] used in the organic EL device of the present invention may be formed by vacuum evaporation, molecular beam evaporation (MBE), dipping of a solution dissolved in a solvent, spinning, or the like. It can be formed by a known method such as a coating method, a casting method, a bar coating method, a roll coating method or the like, but a thin film formation by a vacuum evaporation method is particularly preferable.

The thickness of each organic layer of the organic EL device of the present invention is not particularly limited. In general, if the thickness is too small, defects such as pinholes are likely to occur. Is usually several nm to 1 μm
The range of m is preferred.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 FIG. 1 shows a cross-sectional structure of an element used in Example 1. Hereinafter, a procedure for manufacturing the organic thin film EL device used in Example 1 of the present invention will be described. The device is composed of anode 2 / hole injection zone 3 / emission zone 4 / cathode 5. ITO is deposited on the glass substrate 1 by sputtering so that the sheet resistance becomes 20 Ω / □,
The anode was used. The ITO substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. Washed I
Set the TO substrate on the Xe ₂ ^* UV irradiation device,
Irradiation with ultraviolet light of 72 nm was performed for 3 minutes. This substrate was mounted on a vapor deposition apparatus, and a compound <1> was formed to a thickness of 25 nm by vacuum vapor deposition as a hole injection zone. Next, as an emission band, the compound (1) was formed to a thickness of 60 nm by vacuum evaporation. Next, a magnesium-silver alloy was formed as a cathode by a vacuum evaporation method to a thickness of 150 nm.
Thus, an organic EL device was manufactured. When a DC voltage of 10 V was applied to this device, blue light emission of 1100 cd / m ² was obtained.

Example 2 FIG. 2 shows a cross-sectional structure of an element used in Example 2. The device is composed of anode 2 / hole injection zone 3 / emission zone 4 / electron injection zone 6 / cathode 5. ITO was formed on the glass substrate 1 by sputtering so that the sheet resistance became 20 Ω / □, and used as an anode. The ITO substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. The washed ITO substrate was set on a Xe ₂ ^* ultraviolet irradiation device, and the substrate was set at 172 nm.
For 3 minutes. This substrate was mounted on a vapor deposition apparatus, and compound <2> was vacuum-deposited for 2 hours as a hole injection zone.
5 nm was formed. Next, as an emission band, compound (12)
Was formed to 60 nm by vacuum evaporation. Next, a compound [11] was formed in a thickness of 25 nm by vacuum evaporation as an electron injection zone. Next, a magnesium-silver alloy was formed as a cathode to a thickness of 150 nm by a vacuum evaporation method to produce an organic EL device. When a DC voltage of 10 V was applied to this element, 6800 cd
/ M ² of green light was obtained. The highest efficiency of this device is 1
4.3 cd / A.

(Embodiment 3) FIG. 3 shows a sectional structure of an element used in Embodiment 3. The device is composed of an anode 2 / a hole injection zone 3 having a hole injection layer 7 and a hole transport layer 8 / a light emission zone 4 / an electron injection zone 6 / a cathode 5. Sheet resistance is set to 2 by sputtering ITO on a glass substrate 1.
A film was formed so as to have a resistance of 0 Ω / □ to form an anode. This ITO
The substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. The washed ITO substrate was set in a Xe ₂ ^* ultraviolet irradiation apparatus, and the substrate was irradiated with ultraviolet rays of 172 nm for 3 minutes. This substrate was mounted on a vapor deposition apparatus, and a compound <3> was formed as a hole injection layer in a hole injection zone by vacuum evaporation to a thickness of 25 nm. Next, N, N'-diphenyl-N, N'-bis (1-naphthyl) -1,1'-diphenyl-4,4'-diamine was used as a hole transport layer in the hole injection zone by vacuum evaporation to a thickness of 20 nm. Formed. Next, a compound (12) was formed to a thickness of 60 nm by vacuum evaporation as an emission band. Next, a compound [11] was formed in a thickness of 25 nm by vacuum evaporation as an electron injection zone. Next, a magnesium-silver alloy is formed as a cathode to a thickness of 150 nm by a vacuum evaporation method to form an organic EL.
An element was manufactured. When a DC voltage of 10 V was applied to this device, green light emission of 8,800 cd / m ² was obtained. The highest efficiency of this device was 16.5 cd / A.

Example 4 The same operation as in Example 2 was carried out except that the compound <1> was used as the hole injection zone, the compound (15) was used as the emission band, and the compound [14] was used as the electron injection zone. An EL device was manufactured. When a DC voltage of 10 V was applied to this device, red light emission of 1,800 cd / m ² was obtained. The highest efficiency of this device is 4.5 cd
/ A.

Example 5 The same operation as in Example 3 was carried out except that the compound <2> was used as the hole injection zone, the compound (18) was used as the emission band, and the compound [05] was used as the electron injection zone. An EL device was manufactured. When a DC voltage of 10 V was applied to this element, red-orange light emission of 8,500 cd / m ² was obtained. The highest efficiency of this device is 12.6
cd / A.

Example 6 The same operation as in Example 3 was carried out except that the compound <4> was used as the hole injection zone, the compound (28) was used as the light emission zone, and the compound [11] was used as the electron injection zone. An EL device was manufactured. When a DC voltage of 10 V was applied to this device, green-white luminescence of 7,600 cd / m ² was obtained. The highest efficiency of this device is 13.1
cd / A.

The organic EL devices manufactured in Examples 1 to 6
All exhibited excellent life characteristics.

(Comparative Example 1) An organic EL device was manufactured by performing the same operation as in Example 1 except that ultraviolet irradiation was not performed on the cleaned ITO substrate. Apply a DC voltage of 10 V to this element.
Upon application, blue light emission of 870 cd / m ² was obtained.

(Comparative Example 2) An organic EL device was manufactured in the same manner as in Example 2 except that ultraviolet light was not irradiated on the cleaned ITO substrate. Apply a DC voltage of 10 V to this element.
When applied, green light emission of 4900 cd / m ² was obtained. The highest efficiency of this device was 11.2 cd / A.

(Comparative Example 3) K was applied to the cleaned ITO substrate.
An organic EL device was manufactured in the same manner as in Example 3, except that irradiation with ultraviolet light of 222 nm was performed for 3 minutes using rCl ^* ultraviolet light. When a DC voltage of 10 V was applied to this device, green light emission of 5000 cd / m ² was obtained. The highest efficiency of this device was 11.1 cd / A.

(Comparative Example 4) An organic EL device was manufactured in the same manner as in Example 3 except that ultraviolet irradiation was not performed on the cleaned ITO substrate. Apply a DC voltage of 10 V to this element.
Upon application, green light emission of 6,600 cd / m ² was obtained. The highest efficiency of this device was 11.2 cd / A.

(Comparative Example 5) An organic EL device was manufactured in the same manner as in Example 4 except that ultraviolet light was not irradiated on the cleaned ITO substrate. Apply a DC voltage of 10 V to this element.
When applied, red light emission of 1100 cd / m ² was obtained. The highest efficiency of this device was 2.7 cd / A.

(Comparative Example 6) An organic EL device was manufactured by performing the same operation as in Example 5 except that no ultraviolet irradiation was performed on the cleaned ITO substrate. Apply a DC voltage of 10 V to this element.
When applied, red-orange light emission of 5300 cd / m ² was obtained. The highest efficiency of this device was 10.2 cd / A.

(Comparative Example 7) An organic EL device was manufactured by performing the same operation as in Example 6, except that the irradiated ITO substrate was not irradiated with ultraviolet rays. Apply a DC voltage of 10 V to this element.
Upon application, a green-white luminescence of 4800 cd / m ² was obtained. The highest efficiency of this device was 10.8 cd / A.

Comparative Example 8 An organic EL device was manufactured in the same manner as in Example 3, except that a triphenylamine derivative represented by the following chemical formula [7] was used as a hole injection zone. When a DC voltage of 10 V was applied to this element, 8
Green light emission of 300 cd / m ² was obtained.

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(Comparative Example 9) An organic EL device was manufactured by performing the same operation as in Comparative Example 8 except that no ultraviolet irradiation was performed on the cleaned ITO substrate. Apply a DC voltage of 10 V to this element.
Upon application, green light emission of 9,700 cd / m ² was obtained.

FIG. 4 is a graph showing the relationship between the voltage and the luminance when a DC voltage was applied to the devices manufactured in Example 3 and Comparative Examples 3, 4, 8, and 9, and FIG. FIG. 5 is a graph showing the relationship.

As can be seen from FIG. 4 and FIG. 5, the organic EL device having the material represented by the general formula [1] in the hole injection zone is obtained by using an anode which has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm. The voltage at which light emission of 100 cd / m ² is obtained is reduced from 5.4 V to 4.2 V, and the maximum luminance is 5
Increased from 3000 cd / m ² to 42000cd / m ^2, the maximum brightness is 13.4cd / A from 11.2cd / A
Has improved. However, the organic EL device having the chemical formula [7] as the hole injection zone has a wavelength of 100 nm to 20 nm.
The performance was not improved even with the use of the anode that had been subjected to the ultraviolet irradiation treatment of 0 nm.

[0068]

As described above, according to the present invention,
In an organic electroluminescence device in which a layer forming a hole injection zone contains the material represented by the general formula [1] alone or as a mixture, by using an anode that has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm, high luminance and high brightness can be obtained. A high-efficiency organic EL device having a long life and low-voltage driving can be obtained, and the effect of the present invention is great.

[Brief description of the drawings]

FIG. 1 is a sectional view of an element of the present invention.

FIG. 2 is a sectional view of the device of the present invention.

FIG. 3 is a sectional view of the device of the present invention.

FIG. 4 is a graph showing the relationship between the voltage and the luminance of the organic EL devices of Example 3 and Comparative Examples 3, 4, 8, and 9 of the present invention.

FIG. 5 is a graph showing the relationship between the current density and the current efficiency of the organic EL devices of Example 3 and Comparative Examples 3, 4, 8, and 9 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection zone 4 Emission zone 5 Cathode 6 Electron injection zone 7 Hole injection layer 8 Hole transport layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hitoshi Ishikawa 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Tatsu Higashiguchi 5-7-1 Shiba, Minato-ku, Tokyo Japan Inside Electric Co., Ltd. (72) Inventor Hiroshi Tada 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation F-term (Reference) 3K007 AB00 AB02 AB03 AB04 AB06 CA01 CB01 DA00 DB03 EB00 FA00 FA01

Claims (6)

[Claims] 1. A layer having at least an anode, a hole injection zone, an organic light emitting zone, and a cathode as constituent elements, and a layer forming the hole injection zone contains a material represented by the following general formula [1] alone or as a mixture. An organic electroluminescent device, wherein an anode which has been subjected to an ultraviolet irradiation treatment with a wavelength of 100 nm to 200 nm is used in the organic electroluminescent device. Embedded image (Where, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted arylene group having a carbon number of 5 to 42, Ar ₃ ~
Ar ₇ is independently a substituted or unsubstituted carbon number of 6 to 2
0 is an aryl group. Here, the substituent includes a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group. Group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxycarbonyl group, Or a carboxyl group is mentioned. ) 2. The organic electroluminescent device according to claim 1, wherein the layer forming the organic light emitting band contains a material represented by the following general formula [2] alone or as a mixture. Embedded image (However, Ar ₈ is a substituted or unsubstituted arylene group having 5 to 42 carbon atoms, and Ar _{9 to} Ar ₁₂ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
Here, as the substituent, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group,
Examples thereof include a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, and a carboxyl group. ) 3. The organic electroluminescent device according to claim 1, further comprising an electron injection zone between the organic light emitting zone and the cathode. 4. The organic electroluminescence device according to claim 1, wherein the anode has an oxide conductor having a work function of 4 eV or more. 5. A step of subjecting the anode to ultraviolet irradiation with a wavelength of 100 nm to 200 nm, a step of forming a hole injection zone on the anode, a step of forming an organic light-emitting zone, and forming a cathode on the organic layer. Forming an organic electroluminescent device. 6. A step of irradiating the anode with ultraviolet light having a wavelength of 100 nm to 200 nm, a step of forming a hole injection zone on the anode, a step of forming an organic light emitting zone, and a step of forming an electron injection zone. And a step of forming a cathode on the organic layer.