CN103187531A

CN103187531A - Organic light-emitting device and purpose of double-polarity organic compound

Info

Publication number: CN103187531A
Application number: CN2011104552638A
Authority: CN
Inventors: 邱勇; 谢静; 段炼
Original assignee: Tsinghua University; Beijing Visionox Technology Co Ltd; Kunshan Visionox Display Co Ltd
Current assignee: Tsinghua University; Beijing Visionox Technology Co Ltd; Kunshan Visionox Display Co Ltd
Priority date: 2011-12-30
Filing date: 2011-12-30
Publication date: 2013-07-03
Anticipated expiration: 2031-12-30

Abstract

The invention provides an organic light-emitting device and a purpose of a double-polarity organic compound. The organic light-emitting device comprises a cathode, an anode, an electron transferring layer, a hole transferring layer and an organic luminescent layer, wherein the double-polarity organic compound is applied to the electron transfer layer and/or the hole transferring layer. The structural general formula of the double-polarity organic compound is Ar1-Ar-Ar2, wherein the Ar is a sub-conjugate-condensed-nucleus group with an aromatic ring, the Ar1 and the Ar2 are respectively and independently chosen from substituted or unsubstituted carbazolyl, aryl group, oxygen group, alkoxyl group, thienyl, benzothiophene group, indeno carbazolyl, triazinyl, phenanthroline group, pyridyl, aryl group or alkane group; molecule frontier orbital of the double-polarity organic compound is in the same conjugate big condensed nucleus; difference between reorganization energy of a hole and an electron is less than 0.2 eV; and electron mobility and hole mobility are larger than 10 to 4 cm<2>/vs. Both the mobility and the stability are considered according to the organic light-emitting device and the purpose of the double-polarity organic compound, and the organic light-emitting device and the purpose of the double-polarity organic compound are in favor of improvement of the efficiency of the device and prolonging the service life of the device.

Description

The purposes of organic electroluminescence device and bipolarity organic compound

Technical field

The present invention relates to a kind of organic electroluminescence device, particularly relate to a kind of bipolarity organic compound of non-donor-receiver structure of using as the organic electroluminescence device of electron transfer layer and/or hole transmission layer.

Background technology

External quantum efficiency (the η of OLED device _Ext) represented by following formula:

η _ext＝γ×η _ex×

×η _ph

Wherein, γ is the ratio in electronics and hole; η _ExBe single triplet state ratio;

Photo-quantum efficiency for material; η _PhFor light takes out efficient.

By the formula of external quantum efficiency as can be known, the ratio in electronics and hole (γ) will influence final light extraction efficiency in the OLED device.Therefore, the balance in reinforcement electronics and hole becomes the important means that OLED efficient improves.

(the bipolarity transport property refers to the bipolarity transport property of organic material, can pass the hole son that can conduct electricity again, its direct parameter characterization is that hole mobility is consistent with electron mobility, be the same order of magnitude), raising for the OLED device performance is extremely important, because it is conducive to the balance of charge carrier in the exciton recombination zone territory, avoid excessive charge carrier to the quencher of exciton.But the organic material with bipolarity transport property is also few.Therefore researching and developing ambipolar material is significant.

The mentality of designing of modal bipolarity molecule, be to introduce at molecule simultaneously to pass hole (Donor) and conduct electricity son (Acceptor) group, be Donor-Acceptor (D-A) system, the frontier orbit of this quasi-molecule (HOMO and LUMO) is distributed on the different groups.But the problem of this type of material is: because the group of transporting holes and transmission electronic is diluted, the bipolar materials mobility of D-A system is not high usually; Because transmit by different groups with electronics in the hole, the bipolar materials hole of D-A system and the mobility of electronics do not match usually.For example, people such as S.O.Jeon (Adv.Mater.2010,22,1872.) the synthetic molecule with bipolarity transport property of design, adopting carbazole is the group of transporting holes, hexichol phosphorus sulphur is the group of transmission electronic, but its hole mobility still than high 2 orders of magnitude of electron mobility, the ability of bipolarity transmission is mated inadequately.The bipolar materials of people (Org. Lett., 2007,9,4511) such as Y.L.Liao report adopts the diphenylamino group that passes the hole in addition and the benzimidazole group of the son that conducts electricity, but electron mobility and hole mobility still differ 2 orders of magnitude.

2002, Kodak adopted 9,10-two (2-naphthyl) anthracene (ADN) as luminescent layer material of main part (J.M.Shi, etc., Appl.Phys.Lett.2002,80,3201).The hole of ADN molecule and electronics all transmit at same group, and hole mobility and electron mobility are very close, belong to Non-Donor-Acceptor (Non-D-A) system bipolar materials.Two kinds of groups of this type of material do not exist mutual weakening and dilution, obtain higher carrier mobility easily.

On the other hand, the bipolar materials of Non-D-A system, its oxidation and reduction process all are reversible, and corresponding, from the electrochemistry angle, cation and the anion of molecule are highly stable.Then this type of bipolar materials can keep stable in the OLED device course of work, increases substantially the life-span of device.

Yet, do not see Non-D-A system bipolar materials so far as yet as the report of hole or electron transport material.

Summary of the invention

Technical problem to be solved by this invention is, a kind of novel electroluminescent device is provided, use existing Non-D-A bipolar materials as hole mobile material and/or electron transport material, overcome Donor-Acceptor (D-A) system in the past, mobility is not high usually, the unmatched defective of the mobility of hole and electronics.The present invention selects the Non-D-A bipolar materials by rational analysis of molecules, and it as hole mobile material or electron transport material, is taken into account mobility and stability, will be conducive to the raising in device efficiency and life-span.

For solving the problems of the technologies described above, the invention provides a kind of novel electroluminescent device, adopt the bipolar materials of non-donor-receiver structure as hole mobile material or electron transport material, its frontier orbit (HOMO and LUMO) all is distributed on the same conjugated structure, such material oxidation reduction process is reversible and stable, and hole and electron mobility all are the same orders of magnitude (10 ^-4) and higher.

Particularly, first technical scheme that the present invention adopts is, a kind of organic electroluminescence device is provided, and it comprises negative electrode, anode, electron transfer layer, hole transmission layer and organic luminous layer, wherein electron transfer layer and/or hole transmission layer applying double pole organic compound; The general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl, triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

Conjugation aryl of the present invention refers to form the aryl of non-donor-receiver structure, can have substituting group on it as required.

Aforesaid organic electroluminescence device, described Ar is inferior conjugation virtue condensed ring radical, is selected from the divalent group of following replacement or unsubstituted aromatic hydrocarbons: naphthalene, anthracene, phenanthrene, fluorenes, naphtho-thiadiazoles, perylene, pyrene, triphenylene, benzanthracene, dibenzanthracene, fluoranthene, benzofluoranthrene, naphtho-fluoranthene, benzfluorene, BaP, benzophenanthrene or naphtho-phenanthrene.

Aforesaid organic electroluminescence device, described Ar are inferior conjugation virtue condensed ring radical, are selected from following group:

Wherein, R is hydrogen atom, halogen atom or C ₁-C ₆₀Alkyl, alkane silica-based, aromatic hydrocarbons is silica-based, aryl or heterocyclic arene base, preferred hydrogen atom or methyl.

Above-mentioned halogen atom is selected from fluorine, chlorine, bromine.Above-mentioned C ₁-C ₆₀The preferred C of alkyl ₁-C ₁₀Alkyl, for example methyl, ethyl, propyl group.The silica-based preferred C of above-mentioned alkane ₁-C ₁₀Alkane silica-based, for example trimethyl silicon based, the methyl diethyl is silica-based.It is silica-based that the silica-based preferred benzene of above-mentioned aromatic hydrocarbons, naphthalene, phenanthrene, aphthacene, pentacene, fluorenes replace, and for example diphenyl is silica-based, and naphthyl is silica-based.Above-mentioned aryl comprises and replacing or unsubstituted following group: benzene, naphthalene, phenanthrene, aphthacene, pentacene, fluorenes, naphtho-thiadiazoles, perylene, pyrene, triphenylene, benzanthracene, dibenzanthracene, fluoranthene, benzofluoranthrene, naphtho-fluoranthene, benzfluorene, BaP or benzophenanthrene.Above-mentioned heterocyclic arene base comprises the aryl that pyridine, thiophene, furans replace, or pyridine, thiophene, the furans of aryl replacement.

Aforesaid organic electroluminescence device, described Ar is the divalent group that contains the heterocycle of aromatic hydrocarbon ring, is selected from:

Aforesaid organic electroluminescence device, the substituting group of the bipolarity organic compound of using in the described electron transfer layer is for replacing or unsubstituted triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl.

Aforesaid organic electroluminescence device, the triazine radical of described replacement are the triazine radicals that diphenyl replaces.

Aforesaid organic electroluminescence device, described aryl are to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

Aforesaid organic electroluminescence device, the pyridine radicals of described replacement is phenylpyridyl.

Aforesaid organic electroluminescence device, described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

Aforesaid organic electroluminescence device, the substituting group of the bipolarity organic compound of using in the described hole transmission layer is for replacing or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl or aryl.

Aforesaid organic electroluminescence device, described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

Aforesaid organic electroluminescence device, described alkoxyl phenyl is C _1-10Alkoxyl phenyl, preferred methoxyphenyl.

Aforesaid organic electroluminescence device, the thienyl of described replacement are the phenyl thienyls.

Aforesaid organic electroluminescence device, described aryloxy are phenyl oxygen base, xenyl oxygen base.

Aforesaid organic electroluminescence device, described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

A kind of bipolarity organic compound is as the purposes of the electric transmission layer material in the organic electroluminescence device, and the general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl.

Aforesaid bipolarity organic compound is as the purposes of the electric transmission layer material in the organic electroluminescence device, and the triazine radical of described replacement is the triazine radical that diphenyl replaces.

Aforesaid bipolarity organic compound is as the purposes of the electric transmission layer material in the organic electroluminescence device; described aryl is to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

Aforesaid bipolarity organic compound is as the purposes of the electric transmission layer material in the organic electroluminescence device, and the pyridine radicals of described replacement is phenylpyridyl.

Aforesaid bipolarity organic compound is as the purposes of the electric transmission layer material in the organic electroluminescence device, and described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

A kind of bipolarity organic compound is as the purposes of the hole transport layer material in the organic electroluminescence device, and the general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl or aryl.

The bipolarity organic compound is as the purposes of the hole transport layer material in the organic electroluminescence device, it is characterized in that, described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

Aforesaid bipolarity organic compound is as the purposes of the hole transport layer material in the organic electroluminescence device, and described alkoxyl phenyl is C _1-10Alkoxyl phenyl, preferred methoxyphenyl.

Aforesaid bipolarity organic compound is as the purposes of the hole transport layer material in the organic electroluminescence device, and the thienyl of described replacement is the phenyl thienyl.

Aforesaid bipolarity organic compound is as the purposes of the hole transport layer material in the organic electroluminescence device, and described aryloxy is phenyl oxygen base, xenyl oxygen base.

Aforesaid bipolarity organic compound is as the purposes of the hole transport layer material in the organic electroluminescence device, and described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

The bipolarity organic compound is as the electric transmission layer material in the organic electroluminescence device and the application of hole transport layer material, and the general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl, triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

Aforesaid application, wherein consistent with hole mobility as the electronics of the bipolarity organic compound of described electron transfer layer and hole transmission layer.

Following is the bipolarity organic compound that preferably is used as the electric transmission layer material.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from triazine radical or phenanthroline base respectively.Described triazine radical and phenanthroline base can be to replace or unsubstituted group, triazine radical or phenanthroline base that preferred diphenyl replaces.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from triazine radical or pyridine radicals respectively.Described triazine radical and pyridine radicals can be to replace or unsubstituted group, triazine radical or phenylpyridyl that preferred diphenyl replaces.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from triazine radical or aryl respectively.Described triazine radical can be to replace or unsubstituted group, the triazine radical that preferred diphenyl replaces.Described aryl can be to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from triazine radical or alkyl respectively.Described triazine radical can be to replace or unsubstituted group, the triazine radical that preferred diphenyl replaces.Described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from pyridine radicals or aryl respectively.Described pyridine radicals can be to replace or substituted radical not preferred phenylpyridyl.Described aryl can be to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from pyridine radicals or alkyl respectively.Described pyridine radicals can be to replace or substituted radical not preferred phenylpyridyl.Described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryl or alkyl respectively.Described aryl is to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.Described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from pyridine radicals or aryl respectively.Described pyridine radicals can be to replace or substituted radical not preferred phenylpyridyl.Described aryl can be to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from triazine radical or pyridine radicals respectively.Described triazine radical and pyridine radicals can be to replace or unsubstituted group, triazine radical or phenylpyridyl that preferred diphenyl replaces.

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from triazine radical or aryl respectively.Described triazine radical can be to replace or unsubstituted group, the triazine radical that preferred diphenyl replaces.Described aryl can be to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

When Ar is

Or Ar is

When Ar is

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from triazine radical or phenanthroline base respectively.Described triazine radical and phenanthroline base can be to replace or unsubstituted group, triazine radical or phenanthroline base that preferred diphenyl replaces.

When Ar is

Or Ar is

When Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryl or alkyl respectively.Described aryl is to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.Described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from triazine radical or pyridine radicals respectively.Described triazine radical and pyridine radicals can be to replace or unsubstituted group, triazine radical or phenylpyridyl that preferred diphenyl replaces.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

When Ar is

Or Ar is

When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from pyridine radicals or aryl respectively.Described pyridine radicals can be to replace or substituted radical not preferred phenylpyridyl.Described aryl can be to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from triazine radical or phenanthroline base respectively.Described triazine radical and phenanthroline base can be to replace or unsubstituted group, triazine radical or phenanthroline base that preferred diphenyl replaces.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

Following is the bipolarity organic compound that preferably is used as hole transport layer material.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from carbazyl or aryloxy respectively.Described carbazyl can be to replace or unsubstituted group.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or alkoxyl respectively.Described carbazyl can be to replace or unsubstituted group.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from carbazyl or thienyl respectively.Described carbazyl and thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from carbazyl or benzothienyl respectively.Described carbazyl and benzothienyl can be to replace or unsubstituted group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from carbazyl or indeno carbazyl respectively.Described carbazyl and indeno carbazyl can be to replace or unsubstituted group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from carbazyl or aryl respectively.Described carbazyl can be to replace or unsubstituted group.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryloxy or alkoxyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryloxy or thienyl respectively.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryloxy or benzothienyl respectively.Described benzothienyl can be to replace or unsubstituted group.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryloxy or indeno carbazyl respectively.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryloxy or aryl respectively.Described aryloxy is phenyl oxygen base, xenyl oxygen base.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or thienyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.

When Ar is Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or benzothienyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described benzothienyl can be to replace or unsubstituted group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or indeno carbazyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or aryl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from thienyl or benzothienyl respectively.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.Described benzothienyl can be to replace or unsubstituted group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from thienyl or indeno carbazyl respectively.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from thienyl or aryl respectively.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from benzothienyl or indeno carbazyl respectively.Described benzothienyl can be to replace or unsubstituted group.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from benzothienyl or aryl respectively.Described benzothienyl can be to replace or unsubstituted group.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryl or indeno carbazyl respectively.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is Or Ar is

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from carbazyl or alkoxyl respectively.Described carbazyl can be to replace or unsubstituted group.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryloxy or indeno carbazyl respectively.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from aryloxy or aryl respectively.Described aryloxy is phenyl oxygen base, xenyl oxygen base.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or aryl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

Or Ar is

When Ar is

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from benzothienyl or aryl respectively.Described benzothienyl can be to replace or unsubstituted group.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or indeno carbazyl respectively.Described carbazyl and indeno carbazyl can be to replace or unsubstituted group.

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When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryloxy or benzothienyl respectively.Described benzothienyl can be to replace or unsubstituted group.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

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When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryl or indeno carbazyl respectively.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or benzothienyl respectively.Described carbazyl and benzothienyl can be to replace or unsubstituted group.

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Or Ar is

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or aryl respectively.Described carbazyl can be to replace or unsubstituted group.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryloxy or alkoxyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from thienyl or indeno carbazyl respectively.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.

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When Ar is

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When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from benzothienyl or aryl respectively.Described benzothienyl can be to replace or unsubstituted group.Described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

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When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or aryloxy respectively.Described carbazyl can be to replace or unsubstituted group.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or thienyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from alkoxyl or benzothienyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described benzothienyl can be to replace or unsubstituted group.

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When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryloxy or alkoxyl respectively.Described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

When Ar is

Or Ar is The time, Ar ₁And Ar ₂Be independently selected from aryloxy or thienyl respectively.Described thienyl can be to replace or unsubstituted group, preferred phenyl thienyl.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

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Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or aryloxy respectively.Described carbazyl can be to replace or unsubstituted group.Described aryloxy is phenyl oxygen base, xenyl oxygen base.

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When Ar is Or Ar is The time, Ar ₁And Ar ₂Be independently selected from carbazyl or indeno carbazyl respectively.Described carbazyl and indeno carbazyl can be to replace or unsubstituted group.

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Adopt technical scheme of the present invention, at least have following beneficial effect: use bipolarity organic compound of the present invention as electron transfer layer, the obtained device driving voltage reduces obviously, different according to glow color and matching structure, voltage reduces 1-3V usually, and current efficiency is significantly improved.Use bipolarity organic compound of the present invention as hole transmission layer, the current efficiency of obtained device and voltage have comparatively significantly improvement, and the life-span has also prolonged simultaneously.Select the mobility of electronics and hole mobile material at the bipolarity organic compound of the present invention of same horizontal extent, as electron transfer layer and hole transmission layer, the obtained device driving voltage further reduces, current efficiency also further promotes, adopt the device of bipolarity compound of the present invention to compare with only electron transfer layer or hole transmission layer, the life-span of device has prolonged more than one times.

Description of drawings

Fig. 1 is hole and the jump transmission schematic diagram of electronics in organic semiconducting materials.

Fig. 2 is the electron transfer reaction potential energy curve of hole and electric transmission.

Fig. 3 is the energy diagram that electronics vertical transition process relates in the organic semiconducting materials.

Fig. 4 is the structure drawing of device of TOF method of the present invention.

Embodiment

For fully understanding the present invention's purpose, feature and effect, by following concrete execution mode, the present invention is elaborated.

The present invention is by rational analysis of molecules, select existing Non-D-A bipolar materials, its frontier orbit (HOMO and LUMO) all is distributed on the same conjugated structure, with it as hole mobile material or electron transport material, take into account mobility and stability, will be conducive to the raising in device efficiency and life-span.

The invention provides a kind of organic electroluminescence device, it comprises negative electrode, anode, electron transfer layer, hole transmission layer and organic luminous layer, wherein electron transfer layer and/or hole transmission layer applying double pole organic compound; The general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively to be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl, triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

Transporting mechanism from organic semiconducting materials further specifies feature of the present invention and effect below.

For the transporting mechanism of organic semiconducting materials, theory is still immature at present, particularly for the more weak amorphous organic semiconducting materials of intermolecular force.Wherein a kind of theory of being used widely thinks that charge carrier is (hopping) transmission of jumping between adjacent molecule.As shown in Figure 1, after the HOMO of molecule track is seized 1 electronics, just produced holoe carrier, (a) transmitted in the hole to the right; Otherwise, after the LUMO of molecule track obtains 1 electronics, just having produced an electronic carrier, electronics transmits (b) left.Electronics is under the effect of extra electric field, and the frontier orbit between adjacent molecule (mainly being HOMO and LUMO track) jumps, and has formed directed movement in statistics, thereby has produced apparent electric current.

So hole and electronics can be regarded as the exchange reaction of electronics between adjacent molecule in the transmission between organic molecule, are expressed as:

M ^+/-+M ^*→M+M ^*+/-

Wherein, M ^+/-Represent molecule and be in cation or anion attitude, M ^*Represent the adjacent molecule that is in middle condition.

The potential energy level curve of this electron transfer reaction as shown in Figure 2.The energy of molecule vertical transition under the situation that geometric configuration before and after the reaction remains unchanged is defined as reorganization can (λ _+/-), according to its computational methods of energy level of molecule organic semiconductor as shown in Figure 3, be that the reorganization of hole transport can λ ₊=λ ₁+ λ ₂, the reorganization energy λ of electric transmission-=λ ₃+ λ ₄Specific explanations is as follows: for hole transport, and cation M ⁺Need be from adjacent neutral molecule M ^*On seize 1 electronics, keeping becoming neutral molecule under the cationic configuration; While neutral molecule M ^*Lose 1 electronics, under the configuration that keeps neutral molecule, become cation M ^*+Get betatopic moment at molecule, M and M ^*+Be not in their minimum energy configuration, but corresponding M ⁺And M ^*Minimum energy configuration, the relaxation energy sum between them are reorganization energy, i.e. λ ₊=λ ₁+ λ ₂The transmission situation of electronics is similar to the hole, M and M ^*-Be not in their minimum energy configuration in the moment of vertical transition, they are reorganization energy in the electronic transmission process to the energy summation of optimizing the configuration relaxation, namely λ-=λ ₃+ λ ₄The reorganization energy of molecule hole and electronics can obtain by the quantum chemistry calculation to condition, cation and anion in the molecule.

The Marucs equation is used to be described under the effect in no outfield, electronics or the hole jump speed k between adjacent two transmission points (site):

k = \frac{4 π^{2}}{h} V_{ab}^{2} \frac{\exp (- λ / 4 k_{B} T)}{\sqrt{4 πλ k_{B} T}}

Wherein, V _AbBe that electric charge shifts integration, λ is reorganization energy, k _BBe Boltzmann (Boltzmann) constant, T is absolute temperature, and h is Planck (Planck) constant.Therefore, shift theoretically according to the electronics of Marcus, under the constant condition of temperature (T), electric charge jump speed (k) only shifts integration (V with electric charge _Ab) relevant with reorganization energy (λ) these two material characteristic parameters.Reorganization can be able to obtain by quantum chemistry calculation, but is difficult to obtain by the method for calculating or test but the electric charge of amorphous organic material shifts integration.

By the Marucs equation, compare hole mobility k (h) and the electron mobility k (e) of organic material, expression formula can be reduced to:

\frac{k (h)}{k (e)} = {(\frac{V_{ab} (h)}{V_{ab} (e)})}^{2} [{(\frac{λ (e)}{λ (h)})}^{1 / 2} \exp (\frac{λ (e) - λ (h)}{4 k_{B} T})]

Choose the molecule with the big π of conjugation ring, and HOMO and LUMO be distributed on this group, therefore, electronics and hole are when intermolecular jumps, and the influence that spatial position change is brought is suitable, thereby the ratio of electric charge transfer integration is close to 1.

If it is also close that reorganization can be worth, the ratio of the mobility when then not having the outfield also should be close to 1, thereby molecule has good bipolar transmission characteristic.

According to above theory, molecule frontier orbit (HOMO and LUMO) is distributed on the same conjugated structure; The ratio that the electric charge of hole and electronics shifts integration is 0.5～2, is preferably 0.9～1.1; The difference of the reorganization energy of hole and electronics is less than 0.2eV.So, molecule has good bipolar transmission characteristic.By choosing suitable conjugated structure, can obtain higher mobility, electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.Simultaneously, adjust suitable substituents, material can be used as hole transmission layer (HTL) or electron transfer layer (ETL).

Organic electroluminescence device of the present invention is the conventional organic electroluminescence device that adopts conventional method to make, and preferably has OLED (OLED).

The typical structure of OLED of the present invention is: substrate/anode/hole transmission layer/organic luminous layer/electron transfer layer/negative electrode.

Substrate can use the substrate in traditional organic luminescent device, for example: glass or plastics.Anode material can adopt transparent high conductivity material, indium tin oxygen (ITO) for example, indium zinc oxygen (IZO), tin ash (SnO ₂), zinc oxide (ZnO).

Hole transmission layer can adopt bipolarity organic compound of the present invention or traditional hole transport layer material.The general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from phenyl, carbazole, alkoxyl, aryl or alkyl that the diphenyl amido replaces respectively; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

The tradition hole transport layer material can be N, N '-two (3-tolyl)-N, N '-diphenyl [1, the 1-xenyl]-4,4 '-diamines (TPD) or N, N '-diphenyl-N, N '-two (the 1-naphthyl]-(1,1 '-xenyl)-4,4 '-diamines tri-arylamine group materials such as (NPB).

Organic luminous layer can adopt conventional monolayers/multilayer organic light emission layer material, preferred doped structure material, for example adopt 9, the material that 10-two (2-naphthyl) anthracene (ADN) and four uncle Ding Ji perylenes (TBP) mix, its doping ratio is conventional organic luminous layer doping ratio, fluorescence 1-5% for example, phosphorescence 1-10%.Luminescent dye can be selected fluorescent material or phosphor material for use.

The electric transmission layer material can adopt bipolarity organic compound of the present invention, or conditional electronic transport layer material, for example Alq ₃The general structure of this bipolarity organic compound is as follows: Ar ₁Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from triazine, phenanthroline, oxadiazole, benzimidazole, phosphorus oxygen base, benzenesulfonyl, aryl or alkyl respectively; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

Negative electrode adopts metal and composition thereof structure, as Mg, Ag, Ca etc., also can be electron injecting layer/metal-layer structure, as LiF/Al, Li ₂Common cathode construction such as O, wherein electron injecting layer can be simple substance, compound or the mixture of alkali metal, alkaline-earth metal, transition metal, also can be the composite cathode structure that multilayer material constitutes.

Embodiment

Below, enumerate the present invention of embodiment and further describe, but the present invention is not limited to following embodiment.

Compounds property is measured

The bipolarity electric transmission layer material that this experiment is adopted sees Table 1, can obtain by commercial.

Table 1

The bipolarity hole transport layer material that this experiment is adopted sees Table 2, can obtain by commercial.

Table 2

Adopt the mobility of compound in following method mensuration table 1 and the table 2, and calculate the reorganization energy.

The mobility of The compounds of this invention was flown by the time, and (Time-Of-Flight, TOF) test obtains method.The structure drawing of device of TOF method as shown in Figure 4.4-1 is electrode, and 4-2 is sample, and 4-3 is transparency electrode, and 4-4 is incident light.

In the device architecture of TOF test, organic layer (thickness is usually at the order of magnitude of several microns to tens microns) is clipped among two electrodes, and one of them electrode is transparency electrode.Laser pulse sees through transparency electrode irradiation organic layer, makes organic layer at the photo-generated carrier near the generation at the interface " thin layer " of transparency electrode, at extra electric field (usually 10 ⁴～10 ⁶In the scope of V/cm) effect under, photo-generated carrier will pass through organic layer along the direction of extra electric field and finally arrive electrode.According to the difference of the direction of extra electric field, can test the mobility that obtains positive carrier (hole mobility) and charge carriers (electron mobility) respectively.Pass through electric current and the time relation of device under the oscillograph recording in the photo-generated carrier transition process, can determine that from figure charge carrier passes through the flight time of organic layer.In the TOF test, carrier mobility can be calculated by following expression formula:

μ＝d ²/Vτ

Wherein, μ represents carrier mobility, and d represents two distance between electrodes (thickness of organic layer), and V represents applied voltage, and τ represents mean time of flight.

The present invention adopts testing equipment shown in Figure 4 according to above-mentioned TOF principle, and test obtains hole mobility (μ _h) and electron mobility (μ _e).

Reorganization can calculate by quantification, carries out according to method shown in Figure 3.Adopt B3LYP/6-31G ^*Optimization geometric configuration and the corresponding energy of middle condition, cation and the anion of (being Becke ' s Three Parameter Hybrid Functional Using the LTP Correlation Functional) function calculation molecule, the condition molecule is optimized energy under the configuration in middle condition respectively at energy, cation and anion that cation and anion are optimized under the configuration respectively in calculating again, calculates λ as shown in Figure 3 at last ₁-λ ₄, and obtain molecular recombination energy λ _+/-All calculating are all finished at Gaussian 03 software.

Compound in table 1 and the table 2 draws as drawing a conclusion after measuring and calculate through said method, and electronics and hole mobility are greater than 10 ^-4Cm ²/ vs, the difference of the reorganization energy of hole and electronics is less than 0.2eV.Table 3 is concrete electronics and hole mobilities of part of compounds, and the reorganization of hole and electronics energy is poor.

Table 3

Device application embodiment

Embodiment 1 electron transfer layer Application Example

(1#)ITO/NPB/ADN:TBP/ET-1/LiF/Al

(2#)ITO/NPB/ADN:TBP/ET-28/LiF/Al

(3#)ITO/NPB/ADN:TBP/ET-56/LiF/Al

(4#)ITO/NPB/ADN:TBP/Alq ₃/LiF/Al

Glass plate ultrasonic processing in commercial cleaning agent of ITO transparency conducting layer will be coated with, wash in deionized water, at acetone: ultrasonic oil removing in the alcohol mixed solvent is baked under clean environment and removes moisture fully, with ultraviolet light and ozone clean, and with low energy cation bundle bombarded surface.

The above-mentioned glass plate substrate that has anode as in the vacuum chamber, is evacuated to 1 * 10 ^-5-9 * 10 ^-3Pa, on above-mentioned anode tunic vacuum evaporation NPB as hole transmission layer, evaporation speed 0.1nm/s, evaporation thickness 40nm.

Vacuum evaporation one deck ADN:TBP is as the luminescent layer of device on hole transmission layer, and thickness is 30nm, and the doping ratio of TBP is that 5%, ADN evaporation speed is 0.1nm/s, and TBP evaporation speed is 0.005nm/s.

At luminescent layer difference vacuum evaporation compd E T-1, ET-28, ET-56 and Alq ₃(Comparative Examples), as the electron transfer layer of device, evaporation speed is 0.1nm/s, evaporation thickness 20nm.

Vacuum evaporation LiF successively on electron transfer layer, Al is as the negative electrode of device, and wherein LiF evaporation speed is 0.05nm/s, evaporation thickness 0.5nm, Al evaporation speed is 1nm/s, evaporation thickness 100nm.

Adopt compd E T-1 according to the method described above, ET-28, ET-56 and Alq ₃(Comparative Examples) obtains sample 1# as electron transfer layer, 2#, 3#, 4#.The performance of above-mentioned sample sees Table 4, and wherein x and y represent chromaticity coordinates.

Table 4

" 50% life-span " refers to: brightness decay is life-span half-life of device to half employed time of initial value.

From table 3 and table 4 data as can be seen, sample 1#-3#, electron transfer layer have adopted bipolarity compd E T-1, ET-28 and ET-56, because its electron mobility is obviously than the Alq among the sample 4# ₃High 2 therefore, the raising of electron mobility has increased the electron concentration of recombination region more than the order of magnitude, and the probability of recombination luminescence increases, and effectively reduces driving voltage, has improved luminous efficiency.Because the bipolarity characteristics of ET compound itself, make compound this in must electronics and betatopic two states under, can both keep also ability of fabulous oxygen, thereby material itself is highly stable, shows in the device it then is to have prolonged device lifetime.

Embodiment 2 hole transmission layer Application Examples

(5#)ITO/HT-7/ADN:TBP/Alq ₃/LiF/Al

(6#)ITO/HT-46/ADN:TBP/Alq ₃/LiF/Al

(7#)ITO/HT-79/ADN:TBP/Alq ₃/LiF/Al

(8#)ITO/NPB/ADN:TBP/Alq ₃/LiF/Al

The above-mentioned glass plate substrate that has anode as in the vacuum chamber, is evacuated to 1 * 10 ^-5-9 * 10 ^-3Pa, at above-mentioned anode tunic vacuum evaporation compound H T-7 respectively, HT-46, HT-79 and NPB (Comparative Examples) be as hole transmission layer, evaporation speed 0.1nm/s, evaporation thickness 40nm.

Vacuum evaporation Alq on luminescent layer ₃, as the electron transfer layer of device, evaporation speed is 0.1nm/s, evaporation thickness 20nm.

Vacuum evaporation LiF successively on electron transfer layer, Al is as the negative electrode of device, and wherein LiF evaporation speed is 0.05nm/s, evaporation thickness 0.5nm, Al evaporation speed is lnm/s, evaporation thickness 100nm.

Adopt compound H T-7 according to the method described above, HT-46, HT-79 and NPB obtain sample 5# as hole transmission layer, 6#, 7#, 8#.The performance of above-mentioned sample sees Table 5, and wherein x and y represent chromaticity coordinates.

Table 5

From table 3 and table 5 data as can be seen, bipolarity compound H T-7, HT-46 and HT-79 respectively in sample 5#, 6# and 7# as hole transmission layer, the relative sample 8# with voltage of the current efficiency of device (NPB) has comparatively significantly improvement, and the life-span has also prolonged simultaneously.The hole mobility of HT-7, HT-46 and HT-79 is all slightly high than NPB, have in addition exceed 2 orders of magnitude, so the increase of hole concentration has guaranteed the efficient of device in the device, the bipolarity characteristics of compound itself have also guaranteed the stability of device.

Embodiment 3 electron transfer layers and hole transmission layer Application Example

(9#)ITO/HT-7/ADN:TBP/ET-1/LiF/Al

(10#)ITO/HT-21/ADN:TBP/ET-6/LiF/Al

(11#)ITO/HT-33/ADN:TBP/ET-9/LiF/Al

(12#)ITO/NPB/ADN:TBP/Alq ₃/LiF/Al

The above-mentioned glass plate substrate that has anode as in the vacuum chamber, is evacuated to 1 * 10 ^-5-9 * 10 ^-3Pa, at above-mentioned anode tunic vacuum evaporation compound H T-7 respectively, HT-21, HT-33 and NPB (Comparative Examples) be as hole transmission layer, evaporation speed 0.1nm/s, evaporation thickness 40nm.

At luminescent layer difference vacuum evaporation compd E T-1, ET-6, ET-9 and Alq3 (Comparative Examples), as the electron transfer layer of device, evaporation speed is 0.1nm/s, evaporation thickness 20nm.

Adopt compd E T-1 according to the method described above, ET-6, ET-9 and Alq ₃(Comparative Examples) adopts compound H T-7 simultaneously as electron transfer layer, and HT-21, HT-33 and NPB obtain sample 9# as hole transmission layer, 10#, 11#, 12#.The performance of above-mentioned sample sees Table 6, and wherein x and y represent chromaticity coordinates.

Table 6

In the present embodiment, the hole transmission layer of sample 9#-11# and electron transfer layer have all adopted the bipolarity compound, and the mobility of electronics and hole mobile material is in same horizontal extent in each device, with only electron transfer layer or hole transmission layer adopt the device of bipolarity compound of the present invention to compare (referring to table 4 and table 5), its driving voltage of device in the present embodiment has further reduced, current efficiency also further promotes, main cause is that the ratio of electronics and hole is mated more in the luminous recombination region, and the balance of the two greatly promotes the improvement of device performance.Simultaneously, stable, the carrier balance of material itself cause recombination region away from the negative electrode anode, all make the stability of device further improve, as shown in table 6, adopt the device of bipolarity compound of the present invention to compare (referring to table 4 and table 5) with only electron transfer layer or hole transmission layer, the life-span of device has prolonged more than one times.

Certainly, the present invention also can have other execution modes, and the above is the preferred embodiments of the present invention only, is not to limit protection scope of the present invention; Under the situation that does not deviate from spirit of the present invention and essence thereof, those of ordinary skill in the art are every to make various corresponding variations and modification according to content of the present invention, all belongs to the protection range of claim of the present invention.

Claims

1. organic electroluminescence device, it comprises negative electrode, anode, electron transfer layer, hole transmission layer and organic luminous layer, wherein electron transfer layer and/or hole transmission layer applying double pole organic compound; The general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl, triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

2. organic electroluminescence device according to claim 1, it is characterized in that, described Ar is the inferior conjugation condensed ring radical that contains aromatic ring, is selected from the divalent group of following replacement or unsubstituted aromatic hydrocarbons: naphthalene, anthracene, phenanthrene, fluorenes, naphtho-thiadiazoles, perylene, pyrene, triphenylene, benzanthracene, dibenzanthracene, fluoranthene, benzofluoranthrene, naphtho-fluoranthene, benzfluorene, BaP, benzophenanthrene or naphtho-phenanthrene.

3. organic electroluminescence device according to claim 2 is characterized in that, described Ar is inferior conjugation virtue condensed ring radical, is selected from following group:

Wherein, R is hydrogen atom, halogen atom or C ₁-C ₆₀Alkyl, alkane silica-based, aromatic hydrocarbons is silica-based, aryl or heterocyclic arene base, preferred hydrogen atom or methyl; Perhaps contain the divalent group of the heterocycle of aromatic hydrocarbon ring, be selected from:

4. according to each described organic electroluminescence device among the claim 1-3, it is characterized in that the substituting group of the bipolarity organic compound of using in the described electron transfer layer is for replacing or unsubstituted triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl.

5. organic electroluminescence device according to claim 4 is characterized in that, the triazine radical of described replacement is the triazine radical that diphenyl replaces.

6. organic electroluminescence device according to claim 4 is characterized in that, described aryl is to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

7. organic electroluminescence device according to claim 4 is characterized in that, the pyridine radicals of described replacement is phenylpyridyl.

8. organic electroluminescence device according to claim 4 is characterized in that, described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

9. according to each described organic electroluminescence device among the claim 1-8, it is characterized in that the substituting group of the bipolarity organic compound of using in the described hole transmission layer is for replacing or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl or aryl.

10. organic electroluminescence device according to claim 9, it is characterized in that, described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

11. organic electroluminescence device according to claim 10 is characterized in that, described alkoxyl phenyl is C _1-10Alkoxyl phenyl, preferred methoxyphenyl.

12. organic electroluminescence device according to claim 9 is characterized in that, the thienyl of described replacement is the phenyl thienyl.

13. organic electroluminescence device according to claim 9 is characterized in that, described aryloxy is phenyl oxygen base, xenyl oxygen base.

14. organic electroluminescence device according to claim 9 is characterized in that, described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

15. a bipolarity organic compound is used as the purposes of the electric transmission layer material in the organic electroluminescence device, the general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl.

16. bipolarity organic compound according to claim 15 is characterized in that as the purposes of the electric transmission layer material in the organic electroluminescence device triazine radical of described replacement is the triazine radical that diphenyl replaces.

17. bipolarity organic compound according to claim 15 is as the purposes of the electric transmission layer material in the organic electroluminescence device; it is characterized in that; described aryl is to replace or unsubstituted phenyl, and substituting group is selected from Ben oxadiazole base, phenyl benzimidazolyl, diphenylphosphine oxygen base, benzenesulfonyl or phenyl here.

18. bipolarity organic compound according to claim 15 is characterized in that as the purposes of the electric transmission layer material in the organic electroluminescence device pyridine radicals of described replacement is phenylpyridyl.

19. bipolarity organic compound according to claim 15 is characterized in that as the purposes of the electric transmission layer material in the organic electroluminescence device described alkyl is C _1-10Alkyl, preferable methyl, ethyl, propyl group.

20. a bipolarity organic compound is used as the purposes of the hole transport layer material in the organic electroluminescence device, the general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl or aryl.

21. bipolarity organic compound according to claim 20 is as the purposes of the hole transport layer material in the organic electroluminescence device, it is characterized in that, described aryl is to replace or unsubstituted phenyl, naphthyl, phenanthryl or anthryl, phenyl, alkoxyl phenyl that the phenyl that the preferred diphenyl amido of the phenyl of described replacement replaces, carbazyl phenyl, phenyl oxygen base phenyl, indeno carbazyl phenyl, benzothienyl phenyl, naphthyl phenyl, diphenyl replace, the preferred phenyl anthryl of the anthryl of described replacement.

22. bipolarity organic compound according to claim 20 is characterized in that as the purposes of the hole transport layer material in the organic electroluminescence device described alkoxyl phenyl is C _1-10Alkoxyl phenyl, preferred methoxyphenyl.

23. bipolarity organic compound according to claim 20 is characterized in that as the purposes of the hole transport layer material in the organic electroluminescence device thienyl of described replacement is the phenyl thienyl.

24. bipolarity organic compound according to claim 20 is characterized in that as the purposes of the hole transport layer material in the organic electroluminescence device described aryloxy is phenyl oxygen base, xenyl oxygen base.

25. bipolarity organic compound according to claim 20 is characterized in that as the purposes of the hole transport layer material in the organic electroluminescence device described alkoxyl is C ₁-C ₁₀Alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group or isopropoxy.

26. the bipolarity organic compound is as the electric transmission layer material in the organic electroluminescence device and the application of hole transport layer material, the general structure of this bipolarity organic compound is as follows: Ar ₁-Ar-Ar ₂, wherein Ar is the inferior conjugation condensed ring radical that contains aromatic ring; Ar ₁And Ar ₂Be independently selected from respectively and replace or unsubstituted carbazyl, aryloxy, alkoxyl, thienyl, benzothienyl, indeno carbazyl, triazine radical, phenanthroline base, pyridine radicals, aryl or alkyl; This bipolarity organic compound molecule frontier orbit is distributed on the big condensed ring of same conjugation; The difference of the reorganization energy of hole and electronics is less than 0.2eV; Electronics and hole mobility are greater than 10 ^-4Cm ²/ vs.

27. application according to claim 26 is characterized in that, and is wherein consistent with hole mobility as the electronics of the bipolarity organic compound of described electron transfer layer and hole transmission layer.