JP5644050B2 - Organic electroluminescence element material - Google Patents

Description

The present invention relates to an organic electroluminescence device materials.

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements). Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements. 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, injects electrons and holes into the light emitting layer, and recombines them to generate excitons (exciton). It is an element that emits light by using light emission (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of about several volts to several tens of volts, and it is self-luminous. In addition, it is attracting attention from the viewpoints of space saving, portability and the like because it is a thin film type complete solid element with a wide viewing angle and high visibility.

  However, in 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.

  In Japanese Patent No. 3093796, a small amount of a phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to achieve an improvement in light emission luminance and a longer device lifetime. Further, 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 thereto (for example, JP-A 63-264692), and an 8-hydroxyquinoline aluminum complex is used as a host compound. For example, an element having an organic light emitting layer doped with a quinacridone dye (for example, JP-A-3-255190) is known.

  As described above, when light emission from excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of luminescent excited species is 25%. Since the efficiency is about 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University reported on an organic EL device using phosphorescence emission from an excited triplet (MA Baldo et al., Nature, 395, 151-154 (1998)), Research on materials that exhibit phosphorescence has become active.

  For example, M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), US Pat. No. 6,097,147, and the like.

  When the excited triplet is used, the upper limit of the internal quantum efficiency is 100%. In principle, the luminous efficiency is four times that of the excited singlet. Therefore, it is attracting attention as a lighting application.

  For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., many compounds are being studied for synthesis centering on heavy metal complexes such as iridium complexes.

  In addition, the aforementioned M.I. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), studies have been made using tris (2-phenylpyridine) iridium as a dopant.

  In addition, M.M. E. Thompson et al., In The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), used L2Ir (acac), for example, (ppy) 2Ir (acac) as a dopant. 0g, Tetsuo Tsutsui, et al. Also used Tris (2- (p-tolyl) pyridine) iridium (y) (Ir3) as dopant in The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu). Studies using benzo [h] quinoline) iridium (Ir (bzq) 3) or the like are being conducted (note that these metal complexes are generally called ortho-metalated iridium complexes).

  In addition, the S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) and Japanese Patent Application Laid-Open No. 2001-247859, etc., attempts have been made to form devices using various iridium complexes.

  In order to obtain high luminous efficiency, in the 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.

  Orthometalated complexes in which the central metal is platinum instead of iridium are also attracting attention. With respect to this type of complex, many examples are known in which ligands are characterized.

  In either case, the light emission brightness and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element. As described above, it is difficult for phosphorescent highly efficient light-emitting materials to shorten the light emission wavelength and improve the light emission lifetime of the device, and the performance that can withstand practical use cannot be sufficiently achieved.

  In addition, regarding wavelength shortening, introduction of electron-withdrawing groups such as fluorine atoms, trifluoromethyl groups, and cyano groups into phenylpyridine as substituents, and picolinic acid and pyrazaball-type secondary ligands as ligands However, with these ligands, the emission wavelength of the luminescent material is shortened to achieve a blue color, and a high-efficiency device can be achieved. There was a need to improve the trade-off.

  A metal complex having phenylpyrazole substituted with a phenyl group as a ligand is known (for example, see Patent Documents 1 and 2). However, although the phenyl radical substitution mode disclosed herein improves the light emitting device lifetime, it is still not sufficient, and there is still room for improvement from the viewpoint of light emission efficiency.

  Although examples in which phenylimidazole is used as a basic skeleton as a ligand and various substituents are introduced have been disclosed (for example, see Patent Documents 3 and 4), there is no significant improvement in the light emission lifetime. There is room left.

As another approach, an example in which a condensed ring structure composed of three or more rings containing a hetero atom is introduced into the structure of the ligand is disclosed (see Patent Documents 5, 6, and 7). Many of the examples show long-wave emission such as yellow to red with an emission maximum of 550 nm or more, few examples of short-wave emission such as blue to blue-green, and none with high efficiency and long emission lifetime. It was.
International Publication No. 04/085450 Pamphlet JP 2005-53912 A International Publication No. 05/007767 Pamphlet International Publication No. 06/046980 Pamphlet JP 2002-332291 A Japanese Patent Laid-Open No. 2004-67658 International Publication No. 04/1101066 Pamphlet

The present invention has been made in view of the above problems, an object of the present invention, the emission wavelength is controlled, showed high luminous efficiency, and to provide a long organic EL device material emission lifetime. In particular, it is to provide an organic EL element material that exhibits high luminous efficiency with short-wave light emission of blue to blue-green, has a long emission lifetime, and 6.

The above-described problems of the present invention have been solved by the following means .

1. An organic electroluminescence element material, which is a metal complex represented by the following general formula (2).

(Wherein, X is _R 1 -N, the .R ₁ is a substituted or unsubstituted representing O or S, the .Y ₁ and _{Y 2} represents an alkyl group or the aryl group _R 2 -N, N or _{R 3} represents -C, .R ₃ .R ₂ represent the atoms necessary to form an imidazole ring or preparative Riazor ring with N-C = N is to represent a substituted or unsubstituted, alkyl group or the aryl group is hydrogen .G representing an original child an aryl group or an alkylsulfonyl group substitution table to. n is _.X 1 _-L 1 -X ₂ 0 or is representing one represents a bidentate ligand, X ₁ and X ₂ are each independently a carbon atom, _{M 1} .L ₁ which represents a nitrogen atom or oxygen atom is. central metal represents an atomic group forming a ligand bidentate with _{X 1} and X _2, iridium, platinum, .M1 representing rhodium or palladium 1, 2 or 3 If represents the number, although m2 represents 0 or 1, m1 + m2 is 2 or 3, which is the same number as the central metal of the positive charge. However, _{the Y 1} and _{Y 2} both represent _R 3 -C And R ₃ are not bonded to each other to form a ring.)
2 . 2. The organic electroluminescent element material according to 1 , wherein the metal complex represented by the general formula (2) is represented by the following general formula (3).

(Wherein, X is _R 1 -N, .R ₁ representing O or S is substituted or unsubstituted, .R ₂ represents an alkyl group or the aryl group is substituted or unsubstituted, alkyl group or the aryl group the representative .G is an aryl group or an alkylsulfonyl group substitution table to. n is _.X 1 _-L 1 -X ₂ 0 or is representing one represents a bidentate ligand, _{X 1} and X ₂ each independently represents a carbon atom, a nitrogen atom or an oxygen atom, L ₁ represents an atomic group forming a bidentate ligand together with X ₁ and X _2. M _{1 as a} central metal is iridium, platinum , .M1 representing rhodium or palladium is an integer of 1, 2 or 3, m2 represents 0 or 1, m1 + m2 is 2 or 3, which is the same number as the positive charge on the central metal.)
3 . In the metal complex represented by the general formula (3), R ₂ is a methyl group , a 2,6-dimethylphenyl group, a mesityl group (2,4,6-trimethylphenyl group) or a tetramethylphenyl group. 3. The organic electroluminescence element material as described in 2 above.

4 . The organic electroluminescence device material according to any one of the 1-3, wherein the central metal M ₁ is iridium.

5 . The organic electroluminescence device material according to any one of the 1-3, wherein the central metal M ₁ is platinum.

6 . Said m2 is 0, The organic electroluminescent element material of any one of said 1-5 characterized by the above-mentioned.

7 . 7. The organic electroluminescent element material according to any one of 1 to 6 , wherein the first emission wavelength is in the range of 400 to 500 nm.

  According to the present invention, an organic EL element material useful for an organic EL element is obtained. By using the organic EL element material, an emission wavelength is controlled, high emission efficiency is exhibited, and an organic EL element having a long emission lifetime is provided. A device and a display device could be provided.

It is an emission spectrum of the metal complex (compound 4) of this invention. It is an emission spectrum of the metal complex (compound 4) of this invention. It is an emission spectrum of the metal complex (compound 14) of this invention. It is an emission spectrum of the metal complex (compound 14) of this invention. It is an emission spectrum of the metal complex (compound 27) of this invention. It is an emission spectrum of the metal complex (compound 27) of this invention. It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. 4 is a schematic diagram of a display unit A. FIG. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full color display device. It is the schematic of an illuminating device. It is a schematic diagram of an illuminating device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 7 Power supply line 10 Organic EL element 11 Switching transistor 12 Drive transistor 13 Capacitor A Display part B Control part 102 Glass cover 105 Cathode 106 Organic EL layer 107 Glass substrate with a transparent electrode 108 Nitrogen gas 109 Water catcher

  In the organic EL element material of the present invention, the organic EL element material useful for the organic EL element was successfully molecularly designed by the configuration defined in any one of claims 1 to 9. 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 emission efficiency and have a long emission lifetime.

  As a result of intensive studies on the above problems, the inventors of the present invention emitted light from an organic EL element containing the metal complex represented by the general formula (1), (2) or (3) as an organic EL element material. We have found that efficiency and light emission lifetime are greatly improved.

  As a result of intensive studies, the inventors of the present invention have found that phenylazole derivatives greatly depend on the stability of the complex due to the influence of the substitution position and type of substituents on the phenyl nucleus, which is the mother nucleus, and this greatly affects the emission lifetime. Found to give. Like a metal complex according to the present invention, by introducing a specific partial structure into phenylazole, a blue metal complex having a conventional phenylpyridine derivative as a ligand, in particular, an emission wavelength is shortened only by an electron withdrawing group. As a result, it has been found that the light emission lifetime which has been a problem of the organic EL element produced using the organic EL element material which has been controlled to be greatly improved, and it is possible to achieve both high light emission efficiency and long light emission lifetime. In addition, the use of a 2-phenylimidazole derivative, among other phenylazole derivatives, and the introduction of a specific substituent into a nitrogen atom that is not liganded to a metal on the imidazole ring, have excellent color purity. It was found that the lifetime of the blue light-emitting element could be further extended, and succeeded in greatly improving the light-emitting lifetime of the organic EL element.

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

《Metal complex》
The metal complex which concerns on the organic EL element material of this invention is demonstrated.
(Wherein X represents R ₁ —N, O, S, Se or Te. R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group. Y ₁ , Y ₂ and Y ₃ represent R ₂ —N, N, or R ₃ —C, and represent an atomic group necessary for forming an imidazole ring, triazole ring, or tetrazole ring together with C and N. R ₂ is substituted or absent. A substituted alkyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group, R ₃ represents a hydrogen atom or a substituent, G represents a substituent, n represents 0, 1 or 2. X ₁ -L ₁ -X ₂ represents a bidentate ligand, X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom or an oxygen atom L ₁ is a bidentate coordination with X ₁ and X ₂ It represents an atomic group forming a child. M ₁ is a center metal in the periodic table of elements M1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3, which is a positive charge of the central metal (However, when Y ₁ and Y ₂ both represent R ₃ -C, R ₃ is not bonded to form a ring.)

(Ligand)
For example, when the metal complex according to the present invention is described by the above general formula (1), the partial structure shown in parentheses having m1 or the partial structure represented by a tautomer thereof is the main ligand, and m2 A partial structure shown in parentheses 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 composed of a combination of a main ligand or a tautomer thereof and a subligand or a tautomer thereof, As will be described later, in the case of m2 = 0, that is, all of the ligands of the metal complex may be composed only of a partial structure represented by the main ligand or a tautomer thereof.

  Further, as a so-called ligand used for forming a conventionally known metal complex, the trader may have a known ligand (also referred to as a coordination compound) as a sub-ligand as necessary.

  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.

  There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin, 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabosha, Akio Yamamoto, published by 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands).

(Transition metal element of group 8-11 of the periodic table)
As the metal used for forming the metal complex represented by the general formula (1), (2) or (3) according to the present invention, a transition metal element of group 8 to 11 of the periodic table (also referred to as a transition metal). Among them, iridium and platinum are preferable transition metal elements.

  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 are preferable, and when contained in the light emitting layer, By using it as a light-emitting dopant in the light-emitting layer, it is possible to improve the external extraction quantum efficiency (higher brightness) of the organic EL device of the present invention and to increase the light emission lifetime.

(Metal complex represented by 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.

In the general formula (1), (2) or (3), X represents R ₁ —N, O, S, Se or Te. X is preferably R ₁ —N, O, or S in terms of the shorter wavelength of light emission maximum, and more preferably R ₁ —N in terms of higher color purity of light emission. .

R ₁ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or aromatic heterocyclic group.

  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, and a pentadecyl group.

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

  Examples of the aryl group include phenyl, mesityl, tolyl, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl and the like.

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group and the like.

  These groups may be further substituted, and examples of the substituent include 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 vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl etc.) Group), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group Acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenyl Eneyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole- 1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, Dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) ), Quinoxalinyl group, pyridazinyl group, triazi Group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl 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, Methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, Phthalylthio group), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, Naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, 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) Propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, Ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group) Group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecyl Carbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, Octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido) Group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), Sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (For example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino 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 (for example, Fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group) , Phenyldiethylsilyl 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.

G represents a substituent, and n represents 0, 1 or 2. Examples of the substituent include the same as those exemplified as the substituent of R ₁ .

Y ₁ , Y _2, and Y ₃ represent R ₂ —N, N, or R ₃ —C, and represent an atomic group necessary for forming an imidazole ring, triazole ring, or tetrazole ring together with C and N.

R ₂ represents a substituted, unsubstituted alkyl group, cycloalkyl group, aryl group or 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 .

These groups may be further substituted, and examples of the substituent include the same as those exemplified as the substituent of R ₁ .

R ₂ is preferably a methyl group, a substituted or unsubstituted aryl group or an aromatic heterocyclic group from the viewpoint of the emission lifetime, and particularly preferably a substituted or unsubstituted aryl group or an aromatic heterocyclic group.

Among the aryl groups, those in which at least one methyl group is substituted at the two ortho positions of the binding site with imidazole are preferable in terms of shortening the emission wavelength, and more preferably the binding site with imidazole. The two ortho positions are both substituted with a methyl group, specifically, a 2,6-dimethylphenyl group, a mesityl group (2,4,6-trimethylphenyl group), a tetramethylphenyl group, or a penta It is a methylphenyl group. The 2,6-dimethylphenyl group may be further substituted, and examples of the substituent include the same as those mentioned as the substituent for R ₁ .

R ₃ represents a hydrogen atom or a substituent. Examples of the substituent include the same as those exemplified as the substituent of R ₁ . 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.

M ₁ which is a central metal represents a metal of Group 8 to 11 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.

Below, the structure of the main ligand is shown together with the central metal M ₁ .

In the formula, X, G, n, R ₂ , R ₃ and M ₁ represent the same as those in the general formula (1).

Y ₃ is preferably R ₂ —N in terms of high emission quantum yield, and Y ₂ is preferably HC in terms of a shorter emission maximum wavelength. The emission lifetime is longer when Y ₁ and Y ₂ are both R ₃ -C.

  That is, as the structure of the main ligand, the above-mentioned structures of imidazole-1, triazole-1, triazole-2 and tetrazole-1 are preferable, and imidazole-1 and triazole-1 are more preferable, and the most preferable is Is the structure of imidazole-1.

In the general formula (1), (2) or (3), X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ are each independently a carbon atom, nitrogen atom, or oxygen Represents an atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .

Specific examples of the bidentate ligand represented by X ₁ -L ₁ -X ₂ include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, picolinic acid , Etc. m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3. Among these, m2 is preferably 0.

  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 to these.

  These metal complexes are described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) New Journal of Chemistry, Vol. 26, page 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and methods of references and the like described in these documents. It can be synthesized by applying.

  Below, the synthesis example of a typical compound is shown.

(Synthesis of Exemplary Compound 4)
It was synthesized according to the following scheme.

  Under nitrogen atmosphere 3- [1- (2,4,6-trimethylphenyl) -1H-imidazol-2-yl] -9-phenyl-9H-carbazole 3.9 g (9.1 mmol) 2-ethoxy To a solution dissolved in 30 ml of ethanol were added iridium chloride trihydrate, 1.06 g (3.0 mmol) and 10 ml of water, 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 2.72 g (yield 84%) of Complex A.

  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. To this suspension, 0.4 g (4.0 mmol) of acetylacetone was added and refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by filtration under reduced pressure. 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, 2.10 g (yield 92%) of complex B was obtained.

Complex B, 1.03 g (0.9 mmol) and 3- [1- (2,4,6-trimethylphenyl) -1H-imidazol-2-yl] -9-phenyl-9H-carbazole 1 under nitrogen atmosphere .28 g (3.0 mmol) was suspended in 40 ml of glycerin. 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 the complex B 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 0.99 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 Exemplary Compound 4 (methylene chloride).
It was confirmed by MASS and 1H-NMR that the purified compound 4 was the target product.

1H-NMR (400 MHz, 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, phenyl group), 6.54 (t, J = 7.4 Hz, 6H, CH, phenyl group), 6.62 (s, 3H, CH, carbazole ring), 6.80 (s, 3H) , CH, carbazole ring), 6.84 (d, J = 7.4 Hz, 6H, CH, phenyl group), 6.89 (d, J = 1.5 Hz, 3H, CH, imidazole ring), 6.92 (D, J = 1.5 Hz, 6H, CH, imidazole ring), 6.97 (t, J = 7.4 Hz, 3H, CH, carbazole ring), 7.11 (d, J = 7.4 Hz, 3H , CH, carbazole ring), 7.14 (s, 3H, CH, mesityl group), 7.16 (s, 3H, CH, meso Butyl group), 7.21 (d, J = 7.4Hz, 3H, CH, carbazole ring) 7.32 (d, J = 7.4Hz, 3H, CH, carbazole ring)
The PL emission maximum wavelength in the solution of Exemplified Compound (4) measured using Hitachi, Ltd. F-4500 was 462 nm (T = 77K, in 2-methyltetrahydrofuran), 470 nm (room temperature, in methylene chloride).

  1 and 2 show emission spectra.

(Synthesis of Exemplified Compound 14)
It was synthesized according to the following scheme.

  Under nitrogen atmosphere, 3- [1- (2,4,6-trimethylphenyl) -1H-imidazol-2-yl] -9-ethyl-9H-carbazole, 3.4 g (9.0 mmol) of 2-ethoxy To a solution dissolved in 30 ml of ethanol, 1.06 g (3.0 mmol) of iridium chloride trihydrate 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 2.54 g (yield 86%) of Complex C.

  Under a nitrogen atmosphere, Complex C (1.97 g, 1.0 mmol) and sodium carbonate (2.0 g) were suspended in 2-ethoxyethanol (35 ml). To this suspension, 0.4 g (4.0 mmol) of acetylacetone was added and refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by filtration under reduced pressure. 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 crystal was further washed with a methanol / water = 1/1 mixed solution, and after drying, 1.91 g (yield 91%) of Complex D was obtained.

Complex D, 0.94 g (0.9 mmol) and 3- [1- (2,4,6-trimethylphenyl) -1H-imidazol-2-yl] -9-ethyl-9H-carbazole 1 under nitrogen atmosphere .14 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 the 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 obtain 0.81 g (yield 67.8%) of Exemplified Compound 14.
It was confirmed by MASS and 1H-NMR that the purified compound 14 was the target product.

1H-NMR (400 MHz, THF-d8)
Spectral attribution (chemical shift δ, peak shape, [coupling constant] proton number, attribution to structure)
: Δ = 0.91 (t, J = 6.8 Hz, 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 = 1.5 Hz, 3H, CH, imidazole ring), 6.84 ( d, J = 7.6 Hz, 3H, CH, carbazole ring), 6.92 (s, 6H, CH, mesityl group), 7.06 (t, J = 7.6 Hz, 3H, CH, carbazole ring), 7.09 (d, J = 7.6 Hz, 3H, CH, carbazole ring), 7.13 (s, 3H, CH, carbazole ring), 7.20 (s, 3H, CH, mesityl group), 7. 27 (d, J = 7.6 Hz, 3H, CH, carbazole ring)
The PL emission maximum wavelength in the solution of Exemplified Compound 14 measured using Hitachi F-4500 was 461 nm (T = 77K in 2-methyltetrahydrofuran) and 465 nm (room temperature in methylene chloride).

  3 and 4 show emission spectra.

(Synthesis of Exemplified Compound 27)
It was synthesized according to the following scheme.

  To a solution of 2.2 g (8.8 mmol) of 1-methyl-2-dibenzo [b, d] furan-2-yl-1H-imidazole in 30 ml of 2-ethoxyethanol under a nitrogen atmosphere was added iridium chloride 3 water. The Japanese product, 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.

  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. To this suspension, 0.4 g (4.0 mmol) of acetylacetone was added and refluxed for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, sodium carbonate and inorganic salts were removed by filtration under reduced pressure. 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, 1.40 g (yield 89%) of Complex F was obtained.

Complex F, 0.63 g (0.8 mmol) and 1-methyl-2-dibenzo [b, d] furan-2-yl-1H-imidazole 0.74 g (3.0 mmol) in glycerol 40 ml under nitrogen atmosphere Suspended in The reaction was performed at a reaction temperature of 150 to 160 ° C. for 2 hours under a nitrogen atmosphere, and when the disappearance of the 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 (methylene chloride) to obtain 0.48 g (yield 64.2%) of Exemplified Compound 27.
It was confirmed by MASS and 1H-NMR that the purified compound 27 was the target product.

1H-NMR (400 MHz, THF-d8)
Spectral attribution (chemical shift δ, peak shape, [coupling constant] proton number, attribution to structure)
: Δ = 3.80 (s, 9H, CH3-, methyl group), 6.37 (d, J = 1.5 Hz, 3H, CH, imidazole ring), 6.91 (s, 3H, CH, dibenzofuran 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 = 1.5 Hz, 3H, CH, imidazole ring), 7.27 (d, J = 7.6 Hz, 3H, CH, dibenzofuran ring), 7.84 (d, J = 7.6 Hz, 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) and 459 nm (room temperature in methylene chloride).

  5 and 6 show emission spectra.

<< Application of organic EL element materials to organic EL elements >>
When fabricating the organic EL device using an organic EL device material of the present invention, among the constituent layers of the organic EL element (the details will be described later), an organic EL device material of the present invention to a light-emitting layer or an electron blocking layer It is preferable to use it. In the light emitting layer, it is preferably used as a light emitting dopant as described above.

(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 less than 0.1 to 30% by mass.

  However, the light emitting dopant may be used by mixing a plurality of types of compounds, and the mixing partner may be a phosphorescent dopant or a fluorescent dopant having other structures having different structures and other structures.

  Here, the dopant (phosphorescent dopant, fluorescent dopant, etc.) that may be used in combination with the metal complex used as the light emitting dopant will be described. Luminescent dopants are roughly classified into two types: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescence.

  Typical 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, Examples include perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Typical examples of the latter (phosphorescent dopant) are preferably complex compounds containing transition metal elements of Groups 8, 9, and 10 in the periodic table, and more preferably iridium compounds and osmium compounds. Of these, iridium compounds are most preferred.

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

  WO 00/70655 pamphlet, JP 2002-280178, JP 2001-181616, JP 2002-280179, JP 2001-181617, JP 2002-280180, JP 2001-247859, JP 2002-299060, JP 2001-313178, JP 2002-302671, JP 2001-345183, JP 2002-324679, International Publication No. 02/15645 pamphlet, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-2002 A. No. 117978, JP 20 JP-A-2-338588, JP-A-2002-170684, JP-A-2002-352960, WO01 / 93642, JP-A-2002-50483, JP-A-2002-1000047, JP-A-2002. No. -173744, JP-A No. 2002-359082, JP-A No. 2002-17584, JP-A No. 2002-363552, JP-A No. 2002-184582, JP-A No. 2003-7469, JP-T-2002-525808. Gazette, JP2003-7471, JP2002-525833, JP2003-31366, JP2002-226495, JP2002-234894, JP2002-2335076 JP 2002-241751 A JP 2001-319779, JP 2001-319780, JP 2002-62824, JP 2002-1000047, JP 2002-203679, JP 2002-343572, JP 2002-203678 gazette etc.

  Some specific examples are shown below.

(Light emitting host)
The host compound, phosphorescence quantum yield of the phosphorescence emission at room temperature (25 ° C.) among the compounds contained in the light-emitting layer represents less than 0.01 compound.

There is no particular limitation on the structural as emitting light host, typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, basic, such oligoarylene compound Examples thereof include those having a skeleton or derivatives 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. Among them, a carbazole derivative or a derivative having a ring structure in which at least one carbon atom of a hydrocarbon ring constituting the carbazole ring of the carbazole derivative is substituted with a nitrogen atom is preferably used.

The following specific examples, but is not limited to these. These compounds are also preferably used as hole blocking materials.

In light emission layer, it may be used in plural kinds in combination known host compound as a host compound. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element 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 (glass transition temperature) of 90 ° C. or higher, more preferably 100 ° C. or higher. Compounds are preferred. Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

Further, the light emission host even in a low molecular weight compound may be a polymer compound having a repeating unit, it says even low molecular compound (an evaporation polymerizing emission host) having a polymerizable group such as a vinyl group and an epoxy group.

  As specific examples of the light-emitting host, compounds described in the following documents are suitable. For example, Japanese Patent Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, JP2002-8860, JP2002-334787, JP2002-15871, JP2002-334788, JP2002-43056, JP2002-334789, JP JP 2002-75645 A, JP 2002-338579 A, JP 2002-105445 A, JP 2002-343568 A, JP 2002-141173 A, JP 2002-352957 A, JP 2002-2002 A. No. 203683, JP-A-2002-3632 7, JP 2002-231453, JP 2003-3165, JP 2002-234888, JP 2003-27048, JP 2002-255934, JP 2002-286061. JP, JP-A-2002-280183, JP-A-2002-299060, JP-A-2002-302516, JP-A-2002-305083, JP-A-2002-305084, JP-A-2002-308837, etc. .

  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 element to be emitted from the other host compound having a fluorescence maximum wavelength. A host compound having a fluorescence maximum wavelength is preferably 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 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 362 (1992, Maruzen) of Spectroscopic II of the Fourth Edition Experimental Chemistry Course 7.

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

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element will be described.

Preferred examples of the layer structure of organic EL device are shown below, but are not limited to these.

(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)》
Deter layer (e.g., electron blocking layer, hole blocking layer) will be described.

Hole blocking layer, it is preferable to use an organic EL device material of the present invention to electron blocking layer or the like, particularly preferably be used for the hole blocking layer.

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

The thickness of the deter layer is preferably 3 to 100 nm, more preferably from 5 to 30 nm.

《Hole blocking layer》
The hole blocking layer has the function of an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons but has a very small ability to transport holes, and blocks holes while transporting electrons. Thus, the probability of recombination of electrons and holes can be improved.

Examples of the hole blocking layer include, for example, JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization thereof (issued by NTT Corporation on November 30, 1998)” the hole blocking (hole blocking) layer according to page 237 such as can be applied as a hole blocking layer. If necessary the structure of an electron transport layer described later can be used as a hole blocking layer.

Organic EL element has a hole blocking layer as a constituent layer, positive as hole blocking layer is a hole blocking material, at least one carbon atom of a hydrocarbon ring constituting a carbazole ring of the carbazole derivative or the carbazole derivative It is preferred to contain a derivative having a ring structure in which one is substituted with a nitrogen atom.

《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 that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.

Adjacent layer adjacent to the light emission layer, i.e. a hole blocking layer, it is preferable to use an organic EL device material of the present invention described above to the electron blocking layer, it is particularly preferable to use the electron blocking layer.

《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. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material is not particularly limited, and is conventionally used as a hole charge injection / transport material in a photoconductive material, or used for a hole injection layer or a hole transport layer of an organic EL device. Any one of known ones can be selected and used.

  The hole transport material has one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole 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, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, 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.

  This hole transport layer can be 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. 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.

《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. The electron transport layer can be provided with a single layer or a plurality of layers.

  Conventionally, in the case of a single-layer electron transport layer and a plurality of layers, the following materials are used as the electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the cathode side with respect to the light emitting layer. Are known.

  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 can be selected and used from conventionally known compounds.

  Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, Fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxadiazole derivative, carboline derivative, or a ring in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom Examples thereof include derivatives having a 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.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-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 , Ca, Sn, Ga, or Pb can also be used as an electron transport material. 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 distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  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. 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 is described to be used as a constituent layer of the organic EL element.

<< Injection Layer >>: Electron Injection Layer, Hole Injection Layer An injection layer is provided as necessary, and includes an electron injection layer and a hole injection layer, and as described above, between the anode and the light emitting layer or the hole transport layer, and the cathode. Between the light emitting layer and the electron transport layer.

  An injection layer is a layer that is provided between an electrode and an organic layer in order to lower drive voltage and improve light emission brightness. “Organic EL elements and the forefront of their industrialization (issued by NTT Corporation on November 30, 1998) 2 of Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  Details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like, and a specific example is represented by copper phthalocyanine. Phthalocyanine buffer layers, oxide buffer layers typified by vanadium oxide, amorphous carbon buffer layers, polymer buffer layers using conductive polymers such as polyaniline (emeraldine) and polythiophene, and the like.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Examples include a metal buffer layer represented by an alkali metal compound buffer layer represented by lithium fluoride, an alkaline earth metal compound buffer layer represented by magnesium fluoride, and an oxide buffer layer represented by aluminum oxide.

  The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 to 100 nm although it depends on the material.

  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. Although there is no restriction | limiting in particular about the film thickness of an injection | pouring layer, Usually, it is about 5-5000 nm. The injection layer may have a single layer structure composed of one or more of the above materials.

"anode"
The anode according to the organic EL element, a large work function (4 eV or more) metals, an alloy, is preferably used a conductive compound and a mixture thereof as an electrode material. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , 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 may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

"cathode"
On the other hand, as the negative electrode, a small work function (also referred to as an electron injecting metal) (4 eV or less) metal, alloy, and an electroconductive compound, or a mixture thereof is used as the electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function 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 preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 to 1000 nm, preferably 50 to 200 nm. In order to transmit light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

<< Substrate (also referred to as substrate, substrate, support, etc.) >>
As the substrate according to the organic EL element, the glass is not particularly limited to a type of plastic, also it is not particularly limited as long as the transparent, the substrate preferably used include glass, quartz, light A permeable resin film can be mentioned. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples include films made of triacetate (TAC), cellulose acetate propionate (CAP), and the like.

An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and the film should be a high barrier film having a water vapor transmission rate of 0.01 g / m ² · day · atm or less. preferable.

Preferably extraction efficiency is not less than 1% at room temperature of emission of the organic EL element, and more preferably at least 2%. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  Further, a hue improving filter such as a color filter may be used in combination.

  When used in lighting applications, a film (such as an antiglare film) that has been roughened to reduce unevenness in light emission can be used in combination.

  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.

<< Method for producing organic EL element >>
As an example of a manufacturing method of the organic EL element, an anode / hole injection layer / hole transport layer / luminescent layer / hole blocking layer / electron transport layer / cathode buffer layer / preparation method of the organic EL element composed of a cathode for a description To do.

  First, a thin film made of a desired electrode material, for example, a material for an anode is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm to produce an anode. . 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.

As a method for 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, etc., but a uniform film is easily obtained and pinholes are not easily generated. In view of the above, the vacuum deposition method or the spin coating method is particularly preferable. Further, different film forming methods may be applied for each layer. When employing a vapor deposition method for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 It is desirable to select appropriately within a range of ˜50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 0.1 to 5 μm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL device is preferably manufactured from the hole injection layer to the cathode consistently by a single vacuum, but 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.

<Display device>
Viewing apparatus will be described. Viewing apparatus having the organic EL element.

Viewing device may be a multi-colored in a single color, but will be described here multicolor display device. 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 vapor deposition, casting, spin coating, ink jet, printing, or the like.

  When patterning is performed only on the light-emitting layer, the method is not limited, but a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.

  Moreover, it is also possible to reverse the production order to produce the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, and the anode in this order.

  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 positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, 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 alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  Light 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 sources for optical sensors, etc. For example, it is not limited to this.

《Lighting device》
The lighting device will be described. Lighting apparatus having the organic EL element.

Organic EL elements may be used as an organic EL element having a resonator structure, as the intended use of the organic EL element having such a resonator structure, the optical storage medium source, the electrophotographic copying machine Examples include, but are not limited to, a light source, a light source of an optical communication processor, and a light source of an optical sensor. Moreover, you may use for the said use by making a laser oscillation.

Further, organic EL elements may be used as a type of lamps, such as illumination lamp or a light source for exposure, the type of projection apparatus that projects an image, display apparatus of the type viewing still images and moving images directly ( It may be used as a display. The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, the organic EL element that have a different emission color by using two or more, it is possible to produce a full color display device.

It will be described below based on an example of a display device having the organic EL elements in the drawings.

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

  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.

  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, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

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

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below.

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

  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 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 are illustrated). Not)

  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 appropriately arranging pixels in the red region, the green region, and the blue region 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. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 9, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through 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 supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

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.

  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 maintains 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. Until then, the light emission of the organic EL element 10 continues. When the 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 light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out. 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, or by turning on / off a predetermined light emission amount by a binary image data signal. Good. The potential of the capacitor 13 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

Not only the active matrix scheme above mentioned, may be a light emission driving a passive matrix type light emission of organic EL element according to the data signal only when the scan signal is scanned.

  FIG. 10 is a schematic diagram of a passive matrix display device. 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.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.

  In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

  The organic EL material of the present invention can be applied as an illumination device to an organic EL element that emits substantially white light. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits 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. It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved. According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

Thus, white color light-emitting organic EL device, the display device, in addition to the display, or various light emission sources, a lighting device, home lighting, interior lighting, and as a kind of lamp, such as the exposure light source, also a liquid crystal display It is also useful for display devices such as device backlights.

  In addition, backlights such as clocks, signboard advertisements, traffic lights, light sources such as optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processing machines, light sources for optical sensors, etc. There are a wide range of uses such as household appliances.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example 1
<< Production of Organic EL Element 1-1 >>
After patterning on a substrate (made by NH Techno Glass Co., Ltd .: NA-45) having a 150 nm ITO film formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with iso-propyl 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 deposition apparatus, while α-NPD, H4, Ir-12, BCP, and Alq ₃ are placed in five tantalum resistance heating boats, respectively. (Vacuum chamber).

  Further, lithium fluoride was placed in a resistance heating boat made of tantalum, and aluminum was placed in a resistance heating boat made of tungsten, and attached to the second vacuum tank of the vacuum evaporation apparatus.

First, after reducing the pressure of the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and the transparent support substrate was deposited at a deposition rate of 0.1 to 0.2 nm / sec. The film was deposited to a thickness of 20 nm, and a hole injection / transport layer was provided.

  Further, the heating boat containing H4 and the boat containing Ir-12 are energized independently to adjust the deposition rate of H4 as a light emitting host and Ir-12 as a light emitting dopant to 100: 6. And it vapor-deposited so that it might become a film thickness of 30 nm, and provided the light emitting layer.

Subsequently, the said heating boat containing BCP was heated by supplying electricity, and a 10-nm-thick hole blocking layer was provided at a deposition rate of 0.1-0.2 nm / second. Further, the heating boat containing Alq ₃ was heated by energization to provide an electron transport layer having a film thickness of 20 nm at a deposition rate of 0.1 to 0.2 nm / second.

  Next, after the element deposited up to the electron transport layer was transferred to the second vacuum chamber while being vacuumed, it was remotely controlled from the outside of the apparatus so that a stainless steel rectangular perforated mask was placed on the electron transport layer. Installed.

After depressurizing the second vacuum tank to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was provided at a deposition rate of 0.01 to 0.02 nm / second by energizing a boat containing lithium fluoride. Next, a boat containing aluminum was energized, a cathode having a film thickness of 150 nm was attached at a deposition rate of 1 to 2 nm / second, and an organic EL device 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-26 >>
In the production of the organic EL element 1-1, organic EL elements 1-2 to 1-26 were produced 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.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 1-1 to 1-26, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material in the periphery, and this is placed on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 11 and 12 was formed and evaluated.

  FIG. 11 is a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (note that the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more). 12 shows a cross-sectional view of the lighting device. In FIG. 12, reference numeral 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.

(External quantum efficiency)
By lighting the organic EL element under a constant current condition of room temperature (about 23 to 25 ° C.) and ^2.5 mA / cm ² , and measuring the emission luminance (L) [cd / m ² ] immediately after the start of lighting, The external extraction quantum efficiency (η) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance. The external extraction quantum efficiency was expressed as a relative value with the organic EL element 1-1 as 100.

(Luminescent life)
The organic EL element was continuously lit at a constant current of ^2.5 mA / cm ² at room temperature, and the time (τ _1/2 ) required to achieve half the initial luminance was measured. The light emission lifetime was expressed as a relative value at which the organic EL element 1-1 was set to 100.

(Luminescent color)
The organic EL element was visually evaluated for the color of light emitted when the organic EL element was continuously lit at a constant current of ^2.5 mA / cm ² at room temperature.

  The obtained results are shown in Table 1.

From Table 1, the organic EL device produced using the metal complex according to the present invention has high emission while having a short-wave emission of pure blue to blue green compared to the organic EL device produced using the metal complex of the comparative example. It is clear that an increase in efficiency and lifetime can be achieved.

Example 2
<< Preparation of Organic EL Element 2-1 >>
An anode of indium tin oxide (ITO, indium / tin = 95/5 molar ratio) was formed on a glass support substrate of 25 mm × 25 mm × 0.5 mm by a sputtering method using a direct current power (thickness: 200 nm). The surface resistance of this anode was 10Ω / □. Polyvinylcarbazole (hole transporting binder polymer) / Ir-13 (blue light-emitting orthometalated complex) / 2- (4-biphenylyl) -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 by a spin coater to obtain a light emitting layer having a thickness of 100 nm. A patterned mask (a mask with a light emission area of 5 mm × 5 mm) is placed on the organic compound layer, and lithium fluoride 0.5 nm is deposited as a cathode buffer layer and aluminum 150 nm is deposited as a cathode in a deposition apparatus to form a cathode. A blue light-emitting organic EL device 2-1 was prepared.

<< Production of Organic EL Elements 2-2 to 2-11 >>
In the production of the organic EL element 2-1, organic EL elements 2-2 to 2-11 were produced in the same manner except that the luminescent dopant was changed as shown in Table 2.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 2-1 to 2-11, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material in the periphery, and this is placed on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 11 and 12 was formed and evaluated.

  Subsequently, the luminance and luminous efficiency were measured as follows.

(Luminance, luminous efficiency)
Using Toyo Technica source measure unit type 2400, a direct current voltage is applied to the organic EL element to emit light, and a light emission luminance (cd / m ² ) and ^2.5 mA / cm ² when a direct current voltage of 10 V is applied. Luminous efficiency (lm / W) when passing current was measured. The obtained results are shown in Table 2. It represents with the relative value which sets the organic EL element 2-1 to 100.

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

Example 3
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL element 1-18 of Example 1 was used as a blue light emitting element.

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

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

  The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full-color display device having a configuration as shown in FIG. FIG. 8 shows only a schematic diagram of the display portion A of the manufactured display device. 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. 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 lattice shape and are connected to the pixels 3 at the orthogonal positions (for details, see FIG. Not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. The image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was manufactured by appropriately juxtaposing red, green, and blue pixels.

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

Example 4
<< Preparation of White Light Emitting Element and White Lighting Device-1 >>
The electrode of the transparent electrode substrate of Example 1 is patterned to 20 mm × 20 mm, and α-NPD is formed as a hole injection / transport layer with a thickness of 25 nm thereon as in Example 1, and further contains H4. The heated boat, the boat containing Exemplified Compound (4) and the boat containing Ir-9 were energized independently, and CBP as a luminescent host and Illustrative Compound (4) and Ir-9 as luminescent dopants The vapor deposition rate was adjusted to 100: 5: 0.6, vapor deposition was performed to a thickness of 30 nm, and a light emitting layer was provided.

Next, BCP was deposited to a thickness of 10 nm to provide a hole blocking layer. Further, Alq ₃ was formed at 40 nm to provide an electron transport layer.

  Next, as in Example 1, a square perforated mask having 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 the cathode buffer layer and aluminum 150 nm was used as the cathode. Evaporated film was formed.

  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. 11 and 12 was produced. When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device. It turned out that white light emission is obtained similarly even if it replaces with the other compound of illustration.

Example 5
<< Production of White Light Emitting Element and White Lighting Device-2 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. After the film formation by spin coating, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  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 carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.

  Next, a solution obtained by dissolving Compound B (60 mg), Compound Ir-14 (3.0 mg), and Compound Ir-15 (3.0 mg) in 6 ml of toluene was spin-coated under a condition of 1000 rpm and 30 seconds. A film was formed. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization / crosslinking, and further heated in vacuum at 150 ° C. for 1 hour to obtain a light emitting layer.

  Furthermore, 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. Ultraviolet light was irradiated for 15 seconds, photopolymerization / crosslinking was performed, and further heating was performed in vacuum at 80 ° C. for 1 hour to form a hole blocking layer.

Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of Alq ₃ was placed in a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus. After reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing Alq ₃ is heated by heating, evaporated onto the electron transport layer at a deposition rate of 0.1 nm / second, and further coated with a film. An electron transport layer having a thickness of 40 nm was provided.

  In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the white light emitting organic EL element was produced.

  When this element was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Claims (7)

The organic electroluminescence element material which is a metal complex body represented by the following following general formula (2).
(Wherein, X is _R 1 -N, the .R ₁ is a substituted or unsubstituted representing O or S, the .Y ₁ and _{Y 2} represents an alkyl group or the aryl group _R 2 -N, N or _{R 3} represents -C, .R ₃ .R ₂ represent the atoms necessary to form an imidazole ring or preparative Riazor ring with N-C = N is to represent a substituted or unsubstituted, alkyl group or the aryl group is hydrogen .G representing an original child an aryl group or an alkylsulfonyl group substitution table to. n is _.X 1 _-L 1 -X ₂ 0 or is representing one represents a bidentate ligand, X ₁ and X ₂ are each independently a carbon atom, _{M 1} .L ₁ which represents a nitrogen atom or oxygen atom is. central metal represents an atomic group forming a ligand bidentate with _{X 1} and X _2, iridium, platinum, .M1 representing rhodium or palladium 1, 2 or 3 If represents the number, although m2 represents 0 or 1, m1 + m2 is 2 or 3, which is the same number as the central metal of the positive charge. However, _{the Y 1} and _{Y 2} both represent _R 3 -C And R ₃ are not bonded to each other to form a ring.) The organic electroluminescent element material according to claim 1 , wherein the metal complex represented by the general formula (2) is represented by the following general formula (3).
(Wherein, X is _R 1 -N, .R ₁ representing O or S is substituted or unsubstituted, .R ₂ represents an alkyl group or the aryl group is substituted or unsubstituted, alkyl group or the aryl group the representative .G is an aryl group or an alkylsulfonyl group substitution table to. n is _.X 1 _-L 1 -X ₂ 0 or is representing one represents a bidentate ligand, _{X 1} and X ₂ each independently represents a carbon atom, a nitrogen atom or an oxygen atom, L ₁ represents an atomic group forming a bidentate ligand together with X ₁ and X _2. M _{1 as a} central metal is iridium, platinum , .M1 representing rhodium or palladium is an integer of 1, 2 or 3, m2 represents 0 or 1, m1 + m2 is 2 or 3, which is the same number as the positive charge on the central metal.) In the metal complex represented by the general formula (3), R ₂ is a methyl group , a 2,6-dimethylphenyl group, a mesityl group (2,4,6-trimethylphenyl group) or a tetramethylphenyl group. The organic electroluminescent element material according to claim 2 , wherein The organic electroluminescence device material according to any one of claims 1 to 3, wherein the central metal M ₁ is iridium. The organic electroluminescence device material according to any one of claims 1 to 3, wherein the central metal M ₁ is platinum. The organic electroluminescence device material according to any one of claims 1 to 5, wherein m2 is 0. The organic electroluminescence element material according to any one of claims 1 to 6 , wherein the first emission wavelength is in a range of 400 to 500 nm.