WO2008044723A1

WO2008044723A1 - Organic electroluminescent device material, organic electroluminescent device, display and illuminating device

Info

Publication number: WO2008044723A1
Application number: PCT/JP2007/069822
Authority: WO
Inventors: Motoaki Sugino; Masato Nishizeki; Tomohiro Oshiyama
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2006-10-13
Filing date: 2007-10-11
Publication date: 2008-04-17
Also published as: JP5099013B2; JPWO2008044723A1

Abstract

Disclosed is an organic EL device using an organic EL device material having controlled emission wavelength, high luminous efficiency and long emission life. Also disclosed are a display and an illuminating device. Specifically disclosed is an organic EL device material represented by the following general formula (1a). [In the formula (1a), A represents a cyclic group; B represents a cyclic group; and A is a group represented by the general formula (1b) below, or alternatively the compound represented by the general formula (1a) has a group represented by the general formula (1b) below asa substituent: (In the formula (1b) wherein X represents O, S or N-R2 (wherein R2 represents an alkyl group, an aryl group or a heteroaryl group); Z1, Z2, Z3 and Z4 represent N or -CR4= (wherein R4 represents a hydrogen atom or a substituent), and one of them is N); X1 and X2 represent C, N or O; L1 represents an atomic group forming a bidentate ligand together with X1 and X2; m1 represents 1, 2 or 3, m2 represents 0, 1 or 2 and m1 + m2 is 2 or 3; and M1 represents a group 8-10 metal of the periodic table.]

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 referred to as organic EL elements! /). Inorganic electoric luminescence elements require an alternating high 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 light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. This is an element that emits light using the emission of light (fluorescence 'phosphorescence) when this exciton is deactivated. It can emit light at a voltage of several volts to several tens of volts. For this reason, it is a thin-film, completely solid element that has a wide viewing angle and high visibility, and is attracting attention from the viewpoints of space saving and portability.

[0003] However, for organic EL elements for practical use in the future, it is desired to develop organic EL elements that emit light with high power and efficiency with lower power consumption.

[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 (ext) is 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 Lon (acac), for example, (ppy) Ir ( acac), Moon— Jae Youn. 0g, Tetsuo Tsutsui, et al. ρ-Tolyl) pyridine) iridium (Ir (ptpy)), tris (benzo [h] quinoline

) Iridium (Ir (bzq)) and other studies are conducted! (These metal complexes are generally called ortho-metalated iridium complexes! /.).

[0012] In addition, in the above-mentioned S. Lamansky et al., J. Am. Chem. Soc., 123, 4304 (2001) and Patent Document 14, etc., attempts are made to form devices using various iridium complexes. But Has been.

[0013] In order to obtain high luminous efficiency, the 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) uses Ikai et al. As a host for phosphorescent compounds. . M. E. Tompson et al. Use various electron transport materials as a host of 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. For this type of complex, many examples of ligands are known! /, E.g. (see patent literature;! -5 and non-patent literature 1).

[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. It is known to introduce ligands (see, for example, Patent Documents 6 to 10 and Non-patent documents;! To 4), but with these ligands, the emission wavelength of the light-emitting material is shortened and blue. As a result, high-efficiency devices can be achieved, while the light-emitting lifetime of the devices is greatly deteriorated, so an improvement in the trade-off has been demanded.

[0017] Metal complexes having phenylbiazole substituted with a phenyl group as a ligand are known (see, for example, Patent Documents 11 and 12). However, the phenyl group substitution mode disclosed here for phenyl groups is not sufficient for improving the light emitting device lifetime, and there is still room for improvement from the viewpoint of light emission efficiency. On the other hand, the knowledge that a ligand having a sterically hindered substituent is good for improving the luminance of light emission has been obtained, and examples of application to a parent nucleus of fenenorepyrazole have also been seen (for example, Patent Documents). (See 13.)

[0018] Examples in which various substituents are introduced using phenylimidazole as a basic skeleton as a ligand have been disclosed. Force S and emission lifetime have not been greatly improved, leaving room for improvement. (For example, see Patent Documents 15 and 16.)

In addition, examples using a compound having a heterocyclic skeleton of a 6-5-6 type tricyclic condensed ring such as carbazole, dibenzofuran, dibenzothiophene and the like as a ligand are disclosed (for example, Patent Documents 1 and 11). 17 and 18)), however, is insufficient in terms of both the light emission lifetime and the light emission efficiency, and further improvement has been desired.

Patent Document 1:: JP 2002-332291 A

Patent Document 2: Japanese Patent Laid-Open No. 2002-332292

Patent Document 3: JP-A-2002-338588

Patent Document 4: Japanese Patent Application Laid-Open No. 2002-226495

Patent Document 5: JP-A-2002-234894

Patent Document 6: International Publication No. 02/15645

Patent Document 7:: Japanese Patent Laid-Open No. 2003-123982

Patent Document 8:: JP 2002-117978 A

Patent Document 9: Japanese Patent Laid-Open No. 2003-146996

Patent Document 10: International Publication No. 04/016711 Pamphlet

Patent Document 11: Pamphlet of International Publication No. 04/085450

Patent Document 12: Japanese Patent Laid-Open No. 2005-53912

Patent Document 13: Japanese Unexamined Patent Publication No. 2003-109758

Patent Document 14: Japanese Patent Laid-Open No. 2001-247859

Patent Document 15: International Publication No. 05/007767 Pamphlet

Patent Document 16: Japanese Patent Laid-Open No. 2005-68110

Patent Document 17: Japanese Unexamined Patent Publication No. 2005-23070

Patent Document 18: Japanese Patent Laid-Open No. 2005-23071

Non-Patent Document 1: Inorganic Chemistry, Vol. 41, No. 12, pp. 3055-3066 (2002)

Non-Patent Document 2: Aplied Physics Letters, 79, 2082 (2001) Non-Patent Document 3: Aplied Physics Letters, 83, 3818 (2003) Non-Patent Document 4: New Journal of Chemistry, 26 Volume 1171 (2002) 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 control an organic EL element using an organic EL element material that has a controlled emission wavelength, exhibits high emission efficiency, and has a long emission lifetime. It is providing an element, an illuminating device, and a display apparatus.

Means for solving the problem

[0021] The above problem has been solved by the following configuration.

[0022] 1. An organic electoluminescence element material, which is a metal complex represented by the following general formula (la):

[0023] [Chemical 1]

[In the general formula (la), C and N are covalently bonded or coordinated to the metal atom M.

1

. A is a cyclic group bonded to the metal atom M through a carbon atom, and B is through a nitrogen atom.

1

Represents a cyclic group bonded to the metal atom M.

1

[0025] Further, in the general formula (la), the cyclic group represented by A is a group represented by the following general formula (lb), or on the metal complex represented by the general formula (la), A group represented by (lb) is included as a substituent.

[0026] [Chemical 2] General formula

In the general formula (lb), X represents ◯, S, N—R ₂ (R ₂ represents an alkyl group, an aryl group, or a heteroaryl group).

[0028] Z, Z, Z, and Z are independently a nitrogen atom or CR = (R represents a hydrogen atom or a substituent.

1 2 3 4 4 4

The ), And one of Z, Z, Z and Z is a nitrogen atom. X -L -X is a two-seat arrangement

1 2 3 4 1 1 2

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

1 2 1

X and X represent a group of atoms that form a bidentate ligand. ml represents an integer of 1, 2, or 3

1 2

M2 represents an integer of 0, 1 or 2 ml + m2 is 2 or 3. M, which is a metal atom, represents a group 8 to group 10 metal in the periodic table. ]

1

2. The organic electroluminescence device material according to 1, wherein the general formula (la) is represented by the following general formula (1).

[0029] [Chemical formula 3] General formula (1)

[Wherein, R represents an alkyl group, an aryl group, or a heteroaryl group. Y and Y are nitrogen atoms

1 1 2

Or CR = (R is a hydrogen atom or a substituent). X, L, X, ml, m2, M

3 3 1 1 2 1 Synonymous with X, L, X, ml, m2, and M in formula (la). ] 3. The organic electroluminescent device material according to 2, wherein the general formula (1) is represented by the following general formula (2).

[0031] [Chemical formula 4] General formula (2)

[In the formula, X L X ml m2 M R Y Y represents X L X in the general formula (1).

1 1 2 1 1 1 2 1 1 2 ml Synonymous with m2 MRY. X Ζ Ζ Ζ にお is the above general formula (lb)

1 1 1 2 1 2 3 4

It is synonymous with each X Z Z Z Z. ]

1 2 3 4

4. In the above general formula (1) or general formula (2), Y Y is-CR = CR = (R R

1 2 4 5 4 5 represents a hydrogen atom or a substituent. 2. The organic electoluminescence device material according to 2 or 3, wherein

[0033] 5. In the general formula (1) or (2), R is a methyl group or an aryl group.

1

The organic electoluminescence device material according to any one of 24, characterized in that

[0034] 6. In the above general formula (1) or general formula (2), R is a ally having a substituent at the 2,6 position.

1

26. The organic electoluminescence device material according to any one of the above 25, which is a ruthenium group.

[0035] 7. In the general formula (1) or (2), M is Ir or Pt,

1

2. The organic electoluminescence device material according to 1 above, wherein any one of the above 2 6 forces.

[0036] 8. In the general formula (1) or the general formula (2), m2 is 0, The organic electoluminescence element material according to any one of ˜7.

[0037] 9. An organic electoluminescence device comprising the organic electroluminescence device material according to item 1 in any one of the above 1 to 8, in a light emitting layer.

[0038] 10. A display device comprising the organic-electric-luminescence element as described in 9 above.

[0039] 11. An illuminating device comprising the organic electoluminescence device described in 9 above.

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

FIG. 2 is a schematic diagram of display unit A.

FIG. 3 is a schematic diagram of a pixel.

FIG. 4 is a schematic diagram of a passive matrix type full-color display device.

FIG. 5 is a schematic view of a lighting device.

FIG. 6 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] Hereinafter, details of each component according to the present invention will be sequentially described.

[0044] The metal complex as the organic EL device material of the present invention will be described.

First, the metal complex represented by the general formula (la) will be described.

In general formula (la), C and N form a covalent bond or a coordinate bond with metal atom M.

1

[0047] A is a cyclic group bonded to the metal atom M through a carbon atom.

1

[0048] The cyclic group represented by A is preferably a 5-membered or 6-membered ring, and more preferably a ring structure represented by the following general formulas A— ;! to A-53.

[0049] (* indicates a position where a bond is formed with the metal atom M! /).

1

[0050] [Chemical 5]

Blasp []]

*

[0052] In general formula A— ;! to A—53, RA

1, RA

2, RA

3, RA is independently a hydrogen atom or substituent 4

Represents.

[0053] Examples of the substituent include an alkyl group (for example, 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). Group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, bur group, allyl group, etc.), alkyl group (for example, etulyl group, propargyl group, etc.) ), Aromatic hydrocarbon ring groups (also called aromatic carbocyclic groups, aryl groups, etc., for example, phenyl groups, p-phenyl groups, mesityl groups, tolyl groups, xylyl groups, naphthyl groups, anthryl groups, Azulenyl group, acenaphthene binole group, fluorenyl group, phenanthryl group, indur group, pyrenyl group, biphenylurine group, etc.), aromatic heterocyclic group (eg For example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazol group, triazolyl group (ex. Ίί, 1, 2, 4 2,3 卜 lyso 'mono- 1- 1-no-re group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothia group, furazanyl group, chenyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzocenyl group, dibenzocenyl group, indolyl group, canolenozolinole group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthaladyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidinole group, morpholyl group, oxazolidinole group, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexylenoreoxy group, etc.), arylenooxy group (for example, phenoxy group, naphthyloxy Etc.), alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (eg, cyclopentylthio group, cyclohexylthio group, etc.), Arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methenoreoxycanolepoinore group, ethenoreoxycanolepoinole group, butinoreoxycarbonyl group, octylo group) Xyloxycarbonyl, dodecyloxycarbonyl, etc.), aryloxycarbonyl (eg, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl (eg, aminosulfonyl, methylaminosulfonyl), Dimethylaminosulfonyl group Butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group ( For example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, Pyridylcarbonyl group, etc.), acyloxy groups (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenyl group) A carbonylcarbonylamino group), an amide group (for example, a methylcarbonylamino group, an ethylcarbonylaminoamino group, a dimethylcarbonylamino group, a propylcarbonylamino group, a pentylcarbonylaminoamino group, a cyclohexylcarbonylamino group, 2-Ethylhexylcarboxy A ruamino group, an octylcarbonylamino group, a dodecylcarbonylamino group, a phenylcarbonylamino group, a naphthylcarbonylamino group, etc., a strong rubamoyl group (for example, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, Propylamino carbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylamino group norbornyl group, phenylaminocarbonyl group, naphthyla Minocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido) Naphthylureido group, 2-pyridylaminoureido group, etc.), sulfininole group (for example, methylsulfiel group, ethylsulfiel group, butylsulfiel group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfenyl group) Group, phenyl sulfier group, naphthyl sulfier group, 2-pyridyl sulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2- Ethylhexylsulfonino group, dodecylsulfonyl group, etc., arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino Group, ethyl Mino group, dimethylolamino group, butyl amino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc., halogen atom (for example, fluorine atom, chlorine atom) , Bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group ( For example, a trimethylsilyl group, a triisopropyl silyl group, a triphenylsilyl group, a phenyljetylsilyl group, and the like.

[0054] In A- ;! to A-53, two of RA, RA, RA and RA are combined with each other

1 2 3 4

A ring may be formed.

[0055] Rings formed by combining two of RA to RA include naphthalene and tetralyl.

14

, Anthracene, phenanthrene, quinoline, isoquinoline, indanol, benzofuran, Examples include ring structures such as Nzochi-aged phen, indazonore, benzimidazole, benzothiazonole, benzoxazole, carbazonole, dibenzofuran, dibenzothiophene, and benzotriazole.

[0056] One preferred form of A is also a ring structure represented by the general formula (lb).

[0057] Next, the cyclic group represented by B will be described.

[0058] B is a cyclic group bonded to the metal atom M through a nitrogen atom.

1

[0059] The cyclic group represented by B is preferably a 5-membered or 6-membered ring, and more preferably a ring structure represented by the following general formulas B-1-B-27.

[0060] (* indicates a position where a bond is formed with the metal atom M! /).

1

[0061] [Chemical 7]

[0062] B represents a cyclic group bonded to the metal atom M through a nitrogen atom.

1

[0063] In the general formulas B— 1 to B— 27, RB, RB, RB, and RB are independently a hydrogen atom or a substituent.

1 2 3 4

Represents.

[0064] Examples of substituents represented by RB, RB, RB, and RB include the above RA, RA, RA, RA

The same examples as the substituents represented by 1 2 3 4 1 2 3 4 can be given.

[0065] Two of RB, RB, RB, and RB may be bonded to each other to form a ring. RB ~ An example of a ring formed by combining two of RB is as follows:

4 1 4 Can give the same thing as the ring formed by bonding.

[0066] Further, in the metal complex represented by the general formula (la), the A part has a force represented by the general formula (lb), and the substitutable site of the metal complex represented by the general formula (la). The ring structure represented by the general formula (lb) is substituted.

In the general formula (lb), X represents ◯, S, N 2 -R. R represents an alkyl group, an aryl group, or a heteroaryl group.

[0068] Examples of the alkyl group, aryl group, and heteroaryl group represented by R include those similar to the alkyl group, aryl group, and heteroaryl group represented by RA, RA, RA, RA.

3 4

The power S

[0069] Z 1, Z 2, Z 3 and Z are independently a nitrogen atom or CR = (R is a hydrogen atom or a substituent)

1 2 3 4 3 3

One of Z, Z, Z and Z is a nitrogen atom.

1 2 3 4

[0070] Examples of the substituent represented by R are the same as the examples of the substituent represented by RA, RA, RA and RA.

3 1 2 3 4

I'm gonna give you that power.

[0071] In the general formula (l a), X—L—X represents a bidentate ligand, and X 1 and X 2 each independently represent carbon

1 1 2 1 2

Represents an elementary atom, nitrogen atom or oxygen atom.

[0072] L represents an atomic group forming a bidentate ligand together with X and X. X — L — 2 represented by X

Specific examples of 1 1 2 1 1 2dentate ligands include substituted or unsubstituted phenylpyrrolidine, phenylpyra zonore, phenylimidazonole, phenyltriazolene, phenyltetrazonole, pyrazabole. Acetylacetone, picolinic acid and the like. ml represents an integer of 1, 2 or 3, m2 represents a force representing an integer of 0, 1 or 2, ml + m2 is 2 or 3. Of these, m2 is preferably 0.

[0073] In the general formula (la), the metal represented by M used for forming the metal complex includes

1

Among the forces in which transition metal elements of Group 8 to Group 10 (also referred to simply as transition metals) of the elementary periodic table are used, iridium and platinum are preferable transition metal elements.

[0074] (Ligand)

The metal complex according to the present invention has, for example, a partial structure shown in parentheses having ml, or a portion represented by a tautomer thereof, when ml> m2 as described in the general formula (la). The structure is called a main ligand, and the partial structure shown in parentheses having m2 or a partial structure represented by a tautomer thereof is called a subligand. In the present invention, as represented by the general formula (la), the metal complex is composed of a combination of a main ligand or a tautomer thereof and a subligand or a tautomer thereof. In the case of m2 = 0, that is, all the ligands of the metal complex may be composed only of a partial structure represented by the main ligand or a tautomer thereof.

[0075] Further, a so-called ligand used in the formation of a conventionally known metal complex has a ligand (also known as a coordination compound) known as a ligand, if necessary, as a ligand! / Well! /

[0076] From the viewpoint of preferably obtaining the effects described in the present invention, the type of the ligand in the complex is preferably composed of 1 to 2 types, more preferably 1 type. .

[0077] There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer—Verlag H. Yersin 1987 Issuance, “Organic Metal Chemistry Basics and Applications” Liu Huabo Company Akio Yamamoto Ligand (for example, halogen ligands (preferably chlorine ligands), nitrogen-containing heterologues, etc. Ring ligands (for example, bibilidyl, phenantorin, etc.) and diketone ligands).

As a preferred embodiment of the present invention, the metal complex represented by the general formula (la) is a compound represented by the general formula

It is mentioned that it is a structure represented by (1).

In general formula (1), R represents an alkyl group, an aryl group, or a heteroaryl group. Y, Y is Nikko

1 1 2 Elemental atom or CR = (R is a hydrogen atom or a substituent). A, X, L, X, ml,

3 3 1 1 2 m2, M is the same as A, X, L, X, ml, m2, M in the general formula (la),

1 1 1 2 1 Alternatively, the group represented by the general formula (lb) is included as a substituent on the metal complex represented by the general formula (1).

[0080] As a preferred embodiment of the present invention, the metal complex represented by the general formula (1) is represented by the general formula (1).

It is mentioned that it is a structure represented by 2).

[0081] In the general formula (2),, 2, 2, 2, 2,,, ml, m2, M is X in the general formula (1),

1 2 3 4 1 1 2 1

Synonymous with Z, Z, Z, Z, X, L, X, ml, m2, M.

1 2 3 4 1 1 2 1

[0082] In general formula (1) or general formula (2), it is more preferable that Y and Y are -CR =, —CR = Yes.

[0083] In general formula (1) or general formula (2), it is more preferable that R is a carbyl group or an aryl group.

1 1 Force S More preferably, it is an aryl group having a substituent at the 2,6-position.

[0084] Specific examples of the metal complex represented by the general formulas (la), (1) and (2) according to the present invention are shown below, but the present invention is not limited to these.

[0085] [Chemical 8]

[0086] [Chemical 9]

[0087] [Chemical 10]

0088

[0089] [Chemical 12]

[0091] [Chemical 14]

[0092] [Chemical 15] s0093

[0094] [Chemical 17]

-General formula (2)

— I—U—X, ™ represents the following 镌 ¾

[0095] [Chemical 18]

[OZ ^] 600]

32

■,

idf / X3d 83 £ Z ^ tO / 800Z OM t LO 2o5 xo N »1i ———

OXXP es o ひ H ■ i け U ——- ί——i

O O

«3] Έ °

xouni i

i Hu—

JT i

OOG poo

] m

ε

X

>

-

X o o

]

ε

] a.o

5 ^ K = H-, -il1

I ^ o x Hn N, i 3 .... 2 i H I !! 1

iΗ ひ ¾¾οί = —- opo

I

X

u

it

X

!

ίί

X

u

i

cm [9] KOTO]

,,

-^ r 3 ^ 32 H i "t! l!

ZZ 690 / L00Zd £ / lDd / 800Z OAV

0

Q

[0104] [Chemical 27] [8 W [90 TO]

263CHCHNH OC == II I I1

2621 H 261CHCHNC O == I —-——

260CHCHNH oC == ———

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[0203] The synthesis examples of typical compounds are shown below.

[0204] <Synthesis of Exemplified Compound 2-425>

[0205] [Chemical 126]

[0206] <Synthesis of Complex A>

15. 2 g of Intermediate 1 was dissolved in 200 ml of 2-ethoxyethanol and 75 ml of water, 4.7 g of iridium chloride was added under a nitrogen atmosphere, and the mixture was heated to reflux for 3 hours. The reaction solution was allowed to cool, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 12. lg of complex A.

[0207] <Synthesis of Complex B> 8.4 g of Complex A was dissolved in 150 ml of 2-ethoxyethanol, 7 ml of acetylylacetone and 7. Og of sodium carbonate were added, and the mixture was refluxed with heating in a nitrogen atmosphere for 3 hours. The reaction solution was allowed to cool, poured into 300 ml of water, and the precipitated solid was collected by filtration and washed with water to obtain Complex B. It was used in the next step without further purification.

Complex B synthesized as described above was dissolved in 200 ml of ethylene glycol, 4.2 g of intermediate 1 was added, and the mixture was stirred for 4 hours while heating at 150 ° C. in a nitrogen atmosphere. The reaction solution was allowed to cool, 200 ml of water was added, and the precipitated solid was collected by filtration and washed with methanol. Further, the product was dissolved in a small amount of methylene chloride and purified by silica gel column chromatography to obtain 7.7 g of the intended exemplified compound 2-425.

[0209] << 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, the organic EL device of the present invention is formed on the light emitting layer or the electron blocking layer in the constituent layers (details will be described later) of the organic EL device. It is preferable to use a material. In the light emitting layer, it is preferably used as a light emitting dopant as described above.

[0210] (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 from 0.;! To less than 30% by mass.

[0211] However, the luminescent dopant may be a mixture of a plurality of types of compounds. The partner to be mixed may have a different structure, and other metal complexes or phosphorescent dopants or fluorescent dopants having other structures may also be used. Good.

[0212] 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.

[0213] Representative examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes , Pyrylium dyes, perylene dyes, steel Examples thereof include rubene dyes, polythiophene dyes, and rare earth complex phosphors.

[0214] 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. An osmium compound, and most preferred is an iridium compound.

[0215] Specifically, it is a compound described in the following patent publications.

[0216] WO 00/70655 pamphlet, JP 2002-280178, JP 2001-18 plate 6, JP 2002-280179, JP 2001-18 plate 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.

[0217] A part of a specific example is shown below.

[0218] [Chemical 127] Pt ~ 1 Pt ~ 2

28]

[0221] (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.

[0222] The luminescent host used in the present invention is not particularly limited in terms of structure, but is typically a force rubazole derivative, triarylamine derivative, aromatic borane derivative, nitrogen-containing bicyclic compound, thiophene derivative. , Basic bones such as furan derivatives and oligoarylene compounds Examples thereof include carboline derivatives and derivatives having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom. Among them, a force rubazole derivative, a carboline derivative, and a derivative having a ring structure in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom are preferably used.

[0223] Power to give specific examples below [0223] The present invention is not limited to these. These compounds are also preferably used as hole blocking materials.

[0224] [Chemical 130]

[0225] [Chemical 131] H10

32]

[0227] [Chemical 133] 隨 H24

[0228] 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. As these known host compounds, compounds that have a hole transporting ability and an electron transporting ability, prevent emission of longer wavelengths, and have a high Tg (glass transition temperature) are preferred! / ,.

[0229] The light-emitting host used in the present invention may be a low-molecular compound or a high-molecular compound having a repeating unit, which may be a low-molecular compound having a polymerizable group such as a bur group or an epoxy group (evaporation polymerizable light-emitting). Even the host) [0230] As the light-emitting host, a compound having a hole transporting ability and an electron transporting ability, which prevents the light emission from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.

[0231] 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.

[0232] 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).

[0233] Next, a configuration of a typical organic EL element will be described.

[0234] <Structure layers of organic EL elements> The constituent layers of the organic EL device of the present invention will be described.

[0235] Preferred specific examples of the layer structure of the organic EL device of the present invention are shown below, but the present invention is not limited thereto.

[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.

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.

[0238] 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 of the present invention described in any one of claims 1 to 7, The element material may be contained in a state of 100% by mass as a layer constituent component such as a hole blocking layer or an electron blocking layer, or may be mixed with other organic compounds.

[0239] The thickness of the blocking layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

[0240] 《Hole blocking layer》

The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons and has an extremely small ability to transport holes, and blocks holes while transporting electrons. By stopping, the recombination probability of electrons and holes can be improved.

[0241] Examples of the hole blocking layer include, for example, Japanese Patent Application Laid-Open Nos. 11 204258 and 11 204359, and “The Forefront of Organic EL Devices and Their 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.

[0242] The organic EL device of the present invention has a hole blocking layer as a constituent layer, and the hole blocking layer is at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring of the strong ruporin derivative or the carboline derivative. It is preferable to include a derivative having a ring structure in which one is substituted with a nitrogen atom.

[0243] 《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.

[0244] In the present invention, it is preferable to use the organic EL device material of the present invention described above 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.

[0245] 《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.

[0246] The hole transport material is not particularly limited, and is conventionally used as a hole charge injection / transport material in photoconductive materials, and used in the hole injection layer and hole transport layer of organic EL devices. Any known medium force can be selected and used.

[0247] The hole transport material has either hole injection or transport or electron barrier properties.

Any of organic substances and inorganic substances may be used. For example, triazole derivatives, oxazia Azole 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, Examples thereof include aniline-based copolymers and conductive polymer oligomers, particularly thiophene oligomers.

[0248] The ability to use the above-mentioned materials as the hole transporting material. It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, particularly an aromatic tertiary amine compound.

[0249] Typical examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N' —tetraphenenole 4, A 'diaminophenol; N, N' — diphenenole N, N , —Bis (3 methylphenyl) 1 [1, 1 ′ — biphenyl] 1, 4, 4 ′ — Diamine (TPD); 2, 2-bis (4 di 1 p trilaminophenyl) propane; 1-bis (4 di-l-triarylaminophenenyl) cyclohexane; N, N, N ', N' —tetra-l-trinore 4, A ′ —diaminobiphenyl; 1, 1-bis (4-di-one) p-tolylaminophenyl) 4-phenylcyclohexan; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-amino-phenyl) phenylmethane; N, N '— diphenyleno N, N ′ —di (4-methoxyphenol) 1 4, 4′—diaminobiphenol; N, N, N ', N' — Tetraphenylol 4,4'-diaminodiphenyl ethereol; 4, A 'bis (diphenylamino) quadrenyl; N, N, N-tri (p-tolyl) amine 4- (di-p-tolylamino) -one [4- (di-p-tolylamino) styryl] stilbene; 4-N, N diphenylamino- (2 diphenylbinole) benzene; 3-methoxy-4 ' N, N diphenylaminostilbenzene; N phenylcarbazole, and further two condensed aromatic rings described in US Pat. No. 5,061, 569 in the molecule, for example 4 , 4 'bis [N- (1 naphthyl) N phenylamino] biphenyl (NPD), three triphenylamine units described in JP-A-4 308688 are connected in a starburst type, 4, 4', 4 '—Tris [N— (3-methylphenyl) N phenyla Roh] triphenyl § Min (MTDATA) and the like.

[0250] Further, these materials are introduced into the polymer chain, or these materials are used as the polymer main chain. High polymer materials can also be used. Inorganic compounds such as p-type Si and p-type SiC can also be used as the hole injecting material and hole transporting material.

[0251] The 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.

[0252] 《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.

Conventionally, in the case of a single electron transport layer and a plurality of layers, as 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, The following materials are known.

[0254] Furthermore, as long as the electron transporting layer has a function of transferring electrons injected from the cathode to the light emitting layer, any material selected from conventionally known compounds should be used. Touch with force S.

[0255] Examples of materials used for the 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. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring, known as an electron withdrawing group, can also be used as an electron transport material.

[0256] Furthermore, these materials are introduced into the polymer chain, or these materials are used as the polymer main chain. High polymer materials can also be used.

[0257] Also, metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-dive mouth 8 quinolinol) Aluminum, tris (2-methyl-8-quinolinol) 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, Metal complexes replacing Ca, 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.

[0258] 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, the injection layer used as the constituent layer of the organic EL element of the present invention will be described.

[0260] << 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.

[0261] The injection layer is a layer that is provided between the electrode and the organic layer in order to reduce the drive voltage and increase the luminance of the light emission. “The organic EL element and the forefront of its 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.

[0262] The details of the anode buffer layer (hole injection layer) are 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. .

[0263] Details of the cathode buffer layer (electron injection layer) are also 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.

[0264] The buffer layer (injection layer) is preferably a very thin film, although the film thickness is preferably in the range of 0.;! To lOOnm.

[0265] 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.

[0266] 《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. Furthermore, although it depends on the material, the film thickness is usually 10 to 1000 nm, preferably 10 to 200 nm. [0267] 《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.

[0268] << 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.

[0269] 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. [0270] On the surface of the resin film, a water vapor transmission rate of 0.01 g / (m ² '24h'MPa) or less is acceptable even if an inorganic or organic film or a hybrid film of both is formed. A barrier film is preferred.

[0271] 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.

[0272] A hue improving filter such as a color filter may be used in combination.

[0273] When used for illumination, a roughened film (such as anti-glare phenol) may be used in combination in order to reduce unevenness in light emission.

[0274] When used as a multicolor display device, it is composed of at least two types of organic EL elements having different emission maximum wavelengths, and a preferred example of producing an organic EL element will be described.

[0275] <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!

[0276] First, a thin film made of a desired electrode material, for example, an anode material, is deposited on a suitable substrate by a method such as vapor deposition or sputtering so that the film thickness is 1 μm 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.

[0277] As a method for reducing the thickness of a thin film containing an organic compound, there are a spin coating method, a casting 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, a different film forming method may be applied for each layer. When a vapor deposition method is used for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is 50 to 450 ° C, the degree of vacuum is 10-6 to 10-2 Pa, and the deposition rate is 0. It is desirable to select as appropriate in the range of 0;! To 50 nm / second, substrate temperature—50 to 300 ° C., and film thickness of 0.1 to 5 m.

[0278] After the formation of these layers, 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.

[0279] <Display device>

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

[0280] The display device of the present invention may be single color or multicolor, but here, the 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.

[0281] 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.

[0282] Further, it is also possible to reverse the production order to produce a cathode, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and an anode in this order.

[0283] 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! /.

[0284] The multicolor display device can be used as a display device, a display, and various light sources. For display devices and displays, full-color display is possible by using three organic EL elements, blue, red, and green light emission.

[0285] Examples of the display device and display include a television, a personal computer, a mopile device, an AV device, a character broadcast display, and an information display in a car. 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.

[0286] Luminescent light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, optical storage media light sources, electrophotographic copying machine light sources, optical communication processor light sources, optical sensor Examples include light sources, but are not limited to this!

[0287] 《Lighting device》

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

[0288] 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.

[0289] Further, the organic EL element 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. 1 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.

[0292] The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

[0293] 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. 2 is a schematic diagram of the display unit A.

[0295] 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.

[0296] The figure shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

[0297] 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).

[0298] When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6, and emits light in accordance with 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. 3 is a schematic diagram of a pixel.

[0301] 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. 3, 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.

[0303] By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10. Current is supplied from the power supply line 7 to the organic EL element 10 in accordance with the potential of the image data signal applied at a time.

[0304] 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 drive transistor 12 as active elements for each of the organic EL elements 10 of each of the plurality of pixels, thereby providing organic EL for each of the plurality of pixels 3. Element 10 is emitting light. Such a light emitting method is called an active matrix method.

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! /.

[0307] The present invention is not limited to the above-described active matrix system, and may be a passive matrix system light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned. .

FIG. 4 is a schematic diagram of a display device using a passive matrix method. In FIG. 4, 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.

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 according to the image data signal.

[0310] With the noisy matrix method, there is no active element in pixel 3, and the manufacturing cost can be reduced.

[0311] The organic EL material of the present invention is an organic EL element that emits substantially white light as a lighting device. Applicable to children. 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.

[0312] A combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials, a fluorescent material or a phosphorescent material, 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.

[0313] The light emitting material used for the light emitting layer is not particularly limited. For example, in the case of a backlight in a liquid crystal display element, the light emitting material according to the present invention is adapted so as to conform to the wavelength range corresponding to the CF (color filter) characteristics. Select any of the metal complexes and known luminescent materials and combine them to whiten! /.

[0314] 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.

[0315] Other light sources such as backlights for watches, billboard advertisements, traffic lights, optical storage media, electronic photocopiers, optical communication processors, photosensors, etc. And a wide range of uses such as general household appliances.

Example

[0316] Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0317] 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 a 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. (Vacuum chamber).

[0318] Further, lithium fluoride was put into a resistance heating boat made of tantalum, and aluminum was put into a resistance heating boat made of tungsten, respectively, and attached to the second vacuum chamber of the vacuum evaporation apparatus.

[0319] 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.

[0320] Further, the heating boat containing H4 and the boat containing Ir 12 are energized independently so that the deposition rate of H4 as a light emitting host and Ir-12 as a light emitting dopant is 100: 6. And a light emitting layer was provided by vapor deposition to a thickness of 30 nm.

[0321] Next, the heating boat containing BCP was energized and heated, and a hole blocking layer having a thickness of lOnm was provided at a deposition rate of 0.2;! To 0.2 nm / sec. Further, the heating boat containing Alq was passed through and heated to provide an electron transporting layer having a film thickness of 20 nm at a deposition rate of 0.2;

[0322] Next, after the element deposited up to the electron transport layer was transferred to the second vacuum chamber while maintaining a vacuum, the stainless steel rectangular perforated mask was placed on the electron transport layer. It was installed with remote control.

[0323] 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.

[0324] [Chemical 134] BCP &-ΡΌ

[0325] << Organic EL device 1-2 ~;!-37 fabrication >>

In the production of organic EL device 1-1, organic EL device 1 1-2 ~ !! ☆ was produced in the same manner except that the light-emitting host, light-emitting dopant, and hole blocking material were changed as shown in Table 1. .

[0326] [Table 1]

Emission Hole blocking external extraction

祷し素子 ^ 発光発光ドードー凳允凳允 lifetime emission color «consideration, strike« material quantum effect *

1 ― Λ H-4 Ir-lE 100 100 'Light blue Comparative example-2 H-4 Comparative compound 1 8 C P 102: 9S Green Comparative example

1 -3 H-4 Comparative compound 2 B C P 105 93 Blue green Comparison «

1-A H— 4Comparison Compound 3: BCP 99 Blue Agate Comparison «

1 — H— 4 Exemplified compounds 1 — 1 BC P 134 332 Green The present invention

1 6 H—4 Ex .: Compound 1 — 4 B C M6 407 Red The present invention

1-7 H 4 Exemplified compound 1. ― 6 BC P: 13? 4SS The present invention

1—BH—4 Illustrative food 1 -44 BC P 156 411 Pure blue The present invention ^:

1 —9 H—Exemplary compound 2—69 B C P 149 400 m The present invention

1 ~ W H— Tetravalent compound 2 -76 B C f 168 689

1 -11 H— 4 Inverted compound. 2 389 B C P 153 Si7 Ken blue Present invention ί -12 H-4 Illustrated compound 2 '-42S B C P 174? 77 Pure present invention

\ H-Exemplified compounds ·?-· »■ 559 · B C P 166 702 Pure blue Present invention —14 H-4 examples. Including inclusions 2 -619 a c ITS 765« Blue Present invention

1 — H-4 Exemplified compound '1-1 H-5 t 9 442

1 -16 H-4 Exemplified Compound 1 -4; H-5 177 4'0 Red The present invention

1 ™ 17 ■-H---— 4---Exemplified compound〗 ~ 8 H-5 178 503

1 -18 H-4 Exemplified compound 1-44 H-5 5 § 6 543 Blue The present invention:

1 -1 H ~ Illustrated platform '2 69 H— ■ 5 158 678

1 ™ 20 H-4 Exemplary compounds 2 7δ H-5 180 747 The present invention

1 -21 H— 4. Display compound 2—389 H— 5! 77 720 The present invention

1 -22 H '― 4 Ex . ^: Chemical base 2 --425 H 1 S 165 769 赫 The present invention 1 —23 H—4 Exemplified compounds' 2—559 H-5 171 677 齊

1 — H— 4 Exemplified compounds 2 -619 ■ H— 5 168 621 * Invention

\ 25. H-6 Inversion compound 1 -44 B C P 159 490 Aomoto Tomoaki -26 H-6 Exemplified compound · 2-42 SO P 170 799 Pure blue The present invention

\ -11 H ~ 6 Exemplified compound 2 -6.19 BC P 567 638 as the present invention

\-"Z & H-6 Exemplified compound 1-44 H-5 178 531 麵 The present invention

1 -23 H ~ 6 Examples include: 2.—389 H-5 161 499 Pure blue

) —30 H-6 Exemplified compound · 2. -4Ζ5 H-5 ϊ81 758 Blue Present invention… H-6 Illustrated compound '2 -6Τ9; H-5 169 731 ate Present invention

1 —32 H-30 1 [Indication: Compound 1 —44 I BC Ρ rn 519

1 -33 H -30 ■ Chemical base 2 -425 B C P 178 800 賨 This invention

1 -34 H-3D Example ^: Compound 2-6 IS BC P 169 707 The present invention

1 1 H-30 剁 Compound〗 — 44 H- 5 165 468 The present invention

1 -36 H-30 Example: Indication: Compound 2— 5 H-5! 81? 90 Pure blue The present invention

1 ™ 37 H-30 Compound 1 6-9 JH-5 167 6S0 Invention 135] Comparative compound 1

Inter-Academic Publication No. 04 / 08S4SO No. 22: Page-Compounds falling under the general formula

[0328] 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. In addition, it can be seen that it is useful as a blue light emitting device having a higher blue purity than the organic EL device of the comparative example.

[0329] Further, the lifetime of the light-emitting element can be further improved by using a more preferable form in the metal complex of the present invention. [0330] Example 2

An anode of indium tin oxide (ITO, indium / tin = 95/5 molar ratio) was formed by sputtering on a glass support substrate of 25 mm X 25 mm X O. 5 mm using a DC power source (thickness 200 nm). The surface resistance of this anode was 10 Ω / mouth. Polyburcarbazole (hole transporting binder polymer) / Ir 13 (blue light-emitting orthometalated complex) / 2 (4-biphenyl) -5- (4 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 buttered mask (a mask with a light emitting area of 5 mm x 5 mm) is placed on the organic compound layer, and 0.5 nm of lithium fluoride is deposited as a cathode buffer layer and 150 nm of aluminum is deposited as a cathode in a deposition apparatus. Thus, a cathode was provided to produce an organic EL device 21 emitting blue light.

[0331] << Production of organic EL elements 2-2 to 2-14 >>

Organic EL elements 2-2 to 2-14 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.

[0332] << Evaluation of organic EL elements >>

When evaluating the obtained organic EL elements 2— ;! to 2-14, the non-light-emitting surface of each organic EL element 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. 5 and 6 was formed and evaluated.

[0333] Next, light emission luminance and light emission efficiency were measured as follows.

[0334] (Luminance, luminous efficiency)

Using a Toyo Tech Yuka source measure unit type 2400, a direct current voltage was applied to the organic EL element to emit light, and the emission luminance (cd / m ² ) and 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. [0335] [Table 2]

[0336] From Table 2, it is clear that the organic EL device produced using the metal complex according to the present invention can achieve higher luminous efficiency and higher luminance than the organic EL device of the comparative example.

Example 3

(Production of blue light-emitting elements)

The organic EL device 112 of Example 1 was used as a blue light emitting device.

[0337] (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.

[0338] (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 11 of Example 1, and this was used as a red light emitting device.

[0339] The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate, and an active matrix full-color display device having a configuration as shown in Fig. 1 was produced. FIG. 2 shows only a schematic view of the display portion A of the display device thus manufactured. That is, a plurality of pixels 3 (light emitting elements) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. And the scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning line 5 and the data line 6 Is orthogonal to the grid and is connected to the pixel 3 at the orthogonal position (details 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.

[0340] 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.

[0341] 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 H The heated boat containing 4 and the example compound 2—425 and Ir 9 containing boat are energized independently, and the light emitting host HI and the example dopant 2—425 and Ir— The vapor deposition rate of 9 was adjusted to 100: 5: 0.6, vapor deposition was performed to a thickness of 30 ηm, and a light emitting layer was provided.

[0342] Next, 10 nm of BCP was formed to provide a hole blocking layer. Furthermore, Alq was deposited at 40 nm to provide an electron transport layer.

[0343] 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 as a cathode buffer layer and a cathode as a cathode buffer layer. Aluminum 150nm was deposited.

[0344] This element was provided with a sealing can having the same method and the same structure as in Example 1, and a flat lamp as shown in Figs. 5 and 6 was produced. 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 could be obtained in the same manner even if it was replaced with other exemplified compounds.

[0345] 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.

[0346] On this transparent support substrate, poly (3,4 ethylene dioxythiophene) polystyrene sulfonate (PEDOT / PSS: Bayer, Baytron P A1 4083) diluted to 70% with pure water 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.

[0347] This 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.

[0348] Next, a solution in which Compound B (60 mg), Ir-14 (3. Omg), 2-637 (3. Omg) was dissolved in 6 ml of toluene was used, and spin coating was performed at 1000 rpm for 30 seconds. To form a film. 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.

[0349] Further, a film in which Compound C (20 mg) was dissolved in 6 ml of toluene was used to form a film by spin coating under conditions of 1000 rpm and 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.

[0350] [Chemical 136]

[0351] Subsequently, this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, and 200 mg of Alq was put into a molybdenum resistance heating boat and attached to the vacuum vapor deposition apparatus. 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.

[0352] The substrate temperature during vapor deposition was room temperature.

[0353] 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.

[0354] When this element was energized, almost white light was obtained, indicating that it could be used as a lighting device.

Claims

The scope of the claims

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

[Chemical 1]

: General formula a)

[In general formula (la), C and N are covalently or coordinated to metal atom M.

1

Represents a cyclic group bonded to the metal atom M.

1

Further, in the general formula (la), the cyclic group represented by A is a group represented by the following general formula (lb), or on the metal complex represented by the general formula (la), It has a group represented by the formula (lb) as a substituent.

«Formula f1W

In the general formula (lb), X represents O, S, NR (R represents an alkyl group, an aryl group, or a heteroaryl group).

Z, Z, Z, Z are independently a nitrogen atom or CR = (R represents a hydrogen atom or a substituent.

1 2 3 4 4 4

1 2 3 4 1 1 2

Represents a ligand, and X and X each independently represent a carbon atom, a nitrogen atom or an oxygen atom. L is Represents a group of atoms that form a bidentate ligand with XX. ml represents an integer of 1 2 or 3

1 2

M2 is 0 or a force representing an integer of 1 or 2 ml + m2 is 2 or 3. M, which is a metal atom, represents a group 8 to group 10 metal in the periodic table. ]

1

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

[Chemical formula 3] General formula (1)

[Wherein, R represents an alkyl group, an aryl group, or a heteroaryl group. Y Y is a nitrogen atom

1 1 2

Or CR = (R is a hydrogen atom or a substituent). A X L X ml m2 M

3 3 1 1 2 1 is a force having the same meaning as A X L X ml m2 M in the general formula (la), or

1 1 2 1

The metal complex represented by the general formula (1) has a group represented by the general formula (lb) as a substituent. ]

[3] The organic electroluminescence device material according to claim 2, wherein the general formula (1) is represented by the following general formula (2).

[Chemical 4]

General formula (2)

1 1 1 2 1 2 3 4

It is synonymous with each X Z Z Z Z. ]

1 2 3 4

In the general formula (1) or (2), Y Y is CR = CR = (R R is water

1 2 4 5 4 5 Represents an elementary atom or a substituent. The organic electoluminescence device material according to claim 2 or 3, characterized in that:

In the general formula (1) or (2), R force S methyl group, aryl group

1

5. The organic electroluminescent element material according to any one of claims 2 to 4, wherein the organic electroluminescent element is a material.

In the above general formula (1) or general formula (2), R is an aryl group having a substituent at the 2,6 position.

1

The organic electroluminescent element material according to any one of claims 2 to 5, characterized in that:

In the general formula (1) or (2), M is Ir or Pt.

1

2. The organic electroluminescence device material according to item 1, wherein any force of items 2 to 6 is obtained.

The organic electoluminescence device material according to any one of claims 2 to 7, wherein m2 is 0 in the general formula (1) or the general formula (2). The organic electoluminescence device according to any one of claims 1 to 8, wherein the organic electroluminescence device material according to claim 1 is contained in a light emitting layer. [10] A display device comprising the organic electoluminescence element according to claim 9.

[11] An illumination device comprising the organic electoluminescence device according to claim 9.