CN101072743A - Pyrene compound and, utilizing the same, light emitting transistor device and electroluminescence device - Google Patents

Abstract

An organic phosphor of the following formula (1) that can be used in both a light emitting transistor device and an organic EL device. There is provided a light emitting transistor device or an organic EL device, wherein luminescence of such a specified asymmetric pyrene compound is utilized in a light emitting layer of transistor device or a luminescent layer, hole transporting layer or electron transporting layer of organic electroluminescence device. wherein R1 is an optionally substituted heteroaryl, etc. and R2 is a hydrogen atom, etc., being different from R1.

Description

Pyrene compound and the light-emitting transistor device and the organic electroluminescent device that have used it

Technical field

The present invention relates to the light-emitting transistor device and the organic electroluminescent device that can be used in the asymmetric pyrene compound of light-emitting transistor device and organic electroluminescent device and used it.

Background technology

Organic electroluminescent device (being designated hereinafter simply as " organic EL ") as the typical case of organic semiconductor device is the luminous element that has utilized luminescence phenomenon, described luminescence phenomenon be with the layer that constitutes by organic fluorescent in electronics and the compound of hole accompany.Specifically, in patent documentation 1, patent documentation 2 etc., put down in writing and comprise the luminescent layer that constitutes by above-mentioned organic compound, inject the electron injection electrode of electronics and to the organic EL of the hole injecting electrode of above-mentioned luminescent layer injected hole to this luminescent layer.

As the organic fluorescent that in this luminescent layer, uses, can enumerate (patent documentations 1), 1,3,6 such as Pai Linong (ベ リ ノ Application) derivative, diphenylethyllene benzene derivatives, (patent documentations 2) such as 8-four different phenyl pyrenes etc.

Patent documentation 1: the spy opens flat 5-315078 communique

Patent documentation 2: the spy opens the 2001-118682 communique

As utilized with the layer that constitutes by organic fluorescent in electronics and the example of the compound luminescence phenomenon that accompanies in hole, except above-mentioned organic EL, known luminescence transistor unit also.

If organic fluorescent can be used for organic EL and light-emitting transistor device, then the efficient activity with these elements manufacturings is relevant.But, can be used for both organic fluorescents of these elements for unknown.

Summary of the invention

Therefore, the objective of the invention is to, the organic fluorescent that can be used for light-emitting transistor device and organic EL is provided.

The present invention has solved above-mentioned problem by using the asymmetric pyrene compound of being made up of following structural formula (1).

[changing 4]

(in formula (1), R ₁Expression is from having substituent heteroaryl, can have substituent aryl, can have substituent main chain carbon number and be 1～20 alkyl, can have substituent cycloalkyl, can have substituent thiazolinyl, can have substituent alkynyl, cyano group, can have substituent carbonyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, with the group of choosing in the halogen atom.

In addition, R ₂Expression is from hydrogen atom, can have substituent heteroaryl, can have substituent aryl, can have substituent main chain carbon number and be 1～20 alkyl, can have substituent cycloalkyl, can have substituent thiazolinyl, can have substituent alkynyl, cyano group, can have substituent carbonyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, with the group of choosing in the halogen atom, and and R ₁Different).

According to the present invention,, therefore can be used as the organic fluorescent that uses in organic EL and the light-emitting transistor device and use owing to use asymmetrical pyrene compound.Its reason is considered to, because asymmetric pyrene compound has the crystallinity (amorphism) of appropriateness, therefore can have suitable luminosity as organic EL, and can have suitable carrier mobility as lighting transistor.

Description of drawings

Fig. 1 (a) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 1 (b) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 2 (a) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 2 (b) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 2 (c) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 3 (a) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 3 (b) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 3 (c) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 4 (a) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 4 (b) is the chemical formula of the asymmetric pyrene compound example of expression.

Fig. 5 is the sectional view of the example of expression light-emitting transistor device involved in the present invention.

Fig. 6 is the orthographic plan of the formation of expression source electrode and drain electrode.

Fig. 7 (a) (b) (c) is the synoptic diagram of the luminescence mechanism of expression light-emitting transistor device.

Fig. 8 has used the motor circuit figure of example of the display unit of light-emitting transistor device involved in the present invention for expression.

Fig. 9 is the sectional view of expression organic EL example involved in the present invention.

Figure 10 has used the motor circuit figure of example of the display unit of organic EL involved in the present invention for expression.

1: luminescent layer

2: the source electrode

2a: broach shape portion

3: drain electrode

3a: broach shape portion

4: gate electrode

5: insulating film

10: light-emitting transistor device

11: hole channel

12: pinch-off point

20: substrate

21: display unit

22: scanning line driver

23: data line driving device

24: controller

30: organic EL

31: substrate

32: the hole injecting electrode layer

33: hole transmission layer

34: luminescent layer

35: electron transfer layer

36: electron injection electrode layer

37: direct supply

40: substrate

41: display unit

42: scan line drive circuit

43: data line drive circuit

S: source electrode

D: drain electrode

G: gate electrode

C: electrical condenser

Ts: select transistor

P11, P12: pixel

LS1, LS2, LS1 ', LS2 ': sweep trace

LD1, LD2, LD1 ', LD2 ': data line

Embodiment

Below the present invention is described in detail.

The present invention relates to the invention of asymmetric pyrene compound.This asymmetric pyrene compound can be used for light-emitting transistor device or organic electroluminescent device (organic EL).

Above-mentioned asymmetric pyrene compound has the compound shown in the following chemical formula (1).

[changing 5]

(in formula (1), R ₁Expression is from having substituent heteroaryl, can have substituent aryl, can have substituent main chain carbon number and be 1～20 alkyl, can have substituent cycloalkyl, can have substituent thiazolinyl, can have substituent alkynyl, cyano group, can have substituent carbonyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, with the group of choosing in the halogen atom.

In addition, R ₂Expression is from hydrogen atom, can have substituent heteroaryl, can have substituent aryl, can have substituent main chain carbon number and be 1～20 alkyl, can have substituent cycloalkyl, can have substituent thiazolinyl, can have substituent alkynyl, cyano group, can have substituent carbonyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, with the group of choosing in the halogen atom, and and R ₁Different.

As above-mentioned R ₁Concrete example, can enumerate can have the regulation substituent heteroaryl (also comprising Ppolynuclear aromatic), be prescribed the alkyl phenyl that alkyl replaces, the phenyl that is replaced by halogen atom, naphthyl (preferred 2-naphthyl), anthryl (preferred 2-anthryl), phenanthryl, can have regulation substituent aryl (also comprising Ppolynuclear aromatic), the main chain carbon number be 1～20 can have substituent straight chain or ramose alkyl, can have substituent cycloalkyl, can have the substituent thiazolinyl of regulation, can have the substituent alkynyl of regulation, cyano group, can have substituent carbonyl, can have the substituent alkoxyl group of regulation, can have the substituent aryloxy of regulation, trimethyl silyls etc. can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, has the group of halogen atom etc.

Can have the substituting group that uses in the substituent heteroaryl of regulation as above-mentioned, can enumerate benzofuryl, pyrryl, benzoxazolyl, pyrazinyl, thienyl, alkylated substituted thiazoline fen base, bithiophene base, phenyl thienyl, benzothienyl, pyridyl, bipyridyl, phenylpyridyl, quinolyl, benzothiazolyl etc.

As the above-mentioned alkyl that uses in the alkyl phenyl of alkyl replacement that is prescribed, can enumerate phenyl, methyl, ethyl etc.In addition,, can enumerate tolyl, 3-alkyl phenyl, 4-alkyl phenyl, 3-trifluoromethyl, 4-trifluoromethyl, 3, two (trifluoromethyl) phenyl of 5-etc. as the concrete example of the alkyl phenyl that is replaced by this alkyl.

As the halogen atom that uses in the above-mentioned phenyl that is replaced by halogen atom, can enumerate fluorine atom, bromine atoms, chlorine atom etc., preferred fluorine atom.In addition, as the concrete example of the phenyl that is replaced by this halogen atom, can enumerate 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 3,4,5-trifluorophenyl etc.

Can have the substituting group that uses in the substituent aryl of regulation as above-mentioned, can enumerate xenyl, terphenyl, phenyl vinylidene phenyl or pyrido phenyl etc.

As above-mentioned main chain carbon number is 1～20 the concrete example that can have substituent straight chain or ramose alkyl, can enumerate methyl, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, dodecyl, octadecyl etc.

Can have the substituting group that uses in the substituent thiazolinyl of regulation as above-mentioned, can enumerate vinyl, phenyl substituted ethylene base, ethyl substituted ethylene base, xenyl substituted ethylene base, allyl group, 1-butylene base etc.

Can have the substituting group that uses in the substituent alkynyl of regulation as above-mentioned, can enumerate ethynyl, phenyl replaced acetylene base, trimethyl silyl replaced acetylene base, proyl etc.

Can have the substituting group that uses in the substituent alkoxyl group of regulation as above-mentioned, can enumerate methoxyl group, oxyethyl group, butoxy etc.

Can have the substituting group that uses in the substituent aryloxy of regulation as above-mentioned, can enumerate phenoxy group, 1-naphthyloxy, 2-naphthyloxy etc.

Have a halogen atom that uses in the group of halogen atom as above-mentioned, can enumerate fluorine atom, bromine atoms, chlorine atom etc., the wherein preferred group that only constitutes, more preferably fluorine atom by these halogen atoms.

In above-mentioned, as R ₁, be preferably selected from the group that can have substituent following radicals, as phenyl, naphthyl, benzofuryl, phenylpyridyl, thienyl, benzothienyl, pyridyl, methyl, vinyl and ethynyl.

Specifically, be preferably selected from 3-alkyl phenyl, 4-alkyl phenyl, 3-fluorophenyl, 4-fluorophenyl, 3-trifluoromethyl, 4-trifluoromethyl, 3 especially, 4-difluorophenyl, 3,5-difluorophenyl, 3, two (trifluoromethyl) phenyl, 3 of 5-, 4, the group of phenyl, 2-naphthyl, benzofuryl, phenylpyridyl, thienyl, benzothienyl, pyridyl, bipyridyl, phenyl, xenyl, methyl, phenyl substituted ethylene base or phenyl replaced acetylene base that 5-trifluorophenyl, tolyl, fluorine replace.

As above-mentioned R ₂Concrete example, can enumerate hydrogen atom and as above-mentioned R ₁Illustrated group, but in the present invention, R ₁And R ₂It is different groups.

Wherein, as R ₂, be preferably selected from hydrogen atom, can have the group of substituent following radicals, as phenyl, naphthyl, benzofuryl, phenylpyridyl, thienyl, benzothienyl, pyridyl, methyl, vinyl and ethynyl.

Specifically, be preferably selected from the group of hydrogen atom, methyl, hexyl, phenyl, xenyl, pyridyl, bipyridyl, naphthyl, xenyl, phenylpyridyl, octyl group, dodecyl, octadecyl, phenyl substituted ethylene base or phenyl replaced acetylene base especially.

Moreover, the molecular weight of asymmetric pyrene compound of the present invention, preferred more than 500, more preferably more than 800, preferred below 5000 in addition, more preferably below 3000.

As the concrete example of above-mentioned chemical formula (1), can enumerate following compound.As R ₂Example during for hydrogen atom can be enumerated R ₁Pyrene compound (Fig. 1 (a) (3-1)), R for thiphene ring (thienyl) ₁Pyrene compound (Fig. 1 (a) (3-2)), R for pyridine ring (pyridyl) ₁Pyrene compound (Fig. 1 (a) (3-3)), R for phenyl ₁Pyrene compound (Fig. 1 (a) (3-4)), R for naphthyl ₁Pyrene compound (Fig. 1 (a) (3-5)), R for xenyl ₁Pyrene compound (Fig. 1 (a) (3-6)), R for methyl ₁Pyrene compound (Fig. 1 (a) (3-7)), R for phenyl substituted ethylene base ₁Pyrene compound (Fig. 1 (a) (3-8)), R for phenyl replaced acetylene base ₁Pyrene compound (Fig. 1 (b) (3-9)), R for xenyl ₁Pyrene compound (Fig. 1 (b) (3-10)), R for thionaphthene ring (benzothienyl) ₁Pyrene compound (Fig. 1 (b) (3-11)), R for tolyl ₁Be pyrene compound (Fig. 1 (b) (3-12)) of fluorine substituted-phenyl etc.

In addition, as R ₂Example for beyond the hydrogen atom time can be enumerated R ₁Be pyridine ring (pyridyl), R ₂Be the pyrene compound (Fig. 2 (a) (4-1)) of methyl, R ₁Be bipyridyl, R ₂Be the pyrene compound (Fig. 2 (a) (4-2)) of octadecyl, R ₁Be phenyl, R ₂Be the pyrene compound (Fig. 2 (a) (4-3)) of methyl, R ₁Be phenyl, R ₂Be the pyrene compound (Fig. 2 (a) (4-4)) of octyl group, R ₁Be phenyl, R ₂Be the pyrene compound (Fig. 2 (a) (4-5)) of dodecyl, R ₁Be xenyl, R ₂Be the pyrene compound (Fig. 2 (a) (4-6)) of octyl group, R ₁Be xenyl, R ₂Be the pyrene compound (Fig. 2 (a) (4-7)) of dodecyl, R ₁Be naphthyl, R ₂Pyrene compound ((4-8) of Fig. 2 (b), R for dodecyl ₁Be phenyl, R ₂Be the pyrene compound (Fig. 2 (b) (4-9)) of phenyl substituted ethylene base, R ₁Be thiphene ring (thienyl), R ₂Be the pyrene compound (Fig. 2 (b) (4-10)) of pyridine ring (pyridyl), R ₁Be phenyl, R ₂Be the pyrene compound (Fig. 2 (b) (4-11)) of pyridine ring (pyridyl), R ₁Be xenyl, R ₂Be the pyrene compound (Fig. 2 (b) (4-12)) of phenylpyridine ring (phenylpyridyl), R ₁Be xenyl, R ₂Be the pyrene compound (Fig. 2 (b) (4-13)～(4-14)) of pyridine ring (pyridyl), R ₁Be pyridine ring (pyridyl), R ₂Be the pyrene compound (Fig. 2 (c) (4-15)) of phenyl, R ₁Be bipyridyl, R ₂Be the pyrene compound (Fig. 2 (c) (4-16)) of xenyl, R ₁Be xenyl, R ₂Be the pyrene compound (Fig. 2 (c) (4-17)) of bipyridyl, R ₁Be phenyl, R ₂Be pyrene compound (Fig. 2 (c) (4-18)) of pyridine ring (pyridyl) etc.

In addition, as other examples of above-mentioned asymmetric pyrene compound, can enumerate R ₂A part have the compound shown in the following formula (2) that can have substituent pyrene ring.

[changing 6]

In above-mentioned formula (2), R ₁Identical with above-mentioned formula (1).In addition, Y represents the connection base of divalence.As this Y, specifically, can use as above-mentioned R ₂The group of the divalence of illustrated group (but not comprising that hydrogen atom, halogen atom etc. can not become the group of divalent group).Wherein, group preferably from selecting from the divalent group of heteroaromatic (heteroaryl), aromatic hydrocarbons ring (aryl), alkane, alkene and alkynes.This divalent group can have substituting group.Moreover in the present invention, heteroaromatic and aromatic hydrocarbons ring mean the ring that comprises Ppolynuclear aromatic.

In addition, as the concrete example of above-mentioned Y, can enumerate divalent group (phenylene, biphenylene, inferior terphenyl etc.), from the divalent group of naphthalene nucleus, from the divalent group of anthracene nucleus, from the divalent group of fluorenes ring, from the divalent group of pyrazine ring, from the divalent group of pyridine ring, from the divalent group of carbazole ring, from the divalent group of thiphene ring, from the divalent group of thiazole ring, from the divalent group of acetylene from phenyl ring.All can have substituting group.In addition, these rings can be the groups (for example can enumerate biphenylene etc.) that connects more than 2.

As the example of the asymmetric pyrene compound shown in such formula (2), can enumerate R ₁For phenyl, Y are the pyrene compound (Fig. 3 (a) (5-1)) of the phenyl of divalence, R ₁For phenyl, Y are the pyrene compound (Fig. 3 (a) (5-2)) of the pyrazine ring of divalence, R ₁For phenyl, Y are the pyrene compound (Fig. 3 (a) (5-3)) of the pyridine ring (pyridyl) of divalence, R ₁For methyl, Y are the pyrene compound (Fig. 3 (a) (5-4)) of the phenyl of divalence, R ₁For methyl, Y are the pyrene compound (Fig. 3 (a) (5-5)) that is substituted with the divalence phenyl of 2 dodecyl ethers, R ₁For tolyl, Y are the pyrene compound (Fig. 3 (b) (5-6)) of the ethynyl of divalence, R ₁For methyl, Y are the pyrene compound (Fig. 3 (b) (5-7)) of the bipyridyl of divalence, R ₁For methyl, Y are the pyrene compound (Fig. 3 (b) (5-8)) of the xenyl of divalence, R ₁For pyridine ring (pyridyl), Y are the pyrene compound (Fig. 3 (c) (5-9)) of the substituted biphenyl base of divalence, R ₁For phenyl, Y are the pyrene compound (Fig. 3 (c) (5-10)) of the xenyl of divalence, R ₁It for phenyl, Y pyrene compound (Fig. 3 (c) (5-11)) of the bipyridyl of divalence etc.

In addition, as other examples of the asymmetric pyrene that uses among the present invention, can enumerate Fig. 4 (a) (6-1)～(6-11) shown in (b) etc.

Above-mentioned asymmetric pyrene compound can adopt following reaction formula＜1〉the method manufacturing.

[changing 7]

Wherein, in reaction formula＜1〉in, R ₁, R ₂Identical with the situation of above-mentioned (1).In addition, X represents the halogen atom chosen from chlorine atom, bromine atoms and iodine atom.

That is, make halogenide and use R ₂The 1-replacement pyrene (1-1) that replaces 1 reacts, the synthetic R that uses ₂Replace 1, the 1-that replaces 3,6 and 8 with above-mentioned halogen and replace-3,6,8-three halo pyrenes (1-2), then, by making boronic acid compounds or being selected from any reaction of the organometallic compound of tin compound, organic zinc compound, organo-magnesium compound, can make asymmetric pyrene compound (1).

Above-mentioned asymmetric pyrene compound uses as the constituent of the luminescent layer of the luminescent layer of light-emitting transistor device, organic EL, hole transmission layer, electron transfer layer etc.More particularly, above-mentioned asymmetric pyrene compound uses as the main composition composition of the luminescent layer of the luminescent layer of light-emitting transistor device, organic EL, in addition, use as the hole transmission layer of organic EL, the main composition composition or the dopant material of electron transfer layer.Moreover so-called luminescent layer is meant and utilizes the compound of hole and electronics and produce luminous layer.In addition, will be explained below for hole transmission layer, electron transfer layer.

So-called above-mentioned main composition composition is meant the composition that can bring into play the effects such as color of luminosity, luminous efficiency, carrier mobility, distinctive light as the center.In addition, so-called above-mentioned dopant material is be added on secondary constituent in the main composition composition a kind of, is the compound that adds for the performance that improves the main composition composition.Moreover, when using above-mentioned asymmetric pyrene compound as the main composition composition, in order further to improve above-mentioned effect, can be as required also with secondary constituents such as other organic fluorescents, dopant materials.

Other organic fluorescents as such are not particularly limited, for example can enumerate anthracene, phenanthrene, Bi, perylene,

Fused rings derivative such as (chrysene), the metal complex of quinolinol derivatives such as three (oxine) aluminium, benzoxazole derivative, stilbene derivatives, benzothiazole derivant, thiadiazoles derivative, thiophene derivant, the tetraphenylbutadiene derivative, cyclopentadiene derivant oxadiazole derivative, the bisstyryl anthracene derivant, double styrene radical derivatives such as diphenylethyllene benzene derivative, made up the metal complex oxadiazole derivant metal complex compound of the part different with quinolinol derivative, the benzothiazole derivant metal complex, coumarin derivatives, Pyrrolopyridine derivatives, Pai Linong (ベ リ ノ Application) derivative, thiadiazoles and pyridine derivate etc.In addition, as the example of other organic fluorescents of polymer class, can enumerate polyphenylene vinylene derivative, poly(p-phenylene) radical derivative, polythiofuran derivative etc.

In addition, as above-mentioned dopant material, be not particularly limited, for example can enumerate phenanthrene, anthracene, pyrene, tetracene, pentacene perylene, the naphtho-pyrene, dibenzo pyrene, fused rings derivative benzoxazole derivatives such as rubrene, benzothiazole derivant, benzimidizole derivatives, benzotriazole derivatives oxazole derivative oxadiazole derivative, thiazole derivative, imdazole derivatives, thiadiazoles derivative, triazole derivative, pyrazoline derivative, stilbene derivatives, thiophene derivant, the tetraphenylbutadiene derivative, cyclopentadiene derivant, the bisstyryl anthracene derivant, double styrene radical derivatives such as diphenylethyllene benzene derivative, diaza benzo two indene derivatives, furan derivatives, benzofuran derivative, the phenyl isobenzofuran, two  base isobenzofuran, two (2-aminomethyl phenyl) isobenzofuran, two (2-trifluoromethyl) isobenzofuran, isobenzofuran derivatives such as phenyl isobenzofuran, the diphenylene-oxide derivative, 7-dialkyl amido coumarin derivatives, 7-piperidino-(1-position only) coumarin derivatives, the umbelliferone derivative, the ayapanin derivative, 7-acetoxyl group coumarin derivatives, 3-benzothiazolyl coumarin derivatives, 3-benzimidazolyl-coumarin derivatives, coumarin derivativess such as 3-benzoxazolyl coumarin derivatives, dicyano methylene radical pyran derivate, the dicyano sulfonium methylide is for pyran derivate, the polymethine derivative, the cyanines derivative, oxo benzanthrene derivative, the xanthene derivative, the rhodamine derivative, fluorescein derivative, pyran derivate, quinolinol derivative, acridine derivatives, two (styryl) benzene derivative oxazine derivative, the oxidation crystalline 1,2-phenylene derivatives, quinoline a word used for translation ketone derivatives, quinazoline derivant, pyrene and pyridine derivate, the furo pyridine derivate, 1,2,5-thiadiazoles and pyrene derivatives, Pai Linong (ベ リ ノ Application) derivative, Pyrrolopyrrole derivatives, Si Kualin (squarylium) derivative, the violanthrone derivative, the azophenlyene derivative, acridone derivatives, diaza flavin derivatives etc.

Below, the light-emitting transistor device that has used above-mentioned pyrene compound is described.

As above-mentioned light-emitting transistor device, can enumerate the element of basic structure with electric field effect transistor npn npn (FET) shown in Figure 5.

This light-emitting transistor device 10 is by hole and the electronics that can carry as current carrier, produce by hole and electronics compound luminous, with above-mentioned pyrene compound be the main composition composition luminescent layer 1, to the hole injecting electrode of this luminescent layer 1 injected hole be so-called source electrode 2, electron injection electrode from electronics to above-mentioned luminescent layer that inject be so-called drain electrode 3 and relative with above-mentioned source electrode 2 and drain electrode 3 and control current carrier distribution in the above-mentioned luminescent layer 1 by N ⁺ The gate electrode 4 that silicon substrate constitutes constitutes.Moreover gate electrode 4 can be made of conductive layer, and this conductive layer is made of the impurity diffusion layer that the skin section at silicon substrate forms.

Specifically, as shown in Figure 5, the insulating film 5 that is made of silicon oxide etc. is set on gate electrode 4, devices spaced apart is provided with active electrode 2 and drain electrode 3 thereon.In addition, be provided with luminescent layer 1, make it cover this source electrode 2 and drain electrode 3, and enter between two electrodes.

In order to make the function of said elements performance lighting transistor, preferred constitute the organic fluorescent of above-mentioned luminescent layer 1, particularly as poor, the carrier mobility or the luminous efficiency of the HOMO energy level of the pyrene compound of main composition composition and lumo energy, satisfy the scope of regulation.Moreover, when using above-mentioned pyrene compound,, can further improve each function by adding secondary constituent such as above-mentioned doping agent with above-mentioned each feature.

At first, with regard to the difference of above-mentioned HOMO energy level and lumo energy, more little then movement of electrons becomes easier, is easy to generate luminous and semiconductive (that is, to the electronics of a direction or the conduction in hole), and is therefore preferred.Specifically, below the preferred 5eV, more preferably below the 3eV, below the further preferred 2.7eV.Moreover this difference is more little preferred more, therefore the following 0eV that is limited to of this difference.

In addition, the big more then semiconductive of above-mentioned carrier mobility is high more, and is therefore preferred.Specifically, preferred 1.0 * 10 ^-5Cm ²More than/the Vs, more preferably 4.0 * 10 ^-5Cm ²More than/the Vs, further preferred 1.0 * 10 ^-4Cm ²More than/the Vs.Moreover, the upper limit of carrier mobility is not particularly limited, if be 1cm ²Then enough about/Vs.

Above-mentioned luminous efficiency is meant the ratio by the light that photon or electronics is entered produce, will be with respect to the luminous energy that injects, the ratio of the luminous energy of emitting is called PL luminous efficiency (or PL quantum yield), will be with respect to the number of injected electrons, the ratio of the number of the photon of emitting is called EL luminous efficiency (or EL quantum yield).

Inject, electrons excited compound and luminous by with the hole, but should be compound may not be with 100% probability generation.Therefore, to the organic compound that constitutes above-mentioned luminescent layer 1 relatively the time,, can compare the synergy of luminous energy discharging amount with respect to the ratio of the ratio of the luminous energy that injects and electronics and hole-recombination by contrast EL luminous efficiency.By contrast PL luminous efficiency, can compare the ratio of luminous energy discharging amount with respect to the luminous energy that injects, therefore, also can compare the compound ratio in electronics and hole by combination contrast PL luminous efficiency and EL luminous efficiency.

Above-mentioned PL luminous efficiency, luminous degree is big more preferred more, and is preferred more than 20%, more preferably more than 30.Moreover, be limited to 100% on the PL luminous efficiency.

In addition, above-mentioned EL luminous efficiency, luminous degree is big more preferred more, and preferred 1 * 10 ^-3More than the %, more preferably 5 * 10 ^-3More than the %.Moreover, be limited to 100% on the EL luminous efficiency.

As the feature of above-mentioned light-emitting transistor device 10, except above-mentioned, can enumerate the light wavelength of sending.This wavelength is in the scope of visible light, but has different wavelength because of the difference of the kind of the organic fluorescent, particularly above-mentioned pyrene compound that use.In addition, have the organic fluorescent of different wave length, can manifest various looks by combination.Therefore, the light wavelength of sending becomes wavelength performance feature itself.

In addition, above-mentioned light-emitting transistor device 10 owing to being feature with luminous, therefore preferably has luminosity to a certain degree.The corresponding luminous quantity of bright degree of the object of feeling when this luminosity is meant and sees object with the people.This luminosity, big more then preferred more in the assay method that adopts photon counter, preferred 1 * 10 ⁴More than the CPS (count per sec), more preferably 1 * 10 ⁵More than the CPS, further preferred 1 * 10 ⁶More than the CPS.

The organic fluorescents that above-mentioned luminescent layer 1 constitutes by evaporation etc. (have when multiple for evaporation) altogether form.The thickness of this luminescent layer is at least about 70nm and gets final product.

Above-mentioned source electrode 2 and drain electrode 3 are the electrodes that are used for to above-mentioned luminescent layer 1 injected hole and electronics, are formed by gold (Au), magnesium-au-alloy (MgAu) etc.Leave slight gap such as 0.4～50 μ m between the two and form relatively.Specifically, for example, as shown in Figure 6, source electrode 2 and drain electrode 3 have the broach shape 2a of portion, the 3a that is made of a plurality of broach respectively and form, by separate predetermined distance dispose alternately formation source electrode 2 the broach shape 2a of portion broach and constitute the broach of the broach shape 3a of portion of drain electrode 3, can bring into play function more expeditiously as light-emitting transistor device 10.

The source electrode 2 of this moment and the interval of drain electrode 3 are promptly below the preferred 50 μ m in the interval of 2a of broach shape portion and the broach shape 3a of portion, more preferably below the 3 μ m, further below the preferred 1 μ m.If surpass 50 μ m, can not bring into play enough semiconductives.

Above-mentioned light-emitting transistor device 10, by above-mentioned source electrode 2 and drain electrode 3 are applied voltage, portion moves hole and electronics within it, and is compound by making both in luminescent layer 1, can produce luminous.At this moment, the hole of moving between two electrodes by luminescent layer 1 and the amount of electronics depend on the voltage that puts on gate electrode 4.Therefore, the voltage that puts on gate electrode 4 by control changes with it, can control the conducting state between above-mentioned source electrode 2 and the drain electrode 3.Moreover this light-emitting transistor device 10 is owing to carry out the driving of P type, so apply with respect to the voltage of source electrode 2 for bearing to drain electrode 3, in addition, applying with respect to source electrode 2 to gate electrode 4 is negative voltage.

Specifically, be negative voltage by applying to gate electrode 4 with respect to source electrode 2, the hole in the luminescent layer 1 attracted to gate electrode 4 sides, becomes the high state of density in hole of the near surface of insulating film 5.If make the voltage between source electrode 2 and the drain electrode 3 suitable, utilize the size of the control voltage put on gate electrode 4, become the hole is injected into luminescent layer 1, electronics is injected into the state of luminescent layer 1 by drain electrode 3 by source electrode 2.That is, source electrode 2 is as hole injecting electrode performance function, and drain electrode 3 is as electron injection electrode performance function.Thus, in luminescent layer 1, produce the compound of hole and electronics, produce accompany with it luminous.This luminance changes by making the control voltage that puts on gate electrode 4, can ON/OFF, or change luminous intensity.

Produce the compound theory of above-mentioned hole and electronics, can as described belowly describe.By applying to gate electrode 4 with respect to source electrode 2 to negative voltage, shown in Fig. 7 (a), in luminescent layer 1, form the raceway groove 11 in hole at the near interface of insulating film 5, its pinch off (pinch off) point 12 is near drain electrode 3.In addition, between pinch-off point 12 and drain electrode 3 and n, form high electric field, shown in Fig. 7 (b), can be with crooked significantly.Like this, the electron production in the drain electrode 3 breaks through FN (Fu Lenuoerdehaimu) channelling effect of the current potential shielding between drain electrode 3 and the luminescent layer 1, is injected in the luminescent layer 1, with hole-recombination.

In addition, hole and electronics compound except the above-mentioned theory of utilizing the FN channelling effect, also can utilize following theory to describe.That is, shown in Fig. 7 (c), the electronics that the organic fluorescent in the luminescent layer 1 is in the HOMO energy level utilizes high electric field to be excited to lumo energy, the hole-recombination in electronics that this is excited and the luminescent layer 1.Meanwhile, by drain electrode 3 to replenishing because of the HOMO energy level that is energized into lumo energy and becomes the room injects electronics.

Above-mentioned light-emitting transistor device 10, a plurality of by the arrangement of bidimensional ground on substrate 20, can constitute display unit 21.The schematic circuit of this display unit 21 is shown in Fig. 8.Promptly, this display unit 21, with above-mentioned light-emitting transistor device 10 be configured in respectively arranged pixel P11, P12 ... P21, P22 ... in, optionally make the light-emitting transistor device 10 of these pixels luminous, in addition, the luminous intensity (brightness) of the light-emitting transistor device 10 by controlling each pixel also can show by bidimensional.Substrate 20 for example, can be to make gate electrode 4 incorporate silicon substrates.That is, gate electrode 4 can be made of the conductive layer that the impurity diffusion layer that forms with pattern on the silicon substrate surface is formed.In addition, as substrate 20, can use glass substrate.

Each light-emitting transistor device 10 gives bias voltage Vd (＜0) because the P type drives to its drain electrode 3 (D), and its source electrode 2 (S) is earthing potential (=0).Be used to select the selection transistor T s of each pixel to keep the electrical condenser C of data to be connected with gate electrode 4 (G) in parallel with being used to.

The pixel P11 of line direction proper alignment, P12 ... P21, P22 ... selection transistor T s gate electrode every row and common sweep trace LS1, LS2 ... connect respectively.In addition, the pixel P11 of column direction proper alignment, P21 ... P12, P22 ... selection transistor T s in, at the opposition side of light-emitting transistor device 10, every row connecting respectively common data line LD1, LD2 ...

By the scan line drive circuit 61 of controlled device 63 control to sweep trace LS1, LS2 ... be used for selecting successively circularly (selections in the lump of a plurality of pixels in the row) each row pixel P11, P12 ... P21, P22 ... scanning drive signal.That is, scan line drive circuit 22 as selecting row successively, makes the selection transistor T s conducting in the lump of selecting a plurality of pixels of going with each row, like this, can produce the scanning drive signal that the selection transistor T s of a plurality of pixels that are used to make non-selection row blocks in the lump.

On the other hand, to data line LD1, LD2 ... input is from the signal of data line drive circuit 23.Import the control signal corresponding by controller 24 to this data line drive circuit 23 with view data.The timing of data line drive circuit 23 makes a plurality of pixels of each row select in the lump by scan line drive circuit 21, will the led control signal corresponding supply with side by side with the luminous grey scale of capable each pixel of this selection data line LD1, LD2 ...

Thus, in each pixel of selecting row, give led control signal by selecting transistor T s to gate electrode 4 (G), so the light-emitting transistor device 10 of this pixel carries out luminous (perhaps turning off the light) in the grey scale corresponding with led control signal.Led control signal is maintained in electrical condenser C, therefore moves to behind another row at the selection row that utilizes scan line drive circuit 61, and the current potential of gate electrode G also is maintained, and the luminance of light-emitting transistor device 10 is kept.Can carry out bidimensional like this shows.

Below, the organic EL that has used above-mentioned pyrene compound is described.

Above-mentioned organic EL be have can carry hole and electronics and by hole and electronics compound produce luminous, be the luminescent layer of main composition composition with above-mentioned pyrene compound, to the hole injecting electrode of this luminescent layer injected hole with inject the element of the electron injection electrode of electronics to above-mentioned luminescent layer.Specifically, can enumerate element shown in Figure 9.This organic EL 30 is the duplexers that stack gradually hole injecting electrode layer 32, hole transmission layer 33, luminescent layer 34, electron transfer layer 35, electron injection electrode layer 36 on substrate 31, utilizes direct supply 37 to apply voltage between hole injecting electrode layer 32 and electron injection electrode layer 36.

Aforesaid substrate 31 supports organic EL 30.With regard to this substrate 31, when the light that produces passes through to arrive the outside, can use for example such transparency carrier of glass substrate in making luminescent layer 34.

Above-mentioned hole injecting electrode layer 32 is layers of accepting the positive voltage that applied by direct supply 37.As material, then be not particularly limited as long as have electroconductibility, when making the light that produces in luminescent layer 34 be fetched into the outside by substrate 31, this hole injecting electrode layer 32 also must have the transparency.As such hole injecting electrode layer, can use indium tin oxide (ITO) etc.

On the other hand, above-mentioned electron injection electrode layer 36 is layers of accepting the negative voltage that applied by direct supply 37.As material, then be not particularly limited as long as have electroconductibility, can use for example aluminium etc.Moreover the light that produces in making luminescent layer 34 as this electron injection electrode layer 36, preferably uses ITO etc. to have the material of the transparency when electron injection electrode layer 36 sides are fetched into the outside.

Above-mentioned hole transmission layer 33 is the layers that are used for the cavity conveying that hole injecting electrode layer 32 produces is arrived luminescent layer 34, and in addition, above-mentioned electron transfer layer 35 is the layers that are used for the electron transport that electron injection electrode layer 36 produces is arrived luminescent layer 34.Can be directly that above-mentioned hole injecting electrode layer 32 or electron injection electrode layer 36 is stacked with above-mentioned luminescent layer 34, but from both connectivity problems, both connectivities of hole injecting electrode layer 32 or electron injection electrode layer 36 and luminescent layer 34 are good, and the good layer of the transport property of hole or electronics is set to hole transmission layer 33 or electron transfer layer 35.Therefore, by the combination of hole injecting electrode layer 32 or electron injection electrode layer 36, can there be hole transmission layer 33 or electron transfer layer 35 with the material of luminescent layer 34.

As the material that constitutes above-mentioned hole transmission layer 33, can enumerate N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines (TPD) etc.In addition, as the material that constitutes above-mentioned electron transfer layer 35, can enumerate 3-(4-xenyl)-4-phenyl-5-(4-tert-butyl-phenyl)-1,2,4-triazole (TAZ) etc.

Above-mentioned luminescent layer 34 is same with the luminescent layer 10 of above-mentioned light-emitting transistor device, is to use the layer of above-mentioned pyrene compound as the main composition composition, as required also with above-mentioned secondary constituent.

Above-mentioned hole transmission layer 33 or electron transfer layer 35, as mentioned above, select the transport property of hole or electronics and the good material of connectivity of hole injecting electrode 32 or electron injection electrode 36 and luminescent layer 34, but ought satisfy above-mentioned two characteristics simultaneously at need, can between hole injecting electrode layer 32 and hole transmission layer 33, hole injection layer be set, between electron injection electrode layer 36 and electron transfer layer 35, electron injecting layer be set.Like this, as above-mentioned hole transmission layer 33 or electron transfer layer 35, owing to the transport property that can more pay attention to hole, electronics is selected material, simultaneously as hole injection layer or electron injecting layer, can more pay attention to connectivity and select material, so the range of choice of material broadens.

In order to make the function of said elements performance as organic EL, the preferred main composition composition that uses above-mentioned pyrene compound as the organic fluorescent that constitutes above-mentioned luminescent layer 34, perhaps use Alq3 (three (oxine)) etc. as the main composition composition, use above-mentioned pyrene compound as doping agent.

With regard to above-mentioned luminescent layer 34, poor, the luminosity of preferred HOMO energy level and lumo energy, PL luminous efficiency and external light emission efficiency satisfy the scope of regulation.Moreover, when having used above-mentioned pyrene compound,, can further improve each function by adding secondary constituents such as above-mentioned doping agent with above-mentioned each feature.

Poor for above-mentioned HOMO energy level and lumo energy, identical with the situation of above-mentioned light-emitting transistor device.

The corresponding luminous quantity of bright degree of the object of feeling when above-mentioned luminosity is meant and sees object with the people, big more preferred more.This luminosity can use the photic diode of Si to measure.If adopt this method, because of applying the difference of electric current (or voltage), the luminosity (cd/m of generation ²) difference.For example, apply 10mA/cm ²Electric current (voltage of 6.0V) time, preferred 50cd/m ²More than, more preferably 75cd/m ²More than, further preferred 100cd/m ²More than.

In addition, apply 100mA/cm ²Electric current (voltage of 8.0V) time, preferred 600cd/m ²More than, more preferably 1000cd/m ²More than, further preferred 2000cd/m ²More than.

Above-mentioned PL luminous efficiency as mentioned above, the said external luminous efficiency is meant externally the luminous efficiency of observation.This external light emission efficiency in normally used fluorochrome, it is said to be limited to 5%.

For organic EL, need luminous degree big especially, preferred more than 80% for the PL luminous efficiency, more preferably more than 85%.Moreover, be limited to 100% on the PL luminous efficiency.In addition, preferred more than 1% for the said external luminous efficiency, more preferably more than 1.4%, further preferred more than 2%.Moreover the upper limit of EL luminous efficiency is stated to be 5%.

As the feature of above-mentioned organic EL 30, except above-mentioned, can enumerate the light wavelength of sending.This wavelength is in the scope of visible light, but has different wavelength because of the difference of the kind of the organic fluorescent, the particularly above-mentioned pyrene compound that use.In addition, have the organic fluorescent of different wave length, can manifest shades of colour by combination.Therefore, the light wavelength of sending becomes wavelength performance feature itself.

Above-mentioned organic EL 30 can be by forming hole injecting electrode layer 32 on substrate 31, thereon each layer of vacuum evaporation and forming successively.The thickness of the luminescent layer 34 of the organic EL 30 that obtains can be for about 10～100nm, and the thickness of above-mentioned hole transmission layer 33 or electron transfer layer 35 can be for about 10～50nm.In addition, the thickness of above-mentioned hole injecting electrode layer 32 or electron injection electrode layer 36 can be for about 5～30nm.

The effect of above-mentioned organic EL 30 is as described below.At first, between hole injecting electrode layer 32 and electron injection electrode layer 36, apply voltage by direct supply 37.The hole that produces in hole injecting electrode layer 32 is sent to luminescent layer 34 by hole transmission layer 33.In addition, the electronics that produces in the electron injection electrode layer 36 is sent to luminescent layer 34 by electron transfer layer 35.Then, in luminescent layer 34, hole and electron recombination and produce luminous.

Above-mentioned organic EL 30, a plurality of by two-dimensional arrangements on substrate 40, can constitute display unit.As the example of this display unit 41, the example of the schematic circuit of passive display unit 41 has been shown among Figure 10.

It is on substrate 40 with sweep trace (LS1 ', LS2 ' ...) and data line (LD1 ', LD2 ' ...) be arranged as reticulation, at its each intersection point configuration organic EL 30.Specifically, an end of the organic EL (1,1) of the 1st row 1 row is connected with the sweep trace of the 1st row, and the other end is arranged on the data line of the 1st row.In addition, and the organic EL of the capable i of j row (j, the sweep trace that end i) and j are capable is connected, and the other end is arranged on the data line that i is listed as.

In addition, (j i), when data line i being set in noble potential and sweep trace j is set in low potential, flows through electric current and luminous with regard to organic EL.During regulating that this electric current flows through, can control luminous grey scale.For example, select and make luminous capable corresponding scanning line, be set in low potential (for example 0V), will be set in noble potential with not making luminous capable corresponding scanning line with scan line drive circuit 42.In addition, by data line drive circuit 43, will be supplied to data line by pulse modulated data signal data as noble potential during regulation according to luminous light and shade grade.Like this, can make the organic EL of selection luminous, can display image.

In addition, in scan line drive circuit 42, switch the sweep trace of selecting by order, the EL element of selection is luminous in turn, therefore can change image in proper order.

Embodiment

Below enumerate embodiment and comparative example, the present invention further is specifically described.At first, the manufacture method to pyrene compound describes.

(Production Example 1) [manufacturing of triphenyl dodecyl pyrene]

[raw material is synthetic]

[changing 8]

According to above-mentioned reaction formula＜2 〉, synthesis material at first.That is, make 200ml band ramose flask have dropping funnel, low-reading thermometer, cooling tube, decompression is carried out the nitrogen displacement after the drying down.Pack into 1-bromine pyrene (Tokyo changes into (strain) system, reagent) 7.0g, dry THF 70ml are stirring below-70 ℃ in dry ice-propanone is bathed.With the hexane solution that dripped the 2.6M butyllithium in 20 minutes (Northeast chemistry (strain) system, reagent) 9.8ml, stirred 1 hour down at 70 ℃.After dripping dodecyl iodine (Aldrich society system, reagent) 6.4ml, stirred 1 hour down, remove cooling bath, with being warmed up to room temperature in 1 hour at 60 ℃.

With vaporizer reaction solution is concentrated, in residue, add chloroform, pure water carries out separatory, water layer is extracted with chloroform.Use the anhydrous magnesium sulfate drying organic layer, concentrate.

In reclaiming residue, add hexane, reclaim precipitation, obtain dodecyl pyrene 5.9g with yield 64% with suction strainer.

Then, the dodecyl pyrene 4.4g that packs into, carry out nitrogen displacement after, the DMF that packs into (pure medicine (strain) system, reagent) 30ml carries out heated and stirred under 70 ℃ and becomes homogeneous solution in oil bath.Make N-bromine succinimide (NBS, Tokyo change into (strain) system, reagent) 5.3g be dissolved in above-mentioned DMF20ml, dripped with 20 minutes, stirred 6 hours down for 70 ℃ in interior temperature by dropping funnel.Put cold after, with the precipitation that suction strainer reclaim to generate, wash, thereby after high polar component and DMF removed, under reduced pressure carry out drying with methyl alcohol, obtain the solid (yield 71%) of 4.5g.By FAB-MS as can be known, obtain m/z=606, determine that this becomes and be 1-dodecyl-3,6,8-tribromo pyrene.

[manufacturing of triphenyl dodecyl pyrene]

[changing 9]

According to above-mentioned reaction formula＜3 〉, make triphenyl dodecyl pyrene (Fig. 2 (a) is (4-5)).Promptly, the 1-dodecyl-3 of in having the 500ml four-hole boiling flask of reflux cooling pipe, three-way tap and thermometer, packing into above-mentioned, 6,8-tribromo pyrene 2.5g, phenyl-boron dihydroxide (Aldrich society system, reagent) 3.3g, cesium carbonate 17.5g, toluene 180ml, ethanol 80ml, pure water 40ml.After carrying out 5 decompressions and nitrogen displacement, carry out the nitrogen bubbling as degassing operation to solution inside.Then, above-mentioned four (triphenyl phosphine) palladium (O) 0.3g that packs into carried out heated and stirred 8 hours under 80 ℃ in oil bath.

Separate organic layer,,, carry out drying, concentrate with vaporizer with anhydrous magnesium sulfate with pure water 300ml washing and recycling organic layer with chloroform 50ml aqueous layer extracted.In resistates, add hexane, reclaim precipitation with suction strainer.Remove with the palladium that column chromatography (silica gel, chloroform) will be mixed in wherein, will reclaim by concentrating the solid suspension washing of separating out with methyl alcohol.Make with extra care reclaiming solid with GPC, obtain the yellow crystal of 530mg.Be defined as 1-dodecyl-3,6 by 1H-NMR, 8-triphenyl pyrene (yield 21%).

· ¹H NMR(CDCl ₃)δ8.26(s)1H、δ8.25(s)1H、δ8.08(s)1H、δ8.08(s)1H、δ7.97(s)1H、δ7.87(s)1H、δ7.75-7.41(m)15H、δ3.34(t)2H、δ1.87(m)2H、δ1.50(m)2H、δ1.45-1.15(m)16H、δ0.86(t)3H

(Production Example 2) [manufacturings of three (4-xenyl)-dodecyl pyrenes]

[changing 10]

According to above-mentioned reaction formula＜4 〉, make three (4-xenyl) dodecyl pyrene (Fig. 2 (a) is (4-7)).Promptly, the three-way tap, the thermometer that in having the 500ml there-necked flask of reflux cooling pipe, three-way tap and thermometer, the backflow cooling tube is installed, are connected with the nitrogen pipeline, to the 1-dodecyl-3 of wherein packing into above-mentioned, 6,8-tribromo pyrene 4.00g, 4-xenyl boric acid (Aldrich society system, reagent) 6.54g, yellow soda ash (Northeast chemistry (strain) system, reagent) 7.00g, toluene (pure chemistry (strain) system, reagent) 150ml, ethanol (pure chemistry (strain) system, reagent) 70ml, pure water 30ml at room temperature stir.Carry out 5 decompression degassings, nitrogen displacement repeatedly, carry out the nitrogen displacement after, in reaction solution, carry out nitrogen bubbling 30 minutes.Then, add above-mentioned four (triphenyl phosphine) palladium (0) 0.48g, after in oil bath, refluxing 10 hours under 80 ℃, under nitrogen atmosphere, leave standstill whole night.

Reclaim because of putting cold solid of separating out with suction strainer, carry out recrystallize and obtain yellow solid by toluene.By ¹H NMR determines that this yellow solid is a target compound 1,3,6-three (4-xenyl)-8-dodecyl pyrene (yield 64%).

· ¹H NMR(CDCl ₃)δ8.34(s)1H、δ8.33(s)1H、δ8.21(s)2H、δ8.08(s)1H、δ7.94(s)1H、δ7.87-7.67(m)18H、δ7.58-7.47(m)6H、δ7.45-7.35(m)3H、δ3.38(t)2H、δ1.92(m)2H、δ1.55(m)2H、δ1.47-1.17(m)18H、δ0.86(t)3H

(Production Example 3) [manufacturing of three (2-naphthyl) dodecyl pyrene]

[changing 11]

The 1-dodecyl-3 of in having the 500ml four-hole boiling flask of reflux cooling pipe, three-way tap and thermometer, packing into, 6,8-tribromo pyrene 3.0g, 2-naphthyl boric acid (Aldrich society system, reagent) 4.4g, yellow soda ash (Northeast chemistry (strain) system, reagent) 5.3g, toluene (pure chemistry (strain) system, reagent) 120ml, ethanol (pure chemistry (strain) system, reagent) 60ml, pure water 30ml.After nitrogen displacement in the system, four (triphenyl phosphine) palladium (0) of packing into (Tokyo changes into (strain) system, reagent) 0.4g carried out heated and stirred 9 hours under 80 ℃ in oil bath.

Separate organic layer, use CHCl ₃50ml aqueous layer extracted 2 times.With pure water 200ml washing and recycling organic layer, carry out dewatering and filtering with anhydrous magnesium sulfate after, concentrate with vaporizer.With column chromatography (SiO ₂, CHCl ₃) the high polar component in the gained solid removed after, with GPC the solid that concentrates the distillate gained is made with extra care, obtain the yellow solid of 2.1g.

By the quality in the ionization of adopting FAB, confirm that it is 748, is M-1 with respect to target compound molecular weight 749.In addition, be defined as 1-dodecyl-3,6,8-three (2-naphthyl) pyrene by 1H NMR.

· ¹H NMR(270MHz，CDCl ₃)8.32ppm(s，2H)，8.20-8.05(m，6H)，8.04-7.76(m，13H)，7.61-7.49(m，6H)，3.38(t，2H，J＝7.56)，1.98-1.85(m，2H)，1.58-1.45(m，2H)，1.44-1.18(m，16H)，0.85(t，3H，J＝6.75))

·Mass(MALDI-TOF)：Obs.m/z＝748(M ⁺-1)、593，580，465；Calc.for C58H52，749.05.

(Production Example 4) [manufacturing of three (3-pyridyl) dodecyl pyrene]

[changing 12]

The 1-dodecyl-3 of in having the 500ml four-hole boiling flask of reflux cooling pipe, three-way tap and thermometer, packing into, 6,8-tribromo pyrene 3.3g, 2-pyridyl boric acid pinacol ester (Aldrich society system, reagent) 5.7g, yellow soda ash (Northeast chemistry (strain) system, reagent) 5.7g, toluene (pure chemistry (strain) system, reagent) 120ml, ethanol (pure chemistry (strain) system, reagent) 60ml, pure water 10ml.After the nitrogen displacement, four (triphenyl phosphine) palladium (0) of packing into (Tokyo changes into (strain) system, reagent) 0.3g carried out heated and stirred 7 hours under 80 ℃ in oil bath.

Separate organic layer, use CHCl ₃The 50ml aqueous layer extracted.With pure water 100ml washing and recycling organic layer, carry out dewatering and filtering with anhydrous magnesium sulfate after, concentrate with vaporizer.In the residue that obtains, add hexane and reflux, remaining Pd, other inorganic salt are removed with heat filtering.Reclaim the solid of separating out with suction strainer, with hexane this solid is carried out recrystallization once more.With column chromatography (SiO ₂, CHCl ₃-acetone) will reclaim the solid desalination after, make with extra care with GPC, obtain the yellow solid of 1.1g.By FAB mass analysis (M+1:602), ¹H NMR is defined as 1-dodecyl-3,6,8-three (3-pyridyl) pyrene.

· ¹H NMR(270MHz，CDCl ₃)8.95-8.88(m，3H)，8.79-8.71(m，3H)，8.37(d，1H，J＝9.72)，8.19(d，1H，J＝9.45)，8.10-7.88(m，7H)，7.57-7.47(m，3H)，3.38(t，3H，J＝7.56)，1.95-1.82(m，2H)，1.57-1.45(m，2H)，1.44-1.18(m，16H)，0.86(t，3H，J＝6.48)

·Mass(MALDI-TOF)：Obs.m/z＝602(M ⁺+1)，446；Calc.for C43H43N3，601.83.

(Production Example 5) [manufacturings of three naphthyl pyrenes]

[3,6, the manufacturing of 8-tribromo pyrene]

[changing 13]

In the DMF80mL solution of pyrene (Aldrich society system, reagent) 5.0g, slowly drip the DMF100mL solution of NBS (Tokyo changes into (strain) system, reagent) 26.8g, temperature of reaction is brought up to 130 ℃ then, carry out heated and stirred.

After with suction strainer the solid of separating out being reclaimed, use CHCl ₃Wash, carry out recrystallization, obtain needle crystal 9.7g by orthodichlorobenzene.By the FAB mass analysis as can be known this needle crystal be molecular weight 435, be defined as 3,6,8-tribromo pyrene.

[manufacturings of three naphthyl pyrenes]

[changing 14]

3,6, add toluene (pure chemistry (strain) system, reagent) 200ml, ethanol (pure chemistry (strain) system, reagent) 25ml, pure water 25ml among 8-tribromo pyrene 4.3g, 2-naphthyl boric acid (Aldrich society system, reagent) 8.6g, cesium carbonate (Northeast chemistry (strain) system, the reagent) 6.0g, after carrying out the nitrogen displacement, pack into four (triphenyl phosphine) palladium (0) (Tokyo change into (strain) system, reagent) 1.0g, carried out reflux 9 hours.

After solvent heated up in a steamer, add entry 100mL, use CH ₂Cl ₂50ml extraction 2 times.After the adding anhydrous sodium sulphate is carried out dewatering and filtering in the dichloromethane solution that obtains, concentrate with vaporizer.With toluene the solid that obtains is carried out recrystallization.Make with extra care with GPC again, thereby obtain the 1g yellow solid.

·Mass(MALDI-TOF)：Obs.m/z＝580(M ⁺)；Calc.for C46H28，580.73.

(Production Example 6) [manufacturing of triphenyl pyrene]

[manufacturing of tribromo pyrene]

[changing 15]

Make the 1000ml four-hole boiling flask have dropping funnel, reflux cooling pipe, three-way tap, thermometer, carry out the nitrogen displacement.Pack into pyrene (Aldrich society system, reagent) 20.0g, DMF200mL carry out the nitrogen displacement once more, heat to make the pyrene dissolving under 70 ℃ of interior temperature.Make NBS (Tokyo changes into (strain) system, reagent) 108.9g be dissolved in DMF 400mL, from dropping funnel it was dripped with 20 minutes.Heat from 70 ℃ to 130 ℃ after dripping end, under this temperature, carry out reaction in 8 hours.After the cooling, reclaim solid, it is washed, obtain 1,3, the runic 39.3g (yield: 92.3%) of 6-tribromo pyrene with ethanol by suction strainer.

Orthodichlorobenzene with 15 times of volumes of sample size carries out recrystallization to the runic that obtains, and reclaims linen needle crystal.Analyzed as can be known by LC, the purity of regenerant is 91% (as other compositions, confirming as dibromo pyrene, tetrabromo pyrene).

[manufacturing of triphenyl pyrene]

[changing 16]

Have stirring motor, reflux cooling pipe, connecting 1 of the LC purity 91% of packing in the 1000ml four-hole boiling flask of three-way tap of nitrogen pipeline, 3,6-tribromo pyrene 20.1g, phenyl-boron dihydroxide (Aldrich society system, reagent, purity 95%) 23.9g, yellow soda ash (Northeast chemistry (strain) system, reagent) 39.4g, toluene (pure chemistry (strain) system, reagent) 400ml, ethanol (pure chemistry (strain) system, reagent) 200ml, de-salted water 80ml.The limit is stirred the limit and will be reduced pressure in the reactor, then replace with nitrogen, and after above-mentioned operation was carried out 2 times, with the nitrogen bubbling, processing outgased in reaction solution.Add four (triphenyl phosphine) palladium (0) 2.8g, in oil bath, carry out 9 hours heated and stirred under 80 ℃.

After the reaction, add de-salted water 200ml, reaction solution is carried out suction strainer.Add toluene 200ml in filtrate, carry out separatory, the toluene with 200ml extracts water layer again.Organic layer is merged, dewater, concentrate with vaporizer with anhydrous magnesium sulfate.With acetonitrile the runic that obtains is washed, obtain 1,3,6-triphenyl pyrene 15.1g (yield 84.9%).Analyzed as can be known by LC, the purity of regenerant is 88.2%.Should illustrate that in this specification sheets, in the chemical formula, " Ph " represents phenyl.

(Production Example 7) [manufacturing of triphenyl bromo pyrene]

[changing 17]

Three-way tap, dropping funnel, the thermometer of backflow cooling tube, connection nitrogen pipeline are installed in the 200ml there-necked flask, inside reactor are replaced with nitrogen.Pack 1,3 into, 6-triphenyl pyrene 6.2g, DMF (pure chemistry (strain) system, reagent) 80ml stirs under 90 ℃ of interior temperature.Make NBS 2.6g be dissolved in the solution of DMF 20ml gained with dripping in 5 minutes from dropping funnel, under 90 ℃, carry out stirring in 1 hour.

To reclaim because of the solid that cooling is separated out by suction strainer, runic is washed with methyl alcohol.About 3 times toluene with sample size carries out recrystallization to the runic that reclaims, and obtains 1-bromo-3,6,8-triphenyl pyrene 3.8g (yield: 52.2%).With ¹H NMR analyzes, and purity is 90% as a result.

(Production Example 7-1) [manufacturing of TOPOT 2,2 (3,6,8-triphenyl pyrene)]

[changing 18]

The reflux cooling pipe is being installed, is connecting the 1-bromo-3 of packing in the 200ml there-necked flask of three-way tap, thermometer of nitrogen pipeline, 6,8-triphenyl pyrene 3.9g, TOPOT 2,2 boric acid (Aldrich society system, reagent) 0.37g, yellow soda ash (Northeast chemistry (strain) system, reagent) 1.2g, toluene (pure chemistry (strain) system, reagent) 50ml, ethanol (pure chemistry (strain) system, reagent) 20ml, de-salted water 5ml.Carry out 5 decompressions, the operation of nitrogen metathetical, fed nitrogen 30 minutes again in reaction solution, operation outgases.Add four (triphenyl phosphine) palladium (0) 0.32g, in oil bath, carry out 11 hours heated and stirred under 80 ℃.

After the cooling, reclaim the solid of separating out, wash, obtain the 1.7g white solid with methyl alcohol by suction strainer.By the Ionized mass analysis of DEI as can be known, obtain m/Z=934, determine that it is target compound TOPOT 2,2 (3,6,8-triphenyl pyrene) (receipts amount 1.72g, yield: 83%).

·Mass(DEI)Obs.m/Z＝934(M ⁺)、Calc.for C ₇₄H ₄₆

(Production Example 7-2) [4, the manufacturing of 4 '-biphenylene two (3,6,8-triphenyl pyrene)]

[changing 19]

The reflux cooling pipe is being installed, is connecting the 1-bromo-3 of packing in the 200ml there-necked flask of three-way tap, thermometer of nitrogen pipeline, 6,8-triphenyl pyrene 9.8g, 4, the two boric acid of 4 '-biphenylene (Lancaster: ラ Application カ ス one reagent) 1.3g, yellow soda ash (Northeast chemistry (strain) system, reagent) 2.9g, toluene (pure chemistry (strain) system, reagent) 100ml, ethanol (pure chemistry (strain) system, reagent) 30ml, de-salted water 10ml.Carry out 5 decompressions, the operation of nitrogen metathetical, fed nitrogen 30 minutes again in reaction solution, operation outgases.Add four (triphenyl phosphine) palladium (0) 0.7g, in oil bath, carry out 12 hours heated and stirred under 80 ℃.

After the cooling, reclaim the solid of separating out, wash successively, obtain runic with de-salted water, methyl alcohol by suction strainer.Toluene with 30 times of sample sizes carries out recrystallization to the runic that reclaims, and obtains 4 of 2.5g, two (3,6,8-triphenyl pyrene) (receipts amount: 3.4g, the yields: 65%) of 4 '-biphenylene.Analyzed as can be known by LC, the purity of regenerant is 99.4%.

· ¹H NMR(400MHz、CDCl ₃)δ8.30(d、J＝10.00、2H)、8.22(d、J＝9.60、2H)、8.18(s、4H)、8.08(s、2H)、8.02(s、2H)、7.89(dd、J＝8.40、4H)、7.81(dd、J＝8.40、4H)、7.72-7.66(m、12H)、7.58-7.51(m、12H)、7.50-7.42(m、6H)

·Mass(DEI)Obs.m/Z＝1010(M ⁺)、Calc.for C ₈₀H ₅₀

(Production Example 7-3) [9,9 '-dihexyl-2, the manufacturing of 7-fluorenes two (3,6,8-triphenyl pyrene)]

[changing 20]

In the 100ml there-necked flask that reflux cooling pipe, the three-way tap that connects the nitrogen pipeline, thermometer are installed, the 1-bromo-3 of packing into, 6,8-triphenyl pyrene 3.0g, 9,9 '-dihexyl-2, two boric acid (Aldrich society system, the reagent) 0.7g of 7-fluorenes, yellow soda ash (Northeast chemistry (strain) system, reagent) 0.9g, toluene (pure chemistry (strain) system, reagent) 40ml, ethanol (pure chemistry (strain) system, reagent) 15ml, de-salted water 4ml.Carry out 5 decompressions, the operation of nitrogen metathetical, fed nitrogen 30 minutes again in reaction solution, operation outgases.Add four (triphenyl phosphine) palladium (0) 0.3g, in oil bath, carry out 12 hours heated and stirred under 80 ℃.

In reaction mixture, add de-salted water 40ml and carry out separatory, with chloroform 30ml water layer is carried out 2 times again and extract, after with anhydrous magnesium sulfate the organic layer that lumps together being dewatered, concentrate and obtain runic.With GPC the runic that reclaims is made with extra care, obtained 9,9 '-dihexyl-2, two (3,6,8-triphenyl pyrene) (receipts amount: 1.7g, the yields: 79%) of 7-fluorenes.

· ¹H NMR(400MHz、CDCl ₃)δ8.21(d、J＝10.00、2H)、8.19-8.16(m，6H)、8.11(s、2H)、8.02(s、2H)、7.78-7.65(m、14H)、7.60-7.51(m、12H)、7.50-7.42(m、6H)、2.12-2.05(m、4H)、1.30-1.22(m、4H)1.08(s、12H)、0.67(t、J＝6.80、6H)

·Mass(DEI)Obs.m/Z＝1190(M ⁺)、Calc.for C ₉₃H ₇₄

(Production Example 8) [3,6, the manufacturing of 8-triphenyl pyrene boric acid]

[changing 21]

To the stirrer of packing into, low temperature be installed use vacuum pump with thermometer, dropping funnel, the 300ml there-necked flask that is connected with the three-way tap of nitrogen pipeline, heat with hot rifle, make the inside reactor drying, replace with nitrogen.The limit feeds the nitrogen stream limit triphenyl monobromo pyrene 7.6g that packs in this reaction vessel, with nitrogen inside is replaced once more.The dry THF of packing into (Northeast chemical reagent) 200ml uses dry ice-propanone to bathe then and reaction solution is cooled to-78 ℃.Splash into n-Butyl Lithium/hexane solution (Northeast chemical reagent, 1.6N) 12ml with 15 minutes, under this temperature, carry out stirring in 2 hours.After splashing into trimethyl borate (Northeast chemical reagent) 5ml by syringe, continue to stir 1 hour, remove cooling bath then, be warmed up to room temperature.With vaporizer reaction solution is concentrated, residue is carried out separatory, reclaim organic layer, concentrate with the chloroform of 200ml and the 1N-HCl of 100ml.With methyl alcohol the runic that obtains is washed, obtain xanchromatic crystallization (receipts amount 6.3g, yield: 87%).

(Production Example 8-1) [2,2 '-bipyridyl-6,6 '-two (3,6,8-triphenyl pyrene) manufacturing]

[changing 22]

In the 300ml there-necked flask that reflux cooling pipe, the three-way tap that connects the nitrogen pipeline, thermometer are installed, pack 3 into, 6,8-triphenyl pyrene boric acid 2.7g, 4,4 '-dibromo dipyridyl 0.6g, yellow soda ash (Northeast chemical reagent) 1.2g, toluene (pure chemical reagent) 50ml, ethanol (pure chemical reagent) 20ml, de-salted water 10ml.Carry out 5 decompressions, the operation of nitrogen metathetical, fed nitrogen 30 minutes again in reaction solution, operation outgases.Add four (triphenyl phosphine) palladium (0) 0.2g, in oil bath, carry out 10 hours heated and stirred under 80 ℃.

After the cooling, reclaim the solid of separating out, wash, obtain yellow solid (receipts amount 1.7g, yield: 81%) with methyl alcohol by suction strainer.

·Mass(DEI)Obs.m/Z＝1012(M ⁺)、Calc.for C ₇₈H ₄₈N ₂

(Production Example 8-2) [2, the manufacturing of 2 '-biphenylene two (3,6,8-triphenyl pyrene)]

[changing 23]

In the 200ml there-necked flask that reflux cooling pipe, the three-way tap that connects the nitrogen pipeline, thermometer are installed, pack 3 into, 6,8-triphenyl pyrene boric acid 4.3g, 3,3 '-'-dibromobiphenyl 0.9g, yellow soda ash (Northeast chemical reagent) 1.9g, toluene (pure chemical reagent) 60ml, ethanol (pure chemical reagent) 4ml, de-salted water 4ml fed nitrogen 40 minutes in reaction solution.Add four (triphenyl phosphine) palladium (0) 0.2g, in oil bath, carry out 10 hours heated and stirred under 80 ℃.

Reclaim the solid of separating out by suction strainer, wash, obtain yellow solid (receipts amount 2.5g, yield: 82%) with toluene, THF, DMF.

Mass(DEI)Obs.m/Z＝1010(M ⁺)、Calc.for C ₇₈H ₄₈N ₂

(Production Example 9) [4, the manufacturing of 4 '-biphenylene two (3,6,8-a three-tolyl pyrene)]

[changing 24]

Have the reflux cooling pipe, connecting 1 of the LC purity 94% of packing in the 300ml there-necked flask of three-way tap, thermometer of nitrogen pipeline, 3,6-tribromo pyrene 5.7g, a tolyl boric acid (Aldrich reagent) 8.0g, yellow soda ash (Northeast chemical reagent) 12.4g, toluene (pure chemical reagent) 150ml, ethanol (pure chemical reagent) 50ml, de-salted water 15ml.Carry out 5 decompressions, the operation of nitrogen metathetical, fed nitrogen 30 minutes again in reaction solution, operation outgases.Add four (triphenyl phosphine) palladium (0) 1.0g, in oil bath, carry out 11 hours heated and stirred under 80 ℃.

After the cooling, add de-salted water 150ml and carry out separatory in reaction solution, the toluene with 100ml extracts 2 times water layer again.With anhydrous magnesium sulfate the organic layer that lumps together is carried out drying, concentrate with vaporizer.With column chromatography (silica gel, CHCl ₃) residue that reclaims is carried out desalting treatment, obtain 1,3,6-three (tolyl) pyrene.LC purity is 94%, the water absorbability height, and therefore dry back weighing value is than theoretical yield big (receipts amount: 5.9g, yield: 102%).Should illustrate, in this specification sheets, " Me " expression methyl in the chemical formula, tolyl between " m-tolyl " expression.

· ¹H NMR(400MHz、CDCl ₃)δ8.24(d、1H、J＝9.20)、8.20(d、1H、J＝8.40)、8.15(d、2H、J＝3.20)、8.05(d、1H、J＝9.20)、7.99(d、1H、J＝8.00)、7.98(s、1H)、7.51-7.35(m、9H)、7.34-7.23(m、3H)、2.49(s、3H)、2，47(s、3H)2.45(s，3H)

Then, dropping funnel is being installed, is connecting in the 200ml there-necked flask of three-way tap of nitrogen pipeline, 1,3 of the LC purity 94% of packing into, 6-three (tolyl) pyrene 5.2g, DMF (pure chemical reagent) 70ml stirs under nitrogen atmosphere, under the room temperature.Splashed in this solution with 10 minutes and to make N-bromine succinimide (Tokyo changes into reagent, purity 98%) 2.0g be dissolved in the solution of above-mentioned DMF 30ml gained.Under nitrogen atmosphere, under the room temperature, stirred 6 hours, confirm that raw material disappears after, add de-salted water 50ml, MeOH (pure chemical reagent) 50ml, make the target compound precipitation, with the solids wash that reclaims, obtain runic with MeOH.With GPC that the runic that obtains is refining, obtain 3,6,8-three (tolyl)-1-bromine pyrene (receipts amount 3.7g, yield 60%).

· ¹H NMR(400MHz、CDCl ₃)δ8.44(d、1H、J＝9.60)、8.34(d、1H、J＝9.60)、8.25(s、1H)、8.18(d、1H、J＝9.60)、8.08(d、1H、J＝9.60)、8.01(s、1H)、7.50-7.38(m、9H)、7.32-7.26(m、3H)、2.49(s、3H)、2，47(s、3H)2.45(s，3H)

Then, in the 100ml there-necked flask that reflux cooling pipe, the three-way tap that connects the nitrogen pipeline, thermometer are installed, pack 3 into, 6,8-three (tolyl)-1-bromine pyrene 3.0g, 4,4 '-xenyl two boric acid (Aldrich reagent) 0.5g, yellow soda ash (Northeast chemical reagent) 0.9g, toluene (pure chemical reagent) 30ml, ethanol (pure chemical reagent) 15ml, de-salted water 5ml.Carry out 5 decompressions, the operation of nitrogen metathetical, fed nitrogen 30 minutes again in reaction solution, operation outgases.Add four (triphenyl phosphine) palladium (0) 0.2g, in oil bath, carry out 12 hours heated and stirred under 80 ℃.

Reclaim the precipitation that generates with suction strainer, solid is washed with MeOH.The recovery solid is dissolved in the toluene, carries out heat filtering, inorganic salt are removed.Filtrate is concentrated, wash, obtain target compound (receipts amount: 2.0g, yield: 90%) with MeOH.

· ¹H NMR(400MHz、CDCl ₃)δ8.29(d、2H、J＝9.60)、8.23(d、2H、J＝9.60)、8.19(s、4H)、8.07(s、2H)、8.00(s，2H)、7.90(dd、4H、J＝8.00)、7.82(dd、4H、J＝8.00)、7.53-7.39(m、18H)、7.30-7.23(m、6H)、2.48(s、6H)、2，47(s、12H)

·Mass(DEI)Obs.m/Z＝1094(M ⁺)、Calc.for C ₈₆H ₆₂

(carrier mobility, EL luminous efficiency, the mensuration of PL luminous efficiency, calculating) carrier mobility, EL luminous efficiency, the PL luminous efficiency is as follows measures, calculates.

[carrier mobility μ (cm ²/ V _s)]

Organic semi-conductor drain voltage (V _d) and the relational expression of leakage current by following formula (1) expression, linearly increase (linearity region),

[several 1]

$I_d=\frac{W}{L}\mathrm{\μ}{C}_i[(V_g-V_T)V_d-\frac{1}{2}{V_d}^2]---\left(1\right)$

In addition, if V _dIncrease, since the pinch off of raceway groove, I _dSaturated and reach constant value (zone of saturation), I _dRepresent by following formula (2).

[several 2]

$I_d=\frac{W}{2L}{\mathrm{\μ}}_{\mathrm{sat}}{C}_i{(V_g-V_T)}^2---\left(2\right)$

Moreover each symbol of above-mentioned formula (1) (2) is as described below.

L: channel length [cm]

W: channel width [cm]

C _i: the electrostatic capacitance [F/cm of the per unit area of gate insulating film ²]

μ _Sat: the mobility [cm of zone of saturation ²/ V _s]

I _d: leakage current [A]

V _d: drain voltage [V]

V _g: gate voltage [V]

V _T: (it is illustrated in the drain voltage (V of zone of saturation to gate threshold voltage [V] _d) constant following 1/2 power (V with leakage current _Dsat ^1/2) with respect to gate voltage (V _g) mapping, the point that asymptotic line and transverse axis intersect).

Can be by I in this zone of saturation _d ^1/2And V _gRelation, obtain the mobility (μ) in the organic semiconductor.

In the present invention, be vacuum tightness～5 * 10 making pressure ^-3Pa, to make temperature be under the condition of room temperature, use the analyzing parameters of semiconductor instrument (Agilent, HP4155C), make drain voltage by 10V to-100V, under-1V step, make gate voltage by 0V to-100V, under-20V step, operate, use following formula (2) to calculate mobility.

[EL luminous efficiency]

With regard to EL luminous efficiency η _Ext; use above-mentioned transistor unit; under-1V step-length, make drain voltage by 10V to-100V; under-20V step-length, make gate voltage by 0V to-100V; operate; adopt photon counter (Newport society system, 4155C Semiconductor Parameter Analyzer) measure by element send luminous, after the number of photons [CPS] of using following formula (3) wherein to obtain is converted to light beam [1w], use following formula (4) to calculate EL luminous efficiency η _Ext

[several 3]

$X_{\mathrm{PC}}\left[\mathrm{hv}\right]=\frac{5.71\&times;{10}^{-11}\left(N_{\mathrm{PC}}\right[\mathrm{CPS}]-\mathrm{base})\frac{4}{3}{\mathrm{\&pi;<figure-callout\; id="3"\; label="r"\; filenames="A20058004039900461.png,A20058004039900471.png"\; state="\{\{state\}\}">r</figure-callout>}}^3/\frac{\mathrm{<figure-callout\; id="3"\; label="h"\; filenames="A20058004039900461.png,A20058004039900471.png"\; state="\{\{state\}\}">h</figure-callout>}}{3}{\mathrm{\&pi;<figure-callout\; id="2"\; label="r"\; filenames="A20058004039900431.png,A20058004039900441.png"\; state="\{\{state\}\}">r</figure-callout>}}^2}{1.04\&times;{10}^6}---\left(3\right)$

[several 4]

η _ext＝(100×1239.7/λ×N _PC×X _PC)/I _d (4)

Moreover each symbol of above-mentioned formula (3), (4) is as described below.

N _PC: the number of photons [CPS] that adopts photon counter (PC) observation

X _PC: the value that number of photons is converted to light beam [1w]

R: circular cone or radius of a circle [cm]

H: the distance of photon counter and sample [cm]

(PL luminous efficiency)

The luminous efficiency of PL is following to be calculated: the material evaporation 70nm on quartz base plate that obtains in the present invention under nitrogen atmosphere, form unitary film, use integrating sphere (IS-060, Labsphere Co.) then, the He-Cd laser of illumination wavelength 325nm (IK5651R-G, Kimmon electric Co.) is as exciting light, mensuration is by the luminous Multi-channel photodiode (PMA-11, Hamamatsuphotonics Co.) of sample, thereby calculates.

(embodiment 1,2)

Below, under following condition, make organic EL shown in Figure 9.

The hole flows into electrode 32 ... ITO (110nm)

Hole transmission layer 33 ... α-NPD (50nm)

Luminescent layer 34 ... the asymmetric pyrene compound of CBP+ (Fig. 2 (a) (4-5) or (4-7)) (content of asymmetric pyrene compound is 6 weight % of luminescent layer integral body) (40nm)

Electron transfer layer 35 ... Bphen (20nm)

Electron injecting layer (not shown) ... MgAg (100nm)

Electron injection electrode 36 ... Ag (10nm)

For each element that obtains, measure HOMO and lumo energy, PL peak, EL peak (actual appreciable emission wavelength), PL luminous efficiency, external light emission efficiency and luminosity.It is the results are shown in table 1.

(comparative example 1)

Except using tetraphenyl pyrene (Aldrich society system; Reagent, abbreviation " TPPy ") as outside the pyrene compound, measure similarly to Example 1.It is the results are shown in table 1.Moreover in the table 1, PL luminous efficiency and external light emission efficiency are represented the luminescent layer 34 (content of asymmetric pyrene compound: luminous efficiency 6 weight %).

Table 1

		Embodiment		Comparative example
					1	2	1
		Compound		(4-5)				(4-7)	TPPy
HOMO/LUMO energy level (eV)					5.6/2.6	5.3/2.4	5.6/2.7
		PL peak (nm)		448				468	454
EL peak (nm)					433	446	433
		PL luminous efficiency (%)		86				83	88
External light emission efficiency (%)					1.4	2.5	1.3
		Luminosity (cd/m 2)	10mA/cm 2 (6.0V)	76.63				253.40	70.81
100mA/cm 2(8.0V)	627.30				2107.00	595.70

(embodiment 3～4)

Then, under following condition, shop drawings 5 and light-emitting transistor device shown in Figure 6.Source electrode 2 and drain electrode 3 ... form the electrode (Au, thick 40nm) that has the broach shape portion that is made up of 20 broach respectively, as shown in Figure 8, the mode by the mutual configuration of each broach shape portion is configured on the insulating film 5.At this moment, the layer (1nm) that is formed by chromium is set between insulating film 5 and two electrodes.In addition, making the width of the groove (between each broach shape portion) of this moment is that 25 μ m, length are 4mm.

Insulating film 5 ... evaporation forms the silicon oxide film of 300nm.

Luminescent layer 1 ... evaporation adopts the pyrene compound that above-mentioned manufacturing process makes (Fig. 2 (a) (4-5) and (4-7)) individually respectively, with cover insulating film, source electrode 2 and drain electrode 3 around, thereby form luminescent layer 1.

For each element that obtains, measure HOMO and lumo energy, fluorescent absorption wavelength, PL luminous efficiency, EL luminous efficiency, luminosity and carrier mobility.It is the results are shown in table 2.

(comparative example 2)

, measure similarly to Example 2 as the pyrene compound except using tetraphenyl pyrene (Aldrich society system, reagent).It is the results are shown in table 2.

Table 2

	Embodiment		Comparative example
				3	4	2
	Compound	(4-5)	(4-7)				TPPy
HOMO/LUMO energy level (eV)				5.6/2.6	5.3/2.4	5.6/2.7
	Fluorescent absorption wavelength (nm)	448	468				505
PL luminous efficiency (%)				33	31	34
	EL luminous efficiency (%)	-	7.4×10 -3				9.0×10 -2
Luminosity (CPS)				-	3.5×10 5	1.2×10 6
	Carrier mobility (cm 2/V·s)	-	4.9×10 -5				5.5×10 -5

Claims (12)

1. asymmetric pyrene compound of forming by following structural formula (1),

[changing 1]

In formula (1), R ₁Expression is from having substituent heteroaryl, can have substituent aryl, can have substituent main chain carbon number and be 1～20 alkyl, can have substituent cycloalkyl, can have substituent thiazolinyl, can have substituent alkynyl, cyano group, can have substituent carbonyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, with the group of choosing in the halogen atom;

In addition, R ₂Expression is from hydrogen atom, can have substituent heteroaryl, can have substituent aryl, can have substituent main chain carbon number and be 1～20 alkyl, can have substituent cycloalkyl, can have substituent thiazolinyl, can have substituent alkynyl, cyano group, can have substituent carbonyl, can have substituent alkoxyl group, can have substituent aryloxy, can have substituent silyl, can have substituent aryl borane base, can have substituent ester group, with the group of choosing in the halogen atom, and and R ₁Different.

2. asymmetric pyrene compound as claimed in claim 1, wherein,

In described formula (1), R ₁Can have substituent following radicals for being selected from, i.e. group in phenyl, naphthyl, benzofuryl, phenylpyridyl, thienyl, benzothienyl, pyridyl, methyl, vinyl and the ethynyl;

In addition, R ₂For being selected from hydrogen atom, can have substituent following radicals, i.e. group in phenyl, naphthyl, benzofuryl, phenylpyridyl, thienyl, benzothienyl, pyridyl, methyl, vinyl and the ethynyl, and be and R ₁Different groups.

3. asymmetric pyrene compound as claimed in claim 1 or 2, wherein,

In described formula (1), R ₁For being selected from 3-alkyl phenyl, 4-alkyl phenyl, 3-fluorophenyl, 4-fluorophenyl, 3-trifluoromethyl, 4-trifluoromethyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 3, two (trifluoromethyl) phenyl, 3 of 5-, 4, the group of phenyl, 2-naphthyl, benzofuryl, phenylpyridyl, thienyl, benzothienyl, pyridyl, bipyridyl, phenyl, xenyl, methyl, phenyl substituted ethylene base or phenyl replaced acetylene base that 5-trifluorophenyl, tolyl, fluorine replace;

In addition, R ₂For being selected from hydrogen atom, methyl, hexyl, phenyl, xenyl, pyridyl, bipyridyl, naphthyl, xenyl, phenylpyridyl, octyl group, dodecyl, octadecyl, phenyl substituted ethylene base or phenyl replaced acetylene base, and and R ₁Different groups.

4. the asymmetric pyrene compound shown in the following formula (2),

[changing 2]

In formula (2), R ₁With described identical, Y represents the connection base of divalence.

5. asymmetric pyrene compound as claimed in claim 4, wherein,

Described Y is the group of selecting from the divalent group of, heteroaromatic substituent from having, aromatic hydrocarbons ring, alkane, alkene and alkynes.

6. as each described asymmetric pyrene compound of claim 1～5, wherein,

Be used for light-emitting transistor device or organic electroluminescent device.

7. light-emitting transistor device, wherein, contain:

Can carry as the hole of current carrier and electronics, be the main composition composition, utilize the luminous luminescent layer of compound generation of hole and electronics with the described asymmetric pyrene compound of claim 6,

To the hole injecting electrode of described luminescent layer injected hole,

To the electron injection electrode of described luminescent layer injection electronics, and

Relative with described hole injecting electrode and electron injection electrode, as to control the distribution of the current carrier in described luminescent layer gate electrode.

8. light-emitting transistor device as claimed in claim 7, wherein,

Described hole injecting electrode and electron injection electrode have the broach shape portion that is made up of a plurality of broach separately, and separate the broach that predetermined distance disposes the broach of the broach shape portion that constitutes described hole injecting electrode alternately and constitutes the broach shape portion of electron injection electrode.

9. a plurality of claims 7 or 8 described light-emitting transistor devices are arranged on the substrate and the display unit that constitutes.

10. organic electroluminescent device has:

The hole transmission layer and the electron transfer layer that utilize the luminous luminescent layer of the compound generation of hole and electronics, inject the electron injection electrode of electronics and be used for carrying to luminescent layer hole or electronics from described hole injecting electrode or electron injection electrode to the hole injecting electrode of this luminescent layer injected hole, to described luminescent layer;

As the constituent of described luminescent layer, and, used the described asymmetric pyrene compound of claim 6 as at least 1 layer the constituent that is selected from hole transmission layer and electron transfer layer.

The display unit that constitutes 11. the described organic electroluminescent device of a plurality of claims 10 is arranged on the substrate.

12. the manufacture method of an asymmetric pyrene compound, wherein,

According to following reaction formula＜1〉1-replacement pyrene (1-1) and halogenide are reacted, synthetic 1-replaces-3,6,8-three halo pyrenes (1-2), the at least a of organometallic compound that is selected from boronic acid compounds, tin compound, organic zinc compound and organo-magnesium compound reacted, thereby make asymmetric pyrene compound (1)

[changing 3]

In reaction formula＜1〉in, R ₁, R ₂Identical with the situation of described formula (1), in addition, X represents to be selected from the halogen atom of chlorine atom, bromine atoms and iodine atom.

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