CN100366703C

CN100366703C - Material for organic electroluminescent device and organic electroluminescent device using the same

Info

Publication number: CN100366703C
Application number: CNB038066890A
Authority: CN
Inventors: 岩隈俊裕; 山本弘志; 弘中义雄; 池田秀嗣; 细川地潮; 富田诚司; 荒金崇士
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2002-03-22
Filing date: 2003-03-19
Publication date: 2008-02-06
Anticipated expiration: 2023-03-19
Also published as: CN1701111A

Abstract

The present invention provides a material for an organic electroluminescent device comprising a compound in which a nitrogen-containing heterocyclic group is linked to an aryl carbazolyl group or a carbazolylalkylene group, and an organic electroluminescent device comprising a cathode, an anode and an organic thin film layer comprising at least one layer and located between the cathode and the anode, wherein at least one of the organic thin film layers comprises the above-described material for an organic electroluminescent device. The material can provide an organic electroluminescent device emitting blue light of high color purity. The organic electroluminescent device utilizes the material.

Description

The organic electroluminescence device that is used for the material of organic electroluminescence device and uses this material

Technical field

The organic EL device that the present invention relates to be used for the material of organic electroluminescence device (organic EL device) and use this material more particularly, the present invention relates to launch the organic EL device of the blue light with high colour purity.

Background technology

Utilize the organic EL device of organic substance to be supposed to, and people are carrying out the various exploitations of organic EL device as the cheap full-color display of solid luminescence type with large-size.Organic EL device has the structure that comprises luminescent layer and be positioned at the pair of electrodes of described luminescent layer both sides usually.

The luminous of organic EL device is a kind of like this phenomenon, wherein, when between two electrodes, applying electric field, electronics injects from negative side, the hole is injected from side of the positive electrode, electronics combines in luminescent layer to form excited state with the hole again, and the energy that produces when excited state turns back to ground state then is with the form emission of light.

As luminescent material, it is known that inner complex closes aluminium, coumarin derivatives, tetraphenylbutadiene derivative, diphenylethyllene arylene derivatives and  oxadiazole derivative as three (oxine roots).It is reported, these luminescent materials are luminous to the visible region of ruddiness at blue light, and expection can obtain color monitor (for example, Japanese patent application is not examined publication number Heisei 8 (1996)-239655, Heisei 7 (1995)-138561 and Heisei3 (1991)-200289) by using these luminescent materials.

Although begun to utilize the practical application of the indicating meter of organic EL device recently, full-color display is still among exploitation.Especially always need to send the organic EL device of blue light with excellent colour purity and luminous efficiency.

As the device of attempting to satisfy above needs, for example, use the phenylanthracene derivative to be disclosed in the careful publication number Heisei8 (1996)-12600 of Japanese patent application as the device of the material of emission blue light.The phenylanthracene derivative is as sending the luminescent material of blue light, and closes the form use of the laminate structure that aluminium (Alq) complex layer forms usually with the material layer and three (oxine root) by the emission blue light.Yet luminous efficiency, life-span and blue light purity all are not enough to be used for practical application.Examine among the publication number 2001-288462 at Japanese patent application, disclose wherein and will be used for the device of the emission blue light of luminescent layer based on the aromatics of amine.Yet the luminous efficiency of this device is low to moderate 2 to 4cd/A.Do not examine among the publication number 2001-160489 at Japanese patent application, disclose a kind of device, wherein the azepine fluoranthene compound is joined in the luminescent layer.Yet this device sends yellow to green light, and can not send and have enough blue lights of high colour purity.

Summary of the invention

Made the present invention in order to overcome the problems referred to above, and an object of the present invention is to provide material that is used for organic EL device that can send blue light and the organic EL device that utilizes this material with excellent colour purity.

Result as inventor's further investigation has now found that, is used as material of main part by having the compound that is connected to the nitrogen heterocyclic ring group on aryl carbazyl or the carbazyl alkylidene group, can obtain having the organic EL device of excellent blue purity.The present invention is based on this knowledge just is accomplished.

The invention provides the material that is used for organic electroluminescence device, this material comprises the compound shown in following general formula (1) or (2):

(Cz-) _nA (1)

Cz(-A) _m (2)

Wherein Cz represents to replace or unsubstituted aryl carbazyl or carbazyl alkylidene group, and A represents the group shown in the following general formula (A):

(M) _p-(L) _q-(M’) _r (A)

Wherein M and M ' represent to contain the hetero-aromatic ring of 2 to 40 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring independently of one another, M can represent identical ring or different rings with M ', L represents singly-bound, contains replacement or the unsubstituted aryl or the arylidene of 6 to 30 carbon atoms, the replacement or the unsubstituted cycloalkylidene that contain 5 to 30 carbon atoms, or contain the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms, p represents 0 to 2 integer, q represents 1 or 2 integer, r represents 0 to 2 integer, and p+r represents 1 or bigger integer; And

N and m represent 1 to 3 integer separately.

The present invention also provides a kind of organic electroluminescence device, it comprises positive pole, negative pole and comprises one deck and the organic thin film layer between positive pole and negative pole at least that wherein the one deck at least in the organic thin film layer comprises the above-described material that is used for organic electroluminescence device.In above organic thin film layer, luminescent layer, electron transfer layer or hole transmission layer can comprise the top material that is used for organic EL device.

Implement most preferred scheme of the present invention

The material that is used for organic electroluminescence device of the present invention comprises the compound shown in following general formula (1) or (2):

(Cz-) _nA (1)

Cz(-A) _m (2)

In above formula, Cz represents to replace or unsubstituted aryl carbazyl or carbazyl alkylidene group, and n and m represent 1 to 3 integer separately.

Aryl in the preferred aryl groups carbazyl contains 6 to 30 carbon atoms.The example of aryl comprises phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pyrenyl, fluorenyl, xenyl and terphenyl.In the middle of these groups, phenyl, naphthyl, xenyl and terphenyl are preferred.

Alkylidene group in the preferred carbazyl alkylidene group contains 1 to 10 carbon atom.The example of alkylidene group comprises methylene radical, ethylidene, propylidene, isopropylidene, inferior normal-butyl, inferior sec-butyl, isobutylidene, the inferior tertiary butyl, inferior n-pentyl, inferior n-hexyl, inferior n-heptyl, inferior n-octyl, inferior hydroxymethyl, inferior chloromethyl and iminomethyl.In the middle of these groups, methylene radical, ethylidene, propylidene, isopropylidene, inferior normal-butyl, the inferior tertiary butyl and inferior n-pentyl are preferred.

In general formula (1) and (2), A represents the group shown in the following general formula (A):

(M) _p-(L) _q-(M’) _r (A)

M and M ' represent to contain the hetero-aromatic ring of 2 to 40 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring independently of one another, and M can represent identical ring or different rings with M '.

The example that contains the hetero-aromatic ring of nitrogen-atoms comprises the ring of pyridine, pyrimidine, pyrazine, triazine, aziridine, azaindole alkane (azaindolidine), indoles alkane (indolidine), imidazoles, indoles, isoindole, indazole, purine, puteridine, β-Ka Lin, naphthyridines, quinoxaline, terpyridyl, dipyridyl, acridine, phenanthroline, azophenlyene and imidazopyridine.In the middle of these rings, the ring of pyridine, terpyridyl, pyrimidine, imidazopyridine and triazine is preferred.

L represents singly-bound, contains replacement or unsubstituted aryl or arylidene, the replacement that contains 5 to 30 carbon atoms or the unsubstituted cycloalkylidene of 6 to 30 carbon atoms, or contains the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms.

P represents 0 to 2 integer, and q represents 1 or 2 integer, and r represents 0 to 2 integer, and p+r represents 1 or bigger integer.

The example that contains the aryl of 6 to 30 carbon atoms comprises phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, sugarcane base, fluoranthene base and perfluor aryl.In these groups, phenyl, xenyl, terphenyl and perfluor aryl are preferred.

The example that contains the arylidene of 6 to 30 carbon atoms comprises phenylene, biphenylene, inferior terphenyl, naphthylidene, anthrylene, phenanthrylene, inferior pyrenyl, inferior sugarcane base, inferior fluoranthene base and inferior perfluor aryl.In these groups, phenylene, biphenylene, inferior terphenyl and inferior perfluor aryl are preferred.

The example that contains the cycloalkylidene of 5 to 30 carbon atoms comprises cyclopentylidene, cyclohexylidene and inferior suberyl.In these groups, cyclohexylidene is preferred.

The example that contains the heteroaryl of 2 to 30 carbon atoms comprises the 1-pyrryl, the 2-pyrryl, the 3-pyrryl, pyridyl, the 2-pyridyl, the 3-pyridyl, the 4-pyridyl, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-pseudoindoyl, the 2-pseudoindoyl, the 3-pseudoindoyl, the 4-pseudoindoyl, the 5-pseudoindoyl, the 6-pseudoindoyl, the 7-pseudoindoyl, the 2-furyl, the 3-furyl, the 2-benzofuryl, the 3-benzofuryl, the 4-benzofuryl, the 5-benzofuryl, the 6-benzofuryl, the 7-benzofuryl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridyl, the 2-acridyl, the 3-acridyl, the 4-acridyl, the 9-acridyl, 1,7-phenanthroline-2-base, 1,7-phenanthroline-3-base, 1,7-phenanthroline-4-base, 1,7-phenanthroline-5-base, 1,7-phenanthroline-6-base, 1,7-phenanthroline-8-base, 1,7-phenanthroline-9-base, 1,7-phenanthroline-10-base, 1,8-phenanthroline-2-base, 1,8-phenanthroline-3-base, 1,8-phenanthroline-4-base, 1,8-phenanthroline-5-base, 1,8-phenanthroline-6-base, 1,8-phenanthroline-7-base, 1,8-phenanthroline-9-base, 1,8-phenanthroline-10-base, 1,9-phenanthroline-2-base, 1,9-phenanthroline-3-base, 1,9-phenanthroline-4-base, 1,9-phenanthroline-5-base, 1,9-phenanthroline-6-base, 1,9-phenanthroline-7-base, 1,9-phenanthroline-8-base, 1,9-phenanthroline-10-base, 1,10-phenanthroline-2-base, 1,10-phenanthroline-3-base, 1,10-phenanthroline-4-base, 1,10-phenanthroline-5-base, 2,9-phenanthroline-1-base, 2,9-phenanthroline-3-base, 2,9-phenanthroline-4-base, 2,9-phenanthroline-5-base, 2,9-phenanthroline-6-base, 2,9-phenanthroline-7-base, 2,9-phenanthroline-8-base, 2,9-phenanthroline-1 0-base, 2,8-phenanthroline-1-base, 2,8-phenanthroline-3-base, 2,8-phenanthroline-4-base, 2,8-phenanthroline-5-base, 2,8-phenanthroline-6-base, 2,8-phenanthroline-7-base, 2,8-phenanthroline-9-base, 2,8-phenanthroline-10-base, 2,7-phenanthroline-1-base, 2,7-phenanthroline-3-base, 2,7-phenanthroline-4-base, 2,7-phenanthroline-5-base, 2,7-phenanthroline-6-base, 2,7-phenanthroline 8-base, 2,7-phenanthroline-9-base, 2,7-phenanthroline-10-base, 1-fen  piperazine base, 2-fen  piperazine base, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, 1-fen  piperazine base, 2-fen  piperazine base, 3-fen  piperazine base, 4-fen  piperazine base, 1 0-fen  piperazine base, 2- azoles base, 4- azoles base, 5- azoles base, 2- di azoly, 5- di azoly, 3-furazan base (3-furazanyl), the 2-thienyl, the 3-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tertiary butyl-1-indyl, the 4-tertiary butyl-1-indyl, the 2-tertiary butyl-3-indyl and the 4-tertiary butyl-3-indyl.In these groups, pyridyl and quinolyl are preferred.

In general formula (1), (2) and (A) use Cz in, substituent example in the group of M or M ' expression comprises halogen atom such as chlorine atom, bromine atoms and fluorine atom, carbazyl, hydroxyl, replace or unsubstituted amino, nitro, cyano group, silyl, trifluoromethyl, carbonyl, carboxyl, replace or unsubstituted alkyl, replace or unsubstituted alkenyl, replace or unsubstituted arylalkyl, replace or unsubstituted aryl, replace or unsubstituted heteroaromatic heterocyclic group, replace or unsubstituted aralkyl, replace or unsubstituted aryloxy and replacement or unsubstituted alkoxyl group.In these groups, fluorine atom, methyl, perfluorophenyl, phenyl, naphthyl, pyridyl, pyrazolyl, pyrimidyl, adamantyl, benzyl, cyano group and silyl are preferred.

According to the numerical value that n and m represent, the one-tenth key mode of the compound shown in above-mentioned general formula (1) or (2) is illustrated in the following table 1.

Table 1

According to the numerical value that p, q and r represent, the one-tenth key mode of the group shown in the above-mentioned general formula (A) is illustrated in the following table 2.

Table 2

The represented group of the Cz that is connected with the group shown in the A can with M, L in the general formula of representing group shown in the A (A) or any one Cheng Jian in the group shown in the M '.

For example, when the group shown in the A has one-tenth key mode [6] in the table 2 (p=q=r=1) time in the compound shown in the Cz-A (wherein m=n=1 in general formula (1) or (2)), become the key mode to comprise that three kinds become the key modes: Cz-M-L-M ', M-L (Cz)-M ' and M-L-M ' Cz.

When the group shown in the A has one-tenth key mode [7] (p=q=1 and r=2) in the table 2 in the compound shown in the Cz-A-Cz (wherein n=2 in general formula (1)), become the key mode to comprise one-tenth key mode shown below:

Cz-M-L-M′-M′-Cz，

About general formula (1), (2) or the one-tenth key mode of the group (A) and above shown in the combination of group as an example, the material that is used for organic EL device that comprises following (i) compound shown in (iv) is preferred.

(i) be used for the material of organic EL device, wherein

N=1 in the general formula (1), and middle p=1 of general formula (A) and r=0;

In general formula (1), Cz represents to replace or unsubstituted aryl carbazyl or carbazyl alkylidene group; And

In general formula (A), M represents to contain the hexa-atomic or seven-membered ring of heterocycle of 4 or 5 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, the heterocycle five-ring that contains 2 to 4 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, the heterocycle that contains 8 to 11 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, or replacement or unsubstituted imidazopyridine ring, L represents to contain replacement or the unsubstituted aryl or the arylidene of 6 to 30 carbon atoms, or contains the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms.

The material that (ii) is used for organic EL device, wherein

N=2 in the general formula (1), and middle p=1 of general formula (A) and r=0;

The material that (iii) is used for organic EL device, wherein

N=1 in the general formula (1), and middle p=2 of general formula (A) and r=0;

In general formula (A), M represents to contain the hetero-aromatic ring of 2 to 40 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, L represents to contain replacement or the unsubstituted aryl or the arylidene of 6 to 30 carbon atoms, or contains the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms.

The material that (iv) is used for organic EL device, wherein

M=2 in the general formula (2), and p=q=1 in the general formula (A);

In general formula (2), Cz represents to replace or unsubstituted aryl carbazyl or carbazyl alkylidene group; And

In general formula (A), M and M ' represent to contain the hetero-aromatic ring of 2 to 40 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring independently of one another, and M can represent identical ring or different rings with M ', L represents to contain replacement or the unsubstituted aryl or the arylidene of 6 to 30 carbon atoms, contain the replacement or the unsubstituted cycloalkylidene of 5 to 30 carbon atoms, or contain the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms.

In superincumbent general formula (1) and (2), preferred Cz represents to replace or unsubstituted aryl carbazyl, more preferably phenyl carbazole base.The aryl moiety of preferred aryl groups carbazyl is replaced by carbazyl.

The object lesson of the compound shown in the general formula (1) is as follows.Yet the compound shown in the general formula (1) is not limited to these compounds.

The object lesson of the compound shown in the general formula (2) is as follows.Yet the compound shown in the general formula (2) is not limited to these compounds.

The triplet state energy gap of the compound shown in preferred formula (1) or (2) is 2.5 to 3.3eV, and more preferably 2.5 to 3.2eV.

The singlet energy gap of the compound shown in preferred formula (1) or (2) is 2.8 to 3.8eV, and more preferably 2.9 to 3.7eV.

The organic thin film layer that organic EL device of the present invention comprises positive pole, negative pole and comprises the one deck at least between positive pole and negative pole, wherein the one deck at least in the organic thin film layer comprises the material that is used for organic electroluminescence device that contains compound shown in above general formula (1) or (2).

Preferred organic EL device of the present invention comprises the material that is used for organic electroluminescence device that contains compound shown in above general formula (1) or (2) in luminescent layer, electron transfer layer or hole transmission layer.

Organic EL device of the present invention sends blue light, and the colour purity of the light that sends up to (0.12,0.10) to (0.17,0.20).The reason that shows this performance is that the material that is used for organic EL device that contains compound shown in general formula of the present invention (1) or (2) has big energy gap.

Preferred organic EL device of the present invention is undertaken luminous by the multiplicity excitation, it is to be excited to triplet state or higher exciting that described multiplicity excites.

The material of main part that the preferred described material that is used for organic electroluminescence device is an organic EL device.Material of main part is can be to wherein injected hole and electronics, and have transporting holes and electronics and by hole and electronics again in conjunction with the materials with function of sending fluorescence.

In the present invention, compound also can be used as the organic main body material of phosphorescence device shown in general formula (1) and (2) because the singlet energy gap is up to 2.8 to 3.8eV, and the triplet state energy gap up to 2.5 to 3.3eV.

The phosphorescence device is a kind of organic assembly, it comprises based on the transition of the singlet energy level from the triplet energy level to ground state, with greater than the luminous material of the intensity of the light intensity of sending from other material, it is phosphor material, as comprise at least a metal that is selected from the 7th to 11 family of periodictable, and under current field condition, utilize the luminous organometallic complex of so-called phosphorescence.

In the luminescent layer of organic EL device, in the excited molecule that forms, is blended singlet exciton and triplet exciton usually, and it is said that the ratio of amount and the amount of triplet exciton of singlet exciton is 1: 3, and with bigger amount formation triplet exciton.In utilizing the conventional organic EL device of phosphorescence, be singlet exciton to the luminous exciton that contributes, and triplet exciton is not luminous.Therefore, triplet exciton consumes with form of heat at last, and the singlet exciton emission of light by forming with less amount.Therefore, in these organic EL devices, the energy that is delivered to triplet exciton in the energy that is produced of combination again by hole and electronics causes bigger loss.

On the contrary, can think that by utilizing the compound that is used for the phosphorescence device of the present invention, available luminous efficiency is to utilize three times of device of fluorescence, because triplet exciton can be used for the emission of light.Can also think, when compound of the present invention is used for the luminescent layer of phosphorescence device, form the excited triplet state that energy level is higher than the excited triplet state energy level of the phosphorescence organic complex that comprises the metal that is selected from periodictable the 7th to 11 family; Form the more film of stable form; Second-order transition temperature higher (Tg: 80 to 160 ℃); Hole and electronics are more effectively transmitted; Described compound is an electrochemistry and chemically stable; In preparation and use, the formation that can suppress to be used as trap or cause the impurity of luminous loss.

As mentioned above, organic EL device of the present invention is included in the one or more organic thin film layers that form between positive pole and the negative pole.When described device comprises individual layer, between positive pole and negative pole, form luminescent layer.Described luminescent layer comprises luminescent material and is used for and will is transferred to the hole-injecting material of luminescent material from anodal injected holes or is used for and will be transferred to the electronics injecting material of luminescent material from the negative pole injected electrons.Preferred luminescent material has very excellent phosphorescence quantum yield, has the ability of bigger transporting holes and electronics, and forms uniform thin layer.The example of the organic EL device of multilayer type comprises comprising to have multilayered structure, for example the organic EL device of the sandwich of (positive pole/hole injection layer/luminescent layer/negative pole), (positive pole/luminescent layer/electron injecting layer/negative pole) and (positive pole/hole injection layer/luminescent layer/electron injecting layer).

For luminescent layer, except the compound shown in general formula of the present invention (1) or (2), in needs, can also use the combination of conventional material of main part, luminescent material, dopant material, hole-injecting material and electronics injecting material and these materials thereof.By utilizing the multilayered structure of organic EL device, can prevent the brightness that causes because of quencher and the reduction in life-span, and utilize other dopant material can improve the brightness and the luminous efficiency of the light that sends.Help other dopant material of phosphorescing by being used in combination, compare, can improve the brightness and the luminous efficiency of the light that sends with conventional device.

In organic EL device of the present invention, hole injection layer, luminescent layer and electron injecting layer all can have multilayered structure.When hole injection layer has multilayered structure, the hole is called hole injection layer from the layer that electrode injects wherein, and will accept the hole from hole injection layer, transporting holes is called hole transmission layer to the layer of luminescent layer then.Similarly, when electron injecting layer has multilayered structure, electronics is called electron injecting layer from the layer that electrode injects wherein, and will accept electronics from electron injecting layer, transmission electronic is called electron transfer layer to the layer of luminescent layer then.Select each layer according to the energy level of material, thermotolerance and with the tackiness of organic thin film layer or metal electrode.

In organic EL device of the present invention, electron transfer layer and/or hole transmission layer can comprise the material that is used for organic EL device of the present invention, and described material comprises any in the compound shown in general formula (1) and (2).Hole injection layer, electron injecting layer and hole blocking layer can comprise the material that is used for organic EL device of the present invention.Compound that phosphoresces and the material that is used for organic EL device of the present invention can use with form of mixtures.

Can comprise with the example that compound shown in general formula (1) or (2) combination is used for the luminescent material of organic thin film layer and material of main part anthracene, naphthalene, phenanthrene, pyrene, tetracene, cool,

Fluorescein perylene, phthaloperylene, naphthaloperylene, perynone, phthaloperynone, naphthaloperynone, diphenyl diethylene, tetraphenylbutadiene, tonka bean camphor, the  diazole, aldazine, dibenzo  azoles quinoline, bisstyryl, pyrazine, cyclopentadiene, the metal complex of quinoline, the metal complex of quinolylamine, the metal complex of benzoquinoline, imines, diphenylethlene, vinyl anthracene, diaminoanthraquinone-, the diamino carbazole, pyrans, thiapyran, polymethine (polymethine), melocyanine, hydroxyquinoline compounds (oxinoidcompounds) with the imidazoles chelating, quinacridone, rubrene, derivative and phosphorescent pigment based on stilbene.Yet luminescent material and material of main part are not limited to above-described compound.

As luminescent material, the phosphorescent organometallic complex is preferred, because can improve the external quantum efficiency of device.The example of the metal in the phosphorescent organometallic complex comprises ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold.Preferably having organic metal complex is the organometallic compound shown in the following general formula (3):

In above general formula, A ¹Expression replaces or unsubstituted aromatic hydrocarbons cyclic group or aromatic heterocyclic group, preferably phenyl, xenyl, naphthyl, anthryl, thienyl, pyridyl, quinolyl or isoquinolyl.Substituent example comprises halogen atom such as fluorine atom; The alkyl such as methyl and the ethyl that contain 1 to 30 carbon atom; Alkenyl such as vinyl; The alkoxy carbonyl such as methoxycarbonyl and the ethoxy carbonyl that contain 1 to 30 carbon atom; The alkoxyl group such as methoxyl group and the oxyethyl group that contain 1 to 30 carbon atom; Aryloxy such as phenoxy group and benzyloxy; Dialkyl amido such as dimethylamino and diethylamino; Acyl group such as ethanoyl; Haloalkyl such as trifluoromethyl; And cyano group.

A ²Expression replaces or unsubstituted aromatic heterocyclic group, it contains nitrogen-atoms as forming heterocyclic atom, preferably pyridyl, pyrimidyl, pyrazinyl, triazinyl, benzothiazolyl, benzoxazol base, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl or phenanthridinyl.Substituent example comprises as A ¹Shown in described those substituting groups of substituent example of group.

Contain A ¹The ring of shown group with contain A ²The ring of shown group can form a condensed ring.The example of condensed ring comprises 7,8-benzoquinoline group.

Q represents to be selected from the metal of periodictable the 7th to 11 family's metal, preferably ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold.

L represents bitooth ligand, and it is preferably selected from beta-diketon type part such as Acetyl Acetone root and pyromellitic acid.

M and n all represent integer.When Q represents divalent metal, n=2 and m=0.When Q represents trivalent metal, n=3 and m=0 or n=2 and m=1.

The object lesson of the organometallic complex shown in the above general formula (3) is as follows.Yet organometallic complex is not limited to these compounds.

As hole-injecting material, have transporting holes ability, show reception from the excellent effect of anodal injected holes and with the hole be injected into luminescent layer or luminescent material excellent effect, prevent that the exciton transfer that forms the luminescent layer from being preferred to electron injecting layer or electronics injecting material and compound with excellent film forming ability.The example that compound is injected in the hole comprises phthalocyanine derivates, naphthalene cyanines derivative, derivatives of porphyrin,  azoles,  diazole, triazole, imidazoles, imidazolone, imidazole thione, pyrazoline, pyrazolone, imidazolidine, hydrazone, acylhydrazone, gathers derivative and macromolecular material such as Polyvinyl carbazole, polysilane and the conducting polymer of aryl paraffinic hydrocarbons, stilbene, divinyl, the triphenylamine of benzidine-type, the triphenylamine of styrylamine type, the triphenylamine of diamines type, above compound.Yet hole-injecting material is not limited to these compounds.

In these hole-injecting materials, more effective hole-injecting material is aromatic nitrile base derivative and phthalocyanine derivates.The example of aromatic nitrile base derivative comprises triphenylamine, trimethylphenyl amine, the tolyl diphenylamine, N, N '-phenylbenzene-N, N '-(3-aminomethyl phenyl)-1,1 '-symbasis-4,4 '-diamines, N, N, N ', N '-(4-aminomethyl phenyl)-1,1 '-phenyl-4,4 '-diamines, N, N, N ', N '-(4-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines, N, N '-phenylbenzene-N, N '-dinaphthyl-1,1 '-biphenyl-4,4 '-diamines, N, N '-(aminomethyl phenyl)-N, N '-(4-n-butylphenyl)-Fei-9, the 10-diamines, N, N-two (4-two-4-tolyl aminophenyl)-4-phenyl-cyclohexane-, and oligopolymer and superpolymer with skeleton structure of these aromatic nitrile bases.Yet aromatic nitrile base is not limited to these compounds.The example of phthalocyanine (Pc) derivative comprises phthalocyanine derivates and naphthalene cyanines derivative such as H ₂Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂SiPc, (HO) AlPc, (HO) GaPc, VOPc, TiOPc, MoOPc and GaPc-O-GaPc.Yet phthalocyanine derivates is not limited to these compounds.

As the electronics injecting material, have transmission electronic ability, show reception from the excellent effect of negative pole injected electrons and with electronics be injected into luminescent layer or luminescent material excellent effect, prevent that the exciton transfer that forms the luminescent layer from being preferred to hole input horizon and compound with excellent film forming ability.The example of electronics injection compound comprises the derivative of Fluorenone, anthraquinone bismethane (anthraquinodimethane), phenoquinone (diphenoquinone), thiapyran dioxide,  azoles,  diazole, triazole, imidazoles, perylene tetracarboxylic acid, quinoxaline, fluorenylidene methane, anthraquinone bismethane, anthrone and these compounds.Yet the electronics injecting material is not limited to these compounds.

In these electronics injecting materials, more effective electronics injecting material is metal complex and five yuan of derivatives that contain nitrogen-atoms.The example of metal complex comprises that the oxine root closes lithium, two (oxine roots) close zinc, two (oxine roots) close copper, two (oxine roots) close manganese, three (oxine roots) close aluminium, three (2-methyl-oxine root) close aluminium, three (oxine roots) close gallium, two (10-hydroxy benzo [h] quinoline roots) close beryllium, two (10-hydroxy benzo [h] quinoline roots) close zinc, chlorine two (2-methyl-oxine root) closes gallium, two (2-methyl-oxine root) (Ortho Cresol roots) close gallium, two (2-methyl-oxine root) (1-naphthols root) closes aluminium and two (2-methyl-oxine root) (beta naphthal root) and closes gallium.Yet the electronics injecting material is not limited to these compounds.

As five yuan of derivatives that contain nitrogen-atoms, the derivative of  azoles, thiazole,  diazole, thiadiazoles, triazole and these compounds is preferred.The example that contains five yuan of derivatives of nitrogen-atoms comprises two (1-phenyl)-1,3,4- azoles, dimethyl POPOP, 2,5-two (1-phenyl)-1,3, the 4-thiazole, 2,5-two (1-phenyl)-1,3,4- diazole, 2-(4 '-tert-butyl-phenyl)-5-(4 "-xenyl)-1; 3,5- diazole; 2,5-two (1-naphthyl)-1; 3; 4- diazole; 1,4-two [2-(5-phenyl  di azoly)] benzene, 1,4-two [2-(5-phenyl  the di azoly)-4-tertiary butyl] benzene, 2-(4 '-tert-butyl-phenyl)-5-(4 "-xenyl)-1; 3; 4-thiadiazoles; 2,5-two (1-naphthyl)-1,3; 4-thiadiazoles; 1,4-two [2-(5-phenyl thiadiazolyl group)] benzene, 2-(4 '-tert-butyl-phenyl)-5-(4 "-xenyl)-1,3,4-triazole; 2; 5-two (1-naphthyl)-1; 3,4-triazole and 1,4-two [2-(5-Phenyltriazole base)] benzene.Yet five yuan of derivatives that contain nitrogen-atoms are not limited to these compounds.

The performance that electric charge injects can join hole-injecting material and will provide electronics by the compound that will accept electronics compound joins the electronics injecting material to be improved.

As the anodal electro-conductive material that is used for organic EL device of the present invention, the material that has greater than the work content of 4eV suits, and the alloy, metal oxide that can use carbon, aluminium, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, these metals are as being used for the tin-oxide and the Indium sesquioxide of ITO matrix and NESA matrix, and organic conductive resin such as Polythiophene and polypyrrole.As the conducting material that is used for negative pole, the material that has less than the work content of 4eV suits, and can use the alloy of magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminium and these metals.Yet the conducting material that is used for negative pole is not limited to these materials.The exemplary of alloy comprises magnesium/silver, magnesium/indium and lithium/aluminium.Yet alloy is not limited to these alloys.The composition of alloy is by temperature, atmosphere and the vacuum degree control of source vaporize, and can select the composition that suits.When needed, anodal and negative pole can form and have two-layer or the multiwalled structure.

Organic EL device of the present invention can comprise inorganic compound layer between at least one electrode and above-mentioned organic thin film layer.The example that is used for the mineral compound of inorganic compound layer comprises various types of oxide compounds, nitride and oxynitride, for example alkalimetal oxide, alkaline earth metal oxide, rare earth oxide, alkali metal halide, alkaline earth metal halide, rare earth halide, SiO _x, AlO _x, SiN _x, SiON, AlON, GeO _x, LiO _x, LiON, TiO _x, TiON, TaO _x, TaON, TaN _xAnd C.Especially, as the component that contacts with positive pole, SiO _x, AlO _x, SiN _x, SiON, AlON, GeO _xWith C be preferred because form the stable interface layer of injection effect.As the component of contact negative pole, LiF, MgF ₂, CaF ₂With NaF be preferred.

In organic EL device of the present invention, preferably at least one face is enough transparent in the light wavelength scope that this device sends, so that obtain luminous effectively.Preferred substrate also is transparent.

In order to obtain transparent electrode, set the condition of vapour deposition or sputter, with the transparency of guaranteeing to utilize above-mentioned electro-conductive material to obtain being scheduled to.The transmittance of the electrode of preferred light-emitting area is 10% or bigger.Matrix is had no particular limits, as long as this matrix has machinery and hot strength and be transparent.The example of matrix comprises glass matrix and transparent resin film.The example of transparent resin film comprises the film of following material: polyethylene, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polystyrene, polymethylmethacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral acetal, nylon, polyether-ether-ketone, polysulfones, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, fluorinated ethylene propylene, tetrafluoroethylene-ethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, voltalef, polyvinylidene difluoride (PVDF), polyester, polycarbonate, urethane, polyetherimide, polyimide and polypropylene.

In organic EL device of the present invention, can on the surface of device, form protective layer, perhaps entire device scribbles silicone oil or resin, so that improve the stability to temperature, humidity and air.

In order to form each layer of organic EL device of the present invention, can use any method in dry method film such as vacuum vapor deposition, sputter, plasma body plating and ion plating and wet method film such as spin coating, dip-coating and the flow coat.The thickness of each film has no particular limits.Yet, need be with the thickness setting of film in suitable value.When thickness is excessive, need apply bigger voltage for obtaining identical light output, and luminous efficiency reduces.When thickness is too small, forms pin hole and even when applying electric field, can not obtain enough luminous.Usually, 5nm to 10 micron thickness suits, and 10nm to 0.2 micron thickness is preferred.

When using the wet method film, with form the material dissolves of each layer or be suspended in The suitable solvent such as ethanol, chloroform, tetrahydrofuran (THF) and two  alkane in, form film by solution that obtains or suspension then.Can use any in the above solvent.For any one deck in the described layer, can use suitable resin and additive to improve film forming properties and to prevent the formation of pin hole in the film.The example of spendable resin comprises the multipolymer of insulating resin such as polystyrene, polycarbonate, polyacrylic ester, polyester, polymeric amide, urethane, polysulfones, polymethylmethacrylate, polymethyl acrylate, Mierocrystalline cellulose and these resins; Optical resin such as poly-N-vinyl carbazole and polysilane; With electroconductive resin such as Polythiophene and polypyrrole.The example of additive comprises antioxidant, UV light absorber and softening agent.

As mentioned above, by the compound shown in general formula (1) or (2) being used for the organic thin film layer of organic EL device of the present invention, can obtain sending the organic EL device of blue light with high color purity.This organic EL device can be advantageously used for the photosensor of electrofax, the flat-panel monitor of planar light-emitting element such as wall type TV, the back side light of duplicating machine, printer and liquid-crystal display, the light source of instrument, display panel, mark light and annex.

Below with reference to embodiment the present invention is described more specifically.Yet, the invention is not restricted to these embodiment.

The triplet state energy gap and the singlet energy gap of compound are measured in accordance with the following methods.

(1) mensuration of triplet state energy gap

Measure minimum excited triplet state energy level T1.The phosphorescence spectrum of working sample (10 μ mol/l; EPA (ether: iso-pentane: solvent ethanol=5: 5: 2 (volume)); 77K; Quartz cell; The FLUOROLOG II that SPEXCompany produces).The draw tangent line that increases progressively line of short wavelength side of phosphorescence spectrum obtains the wavelength at the place, point of crossing of tangent line and X-coordinate (luminous end) then.The wavelength Conversion that obtains is become energy.

(2) mensuration of singlet energy gap

The singlet energy gap that mensuration excites.Utilize the toluene solution (10 of sample ^-5Mol/l), the spectrophotometer of absorption ultraviolet ray of producing by HITACHI Co.Ltd and the visible light spectrum that is absorbed.The draw tangent line that increases progressively line of spectrographic long wavelength side obtains the wavelength at the place, point of crossing of tangent line and X-coordinate (luminous end) then.The wavelength Conversion that obtains is become energy.

Synthetic embodiment 1 (synthesizing of compound (A5))

The synthetic route of compound (A5) is as follows.

(1) midbody compound (A) is synthetic

With 15g 2,4 '-dibromobenzene ethyl ketone (54mmol) is dissolved in 100ml ethanol.In the solution that obtains, add 7.0g sodium bicarbonate and 5.2g (55mmol) 2-aminopyridine, and the mixture that forms was under refluxad heated 9 hours.After reaction is finished, with the mixture cool to room temperature.By filtering to isolate the crystal of formation, and water and washing with alcohol, 12.5g (yield: midbody compound (A) 85%) obtained.

(2) compound (A5) is synthetic

In reactor, add 6.1g (19mmol) 3,6-phenylbenzene carbazole, 6.3g (23mmol) midbody compound (A), 0.2g copper powder, 1.7g 18-hat-6 and 2.9g (21mmol) salt of wormwood, and add the 30ml orthodichlorobenzene as solvent.The mixture that forms is heated down and under the nitrogen gas stream at 200 ℃ in silicone oil bath, and reaction was carried out 48 hours.After reaction is finished, with the reaction mixture suction filtration, cooling then, and the filtrate that obtains is concentrated with vaporizer.In the oily product that obtains, add 30ml methyl alcohol.The solid matter that forms is separated by filtration under diminished pressure, obtained the gray solid material.With the solid matter that obtains benzene recrystallization, obtain 3.0g (yield: white crystal 31%).Pass through 90MHz ¹H-NMR and FD-MS (field desorption(FD) mass spectrum) confirm that the crystal that obtains is target substance (A5).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₃₇H ₂₅N ₃=511; Measured value: m/z=511 (M ⁺, 100)

Obtain the value of energy gap according to method described above, the result is as shown in table 3.

Synthetic embodiment 2 (synthesizing of compound (A3))

The synthetic route of compound (A3) is as follows.

(1) midbody compound (B) is synthetic

15g 4-bromobenzaldehyde (81mmol) is dissolved in 300ml ethanol.The methanol solution of sodium methylate (81mmol) that in the solution that obtains, adds 10g (83mmol) 2-acetylpyridine and 15g 28%, and the mixture that obtains at room temperature stirred 7 hours.After reaction is finished, by filtering to isolate the crystal of formation, and use washing with alcohol, obtain 9.5g (yield: midbody compound (B) 41%).

(2) midbody compound (C) is synthetic

9.5g midbody compound (B) (33mmol) is dissolved in 80ml ethanol.In the solution that obtains, add 5.2g (34mmol) NSC 2020 and 2.6g (65mmol) sodium hydroxide, and the mixture that obtains was under refluxad heated 15 hours.After reaction is finished, with the mixture cool to room temperature.By filtering to isolate the crystal of formation, and water and washing with alcohol, 3.46g (yield: midbody compound (C) 27%) obtained.

(3) compound (A3) is synthetic

In reactor, add 6.1g (19mmol) 3,6-phenylbenzene carbazole, 8.9g (23mmol) midbody compound (C), 0.2g copper powder, 1.7g 18-hat-6 and 2.9g (21mmol) salt of wormwood, and add the 30ml orthodichlorobenzene as solvent.The mixture that obtains is heated down and under the nitrogen gas stream at 200 ℃ in silicone oil bath, and allow reaction to carry out 48 hours.After reaction is finished, with the reaction mixture suction filtration, cooling then, and the filtrate that obtains is concentrated with vaporizer.In the oily product that obtains, add 30ml methyl alcohol.The solid matter that forms is separated by filtration under diminished pressure, obtained the gray solid material.With the solid matter that obtains benzene recrystallization, obtain 3.9g (yield: white crystal 33%).Pass through 90MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A3).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₅H ₃₀N ₄=626; Measured value: m/z=626 (M ⁺, 100)

According to obtaining the value of energy gap with the described identical method of synthetic embodiment 1, the result is as shown in table 3.

Synthetic embodiment 3 (synthesizing of compound (A26))

The synthetic route of compound (A26) is as follows.

(1) midbody compound (D) is synthetic

In reactor, add 33g (0.20mol) carbazole, 68g (0.24mol) to bromo-iodobenzene, 2.0g copper powder, 18g 18-hat-6 and 30g (0.22mol) salt of wormwood, and add the 300ml orthodichlorobenzene as solvent.The mixture that obtains is heated down and under the nitrogen gas stream at 200 ℃ in silicone oil bath, and allow reaction to carry out 24 hours.After reaction is finished, with reaction mixture B suction filtration, cooling then, and the filtrate that obtains is concentrated with vaporizer.In the oily product that obtains, add 30ml methyl alcohol.The solid matter that forms is separated by filtration under diminished pressure, obtained the gray solid material.With the solid matter that obtains benzene recrystallization, obtain 31g (yield: white crystal 49%).

(2) compound (A26) is synthetic

In reactor, add 5.4g (20mmol) 2-xenyl indoles, 7.7g (24mmol) midbody compound (D), 0.2g copper powder, 1.8g 18-hat-6 and 3.0g (22mmol) salt of wormwood, and add the 30ml orthodichlorobenzene as solvent.The mixture that obtains is heated under 200 ℃ and nitrogen gas stream in silicone oil bath, and allow reaction to carry out 48 hours.After reaction is finished, with the reaction mixture suction filtration, cooling then, and the filtrate that obtains is concentrated with vaporizer.In the oily product that obtains, add 30ml methyl alcohol.The solid matter that forms is separated by filtration under diminished pressure, obtained the gray solid material.With the solid matter that obtains benzene recrystallization, obtain 1.7g (yield: white crystal 17%).By 90 MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A26).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₃₈H ₂₆N ₂=510; Measured value: m/z=510 (M ⁺, 100)

Synthetic embodiment 4 (synthesizing of compound (A27))

The synthetic route of compound (A27) is as follows.

According to synthetic embodiment 3 (2) in the identical step of being carried out, but replace 2-xenyl indoles with 2-xenyl-3-Phenylindole, obtain 2.2g (yield: white crystal 19%).Pass through 90MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A27).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₄H ₃₀N ₂=586; Measured value: m/z=586 (M ⁺, 100)

Synthetic embodiment 5 (synthesizing of compound (A11))

The synthetic route of compound (A11) is as follows.

(1) midbody compound (E) is synthetic

With 7.6g 3,6-phenylbenzene-9-is dissolved in the 70ml ether to bromophenyl carbazole (16mmol).Under-60 ℃, in the solution that obtains, add the hexane solution (1.6M) of 12ml n-Butyl Lithium.The solution that obtains was stirred 2 hours under-60 ℃ to 0 ℃ temperature, then solution is cooled to once more-60 ℃, and drip by diluting the resulting solution of 8.8g triisopropyl borate ester with the 10ml ether.The mixture that obtains was stirred 2 hours under-60 ℃ to 0 ℃ temperature, pass through the aqueous hydrochloric acid termination reaction of adding 5% then.By filtering to isolate the crystal of formation, and water and methanol wash, 4.0g (yield: midbody compound (E) 58%) obtained.

(2) compound (A11) is synthetic

2.0g (7.3mmol) 2-(4 '-bromophenyl) imidazo [1,2-a] pyridine, 3.5g (8.0mmol) midbody compound (E), 0.2g copper powder and 0.17g tetrakis triphenylphosphine palladium are dissolved in 30ml 1, the 2-glycol dimethyl ether.The aqueous sodium carbonate that in the solution that obtains, adds 12ml 2.0M, and the solution that obtains under refluxad heated 8 hours.After reaction is finished, the solid matter that forms is dissolved in methylene dichloride, washes with water, and use dried over sodium sulfate.After steaming desolventizes,, obtain 2.0g (yield: 47%) be with lurid white solid matter with the product methanol wash that obtains.Pass through 90MHz ¹H-NMR and FD-MS confirm that the solid matter that obtains is target substance (A11).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₃H ₂₉N ₃=587; Measured value: m/z=587 (M ⁺, 100)

Synthetic embodiment 6 (synthesizing of compound (A9))

The synthetic route of compound (A9) is as follows.

With the midbody compound (C) that obtains among the synthetic embodiment 2 (2.0g, 5.2mmol), 1.7g (5.8mmol) 4-(9 '-carbazyl)-phenyl-boron dihydroxide and 0.11g tetrakis triphenylphosphine palladium be dissolved in 20ml1, the 2-methyl ethyl ether.The aqueous sodium carbonate that in the solution that obtains, adds 9ml 2.0M, and the solution that obtains under refluxad heated 8 hours.After reaction is finished, the solid matter that forms is dissolved in methylene dichloride, washes with water, use dried over sodium sulfate then.After steaming desolventizes,, obtain 1.8g (yield: 62%) be with lurid white solid matter with the product methanol wash that obtains.Pass through 90MHz ¹H-NMR and FD-MS confirm that the solid matter that obtains is target substance (A9).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₃₉H ₂₆N ₄=550; Measured value: m/z=550 (M ⁺, 100)

Synthetic embodiment 7 (synthesizing of compound (A43))

The synthetic route of compound (A43) is as follows.

Under argon gas stream, with 2.33g (10mmol) 2,3-dicyano-5-(to bromophenyl)-7-methyl-6H-1,4-diazacyclo heptantriene, 2g (12mmol) carbazole, 0.14g (1.5 mol%) three (dibenzalacetones) close two palladiums, 0.06g (3 mol%) tri-butyl phosphine, 2.0g (22mmol) sodium tert-butoxide and 100ml dry toluene and place the 200ml there-necked flask that is equipped with condenser, then with the mixture that obtains heated overnight under agitation under 100 ℃.After reaction is finished,, use the 100ml methanol wash then, obtain 1.2g (3mmol) (yield: buff powder 30%) by filtering to isolate formed crystal.Confirm that by NMR, IR and FD-MS mensuration the powder that obtains is target substance (A43).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₂₆H ₁₇N ₅=399; Measured value: m/z=399 (M ⁺, 100)

Synthetic embodiment 8 (synthesizing of compound (A45))

The synthetic route of compound (A45) is as follows.

Under argon gas stream, with 4.5g (10mmol) 2,3-dicyano-5,7-two (to bromophenyl)-6H-1,4-diazacyclo heptantriene, 4g (24mmol) carbazole, 0.28g (1.5 mol%) three (dibenzalacetones) close two palladiums, 0.12g (3 mol%) tri-butyl phosphine, 4.2g (442mmol) sodium tert-butoxide and 160ml dry toluene and place the 200ml there-necked flask that is equipped with condenser, then the mixture that obtains are under agitation heated under 100 ℃ 18 hours.After reaction is finished,, use the 100ml methanol wash then, obtain 1.8g (2.9mmol) (yield: white powder 29%) by filtering to isolate formed crystal.Confirm that by NMR, IR and FD-MS mensuration the powder that obtains is target substance (A45).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₃H ₂₆N ₆=626; Measured value: m/z=626 (M ⁺, 100)

Synthetic embodiment 9 (synthesizing of compound (B9))

The synthetic route of compound (B9) is as follows.

Under argon atmospher, with 11g (32mmol, 2.6 4-(2 '-phenyl-4 '-pyridyl-pyrimidine-6 '-yl) phenyl-boron dihydroxide, 5g (12mmol) 3 equivalent), 6-two bromo-9-phenyl carbazoles and 0.55g (0.48mmol, 2%Pd) tetrakis triphenylphosphine palladium (0) is suspended in 100ml 1, in the 2-glycol dimethyl ether.The aqueous sodium carbonate (96mmol, 3 equivalents/50ml), and the mixture that obtains under refluxad heated 10 hours that in the suspension that obtains, add 10.2g 2M.Isolate organic layer and concentrated, then product is used the column chromatography purifying, obtain 8.5g (yield: white solid matter 83%).Pass through 90MHz ¹H-NMR and FD-MS confirm that the solid matter that obtains is target substance (B9).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₆₀H ₃₉N ₇=857; Measured value: m/z=857 (M ⁺, 100)

Synthetic embodiment 10 (synthesizing of compound (B11))

The synthetic route of compound (B11) is as follows.

Under argon atmospher, with 7.6g (32mmol, 2.6 equivalents) 4-(imidazopyridine-2 '-yl) phenyl-boron dihydroxide, 5g (12mmol) 3,6-two bromo-9-phenyl carbazoles and 0.55g (0.48mmol, 2%Pd) tetrakis triphenylphosphine palladium (0) is suspended in 100ml 1, in the 2-glycol dimethyl ether.The aqueous sodium carbonate (96mmol, 3 equivalents/50ml), and the mixture that obtains under refluxad heated 10 hours that in the suspension that obtains, add 10.2g 2M.Isolate organic layer and concentrated, then product is used the column chromatography purifying, obtain 5.7g (yield: white solid matter 76%).By 90 MHz ¹H-NMR and FD-MS confirm that the solid matter that obtains is target substance (B11).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₄H ₂₉N ₅=627; Measured value: m/z=627 (M ⁺, 100)

Synthetic embodiment 11 (synthesizing of compound (A72))

The synthetic route of compound (A72) is as follows.

(1) midbody compound (F) is synthetic

According to synthetic embodiment 2 (1) in the identical step of being carried out, different is to replace the 2-acetylpyridine with methyl phenyl ketone, obtains 29.4g (yield: midbody compound (F) 84%).

(2) midbody compound (G) is synthetic

9.0g (31mmol) midbody compound (F), 8.7g (31mmol) 1-phenylpyridine bromide and 19.3g (250mmol) ammonium acetate are suspended in the 27ml acetate, and the suspension that obtains was under refluxad heated 12 hours.Then with the reaction soln cool to room temperature.Add toluene and water, and be divided into the mixture that forms two-layer.Organic layer successively with 10% aqueous sodium hydroxide solution and saturated sodium-chloride water solution washing, is used anhydrous sodium sulfate drying then.After removing organic solvent under reduced pressure, add 27ml ethanol.By filtering to isolate formed crystal and using washing with alcohol, obtain 10.6g (yield: midbody compound (G) 88%).

(3) compound (A72) is synthetic

3.5g (9mmol) midbody compound (G), 1.7g (10mmol) carbazole, 0.09g (0.5mmol) cupric iodide and 4.0g (19mmol) potassiumphosphate are suspended in 18ml 1, in the 4-two  alkane.In the suspension that obtains, add 0.5ml (4mmol) anti-form-1, the 2-cyclohexanediamine.Under argon atmospher, the mixture that obtains was under refluxad heated 18 hours.Then with the reaction soln cool to room temperature.Add methylene dichloride and water, and be divided into the mixture that forms two-layer.Organic layer is used 5% aqueous hydrochloric acid and water washing successively, use anhydrous sodium sulfate drying then.Steam and remove organic solvent, add the 15ml ethyl acetate then.By filtering to isolate formed crystal and, obtaining 3.5g (yield: 83%) be with lurid white crystal with the ethyl acetate washing.By 90 MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A72).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₃₅H ₂₄N ₂=472; Measured value: m/z=472 (M ⁺, 100)

Synthetic embodiment 12 (synthesizing of compound (A73))

The synthetic route of compound (A73) is as follows.

(1) midbody compound (H) is synthetic

According to synthetic embodiment 2 (2) in the identical step of being carried out, different is to replace midbody compound (B) with the midbody compound (F) that synthetic embodiment 11 obtains, and obtains 7.8g (yield: midbody compound (H) 61%).

(2) compound (A73) is synthetic

According to synthetic embodiment 11 (3) in the identical step of being carried out, different is to replace midbody compound (G) with midbody compound (H), obtains 3.3g (yield: 76%) be with lurid white crystal.By 90 MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A73).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₃₄H ₂₃N ₃=473; Measured value: m/z=473 (M ⁺, 100)

Synthetic embodiment 13 (synthesizing of compound (A113))

The synthetic route of compound (A113) is as follows.

According to synthetic embodiment 11 (3) in the identical step of being carried out, different is to replace midbody compound (G) with the midbody compound (C) that synthetic embodiment 2 obtains, and obtains 1.5g (yield: 50%) be with lurid white crystal.By 90 MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A113).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₃₃H ₂₂N ₄=474; Measured value: m/z=474 (M ⁺, 100)

Synthetic embodiment 14 (synthesizing of compound (A98))

The synthetic route of compound (A98) is as follows.

(1) midbody compound (J) is synthetic

According to synthetic embodiment 2 (1) in the identical step of being carried out, different is with 3, the 5-dibromo benzaldehyde replaces the 4-bromobenzaldehyde, and replaces the 2-acetylpyridine with methyl phenyl ketone, obtains 19.2g (yield: midbody compound (J) 92%).

(2) midbody compound (K) is synthetic

According to synthetic embodiment 2 (2) in the identical step of being carried out, different is to replace midbody compound (B) with midbody compound (J), obtains 5.5g (yield: midbody compound (K) 45%).

(3) compound (A98) is synthetic

3.0g (6mmol) midbody compound (K), 2.3g (14mmol) carbazole, 0.12g (0.6mmol) cupric iodide and 4.2g (20mmol) potassiumphosphate are suspended in 21ml1, in the 4-two  alkane.In the suspension that obtains, add 0.8ml (6mmol) anti-form-1, the 2-cyclohexanediamine.Under argon atmospher, the mixture that obtains was under refluxad heated 18 hours.Then with the reaction soln cool to room temperature.Add methylene dichloride and water, and be divided into the mixture that forms two-layer.Organic layer is washed with water, use anhydrous sodium sulfate drying then.Remove organic solvent under reduced pressure, the distillatory resistates is suspended in the 21ml two  alkane then.In the suspension that obtains, add 0.12g (0.6mmol) cupric iodide, 2.9g (14mmol) potassiumphosphate and 0.8ml (6mmol) anti-form-1, the 2-cyclohexanediamine.Under argon atmospher, the mixture that obtains was under refluxad heated 18 hours.Then with the reaction soln cool to room temperature.Add methylene dichloride and water, and be divided into the mixture that forms two-layer.Organic layer is washed with water, use anhydrous sodium sulfate drying then.Remove organic solvent under reduced pressure, add the 30ml ethyl acetate then.By filtering to isolate formed crystal and, obtaining 3.3g (yield: 80%) be with lurid white crystal with the ethyl acetate washing.Pass through 90MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A98).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₆H ₃₀N ₄=638; Measured value: m/z=638 (M ⁺, 100)

Synthetic embodiment 15 (synthesizing of compound (A105))

The synthetic route of compound (A105) is as follows.

(1) midbody compound (M) is synthetic

According to synthetic embodiment 11 (2) in the identical step of being carried out, different is to replace midbody compound (F) with the midbody compound (J) that synthetic embodiment 14 (1) obtains, and obtains 10.0g (yield: midbody compound (M) 88%).

(2) compound (A105) is synthetic

According to synthetic embodiment 14 (3) in the identical step of being carried out, different is to replace midbody compound (K) with midbody compound (M), obtains 2.9g (yield: 71%) be with lurid white crystal.By 90 MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A105).The result that FD-MS measures is as follows:

The calculated value C of FD-MS ₄₇H ₃₁N ₃=637; Measured value: m/z=637 (M ⁺, 100)

Synthetic embodiment 16 (synthesizing of compound (A108))

The synthetic route of compound (A108) is as follows.

(1) midbody compound (N) is synthetic

With 13.0g (41mmol) 1,3,5-tribromo-benzene, 10.0g (45mmol) 3,5-diphenylpypazole, 0.8g (4mmol) cupric iodide and 11.9g (86mmol) salt of wormwood are suspended in 50ml 1, in the 4-two  alkane.In the suspension that obtains, add 4.9ml (41mmol) anti-form-1, the 2-cyclohexanediamine.Under argon atmospher, the mixture that obtains was under refluxad heated 18 hours.Then with the reaction soln cool to room temperature.Add methylene dichloride and water, and be divided into the mixture that forms two-layer.Organic layer is washed with water, use anhydrous sodium sulfate drying then.Remove organic solvent under reduced pressure, with remaining product silica gel chromatography, obtain 2.0g (yield: midbody compound (N) 11%) then.

(2) compound (A108) is synthetic

2.0g (4mmol) midbody compound (N), 1.4g (8mmol) carbazole, 0.08g (0.4mmol) cupric iodide and 2.9g (14mmol) potassiumphosphate are suspended in 15ml 1, in the 4-two  alkane.In the suspension that obtains, add 0.5ml (4mmol) anti-form-1, the 2-cyclohexanediamine.Under argon atmospher, the mixture that obtains was under refluxad heated 18 hours.Then with the reaction soln cool to room temperature.Add methylene dichloride and water, and be divided into the mixture that forms two-layer.Organic layer is washed with water, use anhydrous sodium sulfate drying then.Steam and remove organic solvent, then the distillatory resistates is suspended in 15ml1, in the 4-two  alkane.In the suspension that obtains, add 0.08g (0.4mmol) cupric iodide, 2.9g (14mmol) potassiumphosphate and 0.5ml (4mmol) anti-form-1, the 2-cyclohexanediamine.Under argon atmospher, the mixture that obtains was under refluxad heated 14 hours.Then with the reaction soln cool to room temperature.Add methylene dichloride and water, and be divided into the mixture that forms two-layer.Organic layer is washed with water, use anhydrous sodium sulfate drying then.Remove organic solvent under reduced pressure, add 5ml ethanol and 15ml ethyl acetate then.By filtering to isolate formed crystal, and, obtain 2.4g (yield: 87%) be with lurid white crystal with containing ethyl acetate and ethanol mixed solvent (relative quantity of by volume is 5: 2) washing.By 90 MHz ¹H-NMR and FD-MS confirm that the crystal that obtains is target substance (A108).The result that FD-MS measures is as follows:

Table 3

	Compound	Singlet energy gap (eV)	Triplet state energy gap (eV)
	Compound	Singlet energy gap (eV)	Triplet state energy gap (eV)	Synthetic embodiment 1 synthetic embodiment 2 synthetic embodiment 3 synthetic embodiment 4 synthetic embodiment 5 synthetic embodiment 6 synthetic embodiment 9 synthetic embodiment 10 synthetic embodiment 11 synthetic embodiment 12 synthetic embodiment 13 synthetic embodiment 14 synthetic embodiment 15 synthetic embodiment 16	A5 A3 A26 A27 A11 A9 B9 B11 A72 A73 A113 A98 A105 A108	3.2 3.1 3.1 3.0 3.0 3.1 3.2 3.2 3.5 3.3 3.2 3.5 3.4 3.7	2.7 2.7 2.6 2.6 2.7 2.5 2.6 2.7 2.8 2.8 2.7 2.9 2.9 3.0

Embodiment 1

By in Virahol, applying ultrasonic wave 5 minutes, be exposed to the ultraviolet ozone that produces 30 minutes then, cleaning has the thick glass matrix (being produced by GEOMATEC Company) of 25mm * 75mm * 1.1mm of ito transparent electrode.The glass matrix that has transparent electrode lines that had cleaned is fixed on the matrix clamper of vacuum vapor deposition device.On the surface with transparency electrode one side of the matrix that cleaned, in the mode of the film covering transparent electrode that forms, forming thickness is the N of 60nm, N '-two (N, N '-phenylbenzene-4-aminophenyl)-N, N '-phenylbenzene-4,4 '-diaminostilbene, the film of 1 '-biphenyl (film of TPD232).The film of formed TPD232 is as hole injection layer.On the film of formed TPD232, forming thickness by vapour deposition is the film (film of NPD) of 4,4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl of 20nm.The film of formed NPD is as hole transmission layer.On the film of formed NPD, forming thickness by vapour deposition is the film of the above-claimed cpd (A5) of 40nm.Simultaneously, the compound shown in below (D1) carries out vapour deposition so that the weight ratio of compound (A5) and compound (D1) is 40: 3 a amount.Compound (D1) is the luminophor that the singlet energy is low to moderate 2.79eV, makes to send blue light.The hybrid films of formed compound (A5) and compound (D1) is as luminescent layer.On above formed film, form thickness and be the film (Me is meant methyl) of the BAlq shown in 20nm following.The film of BAlq is as electron injecting layer.Then, will carry out the binary vapour deposition as Li of reductibility doping agent (source of lithium: produced by SAES GETTERSCompany) and Alq, and formation thickness is the Alq:Li film of 10nm, it is second electron injecting layer (negative pole).On formed Alq:Li film, the vapour deposition metallic aluminium makes organic EL device to form the metal negative pole.

When the volts DS with 5.0V is added on the organic EL device of above preparation, with 150cd/m ²Brightness send blue light, luminous efficiency is 6.3cd/A.Tristimulus coordinates is (0.14,0.16), and the purity of color is excellent.

Embodiment 2 to 8

According to embodiment 1 in the identical method of being carried out, but replace compound (A5) with the compound shown in the table 4, make organic EL device, and measure volts DS, the brightness of the light that sends, luminous efficiency, the color of the light that sends and the purity of color.The result is as shown in table 4.

Comparative Examples 1

According to embodiment 1 in the identical method of being carried out, but replace compound (A5) with the compound BCz that routinizes shown in following, make organic EL device, and measure volts DS, the brightness of the light that sends, luminous efficiency, the color of the light that sends and the purity of color.The result is as shown in table 4.

Comparative Examples 2

According to embodiment 1 in the identical method of being carried out, but replace compound (A5) with the compound (C2) (this compound is recorded in Japanese patent application and does not examine publication number 2001-288462) shown in following, make organic EL device, and measure volts DS, the brightness of the light that sends, luminous efficiency, the color of the light that sends and the purity of color.The result is as shown in table 4.

Table 4

	The organic main body material of luminescent layer	Voltage (V)	Brightness (the cd/m of the light that sends ²)	Luminous efficiency (cd/A)	The color of the light that sends	Tristimulus coordinates
	The organic main body material of luminescent layer	Voltage (V)	Brightness (the cd/m of the light that sends ²)	Luminous efficiency (cd/A)	The color of the light that sends	Tristimulus coordinates	Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 Comparative Examples 1 Comparative Examples 2	A5 A3 A26 A27 A11 A9 B9 B11 BCz C2	5.0 5.8 6.0 6.0 5.2 6.2 5.7 5.0 8.5 6.5	150 160 132 154 180 145 151 181 70 65	6.3 5.8 5.2 5.9 6.3 5.1 5.7 6.9 2.4 2.6	Blue blue	(0.14，0.16) (0.15，0.17) (0.14，0.16) (0.14，0.16) (0.15，0.17) (0.15，0.16) (0.15，0.17) (0.15，0.17) (0.14，0.16) (0.14，0.16)

As shown in table 4, compare with the organic EL device of (C2) with using the compound BCz that routinizes in the Comparative Examples 1 and 2 respectively, use the organic EL device of The compounds of this invention under lower voltage, to drive, and send blue light with higher efficient.Because the energy gap of compound of the present invention is bigger, can be mixed into light emitting molecule in the luminescent layer and be used for luminous with big energy gap.

Embodiment 9

By in Virahol, applying ultrasonic wave 5 minutes, be exposed to the ultraviolet ozone that produces 30 minutes then, cleaning has the thick glass matrix (being produced by GEOMATEC Company) of 25mm * 75mm * 0.7mm of ito transparent electrode.The glass matrix that has transparent electrode lines that had cleaned is fixed on the matrix clamper of vacuum vapor deposition device.On the surface with transparency electrode one side of the matrix that cleaned,, form thickness and be the film (film of CuPc) of the CuPc shown in 10nm following in the mode of the film covering transparent electrode that forms.The film of formed CuPc is as hole injection layer.On the film of formed CuPc, forming thickness is the film (film of TPAC) of 1,1 '-two [4-N, N-two (p-methylphenyl) aminophenyl] hexanaphthene of 30nm.The film of formed TPAC is as hole transmission layer.On the film of formed TPAC, forming thickness by vapour deposition is the film of the above-claimed cpd (A72) of 30nm, forms luminescent layer.Simultaneously, adding is as two [(4, the 6-difluorophenyl) pyridine-N, C of phosphorescence Ir metal complex ^{2 '}] pyridine carboxylic acid iridium (being expressed as FIrpic below).The concentration of FIrpic in the luminescent layer is set at 7 weight %.This layer is as luminescent layer.On above formed film, forming thickness is the film of the Alq of 30nm.The film of Alq is as electron injecting layer.Then, LiF is carried out vapour deposition as alkali metal halide, thickness of the film that its amount make to form is 0.2nm, vapour deposition aluminium then, and its amount makes that thickness of the film that forms is 150nm.Formed Alq:Li film is as negative pole.Make organic EL device thus.

When the device that obtains was tested by electric current, sending brightness under the voltage of 6.6V was 89cd/m ²Bluish-green coloured light, current density is 0.59mA/cm ²Tristimulus coordinates is (0.18,0.39), and luminous efficiency is 14.98cd/A.

Embodiment 10 to 12

According to embodiment 9 in the identical method of being carried out, but be to use the compound shown in the table 5 to replace compound (A72), make organic EL device, and measure volts DS, current density, the brightness of the light that sends, luminous efficiency, the color of the light that sends and the purity of color.The result is as shown in table 5.

Comparative Examples 3

According to embodiment 9 in the identical method of being carried out, but be to use the compound BCz that routinizes to replace compound (A72), make organic EL device, and measure volts DS, current density, the brightness of the light that sends, luminous efficiency, the color of the light that sends and the purity of color.The result is as shown in table 5.

Comparative Examples 4

According to Comparative Examples 3 in the identical method of being carried out, but with 4,4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl (following represent with α-NPD) replaces compound TPAC as hole transmission layer, and replace compd A lq as electron transfer layer with the compd B Alq shown in top, make organic EL device, and measure volts DS, current density, the brightness of the light that sends, luminous efficiency, the color of the light that sends and the purity of color.The result is as shown in table 5.

Table 5

	The organic main body material of luminescent layer	Voltage (V)	Current density (mA/cm ²)	Brightness (the cd/m of the light that sends ²)	Luminous efficiency (cd/A)	The color of the light that sends	Tristimulus coordinates
	The organic main body material of luminescent layer	Voltage (V)	Current density (mA/cm ²)	Brightness (the cd/m of the light that sends ²)	Luminous efficiency (cd/A)	The color of the light that sends	Tristimulus coordinates	Embodiment 9 embodiment 10 embodiment 11 embodiment 12 Comparative Examples 3 Comparative Examples 4	A72 A98 A105 A73 BCz BCz	6.6 6.4 6.9 6.0 7.8 7.6	0.59 0.54 0.84 1.00 1.70 1.09	89 86 99 99 98 99	14.98 15.89 11.76 9.91 5.80 9.15	Blue-greenish colour blue-greenish colour blue-greenish colour blue-greenish colour blue-greenish colour blue-greenish colour	(0.18，0.39) (0.18，0.40) (0.17，0.40) (0.16，0.39) (0.16，0.37) (0.17，0.37)

As shown in table 5, compare with using the organic EL device of the compound BCz that routinizes in the Comparative Examples 3 and 4, use the organic EL device of The compounds of this invention under lower voltage, to drive, and send blue light with higher efficient.Because the energy gap of compound of the present invention is bigger, can be mixed into light emitting molecule in the luminescent layer and be used for luminous with big energy gap.

Industrial applicability

As above described in detail, by utilizing the material that is used for organic electroluminescence device that comprises compound shown in general formula (1) or (2) of the present invention, the organic electroluminescence device that can send blue light that can obtain having high-luminous-efficiency and excellent color purity. Therefore, organic electroluminescence device of the present invention is suitable as the light source of various electronic instruments very much.

Claims

1. material that is used for organic electroluminescence device, this material comprises the compound shown in following general formula (1) or (2):

(Cz-) _nA (1)

Cz(-A) _m (2)

(M) _p-(L) _q-(M’) _r (A)

Wherein M and M ' represent to contain the hetero-aromatic ring of 2 to 40 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring independently of one another, described hetero-aromatic ring is selected from pyridine, pyrimidine, pyrazine, triazine, aziridine, azaindole alkane, indoles alkane, imidazoles, indoles, isoindole, indazole, purine, puteridine, β-Ka Lin, naphthyridines, quinoxaline, terpyridyl, dipyridyl, acridine, phenanthroline, azophenlyene, imidazo [1,2-a] pyridine, pyrrolopyridine, dicyano diazacyclo heptantriene and pyrazoles, and optional at least one group that is selected from down group replaces: halogen atom, carbazyl, hydroxyl, amino, nitro, cyano group, silyl, trifluoromethyl, carbonyl, carboxyl, alkyl, alkenyl, arylalkyl, aryl, the heteroaromatic heterocyclic group, aralkyl, aryloxy, alkoxyl group, perfluorophenyl and adamantyl; M can represent identical ring or different rings with M ', L represents singly-bound, the replacement or unsubstituted aryl or the arylidene that contain 6 to 30 carbon atoms, be selected from cyclopentylidene, cyclohexylidene, inferior suberyl, 1, the cycloalkylidene of 1-cyclohexylidene, inferior norcamphyl, inferior adamantyl and inferior double-octane base, or contain the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms, p represents 0 to 2 integer, q represents 1 or 2 integer, r represents 0 to 2 integer, and p+r represents 1 or bigger integer; And

N and m represent 1 to 3 integer separately.

2. the described material that is used for organic electroluminescence device of claim 1, wherein

N=1 in the general formula (1), and middle p=1 of general formula (A) and r=0;

In general formula (A), M represents to contain the hexa-atomic or seven-membered ring of heterocycle of 4 or 5 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, the heterocycle five-ring that contains 2 to 4 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, the heterocycle that contains 8 to 11 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring, or replacement or unsubstituted imidazo [1,2-a] pyridine ring; L represents to contain replacement or the unsubstituted aryl or the arylidene of 6 to 30 carbon atoms, or contains the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms.

3. the described material that is used for organic electroluminescence device of claim 1, wherein

N=2 in the general formula (1), and middle p=1 of general formula (A) and r=0;

4. the described material that is used for organic electroluminescence device of claim 1, wherein

N=1 in the general formula (1), and middle p=2 of general formula (A) and r=0;

In general formula (A), M represents to contain the hetero-aromatic ring of 2 to 40 carbon atoms and nitrogen-atoms and formation replacement or unsubstituted ring; L represents to contain replacement or the unsubstituted aryl or the arylidene of 6 to 30 carbon atoms, or contains the replacement or the unsubstituted hetero-aromatic ring of 2 to 30 carbon atoms.

5. the described material that is used for organic electroluminescence device of claim 1, wherein

M=2 in the general formula (2), and p=q=1 in the general formula (A);

6. the described material that is used for organic electroluminescence device of claim 1, wherein Cz represents to replace or unsubstituted aryl carbazyl.

7. the described material that is used for organic electroluminescence device of claim 6, wherein Cz represents to replace or unsubstituted phenyl carbazole base.

8. the described material that is used for organic electroluminescence device of claim 6, the aryl moiety of wherein said aryl carbazyl is replaced by carbazyl.

9. the described material that is used for organic electroluminescence device of claim 1, the triplet state energy gap of the compound shown in its formula of (1) or (2) is 2.5 to 3.3eV, described triplet state energy gap is measured by measuring minimum excited triplet state energy level T1 as follows: under 77K, use quartz cell, working sample is the phosphorescence spectrum of the EPA solution of 10 μ mol/l in ether-iso-pentane-ethanol of 5: 5: 2 in volume ratio; The tangent line that increases progressively line of short wavelength side of phosphorescence spectrum draws; Obtain the point of crossing of tangent line and X-coordinate, to determine the wavelength of luminous end; Be converted into energy with the wavelength that will obtain.

10. the described material that is used for organic electroluminescence device of claim 1, the singlet energy gap of the compound shown in its formula of (1) or (2) is 2.8 to 3.8eV, and described singlet energy gap is determined by measuring the singlet energy gap that excites as follows: use the spectrophotometer that absorbs ultraviolet ray and visible light to obtain 10 of sample ^-5The absorption spectrum of the toluene solution of mol/l concentration; The tangent line that increases progressively line of spectrographic long wavelength side draws; Obtain the point of crossing of tangent line and X-coordinate, with the wavelength of the end that is absorbed; Be converted into energy with the wavelength that will obtain.

11. organic electroluminescence device, it comprises positive pole, negative pole and comprises one deck and the organic thin film layer between described positive pole and negative pole at least that the one deck at least in the wherein said organic thin film layer comprises the described material that is used for organic electroluminescence device of claim 1.

12. an organic electroluminescence device, it comprises positive pole, negative pole and comprises one deck and the organic thin film layer between described positive pole and negative pole at least that wherein luminescent layer comprises the described material that is used for organic electroluminescence device of claim 1.

13. an organic electroluminescence device, it comprises positive pole, negative pole and comprises one deck and the organic thin film layer between described positive pole and negative pole at least that wherein electron transfer layer comprises the described material that is used for organic electroluminescence device of claim 1.

14. an organic electroluminescence device, it comprises positive pole, negative pole and comprises one deck and the organic thin film layer between described positive pole and negative pole at least that wherein hole transmission layer comprises the described material that is used for organic electroluminescence device of claim 1.

15. the described organic electroluminescence device of claim 11, the wherein said material that is used for organic electroluminescence device is the organic main body material.

16. the described organic electroluminescence device of claim 11, it comprises the inorganic compound layer between at least one electrode and organic thin film layer.

17. the described organic electroluminescence device of claim 11, it is undertaken luminous by the multiplicity excitation, and it is to be excited to triplet state or higher exciting that described multiplicity excites.

18. the described organic electroluminescence device of claim 11, it sends blue light.