WO2008035664A1

WO2008035664A1 - Organic electroluminescent device material, organic electroluminescent device, display and illuminating device

Info

Publication number: WO2008035664A1
Application number: PCT/JP2007/068063
Authority: WO
Inventors: Masato Nishizeki; Noboru Sekine; Dai Ikemizu
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2006-09-20
Filing date: 2007-09-18
Publication date: 2008-03-27
Also published as: JP5644050B2; JPWO2008035664A1

Abstract

Disclosed is an organic EL device material having controlled emission wavelength, high luminous efficiency and long emission life. Particularly disclosed is an organic EL device material which emits a light of short wavelength ranging from blue to blue green, while having high luminous efficiency and long emission life. Also disclosed are an organic EL device, a display and an illuminating device, each using such an organic EL device material. The organic EL device material is characterized by being composed of a metal complex represented by the following general formula (1).

Description

Specification

Organic-elect mouth luminescence element material, organic-elect-mouth luminescence element, display device and lighting device

Technical field

TECHNICAL FIELD [0001] The present invention relates to an organic electoluminescence device material, an organic electroluminescence device, a display device, and a lighting device.

Background art

[0002] Conventionally, as a light-emitting electronic display device, there is an electoric luminescence display (hereinafter referred to as ELD). ELD components include inorganic-electric luminescence elements and organic-electric luminescence elements (hereinafter also referred to as organic EL elements! /). Inorganic electoric luminescence elements require high alternating current voltage to drive the force light-emitting elements that have been used as planar light sources. An organic EL device has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and electrons and holes are injected into the light emitting layer and recombined to generate excitons. It is an element that emits light by using light emission (fluorescence 'phosphorescence) when this exciton is deactivated, it can emit light at a voltage of several V to several tens V, and is self-luminous. For this reason, it is a thin-film, complete solid-state device with a wide viewing angle and high visibility, so it has attracted attention from the viewpoints of space saving and portability.

[0003] However, for organic EL elements for practical use in the future, development of organic EL elements that emit light efficiently and with high luminance with lower power consumption is desired.

[0004] In Japanese Patent No. 3093796, a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative is doped with a trace amount of a phosphor to improve emission luminance and extend the lifetime of the element. Yes. In addition, an element having an organic light emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped to the host compound (for example, JP-A 63-264692), an 8-hydroxyquinoline aluminum complex is used as a host As a compound, an element having an organic light emitting layer doped with a quinacridone dye (for example, Japanese Patent Publication No. 3-255190) is known. [0005] As described above, when using emission from excited singlet, the generation ratio of singlet exciton and triplet exciton is 1: 3, so the generation probability of luminescent excited species is 25%, Since the light extraction efficiency is about 20%, the limit of external extraction quantum efficiency (7] ext) is set to 5%

Yes

[0006] However, Princeton University reported on organic EL devices using phosphorescence emission from excited triplets (MA Baldo et al., Nature, 395, 151-; 154 (1998)). Since then, research on materials that exhibit phosphorescence at room temperature has become active.

[0007] For example, M. A. Baldo et al., Nature, 403, 17, 750-753 (2000

), And US Pat. No. 6,097,147.

[0008] When the excited triplet is used, the upper limit of the internal quantum efficiency is 100%, so that in principle the luminous efficiency is four times that of the excited singlet, and almost the same performance as a cold cathode tube is obtained. It is also attracting attention as a lighting application.

[0009] For example, in S. Lamansky et al., J. Am. Chem. Soc., Vol. 123, p. 4304 (2001), many compounds are synthesized and studied focusing on heavy metal complexes such as iridium complexes. Has been.

[0010] Further, in the above-mentioned MA Baldo et al., Nature, 403, No. 17, 750-753 (2000), there is a study using tris (2-phenylviridine) iridium as a dopant. Has been.

[0011] In addition, ME Tompson et al., The 10th International Workshop on In organic and Organic Electroluminescence (EL'00, Hamamatsu), and L2Ir (acac), for example, (ppy) 2Ir (acac) ), Moon— Jae Youn. 0g, Tetsuo Tsutsui, etc., also said that the 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) was used and tris (2— (ρ —Tolyl) pyridine) iridium (Ir (ptpy) 3), tris (benzo [h] quinolin) iridium (Ir (bzq) 3) etc. Commonly called ortho-metalated iridium complexes!

[0012] In addition, in the above-mentioned S. Lamansky et al., J. Am. Chem. Soc., 123, 4304 (2001), JP 2001-247859, etc., various iridium complexes are used. Elementary Attempts have been made to become children.

[0013] In order to obtain high luminous efficiency, in the 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Use a hole transporting compound as a host of phosphorescent compound. . In addition, M. E. Tompson et al. Use various electron transport materials as hosts for phosphorescent compounds and dope them with a novel iridium complex.

[0014] Orthometalated complexes in which the central metal is platinum instead of iridium are also attracting attention. There are many known examples of this type of complex with ligands!

[0015] In the case of V, the light emission brightness and the light emission efficiency in the case of the light emitting element are greatly improved as compared to the conventional element because the emitted light is derived from phosphorescence. There was a problem that the light emission lifetime was lower than that of the conventional device. As described above, phosphorescent highly efficient light-emitting materials are difficult to shorten the emission wavelength and improve the light emission lifetime of the device. Currently.

[0016] Regarding wavelength shortening, an electron-withdrawing group such as a fluorine atom, a trifluoromethyl group, and a cyano group has been introduced into phenylpyridine as a substituent, and a picolinic acid villaza ball type as a ligand. The force _S , which is known to introduce sub-ligands, allows the emission wavelength of the light-emitting material to be shortened to achieve blue color and achieve a highly efficient device. Since it deteriorated significantly, there was a need to improve the trade-off.

[0017] Metal complexes having phenylbiazole substituted with a phenyl group as a ligand are known (see, for example, Patent Documents 1 and 2). However, the phenyl group substitution mode disclosed here is not sufficient to improve the lifetime of the light emitting device, and there is still room for improvement from the viewpoint of luminous efficiency.

[0018] Examples in which various substituents are introduced using phenylimidazole as a basic skeleton as a ligand have been disclosed (for example, see Patent Documents 3 and 4), but the emission lifetime is greatly improved. There is room for improvement without being seen.

[0019] As another approach, an example is disclosed in which a condensed ring structure composed of three or more rings containing a hetero atom is introduced into the ligand structure (see Patent Documents 5, 6, and 7). Is disclosed All examples show long-wave emission such as yellow to red with emission maxima of 550 nm or more. There are few examples of short-wave emission such as blue to blue-green. It was.

Patent Document 1: International Publication No. 04/085450 Pamphlet

Patent Document 2: JP 2005-53912 A

Patent Document 3: International Publication No. 05/007767 Pamphlet

Patent Document 4: Pamphlet of International Publication No. 06/046980

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-332291

Patent Document 6: Japanese Unexamined Patent Application Publication No. 2004-67658

Patent Document 7: International Publication No. 04/111066 Pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0020] The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic EL element material having a controlled emission wavelength, high emission efficiency, and a long emission lifetime. It is. In particular, it is to provide an organic EL element material that exhibits high luminous efficiency and has a long light emission lifetime with blue to blue-green short-wave light emission. Furthermore, an organic EL element, a display device, and a lighting device using the same are provided.

Means for solving the problem

[0021] The above object of the present invention has been achieved by the following constitution.

[0022] 1. An organic electoluminescence device material characterized by being a metal complex represented by the following general formula (1).

[0023] [Chemical 1] —Killing ceremony

[Wherein, X represents R—N, 0, S, Se or Te. R represents a substituted or unsubstituted alkyl group,

1 1

Represents a chloroalkyl group, an aryl group or an aromatic heterocyclic group. Y, Y and Y are R—N

1 2 3 2

, N or R—C, together with C and N, imidazole ring, triazole ring, tetrazole

Three

Represents a group of atoms necessary to form a ring. R represents a substituted, unsubstituted alkyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group. R is a hydrogen atom or a substituent

Three

Represents. G represents a substituent, and n represents 0, 1 or 2. X—L—X is a bidentate ligand

1 1 2

X and X each independently represent a carbon atom, a nitrogen atom or an oxygen atom. L is X, X

Represents a group of atoms that form a bidentate ligand with 1 2 1 1 2. The central metal M is in the periodic table

1

8 ~; 1 represents a group 1 metal. ml represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, but ml + m2 is 2 or 3, which is the same number as the positive charge of the central metal. )

2. The organic electoluminescence device material as described in 1 above, wherein the metal complex represented by the general formula (1) is represented by the following general formula (2).

[0025] [Chemical formula 2] General formula (2}

(In the formula, X represents R—N, 0, S, Se or Te. R represents a substituted, unsubstituted alkyl group,

1 1

Represents a chloroalkyl group, an aryl group or an aromatic heterocyclic group. Y and Y represent R—N, N or R—C, and N—C═N together with imidazole ring, triazole ring, tetrazole ring

Three

Represents an atomic group necessary for forming. R represents a substituted, unsubstituted alkyl group, cycloanolalkyl group, aryl group or aromatic heterocyclic group. R is a hydrogen atom or a substituent

Three

To express. G represents a substituent, and n represents 0, 1 or 2. X—L —X represents a bidentate ligand

1 1 2

X and X each independently represent a carbon atom, a nitrogen atom or an oxygen atom. L is X, X and

1 2 1 1 2 Both represent a group of atoms forming a bidentate ligand. The central metal M is

1

3. The organic electoluminescence device material as described in 2 above, wherein the metal complex represented by the general formula (2) is represented by the following general formula (3).

[0027] [Chemical 3]

(Wherein X represents R—N, 0, S, Se or Te. R represents a substituted or unsubstituted alkyl group,

1 1

Represents a chloroalkyl group, an aryl group or an aromatic heterocyclic group. R represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. G represents a substituent, and n represents 0, 1 or 2. X—L—X represents a bidentate ligand, and X and X are each

1 1 2 1 2 Independently represents a carbon atom, a nitrogen atom or an oxygen atom. L is X, X and bidentate ligand

1 1 2

Represents an atomic group forming The central metal, M, is 8 ~ in the periodic table; 1 Group 1 gold

1

Represents a genus. ml represents an integer of 1, 2 or 3, m2 represents a force m representing an integer of 0, 1 or 2 m l + m2 is 2 or 3, which is the same number as the positive charge of the central metal. )

4. The organic elect described in 3 above, wherein the metal complex represented by the general formula (3) is an R force S methyl group, a substituted, unsubstituted aryl group or an aromatic heterocyclic group. Mouth luminescence element material.

[0029] 5. In the metal complex represented by the general formula (3), R is 2,6-dimethylphenyl group, mesityl group (2,4,6-trimethylphenyl group), tetramethylphenyl group. 5. The organic electroluminescent element material according to 4 above, which is a pentamethylphenyl group.

[0030] 6. Any one of 1 to 5 above, wherein the central metal M is iridium.

1

The organic electoluminescence device material described in 1.

[0031] 7. The center metal M is platinum;

1

Organic-elect mouth luminescence element material listed.

[0032] 8. The organic electroluminescence element material according to any one of;! To 7, wherein the m2 is 0.

[0033] 9. The organic electroluminescence device material according to any one of 1 to 8, wherein the first emission wavelength is in the range of 400 to 500 nm.

[0034] 10. An organic electoluminescence device comprising the organic electroluminescence device material according to item 1, wherein any one of 1 to 9 is used.

[0035] 11. A light-emitting layer as a constituent layer, wherein the light-emitting layer contains the organic electoluminescence device material according to any one of; Organic electroluminescence device.

[0036] 12. The light-emitting layer has a ring structure in which at least one carbon atom of a hydrocarbon ring constituting a force rubazole ring or a force rubazole ring of the carbazolone derivative is substituted with a nitrogen atom as a host compound. 10. The organic electroluminescent device according to 10 above, which contains a derivative.

[0037] 13. It has a hole blocking layer as a constituent layer, and the hole blocking layer has a carbazole derivative or a carbon atom of a hydrocarbon ring constituting a force rubazole ring of the carbazole derivative as a hole blocking material. Derivatives having a ring structure in which at least one of them is substituted with a nitrogen atom 13. The organic electoluminescence device according to any one of 10 to 12 above, comprising a body.

[0038] 14. A display device comprising the organic electoluminescence device according to any one of 10 to 13.

[0039] 15. An illuminating device comprising the organic-electric-luminescence element according to any one of 10 to 13.

The invention's effect

[0040] According to the present invention, an organic EL element material useful for an organic EL element can be obtained. By using the organic EL element material, the emission wavelength is controlled, the emission efficiency is high, and the emission lifetime is long. We were able to provide organic EL elements, lighting devices, and display devices.

Brief Description of Drawings

FIG. 1 is an emission spectrum of the metal complex (Compound 4) of the present invention.

FIG. 2 is an emission spectrum of the metal complex (Compound 4) of the present invention.

FIG. 3 is an emission spectrum of the metal complex (Compound 14) of the present invention.

FIG. 4 is an emission spectrum of the metal complex (Compound 14) of the present invention.

FIG. 5 is an emission spectrum of the metal complex of the present invention (Compound 27).

FIG. 6 is an emission spectrum of the metal complex of the present invention (Compound 27).

FIG. 7 is a schematic view showing an example of a display device composed of organic EL elements.

FIG. 8 is a schematic diagram of display unit A.

FIG. 9 is a schematic diagram of a pixel.

FIG. 10 is a schematic diagram of a passive matrix type full-color display device.

FIG. 11 is a schematic view of a lighting device.

FIG. 12 is a schematic diagram of a lighting device.

Explanation of symbols

[0042] 1 display

3 pixels

5 scan lines

6 Data line 7 Power line

10 Organic EL devices

12 Driving transistor

13 Capacitor

A Display section

B Control unit

102 Glass cover

105 cathode

106 OLED layer

107 Glass substrate with transparent electrode

108 nitrogen gas

109 Water catcher

BEST MODE FOR CARRYING OUT THE INVENTION

[0043] In the organic EL element material of the present invention, it is possible to molecularly design a useful organic EL element material for an organic EL element by any one of claims 1 to 9, and the configuration specified in item 1. It worked. In addition, by using the organic EL element material, it was possible to provide an organic EL element, an illuminating device, and a display device that exhibit high luminous efficiency and have a long emission lifetime.

[0044] As a result of intensive studies on the above problems, the present inventors have found that the general formula (1), (

By using an organic EL device containing the metal complex represented by 2) or (3) as an organic EL device material

The inventors have found that the luminous efficiency and luminous lifetime are greatly improved.

[0045] As a result of intensive investigations by the present inventors, the stability of the complex of the phenylazole derivative is greatly influenced by the influence of the substitution position and type of the substituent on the phenyl nucleus, which is the mother nucleus, which affects the emission lifetime. I found it to have a big impact. Like the metal complex according to the present invention, by introducing a specific partial structure into phenylazole, light is emitted only by a blue metal complex having a conventional phenylpyridine derivative as a ligand, particularly only by an electron withdrawing group. We found that the light emission lifetime, which was a problem with organic EL devices manufactured using organic EL device materials that had been controlled to have a short wavelength, was significantly improved. It came to be able to balance life. Also, among 2-phenylimidazole derivatives, 2-phenylimidazole derivatives are used, and by introducing specific substituents into nitrogen atoms that are not liganded to metals on the imidazole ring, excellent color purity is achieved. As a result, it was found that the lifetime of the blue light-emitting device could be further extended.

[0046] Hereinafter, details of each component according to the present invention will be sequentially described.

[0047] <Metal complex>

The metal complex according to the organic EL device material of the present invention will be described.

[0048] (Ligand)

The metal complex according to the present invention is, for example, described by the above general formula (1). The partial structure shown in the parenthesis having ml, or the partial structure represented by a tautomer thereof is the main ligand, m A partial structure shown in parentheses having 2 or a partial structure represented by a tautomer thereof is called a subligand.

In the present invention, as represented by the general formula (1), the metal complex is a main ligand or a tautomer thereof and a subligand or a combination of tautomers thereof. As will be described later, when m2 = 0, that is, all the ligands of the metal complex are composed only of a partial structure represented by the main ligand or its tautomer! /, Anyway!

[0050] Furthermore, as a so-called ligand used in the formation of a conventionally known metal complex, the trader has a known ligand (also a coordination compound! /, U) as a sub-ligand as necessary. Then! / But!

[0051] From the viewpoint of preferably obtaining the effects described in the present invention, the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.

[0052] There are various known ligands used in the conventionally known metal complexes. For example, "Photochemistry and Photophysics of Coordination Compounds" Springer—Verlag H. Yersin 1987 Issuance, “Organic Metal Chemistry Fundamentals and Applications” Liu Huabosha Akio Yamamoto's 1982 publication (eg halogen ligands (preferably chlorine ligands), nitrogen-containing heterocycles) Ligands (for example, bibilidyl, phenantine phosphorus, etc.) and diketone ligands).

[0053] (8 to 11 of the Periodic Table of Elements; Group 11 transition metal elements) The metal used for forming the metal complex represented by the general formula (1), (2) or (3) according to the present invention includes a transition metal element of group 8 to 11 of the periodic table (simply a transition). Among these, iridium and platinum are preferable transition metal elements.

[0054] As the containing layer of the metal complex represented by the general formula (1), (2) or (3) according to the present invention, a light emitting layer and / or an electron blocking layer is preferred and contained in the light emitting layer. In this case, by using it as a light-emitting dopant in the light-emitting layer, it is possible to improve the external extraction quantum efficiency (increase the luminance) and prolong the light emission lifetime of the organic EL device of the present invention.

[0055] (Metal complex represented by the general formula (1), (2) or (3))

Here, the metal complex represented by the general formula (1), (2) or (3) according to the present invention will be described.

[0056] In the general formula (1), (2) or (3), X represents R—N, ◯, S, Se or Te. Departure

1

X is preferably R—N, 0, S in that the optical maximum wavelength is shorter.

1

More preferably, X is RN in that the color purity of light emission is higher.

1

[0057] R represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group, or aromatic complex.

1

Represents a cyclic group.

[0058] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and the like. Is mentioned.

[0059] Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0060] Examples of the aryl group include a phenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthyl group, a fluorenyl group, a phenanthryl group, an indur group, a pyrenyl group, and a biphenyl group. Examples include a tolyl group.

[0061] Examples of the aromatic heterocyclic group include a pyridyl group, pyrimidinyl group, furyl group, pyrrolinole group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazyl group, and triazolyl group. , 4 卜 lyso 'monore 1 inole group, 1, 2, 3 卜 lyso' monore 1 inole group, etc.), Group, cenyl group, quinolyl group, benzofuryl group, dibenzofuryl Group, benzophenyl group, dibenzoenyl group, indolinole group, carbazolyl group, force noreborinyl group, quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group and the like.

Examples of the substituents that may be further substituted are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert butyl group, pentyl group, hexyl group, octyl group). , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, bur group, aryl group, etc.), alkynyl group (eg, Etul group, propargyl group, etc.), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-phenyl group, mesityl group, trinole group, xylinole group , Naphthyl group, anthryl group, azulenyl group, acenaphthyl group, fluorenyl group, phenanthryl group, indur group, pyrenyl group, bif Edylyl group, etc.), aromatic heterocyclic groups (for example, pyridinole group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, virazolyl group, pyrazol group, triazolyl group (for example, 1, 2, 4 —Triazole-1-yl group, 1, 2, 3-triazole-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, chenyl group, quinolinole group, Benzofuryl group, dibenzofuryl group, benzocenyl group, dibenzocenyl group, indolinole group, carbazolyl group, canolepolyninole group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is nitrogen ), Quinoxalinyl group, pyridazinyl group, tria Nyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidinole group, imidazolidinole group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group) , Hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, For example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenyl) Thio group, Naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethinole genus xycanole poninore group, butinole genus xycaneno repino nore group, genino chineno genius xycaneno repino nore group, dodecyloxy carbonyl group, etc.), allylo Xycarbonyl group (eg, phenylcarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, propylaminosulfonyl group, hexylaminosulfonyl group) Group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Til group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexynole carbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, Pyridylcarbonyl group, etc.), acyloxy groups (for example, acetyloxy group, ethyl carbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), Amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethyl group) Xylcarbonylamino group Lucarponylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), rubamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group) Propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, Naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (eg methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecinoreureido group, phenylureido group) Naphthylurei Group, 2-pyridylaminoureido group, etc.), sulfier group (for example, methyl sulfier group, ethyl sulfier group, butyl sulfier group, cyclohexyl sulfier group, 2-ethyl hexyl sulfinyl group, dodecyl sulfinyl group) , Phenylsulfinyl group, naphthyls Norefiel group, 2-pyridylsulfier group, etc.), alkylsulfonyl group (for example, methinolesnorehoninore group, ethinoresnorehoninore group, butinoresnorehoninore group, cyclohexenolesnorenore 2-nore group, 2 —Ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group) , Ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylenomino group, do, decinoremino group, dilino group, naphthinoreamino group, 2-pyridinoremino group, etc., halogen atom (for example, , Fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon (For example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyan group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropyl silyl group) Group, triphenylsilyl group, phenyl silylsilyl group, etc.). These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

[0063] G represents a substituent, and n represents 0, 1 or 2. Examples of substituents include R substituent examples

1

The same power that you gave as that.

[0064] Y, Y and Y represent R—N, N, or R—C, together with C and N, an imidazole ring,

1 2 3 2 3

It represents an atomic group necessary for forming an azole ring or a tetrazole ring.

[0065] R represents a substituted, unsubstituted alkyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group. Examples of the alkyl group, cycloalkyl group, aryl group, and aromatic heterocyclic group are the same as those exemplified as R.

1

[0066] Examples of substituents that may be further substituted with these groups include examples of substituents for R and

1

That same power that I gave you.

[0067] R is preferably a methyl group, a substituted or unsubstituted aryl group, or an aromatic heterocyclic group from the viewpoint of light emission lifetime, and particularly preferably a substituted, unsubstituted aryl group, or aromatic heterocyclic group.

[0068] Among aryl groups, those in which at least one methyl group is substituted at the two ortho positions of the binding site with imidazole are more preferable than the point that the emission wavelength is shortened. The two ortho positions of the binding site with imidazole are both substituted with methyl groups. Specifically, it is a 2,6-dimethylphenyl group, a mesityl group (2,4,6-trimethylphenyl group), a tetramethylphenyl group or a pentamethylphenyl group. An example of a substituent that may be further substituted in the 2,6-dimethylphenyl group is the same force S as the substituent for R.

[0069] R is a hydrogen atom! / Represents a substituent. As examples of the substituent, the same ones as exemplified as the substituent for R can be used. A hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group is preferred, and a hydrogen atom or a substituted or unsubstituted aryl group is more preferred.

[0070] M as a central metal represents a group 8 to 11 metal in the periodic table. Examples of preferred central metals include ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold and the like. More preferred are iridium and platinum.

[0071] The structure of the main ligand is shown below together with the central metal M.

[0072] [Chemical 4]

Imidazol 1 Imidazol 1 2

In the formula, X, G, n, R, R, and M represent the same as those in the general formula (1).

2 3 1

[0074] It is preferable that Y is R—N in terms of high emission quantum yield.

3 2

Y is preferably H—C in that it is a force beam shortwave. The emission lifetime is longer when both Y and Y are R–C.

one two Three

[0075] That is, as the structure of the main ligand, the structures of imidazole-1, triazole-1, triazole-2 and tetrazole-1 are more preferable, and imidazolone 1 and triazole-1 are more preferable. Most preferred is the structure of imidazole-1.

[0076] In the general formula (1), (2) or (3), X—L—X represents a bidentate ligand,

1 1 2 1 2 Each independently represents a carbon atom, a nitrogen atom, or an oxygen atom. L is 2 seats with X and X

1 1 2

A group of atoms forming a ligand is represented. [0077] Specific examples of the bidentate ligand represented by XL-X include substituted or unsubstituted phenyl

1 1 2

Examples thereof include norepyridine, phenylpyrazonole, phenylimidazole, phenyltriazolene, phenyltetrazole, virazabol, acetylacetone, and picolinic acid. ml

Represents an integer of 1, 2 or 3, m2 is 0, force representing an integer of 1 or 2 ml + m2 is 2 or

3. Of these, m2 is preferably 0.

[0078] Specific examples of the metal complex represented by the general formula (1), (2) or (3) according to the present invention are shown below, but the present invention is not limited thereto.

[0079] [Chemical 5]

Blasphemy 008

[0081] [Chemical 7] [8 ^] 800]

C90890 / .00Zdf / X3d 03 1799SC0 / 800Z OAV

[0084] [Chemical 10]

[0085] [Chemical 11] 0086

[0087] [Chemical 13] 0088

[0089] [Chemical 15]

[0090] [Chemical 16]

//: ε90890 / -00ί1 £

[0094] [Chemical 20]

[0095] [Chemical 21]

[0096] [Chemical 22]

[0097] [Chemical 23]

^ §S∞60

[0099] [Chemical 25]

[0100] [Chemical 26]

¾001

0031

[0104] [Chemical 30] [τε¾] [9θΐθ]

[0106] [Chemical 32]

[0107] [Chemical 33]

[0108] [Chemical 34]

[0109] [Chemical 35]

[0110] [Chemical 36]

[0111] [Chemical 37]

[0112] [Chemical 38]

C90890 / .00Zdf / X3d

C90890 / .00Zdf / X3d 39

[0115] [Chemical 41]

[0116] [Chemical 42]

]

[0118] [Chemical 44]

[0119] [Chemical 45]

[0120] [Chem 46]

[0121] [Chemical 47]

250

[0123] [Chemical 49]

[0124] [Chemical 50]

C90890 / .00Zdf / X3d 89 1799SC0 / 800Z OAV

[0126] [Chemical 52]

[0127] [Chemical 53]

[0128] [Chemical 54]

[0129] [Chemical 55]

[0130] [Chem 56]

[0131] [Chemical 57]

[0132] [Chemical 58]

[0133] [Chemical 59] Prop.) S0314

[0135] [Chemical 61]

[0136] [Chemical 62]

[0137] [Chemical 63]

[0138] [Chemical 64]

[0139] [Chemical 65] [99] [(MO]

1799SC0 / 800Z OAV

[0141] [Chemical 67]

) ¾

[0143] [Chem 69]

[0144] [Chemical 70]

[0145] [Chemical 71]

[0146] [Chemical 72]

[0147] [Chemical 73]

[0148] [Chemical 74]

[0149] [Chemical 75]

[0150] [Chem 76]

[0151] [Chemical 77]

[0152] [Chemical 78]

These metal complexes are described in, for example, Organic Letter, vol 3, No. 16, 2579-258 1 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-; 1687 (1991), J Am. Chem. Soc., 123, 4304 (2001), Inorganic Chemistry, 40th, No. 7, 1704-; 171 1 (2001), Inorganic Chemistry, 41st, 12th 3055-3066 (2002), New Journal of Chemistry, Vol. 26, 1 171 (2002), European Journal of Organic Chemistry, ^ 4, 695-709 (2004). Apply methods such as references described in It can be synthesized.

[0154]

[0155] [0156]

[0157] 3— [1- (2, 4, 6 Trimethylphenyl) 1H-imidazole 2 —yl] 9 Phenol 9H strength rubazole, 3 · 9 g (9.1 millimonoles) 2 On the night of melting in 30 ml of Tanoinole, salt-iridium trihydrate, 1.06 g (3.0 millimonoles) and 10 ml of water were added and refluxed in a nitrogen atmosphere for 5 hours. The reaction solution was cooled, methanol 5 Oml was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol and dried to obtain 2.72 g (yield 84%) of complex A.

[0158] Under a nitrogen atmosphere, 2.16 g (1.0 mmol) of complex A and 2.2 g of sodium carbonate were suspended in 35 ml of 2 ethoxyethanol. Acetylacetone (0.4 g, 4.0 mmol) was added to the suspension, and the mixture was refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by vacuum filtration. The solid obtained after concentration of the solvent under reduced pressure was suspended by adding 10 Oml of water, and the solid was collected by filtration. The obtained crystals were further washed with a methanol / water = 1/1 mixed solution, and 2.10 g (yield 92%) of complex B was obtained after drying.

[0159] Complex B, 1.03 g (0.9 mmol) and 3— [1— (2, 4, 6 trimethylphenyl) — 1H imidazole-2 yl] —9 phenyl 9H force under nitrogen atmosphere Lubazole 1 · 28 g (3.0 mmol) was suspended in 40 ml of glycerin. The reaction was carried out at a reaction temperature of 150 to 160 ° C for 2 hours under a nitrogen atmosphere, and when the disappearance of complex B was confirmed, the reaction was completed. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol, and after drying, a crude product having a yield of 0.99 g (yield 74.7%) was obtained. This crude product was dissolved in a small amount of methylene chloride and purified by silica gel column chromatography to obtain 0.93 g (yield: 70.2%) of Exemplified Compound 4 (methylene chloride).

It was confirmed by MASS, 1H-NMR that the purified compound 4 was the target product.

[0160] 1H-NMR (400MHz, THF-d8)

Spectral attribution (chemical shift δ, peak shape, [coupling constant,] proton number, attribution to structure)

: Δ = 2.10 (s, 9H, CH3—), 2.48 (s, 9H, CH3—), 2.50 (s, 9H, CH3—), 6. 31 (t, J = 7.4 Hz , 3H, CH, phenylore), 6. 54 (t, J = 7.4Hz, 6H, CH, phenenole), 6.62 (s, 3H, CH, force nonozo, monoole ring) , 6. 80 (s, 3H, CH, force norezo, one nore ring), 6. 84 (d, J = 7.4Hz, 6H, CH, phenenore group), 6. 89 (d, J = l. 5Hz, 3H, CH, imidazo, single ring), 6.92 (d, J = l.5Hz, 6H, CH, imidazo, single ring), 6.97 (t, J = 7.4Hz, 3H, CH, force-norno ring) 7. ll (d, J = 7.4Hz, 3H, CH, carbazono ring), 7.14 (s, 3H, CH, mesityl group), 7.16 (s, 3H, CH, mesityl group), 7.21 (d, J = 7.4Hz, 3H, CH, force nore ヽ nore ring) 7.32 (d, J = 7.4Hz, 3H, CH, force rubazole ring)

The PL emission maximum wavelength in the solution of Exemplified Compound (4) measured using Hitachi F-4500 was 462 nm (T = 77K, in 2-methyltetrahydrofuran), 470 nm (room temperature, in methylene chloride) .

[0161] Figures 1 and 2 show the emission spectra.

[0162] (Synthesis of Exemplified Compound 14)

It was synthesized according to the following scheme.

[0163] [Chemical 80]

In a nitrogen atmosphere, 3- [1- (2, 4, 6-trimethylphenyl) 1H-imidazole-2-yl] 9-ethyl-9H-powered rubazole, 3.4 g (9.0 mmol) was dissolved in 30 ml of 2 ethoxyethanol. To the pre-melted night, 1 · 06 g (3.0 millimonoles) of salt and iridium trihydrate and 1 Oml of water were added and refluxed for 5 hours under a nitrogen atmosphere. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals are further washed with methanol and dried. 2. 54 g (yield 86%) of complex C was obtained.

[0165] Under a nitrogen atmosphere, Complex C, 1.97 g (1.0 mmol) and sodium carbonate 2. Og were suspended in 35 ml of 2-ethoxyethanol. Acetylacetone (0.4 g, 4.0 mmol) was added to the suspension, and the mixture was refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by vacuum filtration. The solid obtained after concentration of the solvent under reduced pressure was suspended by adding 100 ml of water, and the solid was collected by filtration. The obtained crystals were further washed with a methanol / water = 1/1 mixed solution, and after drying, 1.91 g (yield 91%) of Complex D was obtained.

[0166] Complex D under nitrogen atmosphere, 0.94 g (0.9 mmol) and 3- [1— (2, 4, 6-trimethylphenyl) — 1H-imidazole-2-yl] -9-ethyl — 9H—force rubazole 1 · 14 g (3.0 mmol) was suspended in 40 ml of glycerin. The reaction was completed in a nitrogen atmosphere at a reaction temperature of 150 to 160 ° C for 2 hours, and when the disappearance of complex D was confirmed, the reaction was terminated. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol and dried to obtain a crude product with a yield of 0.86 g (yield 72%). This crude product was dissolved in a small amount of methylene chloride and purified by silica gel column chromatography (methylene chloride) to give 0.88 _§ (yield 67.8%) of Exemplified Compound 14.

It was confirmed by MASS, 1H-NMR that the purified compound 14 was the desired product.

[0167] 1H-NMR (400MHz, THF-d8)

: Δ = 0.91 (t, J = 6.8Hz, 9H, CH3—, ethyl group), 1.81 (s, 9H, Me-), 2.16 (s, 9H, CH3-), 2 48 (s, 9H, CH3—), 3.75 (m, 6H, — CH2—, ethyl group), 6. 82 (d, J = l. 5Hz, 3H, CH, imidazole ring), 6. 84 (d, J = 7.6Hz, 3H, CH, force norezo zonore ring), 6.92 (s, 6H, CH, mesitinore group), 7.06 (t, J = 7.6Hz, 3H, CH , Force norezo, one nore ring), 7. 09 (d, J = 7.6Hz, 3H, CH, force norezo, one nore ring), 7 • 13 (s, 3H, CH, force nore zonore Ring), 7.20 (s, 3H, CH, mesitinole group), 7.27 (d, J = 7.6Hz, 3H, CH, force rubazole ring)

PL emission in a solution of Exemplified Compound 14 measured using Hitachi F-4500: 461 nm (T = 77K in 2-methyltetrahydrofuran), 465 nm (room temperature, salt) In methylene chloride).

[0168] Figures 3 and 4 show the emission spectra.

[0169] (Synthesis of Exemplified Compound 27)

It was synthesized according to the following scheme.

[0170] [Chemical 81]

[0171] 1-Methyl-2-dibenzo [b, d] furan 2-Hilou 1H-Imidazo Inore 2 · 2g (8.8mm monole) was melted into 30ml of 2Ethoxyethanolanol in a nitrogen atmosphere. , Iridium chloride trihydrate, 1.06 g (3.0 mmol) and 10 ml of water were added, and the mixture was refluxed for 5 hours under a nitrogen atmosphere. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol and dried to obtain 1.78 g (yield 82%) of complex E.

[0172] Under a nitrogen atmosphere, 1.44 g (1 .0 mmol) of complex E and 2.3 g of sodium carbonate were suspended in 35 ml of 2 ethoxyethanol. Acetylacetone (0.4 g, 4.0 mmol) was added to the suspension, and the mixture was refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by vacuum filtration. The solid obtained after concentration of the solvent under reduced pressure was suspended by adding 10 Oml of water, and the solid was collected by filtration. The obtained crystals were further washed with a methanol / water = 1/1 mixed solution, and after drying, 1.40 g (yield 89%) of complex F was obtained.

[0173] Complex F, 0.63 g (0.8 mmol) and 1-methyl-2 dibenzo [b, d] furan-2-yl-1H imidazole 0.774 g (3.0 millimonole) in 40 ml of glycerol under nitrogen atmosphere Suspended. The reaction was completed at a reaction temperature of 150 to 160 ° C for 2 hours under a nitrogen atmosphere, and when the disappearance of complex F was confirmed, the reaction was terminated. The reaction solution was cooled, 50 ml of methanol was added, and the precipitated crystals were collected by filtration. The obtained crystals were further washed with methanol, and after drying, a crude product having a yield of 0.52 g (yield 69%) was obtained. This crude product was dissolved in a small amount of methylene chloride and purified by silica gel column chromatography to obtain 0.48 g (yield 64.2%) of Exemplified Compound 27 (methylene chloride).

It was confirmed by MASS, 1H-NMR that the purified compound 27 was the target product.

[0174] 1H-NMR (400MHz, THF-d8)

: Δ = 3.80 (s, 9H, CH3-, methinore group), 6.37 (d, J = l. 5Hz, 3H, CH, imidazo mononole ring), 6.91 (s, 3H, CH, Dibenzo, furan ring), 7. 13 (t, J = 7.6 Hz, 3H, CH, dibenzofuran ring), 7.22 (t, J = 7.6 Hz, 3H, CH, dibenzofuran ring), 7. 25 (d, J = l. 5Hz, 3H, CH, imidazole ring), 7.27 (d, J = 7.6Hz, 3H, CH, dibenzofuran ring), 7.84 (d, J = 7.6Hz, 3H, CH, dibenzofuran ring), 8. 16 (s, 3H, CH , Dibenzofuran ring)

The PL emission maximum wavelength in the solution of Exemplified Compound 27 measured using Hitachi F-4500 was 453 nm (T = 77K, in 2-methyltetrahydrofuran), 459 nm (room temperature, in methylene chloride).

[0175] Figures 5 and 6 show the emission spectra.

[0176] << Application of organic EL element materials to organic EL elements >>

When producing the organic EL device of the present invention using the organic EL device material of the present invention,

Among the constituent layers (details will be described later) of the EL element, it is preferable to use the organic EL element material of the present invention for the light emitting layer or the electron blocking layer. In the light emitting layer, it is preferably used as a light emitting dopant as described above.

[0177] (Light-emitting host and light-emitting dopant)

The mixing ratio of the light-emitting dopant to the light-emitting host, which is the host compound as the main component in the light-emitting layer, is preferably adjusted to a range of 0.;! To less than 30% by mass.

[0178] However, the luminescent dopant may be a mixture of two or more types of compounds. The mixed partner may have a different structure, and other metal complexes or phosphorescent dopants or fluorescent dopants having other structures may also be used. Good.

[0179] Here, the dopants (phosphorescent dopant, fluorescent dopant, etc.) that may be used in combination with the metal complex used as the luminescent dopant will be described. Luminescent dopants can be broadly divided into two types: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescence.

[0180] Representative examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes. And pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

[0181] A typical example of the latter (phosphorescent dopant) is preferably a complex compound containing a transition metal element of Group 8, 9, or 10 in the periodic table of elements, and more preferably an iridium compound. And osmium compounds, and most preferred is an iridium compound.

[0182] Specifically, it is a compound described in the following patent publications. [0183] WO 00/70655 pamphlet, JP 2002-280178, JP 2001-18 dish 6, JP 2002-280179, JP 2001-18 dish 7, JP JP 2002-280180, JP 2001-247859, JP 2002-299060, JP 2001-313178, JP 2002-302671, JP 2001-345183, JP 2002- No. 324679, International Publication No. 02/15645 Pamphlet K JP 2002-332291 A, JP 2002-50484 A, JP 2002-33 2292 A, JP 2002-83684 A, Special Table 2002 — 540572, JP 20 02-117978, JP 2002-338588, JP 2002-170684, JP 2002-352960, WO 01/93642, JP 2002

— 50483, JP 2002-100476, JP 2002-173674, JP 2002-359082, JP 2002-175884, JP 2002-363552, JP 2002-184582 Publication, JP 2003-7469, JP 2002-525 808, JP 2003-7471, JP 2002-525833, JP 2003

— 31366, JP 2002-226495, JP 2002-234894, JP 2002-235076, JP 2002-241751, JP 2001-319779, JP 2001-319780 JP, 2002-62824, JP 2002-10474, JP 2002-203679, JP 2002-343572, JP 2002-203678, and the like.

[0184] A part of a specific example is shown below.

[0185] [Chemical 82]

[0187] [Chemical 84]

[0188] (Light-emitting host)

The host compound used in the present invention represents a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.01 at room temperature (25 ° C.) among compounds contained in the light emitting layer.

[0189] The luminescent host used in the present invention is not particularly limited in terms of structure, but is typically a power rubazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing bicyclic compound, a thiophene derivative. , Basic bones such as furan derivatives and oligoarylene compounds Or a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the force rubazole ring of the force rubazole derivative is substituted with a nitrogen atom. Among them, a canolevazole derivative or a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carbazole ring of the carbazole derivative is substituted with a nitrogen atom is preferably used.

[0190] The ability to give specific examples below [0190] The present invention is not limited to these. These compounds are also preferably used as hole blocking materials.

[0191] [Chemical 85]

[98] Κ6ΐ0]

f 0 / 800Z OAV

£ 9089 / L0 Idf / I3d 901 99S

[0193] [Chemical 87] İı9488

H27 H28

In the light emitting layer according to the present invention, a plurality of known host compounds may be used in combination as a host compound. By using multiple types of host compounds, it is possible to adjust the movement of charges, and the organic EL device can be made highly efficient. These known host compounds have a hole transporting ability and an electron transporting ability, prevent the emission of longer wavelengths, and have a high Tg of 90 ° C or higher, more preferably 100 ° C or higher. Glass transition temperature) compounds are preferred. Here, the glass transition point (Tg) is a value determined by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry). [0196] The light-emitting host used in the present invention may be a low-molecular compound or a high-molecular compound having a repeating unit, and a low-molecular compound having a polymerizable group such as a bur group or an epoxy group (evaporation polymerizable light-emitting). Even the host)

[0197] As specific examples of the light-emitting host, compounds described in the following documents are suitable.

For example, JP 2001-257076, JP 2002-308855, JP 2001-313179, JP 2002-319491, JP 2001-357977, JP 2002-334786, JP 2002-8860, JP 2002-334787, JP 2002-15871, JP 2002-334788, JP 2002-4305 6, JP 2002-334789, JP 2002-75645, JP 2002-338579, JP 2002-105445, JP 2002-343568, JP 2002-141173, JP 2002-352957, JP JP 2002-203683, JP 2002-363227, JP 2002-231453, JP 2003-3165, JP 2002-234888, JP 2003-27048, JP 200 JP 2-255934, JP 2002-260861, JP 2002-280183, JP 2002-299060, JP 2002-302516, JP 2002-305083 JP 2002-305084 A, JP 2002-308837 A, etc.

[0198] The light emitting layer may further contain a host compound having a fluorescence maximum wavelength as a host compound. In this case, the energy transfer from the other host compound and the phosphorescent compound to the fluorescent compound allows electroluminescence as an organic EL device to be emitted from the other host compound having a fluorescence maximum wavelength. Preferred as a host compound having a fluorescence maximum wavelength is a compound having a high fluorescence quantum yield in a solution state. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more. Specific examples of host compounds having a maximum fluorescence wavelength include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes. And pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and the like. The fluorescence quantum yield can be measured by the method described in the third edition of Experimental Chemistry Course 7, Spectroscopy II, page 362 (1992 edition, Maruzen).

Next, a configuration of a typical organic EL element will be described. [0200] <Structure layers of organic EL elements>

The constituent layers of the organic EL device of the present invention will be described.

[0201] Preferable specific examples of the layer structure of the organic EL device of the present invention are as follows. The present invention is not limited thereto.

[0202] (i) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(ii) Anode / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(iii) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(iv) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(V) Anode / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode

(vi) Anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer

/ Electron transport layer / cathode buffer layer / cathode

(vii) Anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer

/ Electron transport layer / cathode buffer layer / cathode

《Blocking layer (electron blocking layer, hole blocking layer)》

The blocking layer (for example, electron blocking layer, hole blocking layer) according to the present invention will be described.

[0203] In the present invention, it is preferable to use the organic EL device material of the present invention for a hole blocking layer, an electron blocking layer, and the like.

[0204] When the organic EL device material of the present invention is contained in a hole blocking layer and an electron blocking layer, the organic EL device material of the present invention described in any one of 1 to 7 above is used as a hole. It may be contained in a state of 100% by mass as a layer constituting component such as a blocking layer or an electron blocking layer, or may be mixed with other organic compounds.

[0205] The thickness of the blocking layer according to the present invention is preferably 3 to 100 nm, more preferably

¾) · ο at 5-30nm.

[0206] 《Hole blocking layer》

In a broad sense, the hole blocking layer has the function of an electron transport layer and the function of transporting electrons. However, it is made of a material having a remarkably small ability to transport holes, and the recombination probability of electrons and holes can be improved by blocking holes while transporting electrons.

[0207] Examples of the hole blocking layer include, for example, Japanese Patent Application Laid-Open Nos. 11 204258 and 11 204359, and “The Organic EL Element and the Forefront of Industrialization (November 30, 1998, NTT Corporation) The hole blocking layer described in page 237 of “Issuance)” is applicable as the hole blocking layer according to the present invention. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

[0208] The organic EL device of the present invention has a hole blocking layer as a constituent layer, and the hole blocking layer serves as a hole blocking material and forms the carbazole ring of the force rubazole derivative or the carbazole derivative. It is preferred to contain a derivative having a ring structure in which at least one of the carbon atoms of the hydrogen ring is replaced by a nitrogen atom!

[0209] 《Electron blocking layer》

On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and an extremely small capacity of transporting electrons. The probability of recombination of electrons and holes can be improved by blocking the children. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.

[0210] In the present invention, it is preferable to use the organic EL device material of the present invention for the adjacent layer adjacent to the light-emitting layer, that is, the hole blocking layer and the electron blocking layer, particularly for the electron blocking layer. It is preferable.

[0211] 《Hole transport layer》

The hole transport layer includes a material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. A single hole or multiple hole transport layers should be provided.

[0212] As a hole transport material, there is no particular limitation. Conventionally, it is commonly used as a hole charge injection / transport material in a photoconductive material, or used in a hole injection layer or a hole transport layer of an organic EL device. Any known medium force can be selected and used.

[0213] The hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, Sadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives Aniline-based copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

[0214] The ability to use the above-mentioned materials as the hole transport material. It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, particularly an aromatic tertiary amine compound.

[0215] Typical examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N-tetraphenenole 4, A'-diaminophenolinore; N, N-diphenylenole N, N'-bis (3-Methylphenyl) 1 [1, 1'-Biphenyl] 1, 4, 4'-Diamine (TPD); 2, 2 Bis (4 di-l-triamylaminophenyl) propane; 1, 1-bis (4 di-p-tri-noraminophenyl) cyclohexane; N, N, N ', N' —tetra-p-trinore 4, A'-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) 4-aminophenyl) Hexane; bis (4-dimethylamino-2-methylphenenyl) phenylmethane; bis (4-di-p-triamylaminophenyl) phenylmethane; N, N '— diphenyleno N, N'-di (4-methoxyphenyl) -1,4 diaminobiphenol; N, N, N ' , N ′ —tetraphenyl 4,4′-diaminodiphenyl ether; 4, 4 ′ bis (diphenylamino) quadophenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p —Tolylamino)-1 [4- (Di-p-tolylamino) styryl] stilbene; 4-N, N Diphenylamino- (2 Diphenylenobininole) benzene; 3-Methoxy-1 4 '— N, N Diphenylamino N-phenylcarbazole, and those having two condensed aromatic rings described in US Pat. No. 5,061,569, for example, 4, 4′-bis [ N- (1-naphthyl) N phenylamino] biphenyl (NPD), three triphenylamine units described in JP-A-4308688 are connected in a starburst type 4, 4 ', A' —Tris [N— (3-methylphenyl) N phenyla Roh] triphenyl § Min (MTD ATA) and the like.

[0216] Furthermore, these materials are introduced into the polymer chain, or these materials are combined with the polymer main chain. The polymer material can also be used. Inorganic compounds such as p-type Si and p-type SiC can also be used as the hole injection material and the hole transport material.

[0217] This hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. That power S. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, it is about 5-5000 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

[0218] 《Electron Transport Layer》

The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. For the electron transport layer, a single layer or a plurality of layers are provided.

[0219] Conventionally, when a single electron transport layer and a plurality of layers are used, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is as follows. The following materials are known.

[0220] Furthermore, the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material selected from conventionally known compounds should be used. Touch with force S.

[0221] Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetrafluoride derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, and the like. Carboxylic anhydride, carbopositimide, fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxaziazole derivative, carboline derivative, or at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom. And derivatives having a cyclic structure. Further, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, known as an electron withdrawing group! /, A quinoxaline derivative having a quinoxaline ring can also be used as an electron transport material.

[0222] Furthermore, these materials were introduced into the polymer chain, or these materials were combined with the polymer main chain. The polymer material can also be used.

[0223] Metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5, 7-dichloro-l-quinolinol) aluminum, tris (5, 7-dive mouth 8 quinolinol) Aluminum, tris (2methyl-8quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu, Ca Metal complexes replaced with Sn, Ga or Pb can also be used as electron transport materials. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. In addition, the distyrylvirazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and inorganic semiconductors such as n-type Si and n-type SiC can be used as well as the hole injection layer and the hole transport layer. It can be used as an electron transport material.

[0224] This electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. S can. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, it is about 5-5000 nm. This electron transport layer may have a single layer structure composed of one or more of the above materials.

Next, an injection layer used as a constituent layer of the organic EL element of the present invention will be described.

[0226] << Injection Layer >>: Electron Injection Layer, Hole Injection Layer

The injection layer is provided as necessary, and has an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or hole transport layer and between the cathode and the light emitting layer or electron transport layer. May be.

[0227] The injection layer is a layer provided between the electrode and the organic layer in order to lower the drive voltage and improve the luminance of the light emission. “The organic EL element and the forefront of industrialization (November 30, 1998, NTT) 2) Chapter 2 “Electrode Materials” (pages 123-166) ”of the 2nd volume of“ E.S. Co., Ltd.) ”, the hole injection layer (anode buffer layer), the electron injection layer (cathode buffer layer) There is.

[0228] Details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9260062, JP-A-8-288069 and the like. Lid Examples include a phthalocyanine buffer layer represented by cyanine, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene. .

[0229] The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-917574, JP-A-10-74586, and the like. Metal buffer layer typified by aluminum, etc., alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer typified by aluminum oxide One layer and so on.

[0230] Although the buffer layer (injection layer) is preferably a very thin film, the film thickness is preferably in the range of 0.;! To lOOnm.

[0231] This injection layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. The thickness of the injection layer is not particularly limited, but is usually about 5 to 5000 nm. This injection layer may have a single layer structure composed of one or more of the above materials.

[0232] Anode

As the anode of the organic EL device of the present invention, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as Cul, indium tin oxide (ITO), SnO, and ZnO. Alternatively, an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials can be formed into a thin film by vapor deposition or sputtering, and a pattern of the desired shape can be formed by photolithography, or when pattern accuracy is not so high (about 100 m or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. In the case of taking out light emission from this anode, it is desirable to make the transmittance greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / mouth or less. Further, although the film thickness depends on the material, it is usually selected from 10 to 1000 nm, preferably 10 to 200 nm. [0233] 《Cathode》

On the other hand, as the cathode according to the present invention, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium isotropic lithium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al O) mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron injectability and durability against oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture. Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable. The cathode can be made by forming a thin film of these electrode materials by vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / mouth or less. The film thickness is usually 10 to 1000 nm, preferably 50 to 200 nm. In order to transmit light emission, it is convenient that either the anode or the cathode of the organic EL element is transparent or translucent to improve the light emission luminance.

[0234] << Substrate (also referred to as substrate, substrate, support, etc.) >>

The substrate of the organic EL device of the present invention is not particularly limited as long as it is transparent or transparent, and there are no particular restrictions on the type of glass, plastic, etc. Examples of substrates that are preferably used include glass, Examples thereof include quartz and a light-transmitting resin film. A particularly preferred substrate is a resin film that can give flexibility to the organic EL element.

[0235] Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheroletherketone, polyphenylenesulfide, polyarylate, polyimide, polycarbonate (PC ), A film made of cellulose triacetate (TAC), cellulose acetate propionate (CAP) or the like. [0236] On the surface of the resin film, an inorganic or organic film or a hybrid film of both of them may be formed, and the water vapor transmission rate is 0.01 g / m ² 'day atm or less. A film is preferred.

[0237] The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 2% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted outside the organic EL element / the number of electrons X I 00 flowed to the organic EL element.

[0238] A hue improving filter such as a color filter may be used in combination.

[0239] When used for illumination, a roughened film (such as anti-glare phenolic) may be used in combination in order to reduce unevenness in light emission.

[0240] When used as a multicolor display device, it is composed of at least two types of organic EL elements having different light emission maximum wavelengths. A suitable example for producing an organic EL element will be described.

[0241] <Method for manufacturing organic EL element>

As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising: anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode force I will explain to you!

[0242] First, a desired electrode material, for example, a thin film having a material force for an anode, is deposited on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 111 m or less, preferably 10 to 200 nm. Then, an anode is produced. Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, or an electron transport layer, which is an element material, is formed thereon.

[0243] As a method of thinning a thin film containing an organic compound, there are a spin coat method, a cast method, an ink jet method, a vapor deposition method, a printing method, and the like. The vacuum deposition method or the spin coating method is particularly preferable because it is difficult to form. Further, different film forming methods may be applied for each layer. When employing the vapor deposition film, the deposition conditions may vary due to kinds of materials used, generally boat temperature 50 to 450 ° C, vacuum degree of 10- ⁶ ~; 10- ² Pa, deposition rate 0 0;! -50 nm / sec, substrate temperature 50-300 ° C., film thickness 0.1-5 m are preferably selected as appropriate.

[0244] After these layers are formed, a thin film made of a cathode material is formed thereon with a thickness of 1 μm or less, preferably 50 A desired organic EL device can be obtained by forming the film so as to have a film thickness in the range of ˜200 nm by, for example, vapor deposition or sputtering, and providing a cathode. The organic EL device is preferably manufactured from the hole injection layer to the cathode consistently by a single vacuum, but it may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

[0245] 《Display device》

The display device of the present invention will be described. The display device of the present invention has the organic EL element.

[0246] The display device of the present invention may be monochromatic or multicolor, but here, a multicolor display device will be described. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by a vapor deposition method, a casting method, a spin coating method, an ink jet method, a printing method, or the like.

[0247] When patterning is performed only on the light emitting layer, the method is not limited, but the vapor deposition method, the ink jet method, and the printing method are preferable. When using vapor deposition, patterning with a shadow mask is preferred.

[0248] Further, the production order can be reversed, and the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, and the anode can be produced in this order.

[0249] When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the anode serving as + and the cathode serving as one polarity. In addition, even if a voltage is applied with the opposite polarity, no current flows and no light is emitted. In addition, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The AC waveform to be applied is arbitrary.

[0250] The multicolor display device can be used as a display device, a display, and various light emitting sources. For display devices and displays, full-color display is possible by using three organic EL elements, blue, red, and green light emission.

[0251] Examples of display devices and displays include televisions, personal computers, mopile devices, AV devices, character broadcast displays, and information displays in automobiles. In particular, it may be used as a display device for playing back still images and moving images, and the drive method when used as a display device for moving image playback is either a simple matrix (passive matrix) method or an active matrix method. It may be.

[0252] Light emitting sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sensors Examples include light sources, but are not limited to this!

[0253] 《Lighting device》

The lighting device of the present invention will be described. The lighting device of the present invention has the organic EL element.

[0254] The organic EL element having the resonator structure may be used as an organic EL element having a resonator structure in the organic EL element of the present invention. Examples include a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, and the like. Moreover, you may use for the said use by making a laser oscillation.

[0255] Further, the organic EL device of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, a still image or a moving image directly visible It may be used as a type of display device (display). When used as a display device for video playback, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.

FIG. 7 is a schematic view showing an example of a display device composed of organic EL elements. FIG. 2 is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

[0258] The display 1 includes a display section A having a plurality of pixels, a control section B that performs image scanning of the display section A based on image information, and the like.

[0259] The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside. Sequentially emits light according to the image data signal, scans the image, and sends the image information to the display unit A.

Ik small.

FIG. 8 is a schematic diagram of display unit A. FIG.

[0261] The display portion A includes a wiring portion including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels on a substrate.

It has 3 mag. The main members of the display unit A will be described below.

[0262] In the figure, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

[0263] The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details Is not shown).

[0264] When a scanning signal is applied from the scanning line 5, the pixel 9 receives an image data signal from the data line 6, and emits light according to the received image data. Full color display is possible by arranging pixels in the red region, the green region, and the blue region as appropriate on the same substrate.

Next, the light emission process of the pixel will be described.

FIG. 9 is a schematic diagram of a pixel.

The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. Using organic EL elements that emit red, green, and blue as the organic EL elements 10 in multiple pixels, and arranging them on the same substrate in parallel, full-color display can be achieved with power S.

In FIG. 9, an image data signal is applied from the control unit B to the drain of the switching transistor 11 via the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is transferred to the capacitor 13 and the driving transistor. It is transmitted to the gate of the star 12.

[0269] By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal.

At the same time, the driving transistor 12 is turned on. Drive transistor 12 has a drain Is connected to the power supply line 7 and the source is connected to the electrode of the organic EL element 10, and current is supplied from the power supply line 7 to the organic EL element 10 according to the potential of the image data signal applied to the gate. .

When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 holds the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. The organic EL device 10 continues to emit light until it is seen. When a scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

That is, the organic EL element 10 emits light by providing a switching transistor 11 and a driving transistor 12 as active elements for each of the plurality of pixels. Element 10 is emitting light. Such a light emitting method is called an active matrix method.

[0272] Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials. The light emission amount may be on or off. The potential of the capacitor 13 can be maintained until the next scanning signal is applied, or can be discharged immediately before the next scanning signal is applied! /.

[0273] The present invention is not limited to the above-described active matrix method, and may be a passive matrix type light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned. .

FIG. 10 is a schematic diagram of a display device using a passive matrix method. In FIG. 10, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

[0275] When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixel 3 connected to the applied scanning line 5 emits light in accordance with the image data signal.

[0276] The noisy matrix method has no active element in pixel 3, and can reduce manufacturing costs. [0277] The organic EL material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials, and white light emission is obtained by mixing colors. The combination of multiple emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or the complementary colors such as blue and yellow, and blue-green and orange are used 2 It may be one containing two emission maximum wavelengths.

[0278] A combination of light emitting materials for obtaining a plurality of light emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and a combination of light emitting materials. Any combination with a dye material that emits light as excitation light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed. A mask is provided only at the time of formation of the light emitting layer, hole transport layer, electron transport layer, etc. For example, an electrode film can be formed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is improved. According to this method, unlike the white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves emit white light.

[0279] There are no particular limitations on the light emitting material used for the light emitting layer. Select any of the metal complexes and known luminescent materials and combine them to whiten! /.

[0280] Thus, the white light-emitting organic EL device according to the present invention is not only the display device and the display, but also a variety of light-emitting light sources and lighting devices, such as home lighting, interior lighting, and exposure light source. It is also useful for display devices such as backlights for liquid crystal display devices.

[0281] In addition, backlights for watches, signboard advertisements, traffic lights, optical storage media and other light sources, light sources for electronic photocopiers, light sources for optical communication processors, light sources for optical sensors, and display devices are required. And a wide range of uses such as general household appliances.

Example

[0282] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In addition, In the examples, the force S using the indication “%” represents “mass%” unless otherwise specified.

[0283] Example 1

<< Production of organic EL elements 1 1 >>

After patterning a substrate with 150nm ITO film on glass (NH Techno Glass: NA-45) as the anode, the transparent support substrate with this ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol Then, it was dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. This transparent support substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, while α-NPD, H4, Ir 12, BCP, and Alq are placed in five tantalum resistance heating boats, respectively. Attached to the tank).

[0284] Further, lithium fluoride was put in a resistance heating boat made of tantalum, and aluminum was put in a resistance heating boat made of tungsten, respectively, and attached to the second vacuum chamber of the vacuum evaporation apparatus.

[0285] First, after the vacuum of the first vacuum chamber to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the baud preparative containing the alpha NPD, deposition rate 0.;! ~ 0. 2nm / In a second, vapor deposition was performed on the transparent support substrate to a thickness of 20 nm, and a hole injection / transport layer was provided.

[0286] Further, the heating boat containing H4 and the boat containing Ir 12 are independently energized, so that the deposition rate of H4 as a light emitting host and Ir-12 as a light emitting dopant is 100: 6. The light emitting layer was provided by vapor deposition so that the film thickness was 30 nm.

[0287] Next, the heating boat containing BCP was energized and heated, and a hole blocking layer having a thickness of 10 nm was provided at a deposition rate of 0.2;! To 0.2 nm / sec. Further, the heating boat containing Alq was energized and heated, and an electron transport layer having a film thickness of 20 nm was provided at a deposition rate of 0.2; /-0.2 nm / sec.

Yes

[0288] Next, after the element deposited up to the electron transport layer was transferred to the second vacuum chamber while being vacuumed, the stainless steel rectangular perforated mask was placed on the electron transport layer. It was installed with remote control.

[0289] After decompression of the second vacuum chamber up to 2 X 10- ⁴ Pa, evaporation Chakusokudo 0. 01-0 by energizing the boat lithium fluoride containing. 02nm / sec to a film thickness 0. 5 nm cathode buffer One layer was provided, and then the boat containing the anode was energized, and a cathode with a film thickness of 150 nm was attached at a deposition rate of 1 to 2 nm / second to produce an organic EL device 1-1. [0290] 《Organic EL device 1 2 ～;

In the production of the organic EL device 1-1, the organic EL devices 1-2-1 to 26 were prepared in the same manner except that the light emitting host, the light emitting dopant, and the hole blocking material were changed as shown in Table 1.

; ^^

[0291] [Chemical 89] 'One PD

[0292] [Chemical 90]

[0293] <Evaluation of organic EL devices>

When evaluating the obtained organic EL devices 1-1 to 1-26, the non-light emitting surface of each organic EL device after fabrication was covered with a glass case, and a glass substrate having a thickness of 300 m was used as a sealing substrate. The epoxy photo-curing adhesive (Latus Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is overlaid on the cathode and brought into close contact with the transparent support substrate. It was irradiated with UV light, cured, sealed, and evaluated by forming an illumination device as shown in FIGS.

[0294] Fig. 11 shows a schematic diagram of a lighting device, in which the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is to bring the organic EL element 101 into contact with the atmosphere. A glove box under a nitrogen atmosphere (under a high purity nitrogen gas atmosphere with a purity of 99.999% or more). FIG. 12 shows a cross-sectional view of the lighting device. In FIG. 12, 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

[0295] (External quantum efficiency)

By lighting the organic EL device under room temperature (about 23-25 ° C) and a constant current condition of ^2.5 mA / cm ² and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of lighting The external extraction quantum efficiency (7)) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of luminance. The external extraction quantum efficiency is expressed as a relative straight line with the organic EL element 11 being 100.

[0296] (Luminescence lifetime)

The organic EL device was continuously lit at room temperature at a constant current of ^2.5 mA / cm ^{2 and} the time required to reach half the initial luminance was measured. Luminous lifetime is organic EL

1/2

The element 1 1 is expressed as a relative value set to 100.

[0297] (Luminescent color)

The organic EL device was visually evaluated for the luminescent color when it was lit continuously at room temperature under a constant current condition of ^2.5 mA / cm2.

[0298] The results obtained are shown in Table 1.

[0299] [Table 1]

Organic ^ ¾ Luminescence Hole Suppression External Removal

Luminous life Emission color Remarks

N H. Host Pant Material Quantum efficiency:

― 1 H ~ 4 ir-12 ecp 100 100 Ice color contrast

1 ― 2 Hi— 4 Comparison 1 103 93 Orange Comparison Example-3 H— 4 Comparison 2 8CP 110 33 Orange Comparison Example 卜 4 Comparison 3 BCP 108 76 * • Comparison Example

1 1 5 H-4 BCP 162 765 麵 The present invention

1 ― 6 H-4 1 BCP 156 743 啬 Present invention

1-? Toto 4 27 BCP 640 黉 Present invention

1-8 H-93 8CP 159 726: This invention

1 ― H-4 56 H-5 162 734 Blue The present invention

1 -10 H-4 63 H— 5 1 S 540 The present invention

1 -11 H― 4 1:02 H― 5 155 654 The present invention

';, "12 H- 4 184 H— 5 9 G74 Blue

\ —13 H—-6 75 BCP ΐδδ 668 Blue Present invention —14 H 1 6 4 8CP 163 726 Pure education Present invention

1 -ΐ5 H- 6 1 7 BCP 152 548 Pure blue

1 -16 H— 6 208 ec 151 645 n The present invention

1 —17 H- 6 127 H-5 146 7U The present invention

-18 -18 H— 6 157 H-5 163 6S3 Pure blue

1 — Ϊ9 H— β 165 H-5 158 649

1 —20 H— 8 174 H-5 5 582 Blue The present invention

1 -21 H ~ 30 220 BCP 162 687 Blue The present invention

= -22 H—30 ZZA 153 565 Blue The present invention

] -23 H -30 233 acp 55 673 The present invention

H -.30 247 1 8 534 is

1 -25 H -30 272 H «5 138 63 ΐ Present invention: 1 -26 H-30 273 H-25 1 0 594 Present invention

[0300] From Table 1, the organic EL device produced using the metal complex according to the present invention has higher emission efficiency and longer lifetime while having a short-wave emission of pure blue to blue-green compared to the organic EL device of the comparative example. It is clear that a long life can be achieved.

[0301] Example 2

<< Preparation of organic EL element 2-1 >>

25 mm X 25 mm XO. A positive electrode of indium tin oxide (ITO, indium / tin = 95/5 molar ratio) was formed by sputtering on a 5 mm glass support substrate using a DC power supply (thickness 200 nm). The surface resistance of this anode was 10 Ω / mouth. Polyburcarbazole (hole transporting binder polymer) / Ir 1 13 (blue light emitting orthometalated complex) / 2 1 (4-biphenyl) -5- (4 1 t-butylphenyl) 1 , 3, 4-Oxadiazole (electron transport material) = A dichloroethane solution in which a mass ratio of 200/2/50 was dissolved was applied with a spin coater to obtain a light emitting layer of lOOnm. A mass patterned on this organic compound layer (A mask with a light emitting area of 5 mm x 5 mm), and depositing 0.5 nm of lithium fluoride as the cathode buffer layer and 150 nm of aluminum as the cathode in the vapor deposition system, providing the cathode, and emitting blue organic EL Element 2-1 was produced.

[0302] << Production of organic EL elements 2-2 to 2-11 >>

Organic EL elements 2-2 to 2-11 were prepared in the same manner as in the preparation of organic EL element 2-1, except that the luminescent dopant was changed as shown in Table 2.

[0303] << Evaluation of organic EL elements >>

When evaluating the obtained organic EL device 2— ;! to 2-11, the non-light emitting surface of each organic EL device after fabrication was covered with a glass case, and a glass substrate having a thickness of 300 m was used as the sealing substrate. The epoxy-based photo-curing adhesive (Latus Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the glass substrate, and this is overlaid on the cathode and brought into close contact with the transparent support substrate. Then, UV light was irradiated, cured, sealed, and an illumination device as shown in FIGS. 11 and 12 was formed and evaluated.

[0304] Next, the luminance and luminous efficiency were measured as follows.

[0305] (Luminance, luminous efficiency)

Using a source measure unit model 2400 manufactured by Toyo Tech Niki Co., Ltd., a DC voltage is applied to the organic EL element to emit light, and the light emission luminance (cd / m ² ) when applied with a DC voltage of 10 V is ^2.5 mA / The luminous efficiency (lm / W) was measured when a current of cm ² was passed. Table 2 shows the results obtained. It is expressed as a relative value where the organic EL element 2-1 is 100.

[0306] [Table 2]

Luminance Luminance Luminous efficiency

Organic EL device Light emission

Color.

Ho, dopant (■ cd / V) (Im / W) Remarks

(Relative value) (relative value)

2-1 fr-13 100 100

2 1 2 Hiei 2 110 M2 years old, Noji Comparative example

■ 2-3 Comparison 3 Π2 "5 较 Comparison Example

2-4 4 146 143 Blue green Present invention

2 '― 5 14 2 142 The present invention

2-6 56 36 140 The present invention

2-7 114 1 3 150 Pure blue The present invention

2-8! 47 1 6 1 6 ¾ blue The present invention

Z-9 157 ί50 144 Pure-Back This invention

2— 'ίθ 165 J48 1 3 The present invention

2—! 1 184! 37 142 The present invention

[0307] From Table 2, the organic EL device produced using the metal complex according to the present invention has high luminous efficiency and high luminance while having a short blue light emission of pure blue to blue green compared with the organic EL device of the comparative example. It is clear that can be achieved.

[0308] Example 3

(Production of blue light-emitting elements)

The organic EL device 1-118 of Example 1 was used as a blue light emitting device.

[0309] (Production of green light-emitting element)

A green light-emitting device was produced in the same manner as in Example 1 except that Ir-12 was changed to Ir-1 in the organic EL device 11 of Example 1, and this was used as a green light-emitting device.

[0310] (Production of red light-emitting element)

A red light-emitting device was produced in the same manner as in Example 1 except that Ir-12 was changed to Ir-9 in the organic EL device 1-11, and this was used as a red light-emitting device.

[0311] The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate, and an active matrix type full-color display device having a configuration as shown in FIG. 7 was produced. FIG. 8 shows only a schematic diagram of the display portion A of the display device thus manufactured. That is, a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. Scanning line of wiring part 5 and the plurality of data lines 6 are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (details are not shown). The plurality of pixels 3 are driven by switches that are organic EL elements and active elements corresponding to the respective emission colors. When a scanning signal is applied from the scanning line 5, the pixel 3 receives and receives an image data signal from the data line 6. Emits light according to the image data. In this way, a full-color display device was produced by appropriately juxtaposing red, green, and blue pixels.

[0312] It was found that when this full-color display device is driven, a high-brightness, high-durability and clear full-color moving image display can be obtained.

[0313] Example 4

<< Production of white light-emitting element and white illumination device 1 >>

The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm x 20 mm, and α-NPD was deposited to a thickness of 25 nm as a hole injection / transport layer on the same as in Example 1, and then H4 The heating boat containing, the boat containing Illustrative Compound (4), and the boat containing Ir 9 were energized independently, respectively, and CBP as the luminescent host and Illustrative Compound (4) and Ir as the luminescent dopant were respectively supplied. — The deposition rate of 9 was adjusted to 100: 5: 0.6, deposition was performed to a thickness of 30 nm, and a light emitting layer was provided.

[0314] Next, a 10-nm BCP film was formed to provide a hole blocking layer. Furthermore, Alq was deposited at 40 nm to provide an electron transport layer.

[0315] Next, as in Example 1, a square perforated mask having substantially the same shape as the transparent electrode made of stainless steel was placed on the electron injection layer, and lithium fluoride 0.5 nm was used as a cathode buffer layer and a cathode. Aluminum 150nm was deposited.

[0316] This element was provided with a sealing can having the same method and the same structure as in Example 1, and FIG.

A flat lamp as shown in FIG. When this flat lamp was energized, almost white light was obtained, indicating that it could be used as a lighting device. It was found that white light emission was obtained in the same manner even when the compound was replaced with other exemplified compounds.

[0317] [Chemical 91] CBP

[0318] Example 5

<< Production of white light-emitting element and white illumination device 2 >>

The ITO transparent electrode is formed after patterning on a substrate (ΝΗ Techno Glass Co., Ltd. 45-45) made of ITO (Indium Toxide) on a lOOmmX lOOmm X l. 1mm glass substrate as an anode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

[0319] A solution of poly (3,4 ethylenedioxythiophene) polystyrene sulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P A1 4083) diluted to 70% with pure water on this transparent support substrate. Was formed by spin coating at 3000 rpm for 30 seconds and dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

[0320] The substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound A dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. . After irradiating with ultraviolet light for 180 seconds to perform photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.

[0321] Next, using a solution of Compound B (60 mg), Compound Ir 14 (3. Omg) and Compound Ir 15 (3. Omg) in 6 ml of toluene, spin coating was performed at 1000 rpm for 30 seconds. The film was formed by the method. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization / crosslinking, and further heated in vacuum at 150 ° C. for 1 hour to form a light emitting layer.

[0322] Further, a solution of compound C (20 mg) dissolved in 6 ml of toluene was used to form a film by spin coating under the condition of lOOOrpm for 30 seconds. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization and crosslinking, and further heated in a vacuum at 80 ° C. for 1 hour to form a hole blocking layer.

[0323] Subsequently, this substrate was fixed to the substrate holder of the vacuum evaporation apparatus, and the resistance made of molybdenum was added. 200 mg of Alq was put into a heat boat and attached to a vacuum evaporation system. After pressure in the vacuum tank was reduced by 4 X 10- ⁴ Pa or, and heated by supplying an electric current to the boat charged with Alq, it is deposited on the electron transport layer at a deposition rate of 0. lnm / sec, further film An electron transport layer with a thickness of 40 nm was provided.

[0324] The substrate temperature during vapor deposition was room temperature.

[0325] Subsequently, lithium fluoride 0.5 nm and aluminum 11 Onm were vapor-deposited to form a cathode.

A white light emitting organic EL device was produced.

[0326] When this element was energized, almost white light was obtained, indicating that it could be used as a lighting device.

[0327] [Chem 92]

lr—15 << Compound of the Present Invention >>

Claims

The scope of the claims

Organic electroluminescent element material characterized by being a metal complex represented by the following general formula (1).

[Chemical formula (1)

1 1

1 2 3 2

, N or R—C, together with C and N, imidazole ring, triazole ring, tetrazole

Three

1 1 2

1

2. The organic electroluminescent device material according to claim 1, wherein the metal complex represented by the general formula (1) is represented by the following general formula (2).

[Chemical 2] —Killing ceremony)

1 1

Three

1 1 2

1

3. The organic electroluminescence device material according to claim 2, wherein the metal complex represented by the general formula (2) is represented by the following general formula (3).

[Chemical formula 3] General formula << 3}

1 1

1 1 2

Represents an atomic group forming The central metal, M, is 8 ~ in the Periodic Table; Group 11 gold

1

Represents a genus. ml represents an integer of 1, 2 or 3, m2 represents a force representing an integer of 0, 1 or 2, m l + m2 is 2 or 3, which is the same number as the positive charge of the central metal. )

[4] The metal complex represented by the general formula (3) is an R force S methyl group, or a substituted, unsubstituted aryl group or aromatic heterocyclic group. The organic-elect mouth luminescence element material described.

[5] In the metal complex represented by the general formula (3), R is a 2,6-dimethylphenyl group, a mesityl group (2,4,6-trimethylphenyl group), a tetramethylphenyl group, or 5. The organic electroluminescent element material according to claim 4, which is a pentamethylphenyl group.

6. The center metal M force S iridium.

1

The organic electoluminescence element material according to item 1.

[7] Any one of claims 1 to 5, wherein the central metal M is platinum.

1

The organic electoluminescence element material according to item 1,

[8] The organic electoluminescence device material according to any one of [1] to [7], wherein m2 is 0.

[9] The organic electoluminescence device material according to any one of claims 1 to 8, wherein the first emission wavelength is in the range of 400 to 500 nm.

[10] An organic electroluminescent device comprising the organic electroluminescent device according to any one of claims 1 to 9, wherein the organic electroluminescent device is the organic electroluminescent device.

[11] The light-emitting layer as a constituent layer, wherein the light-emitting layer contains the organic electoluminescence device material according to any one of claims 1 to 9. The organic electoluminescence device according to item 10 in the range.

[12] The light-emitting layer has, as a host compound, a force rubazole derivative or a derivative having a ring structure in which at least one carbon atom of a hydrocarbon ring constituting the force rubazole ring of the carbazole derivative is substituted with a nitrogen atom. 11. The organic electoluminescence device according to claim 10, which is contained.

[13] It has a hole blocking layer as a constituent layer, and the hole blocking layer has at least one carbon atom of a hydrocarbon ring constituting a carbazole derivative or a force rubazole ring of the carbazole derivative as a hole blocking material. 13. The organic electoluminescence device according to any one of claims 10 to 12, comprising a derivative having a ring structure, one of which is substituted with a nitrogen atom.

[14] A display device comprising the organic electoluminescence element according to any one of [10] to [13].

[15] An illumination device comprising the organic electoluminescence device according to any one of [10] to [13].