CN110504373A - A kind of high stability organic electroluminescence device - Google Patents

Abstract

The present invention relates to a kind of high stability organic electroluminescence devices, include successively from the bottom to top substrate, first electrode, organic functional material layer and second electrode, organic functional material layer includes: hole transporting zone, is located on first electrode；Luminescent layer is located on hole transporting zone, including subject and object material；Electron transporting zone is located on luminescent layer；Hole transporting zone successively includes hole injection layer, hole transmission layer and electronic barrier layer from the bottom to top, its hole-transporting layer and electronic barrier layer respectively include the first and second organic materials, about HOMO energy level, the first organic material of hole transmission layer is -5.2 to -5.6eV, its second organic material is -5.4 to -5.7eV, the first organic material of electronic barrier layer is -5.4 to -5.75eV, and the second organic material is -5.6 to -6.0eV, and ︱ HOMO_{First organic material}︱ < ︱ HOMO_{Second organic material}︱.

Description

A kind of high stability organic electroluminescence device

Technical field

The present invention relates to technical field of semiconductors, more particularly, to a kind of organic electroluminescence device and including its display Device.

Background technique

Organic electroluminescence device technology both can be used for manufacturing new display product, can be used for preparing novel illumination Product is expected to substitute existing liquid crystal display and fluorescent lighting, and application prospect is very extensive.Organic electroluminescence device conduct Current device, when to its two end electrodes apply voltage, and pass through positive negative electricity of the electric field action in organic layer functional material film layer On lotus, positive and negative charge is further compound in organic luminous layer, i.e. generation organic electroluminescent.

Organic electroluminescence device is generally multilayered structure, and the various auxiliary functional layers other than luminescent layer are to device It can equally play a crucial role.Reasonable device architecture can effectively improve the performance of device, electron injecting layer, electronics Transport layer, hole blocking layer, luminescent layer, electronic barrier layer, hole transmission layer and hole injection layer are widely used for improving device Performance.

High performance research is proposed to organic electroluminescence device at present to include: the driving voltage for reducing device, improve device Luminous efficiency, improve the service life etc. of device.In order to realize organic electroluminescence device performance continuous promotion, not only Organic electroluminescence device structure and the innovation of preparation process are needed, with greater need for the continuous research of organic electroluminescent functional material And innovation, produce the organic electroluminescent functional material of higher performance.

Carrier (hole and electronics) in organic electroluminescence device is under the driving of electric field respectively by two of device Electrode injection meets recombination luminescence into device, and in luminescent layer.Sky used in known existing organic electroluminescence device Cave transmission and electronic blocking layer material, such as Deng, all there is HOMO energy level and luminescent layer material of main part HOMO energy level difference is larger, is formed easily at material interface and gather charge, shadow Ring the OLED device service life.

In addition, the energy level of not all material can be well matched in organic electroluminescence device, between them Potential barrier seriously hinder being efficiently injected into for hole.Reasonable level structure is conducive to the energy level in device layers and forms ladder gesture It builds, can reduce the potential barrier of hole injection, reduce the driving voltage of device, luminous efficiency and service life so as to improve device.

Therefore, it is constantly needed to the organic electroluminescence device that exploitation has excellent luminous efficiency and service life.

Summary of the invention

The present invention is intended to provide a kind of organic electroluminescence with improved luminous efficiency, heat resistance and service life Part and display including it.

One object of the present invention realized and providing a kind of following organic electroluminescence devices, the organic electroluminescence Luminescent device is disposed with substrate, first electrode, organic functional material layer and second electrode, the organic functions from the bottom to top Material layer includes:

Hole transporting zone is located on the first electrode；

Luminescent layer is located on the hole transporting zone comprising material of main part and guest materials；

Electron transporting zone is located on the luminescent layer；

Wherein, the hole transporting zone successively includes hole injection layer, hole transmission layer and electronic blocking from the bottom to top Layer,

The hole transmission layer includes the first and second organic materials, the first organic material of hole-transporting layer HOMO energy level is -5.2eV to -5.6eV, preferably -5.3eV to -5.5eV, and the HOMO energy level of the second organic material be - 5.4eV to -5.7eV, preferably -5.4eV extremely -5.6eV, and ︱ HOMO the first organic material ︱ < ︱ second organic material of HOMO Expect ︱；And

The electronic barrier layer includes the first and second organic materials, wherein the first organic material of electronic barrier layer HOMO energy level is -5.4eV to -5.75eV, preferably -5.5eV to -5.65eV, and the HOMO energy level of the second organic material be - 5.6eV to -6.0eV, preferably -5.6eV extremely -5.9eV, and ︱ HOMO the first organic material ︱ < ︱ second organic material of HOMO Expect ︱；And lumo energy >=-2.6eV of the first organic material and the second organic material.

Preferably, between the second organic material of the electronic blocking layer material and the HOMO energy level of luminescent layer material of main part Absolute value≤0.4ev of difference.

It is including the organic of hole transmission layer containing the first and second organic materials of the invention and electronic blocking layer material In electroluminescent device, define that the HOMO of first and second organic material, this level-density parameter make anode and luminescent layer Potential barrier between interface reduces, this is conducive to hole and is injected into luminescent layer from anode, improves the injection efficiency in hole, and reduce The driving voltage of device, reduces the Accumulating charge of interface contacts, improves the stability and service life of device.Therefore, institute Hole transport and electronic blocking function can be had the function of simultaneously by stating hole transmission layer and electronic blocking layer material.Meanwhile the sky The exciton generated in luminescent layer can be locked in by the higher triplet excitation energy level of cave transport layer and electronic blocking layer material In luminescent layer, so as to improve the luminous efficiency of device.In addition, hole transmission layer of the present invention and electronic blocking layer material is higher Glass transition temperature improves the heat resistance of device.And the organic film being combined by two kinds of different materials can effectively change Kind molecules align and intermolecular interaction reduce the leakage current of device, improve device so that membranous layer stability is higher Service life.

Another object of the present invention is realized and providing a kind of display including above-mentioned organic electroluminescence device.

Detailed description of the invention

Fig. 1 schematically shows the cross-sectional view of the organic electroluminescence device of one embodiment of the invention.

Fig. 2 schematically shows the energy transfer machines of the organic electroluminescence device of one embodiment of the invention System.

Fig. 3-7 schematically shows the organic electroluminescence device comprising hole transmission layer of the present invention and electronic barrier layer Middle luminescent layer combination assumption diagram.

Specific embodiment

Hereinafter with reference to attached drawing, the present invention will be described in more detail, but is not intended to limit the present invention.

Listed any numberical range means to include being included in listed range to have the complete of identical numerical precision herein Portion's subrange.For example, " 1.0 to 10.0 " mean to include all sons between listed minimum value 1.0 and listed maximum value 10.0 Range (and including 1.0 and 10.0), that is to say, that with the minimum value equal to or more than 1.0 and most equal to or less than 10.0 The whole subranges being worth greatly.Any greatest measure limitation listed herein means to include the smaller numerical value of whole for being included in this paper Limitation, and any minimum value limitation listed herein means to include all bigger numerical value limitation for being included in this paper.Cause This, applicant retain modification include claims this specification right, be expressly recited fall into it is explicitly described herein Any subrange in range.

Abbreviation " EBI and EBII " used in herein means to constitute the organic material of electronic barrier layer, such as EBI meaning Refer to that the first organic material, EBII mean the second organic material；" HTI and HTII " means to constitute the organic material of electronic barrier layer, Such as HTI means that the first organic material, HTII mean the second organic material.

In the accompanying drawings, for the sake of clarity, the size of layer and region can be exaggerated.It will also be understood that when layer or element are known as Another layer perhaps substrate " on " when the layer or element can be directly on another layer perhaps and on substrate or can also deposit In middle layer.In addition, it will also be understood that when layer be known as two layers " between " when, this layer can be unique between the two layers Layer, or one or more middle layer also may be present.Identical appended drawing reference indicates identical element in full text.

Hereinafter, by description according to the organic electroluminescence device of embodiment.

Fig. 1 schematically shows the cross-sectional view of the organic electroluminescence device of one embodiment of the invention.Reference Fig. 1, the organic electroluminescence device of one embodiment of the invention be disposed with from the bottom to top substrate 1, first electrode 2, Hole transporting zone A, luminescent layer 6, electron transporting zone B and second electrode 10, wherein hole transporting zone A is from the bottom to top successively Including hole injection layer 3, hole transmission layer 4 and electronic barrier layer 5, and electron transporting zone B successively includes sky from the bottom to top Cave barrier layer 7, electron transfer layer 8 and electron injecting layer 9.

As the substrate of organic electroluminescence device of the present invention, any commonly employed base in organic electroluminescence device can be selected Plate.Example is transparent substrate, such as glass or transparent plastic substrate；Opaque substrate, such as silicon substrate；Flexible PI ilm substrate.It is different Substrate has different mechanical strengths, thermal stability, the transparency, surface flatness, waterproofness, according to property difference, user To difference.In the present invention, it is preferred to use transparent substrate.The thickness of substrate is not particularly limited.

First electrode is formed on substrate, first electrode can be relative to each other with second electrode.First electrode can be anode. First electrode can be transmission electrode, half transmitting electrode or reflecting electrode.When first electrode is transmission electrode, first electrode Transparent metal oxide can be used to be formed, for example, indium tin oxide (ITO), indium-zinc oxide (IZO), zinc oxide (ZnO) or Indium tin zinc oxide (ITZO) etc..When first electrode is half transmitting electrode or reflecting electrode, first electrode may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr or metal mixture.The thickness of first electrode layer depends on used material, usually 50-500nm, preferably 70-300nm and more preferably 100-200nm.

The organic functional material layer being set between first electrode and second electrode successively includes hole transport from the bottom to top Region, luminescent layer and electron transporting zone.

Hole transporting zone may be provided between first electrode and luminescent layer.Hole transporting zone may include hole injection Layer, hole transmission layer and electronic barrier layer, but not limited to this.For example, referring to Fig. 1, hole transporting zone may include from the bottom to top Hole injection layer, hole transmission layer and the electronic barrier layer being successively set on first electrode.

In general, the organic material --- its be easily oxidized and electrochemically stable when it is oxidized --- with p-type property It is mainly used as hole-injecting material or hole mobile material.Meanwhile with N-shaped property organic material --- its be easily reduced and It is electrochemically stable when being reduced --- it is used as electron injection material or electron transport material.As emitting layer material, preferably both There is the material of N-shaped property again with p-type property, it is stable when it is oxidized and reduced, further preferably have when forming exciton Have higher for converting exciton to the material of the luminous efficiency of light.

The material of hole injection layer is usually preferably with the material of high work function, so that hole is easily injected into organic material In the bed of material.In the present invention, the material of hole injection layer at least contains one in material shown in general formula (17), (18) or (19) Kind:

Wherein, in general formula (17), F₁-F₃It is independently represented each other substituted or unsubstituted C_6-30Aryl, substitution do not take 3 to 30 unit's heteroaryls in generation, and F₁-F₃It can be identical or different；

In general formula (18) and general formula (19), G₁-G₆Be independently represented each other hydrogen, itrile group, halogen, amide groups, alkoxy, Ester group, nitro, C-R₁₁, substituted or unsubstituted C_6-30Aryl, 3 to 30 unit's heteroaryls, wherein R₁₁For the C of linear chain or branched chain_1-20 Alkyl, condition are G₁-G₆It is not simultaneously hydrogen；

Wherein in the case where heteroaryl, the hetero atom is selected from least one of N, O and S atom.

In a preferred embodiment of the invention, the material of used hole injection layer is selected from following (a) to (j) One of:

The thickness of hole injection layer of the invention can be 5-100nm, preferably 5-50nm and more preferably 5-20nm.

Hole injection layer can also be comprising for improving conductive charge generating material.The charge generating material can be with For p-doping object.The example of the non-limiting compound of P- dopant is, for example, quinone derivative, such as four cyano quinone bismethane (TCNQ) and the fluoro- four cyano -1,4- benzoquinones bismethane (F4-TCNQ) of 2,3,5,6- tetra-；Six azepine Sanya benzene derivatives, such as 2, Six cyano -1,4,5,8,9,12- of 3,6,7,10,11-, six azepine triphenylene (HAT-CN)；Cyclopropane derivative, such as 4,4 ', 4 "-((1E, 1 ' E, 1 " E)-cyclopropane -1,2,3- trimethylene three (cyano formyl subunit)) three (2,3,5,6- ptfe benzyls)； Metal oxide, such as tungsten oxide and molybdenum oxide.

Hole transmission layer of the invention may be provided on hole injection layer.The hole transport layer material has including first Machine material and the second organic material, wherein the ratio of the first organic material and the second organic material is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 30:70 are to 70:30, based on quality.In addition, first organic material of the hole transmission layer The HOMO energy level of material is -5.2eV to -5.6eV, preferably -5.3eV extremely -5.5eV, and the HOMO energy level of its second organic material For -5.4eV to -5.7eV, preferably -5.4eV to -5.6eV, and ︱ HOMO_{First organic material}︱ < ︱ HOMO_{Second organic material}︱；And it is described Absolute value≤0.4ev of the first organic material of transport layer and hole injection layer material HOMO energy level difference.

Electronic blocking of the invention may be provided at layer by layer hole transport layer by layer on.The electronic blocking layer material includes the One organic material and the second organic material, wherein the ratio of the first organic material and the second organic material is 1:99 to 99:1, it is excellent It is selected as 10:90 to 90:10, more preferably 30:70 to 70:30, based on quality.In addition, the first of the electronic barrier layer has The HOMO energy level of machine material is -5.4eV to -5.75eV, preferably -5.5eV to -5.65eV, and its second organic material HOMO energy level is -5.6eV to -6.0eV, preferably -5.6eV to -5.9eV, and ︱ HOMO_{First organic material}︱ < ︱ HOMO_{Second organic material}︱； And lumo energy >=-2.6eV of the first organic material and the second organic material.

Fig. 2 schematically shows the energy transfer machines of the organic electroluminescence device of one embodiment of the invention System, wherein a represents hole transmission layer, and b represents electronic barrier layer, and c represents the object of luminescent layer, and d represents the main body of luminescent layer, with And e represents electron transfer layer.

In one embodiment, the HOMO energy level of second organic material of electronic barrier layer and luminescent layer material of main part Between difference absolute value be≤0.4ev.Lesser energy barrier makes between the electronic blocking layer material and emitting layer material Obtaining hole can easily be injected into luminescent layer via hole transporting zone.In one embodiment, the electronic barrier layer The first and second organic materials lumo energy and the luminescent layer master, guest materials lumo energy between difference be >= 0.2ev, preferably >=0.3ev and more preferably >=0.5ev, this can be effectively prevented electronics and is injected into hole transport from luminescent layer In region.Therefore, the electronic barrier layer had not only had the function of hole transport but also had had the function of electronic blocking.

In a preferred embodiment of the present invention, the first and of hole transmission layer of the invention and electronic barrier layer Two organic materials are each independently selected from one of general formula (1), general formula (2) and general formula (3):

Wherein, in general formula (1), X, X₁It is each independently selected from singly-bound, carbon atom, N- (R₅), sulphur atom, oxygen atom, Asia The C of vinyl, linear chain or branched chain_1-20The C of alkyl-substituted alkylidene, linear chain or branched chain_1-20Alkyl-substituted silicylene, C_6-20One of the alkylidene that aryl replaces；

If there is R₅, then its may be the same or different selected from hydrogen atom, protium atom, D-atom, tritium atom, fluorine atom, The C of phosphoric acid or its salt, linear chain or branched chain_1-20The C of alkyl-substituted alkyl, linear chain or branched chain_1-20Alkyl-substituted silicylene, Aryl with 5 to 30 carbon atoms, with 5 to 30 carbon atoms and at least one be selected from heteroatomic heteroaryl of N, O and S Base, wherein the group can be optionally by the C of linear chain or branched chain in the case where rear the two_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl Base replaces；

Z represents nitrogen-atoms or C-R₆, wherein R₆May be the same or different selected from hydrogen atom, protium atom, D-atom, tritium atom, Fluorine atom, cyano, phosphoric acid or its salt, linear chain or branched chain C_1-20The C of alkyl-substituted alkyl, linear chain or branched chain_1-20Alkyl replaces Silicylene, the aryl with 5 to 30 carbon atoms, with 5 to 30 carbon atoms and at least one be selected from N, O and S it is miscellaneous The heteroaryl of atom, wherein the group can be optionally by the C of linear chain or branched chain in the case where rear the two_1-20Alkyl, C_6-20Virtue Base, C_5-20Heteroaryl replaces, two of them or more R₆Group can be connected to each other and can form ring structure；

Ar₁、Ar₂、Ar₃、Ar₄It is independently represented each other the C of singly-bound, linear chain or branched chain_1-20Alkylidene has 5 to 30 carbon The C of the arlydene of atom, linear chain or branched chain_1-20Alkyl-substituted silicylene has 5 to 30 carbon atoms and at least one choosing From the heteroatomic inferior heteroaryl of N, O and S, wherein the group can be optionally by linear chain or branched chain in the case where rear the two C_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces, and wherein Ar1, Ar2 group can also connect cyclization；

M, n, p, q, s and t are equal to 0 or 1；And m+n+p+q >=1 and m+n+s+t >=1；

R₁、R₂、R₃And R₄It is independently represented each other hydrogen atom, general formula (4), structure shown in general formula (5) or general formula (6), item Part is R₁、R₂、R₃And R₄It is not simultaneously hydrogen atom；

Wherein, in general formula (4) and general formula (5): X₂、X₃It is independently represented each other singly-bound, oxygen atom, sulphur atom, sub- ethylene The C of base, linear chain or branched chain_1-20The C of alkyl-substituted alkylidene, linear chain or branched chain_1-20Alkyl-substituted silylation, C_6-20Aryl Substituted alkylidene, C_1-20Alkyl-substituted imido grpup, C_6-20Imido grpup, the C of aryl substitution_5-20The imido grpup that heteroaryl replaces One of；

Y₁Represent N atom or C-R with may be the same or different, wherein R represent with may be the same or different hydrogen atom, protium atom, D-atom, tritium atom, fluorine atom, cyano, phosphoric acid or its salt, linear chain or branched chain C_1-20Alkyl-substituted alkyl, straight chain or branch The C of chain_1-20Alkyl-substituted silylation, has 5 to 30 carbon atoms and at least one at the aryl with 5 to 30 carbon atoms Heteroatomic heteroaryl selected from N, O and S, wherein the group can be optionally by linear chain or branched chain in the case where rear the two C_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Two of them or more R group can be connected to each other and can form ring knot Structure；

R₆、R₇It is independently represented each other hydrogen atom, protium atom, D-atom, tritium atom, fluorine atom, phosphoric acid or its salt, straight chain Or the C of branch_1-20The C of alkyl-substituted alkyl, linear chain or branched chain_1-20Alkyl-substituted silylation has 5 to 30 carbon atoms Aryl, with 5 to 30 carbon atoms and at least one be selected from N, O and S heteroatomic heteroaryl, general formula (7) or general formula (6) Shown structure；Wherein in the case where aryl and heteroaryl, the group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20 Aryl, C_5-20Heteroaryl replaces；

Wherein, in general formula (7): Y₂Represent N atom or C-R with may be the same or different₁₀, wherein R₁₀It may be the same or different Ground represents hydrogen atom, protium atom, D-atom, tritium atom, fluorine atom, cyano, phosphoric acid or its salt, linear chain or branched chain C_1-20Alkyl takes The C of the alkyl in generation, linear chain or branched chain_1-20Alkyl-substituted silylation, has 5 to 30 at the aryl with 5 to 30 carbon atoms Carbon atom and at least one heteroatomic heteroaryl selected from N, O and S, wherein the group can appoint in the case where rear the two Choosing is by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；

X₄、X₅Be independently represented each other singly-bound, oxygen atom, sulphur atom, ethenylidene, linear chain or branched chain C_1-20Alkyl takes The C of the alkylidene in generation, linear chain or branched chain_1-20Alkyl-substituted silylation, C_6-20Alkylidene, the C of aryl substitution_1-20Alkyl replaces Imido grpup, C_6-20Imido grpup, the C of aryl substitution_5-20One of the imido grpup that heteroaryl replaces；

General formula (7) is connected by simultaneously ring mode with general formula (4) or general formula (5), and * is expressed as connection site, can only when being connected Take two adjacent sites, general formula (7) and general formula (4) or general formula (5) and when ring connects, connection site Y₁It is expressed as carbon atom；

In general formula (6): R₈、R₉It is independently represented each other the aryl with 5 to 30 carbon atoms, there are 5 to 30 carbon originals Son and at least one heteroatomic heteroaryl selected from N, O and S, the group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；R₈、R₉Cyclization can also be connected；

In general formula (2): L₁、L₂、L₃It is independently represented each other singly-bound, the arlydene with 5 to 30 carbon atoms, has 5 Heteroatomic inferior heteroaryl of N, O and S are selected from at least one to 30 carbon atoms, wherein in the case where rear the two, it is described Group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；L₁、L₂、L₃It can be connected to each other two-by-two And ring structure can be formed；

Ar₅、Ar₆、Ar₇Be independently represented each other arlydene with 5 to 30 carbon atoms, have 5 to 30 carbon atoms and At least one is selected from the imido grpup of the heteroatomic inferior heteroaryl of N, O and S, 5 to 30 carbon atoms, and the group can be optionally straight The C of chain or branch_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Ar₅、Ar₆、Ar₇It can be connected to each other and can be formed two-by-two Ring structure；

Ar₅、Ar₆、Ar₇It is also denoted as general formula (4), general formula (5), one in general formula (6), wherein on the general formula Group X₂、X₃、Y₁、R₆、R₇There is meaning as described above with *；

In general formula (3): D₁、D₂、D₃It is independently represented each other singly-bound, the arlydene with 5 to 30 carbon atoms, has 5 Heteroatomic inferior heteroaryl of N, O and S are selected from at least one to 30 carbon atoms, wherein in the case where rear the two, it is described Group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；L₁、L₂、L₃It can be connected to each other two-by-two And ring structure can be formed；

Ar₈、Ar₉、Ar₁₀It is independently represented each other the arlydene with 5 to 30 carbon atoms, there are 5 to 30 carbon atoms It is selected from the imido grpup of the heteroatomic inferior heteroaryl of N, O and S, 5 to 30 carbon atoms at least one, the group can optional quilt The C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Ar₈、Ar₉、Ar₁₀It can be connected to each other two-by-two and can shape At ring structure；

Ar₈、Ar₉、Ar₁₀In at least one be general formula (4), general formula (5), one in general formula (6)；Wherein on the general formula Group X₂、X₃、Y₁、R₆、R₇Respectively there is meaning as described above with *.

In a preferred embodiment of the present invention, general formula (2) is expressed as general formula (9) one of to general formula (12):

Wherein, Ar₅To Ar₇It indicates the arlydene with 5 to 30 carbon atoms, there are 5 to 30 carbon atoms and at least one The imido grpup of heteroatomic inferior heteroaryl selected from N, O and S, 5 to 30 carbon atoms, the group can be optionally by linear chain or branched chain C_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；

And L₁-L₃、R₆-R₉、Y₁And X₂-X₃All have meaning described above.

In a preferred embodiment of the present invention, general formula (3) is expressed as general formula (13) one of to general formula (16):

Wherein, Ar₈And Ar₁₀It indicates the arlydene with 5 to 30 carbon atoms, there is 5 to 30 carbon atoms and at least one The imido grpup of a heteroatomic inferior heteroaryl selected from N, O and S, 5 to 30 carbon atoms, the group can be optionally by straight chain or branch The C of chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；

And D₁-D₃、R₆-R₉、Y₁And X₂-X₃All have meaning described above.

In a preferred embodiment of the present invention, in general formula (1)Part is selected from one of the following:

And wherein Z, Ar₁、Ar₂And R₅With meaning described above.

In a preferred embodiment of the present invention, first organic material of hole transmission layer is selected from following compounds One of:

In a preferred embodiment of the present invention, second organic material of hole transmission layer is selected from following compounds One of:

In a preferred embodiment, first organic material of electronic barrier layer is selected from one of following compound:

In a preferred embodiment, second organic material of electronic barrier layer is selected from one of following compound:

The hole mobility of hole transmission layer and electronic blocking layer material of the invention is 1 × 10^-5To 1 × 10^-2cm²/ It (Vs), is preferably 1 × 10^-4To 1 × 10^-2cm²/ (Vs) and more preferably 1 × 10^-4To 1 × 10^-3cm²/(V·s)。

The glass transition temperature of hole transmission layer and electronic blocking layer material of the invention is >=120 DEG C, preferably >= 130 DEG C and more preferably >=140 DEG C.

The thickness of electronic barrier layer of the invention can be 1-200nm, preferably 10-100nm.

The thickness of hole transmission layer of the invention can be 1-200nm, preferably 10-100nm.

Luminescent layer may be provided on hole transporting zone.The material of luminescent layer is a kind of by being received respectively from hole The hole and electronics of transport layer and electron transfer layer, and by received hole and electronics in conjunction with and the material of visible light can be issued Material.Its specific example includes the metal complex, various metal complexes, anthracene derivant, double benzene second of 8-hydroxyquinoline derivative Alkene benzene derivative, pyrene derivatives, oxazole derivatives and poly- to styrene derivative etc., but not limited to this.In addition, luminescent layer can be with Include material of main part and guest materials.As the material of main part and guest materials of organic electroluminescence device luminescent layer of the present invention, Can be used the emitting layer material commonly known in the art for organic electroluminescence device, the material of main part can for Such as thiazole, benzimidizole derivatives, poly-diakyl fluorene derivative or bis- (9- carbazyl) biphenyl (CBP) of 4,4'-；It is described Guest materials can be derivative for such as quinacridone, cumarin, rubrene and its derivative, 1-benzopyran derivatives, rhodamine Object or aminostyrl derivative.In a preferred embodiment of the invention, used luminescent layer material of main part is selected from One of following EMH-1 to EMH-22 or a variety of combinations:

In addition, in order to improve fluorescence or phosphorescent characteristics, luminescent material may also include phosphorescence or fluorescent material.Phosphor material Specific example includes the phosphor material of the metal complex of iridium, platinum etc..It is, for example, possible to use Ir (ppy)₃[(the 2- phenyl of fac- tri- Pyridine) iridium] etc. green phosphorescent materials, the red phosphorescence materials such as the blue phosphor materials such as FIrpic, FIr6 and Btp2Ir (acac). For fluorescent material, can be used it is usually used in this field those.In a preferred embodiment of the invention, it is used Luminescent layer guest materials be selected from one of following EMD-1 to EMD-23:

In luminescent layer of the invention, the ratio of used material of main part and guest materials is 99:1-70:30, preferably For 99:1-85:15 and more preferably 97:3-87:13, based on quality.

In addition, efficient organic electroluminescence device in order to obtain, in addition to above-mentioned used fluorescence or phosphorescence host and guest Except body material, other guest materials is also can be used in luminescent layer, or uses a variety of guest materials, and guest materials can be simple Fluorescent material, delayed fluorescence (TADF) material or phosphor material, or by different fluorescent materials, TADF material, phosphorescence collocation group It closes, luminescent layer can be single emitting layer material, or the recombination luminescence layer material being laterally or longitudinally superimposed.Structure Following a variety of constructions are enumerated at the luminescent layer of above-mentioned organic electroluminescence device:

(1) single light emitting layer material；

(2) any combination of blue light emitting layer material and green, yellow or emitting red light layer material, and regardless of Tandem, as shown in Figure 3；

(3) any two combinations of blue light emitting layer material and green, yellow or emitting red light layer material, and regardless of Tandem, as shown in Figure 4；

(4) blue light emitting layer material, green light emitting layer material, red light emitting layer material are laterally arranged, As shown in Figure 5；

(5) any combination of blue light emitting layer material and green, yellow or emitting red light layer material, and pass through Articulamentum carries out charge transmission, forms two stacked device architectures, as shown in Figure 6；

(6) any two combinations of blue light emitting layer material and green, yellow or emitting red light layer material, and pass through company It connects layer and carries out charge transmission, form three stacked device architectures, as shown in Figure 7.

Preferably, the organic luminescence function layer includes such luminescent layer comprising blue, green, red, yellow have 1 kind or at least two kinds of of combination in machine emitting layer material.

As described above, G represents light in Fig. 3 into Fig. 5,6 represent luminescent layer, and EM1, EM2 and EM3 represent different shine Layer material.

In figs. 6 and 7,6 luminescent layer is represented, 300 represent organic luminescence function layer, and 610,620 and 630 represent articulamentum.

In order to adjust effective combination of the carrier electric charge in luminescent layer, the luminescent layer 6 of above-mentioned composition OLED illuminant Film thickness can be adjusted arbitrarily as needed, or the luminescent layer of different color is replaced stack combinations as needed, can also be in adjoining The electric charge barrier layer etc. of different function purposes is added in the organic layer of luminescent layer.Preferably, the thickness of luminescent layer of the invention can Think 5-60nm, preferably 10-50nm, more preferably 20-45nm.

In the present invention, electron transporting zone can successively include the hole barrier being arranged on luminescent layer from the bottom to top Layer, electron transfer layer and electron injecting layer, but not limited to this.

Hole blocking layer is to stop to pass through luminescent layer from anode injected holes and enter cathode, thus extends the longevity of device Order and improve the layer of the efficiency of device.Hole blocking layer of the invention may be provided on luminescent layer.As Organic Electricity of the present invention The public known chemical combination with hole barrier effect in the prior art can be used in the hole barrier layer material of electroluminescence device Object, for example, bis- (2- methyl -8- the quinoline) -4- phenyl phenates of the phenanthroline derivatives such as bathocuproine (referred to as BCP), aluminium (III) (BAlq) metal complex of 8-hydroxyquinoline derivatives, various rare earth complexes, oxazole derivatives, the triazole derivative, three such as Oxazine derivatives etc..The thickness of hole blocking layer of the invention can be 2-200nm, preferably 5-150nm and more preferably 10- 100nm。

Electron transfer layer may be provided on luminescent layer or (if present) hole blocking layer.Electron transport layer materials are A kind of easy electronics for receiving cathode and by the material of received electronics transfer to luminescent layer.It is preferred that having high electron mobility Material.As the electron transfer layer of organic electroluminescence device of the present invention, can be used commonly known in the art for having The electron transport layer materials of organic electroluminescence devices, for example, with Alq₃, BAlq be representative 8-hydroxyquinoline derivative metal network Close object, various metal complexes, triazole derivative, pyrrolotriazine derivatives, oxadiazole derivatives, thiadiazoles derivative, two Asia of carbonization Amine derivative, quinoxaline derivant, phenanthroline derivative, silicon base compound derivative etc..The thickness of electron transfer layer of the invention Degree can be 10-80nm, preferably 20-60nm and more preferably 25-45nm.

Electron injecting layer may be provided on electron transfer layer.Electron injecting layer material usually preferably has low work function Material so that electronics is easily injected into organic functional material layer.Electronics as organic electroluminescence device of the present invention is infused Enter layer material, the electron injecting layer material commonly known in the art for organic electroluminescence device can be used, for example, Lithium；Lithium salts, such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or Lithium Azide；Or cesium salt, cesium fluoride, cesium carbonate or Azide Caesium.The thickness of electron injecting layer of the invention can be 0.1-5nm, preferably 0.5-3nm and more preferably 0.8-1.5nm.

Second electrode may be provided on electron transporting zone.Second electrode can be cathode.Second electrode EL2 can be Transmission electrode, half transmitting electrode or reflecting electrode.When second electrode is transmission electrode, second electrode may include for example Li, Yb, Ca, LiF/Ca, LiF/Al, Al, Mg, BaF, Ba, Ag or its compound or mixture；When second electrode is half transmitting When electrode or reflecting electrode, second electrode may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/ Ca, LiF/Al, Mo, Ti or its compound or mixture.

Depending on material used, organic electroluminescence device of the invention can for top emission type, bottom emission type or Dual-side luminescent type.

In the case where organic electroluminescence device is top light emitting type, first electrode can be reflecting electrode, and Two electrodes can be transmission electrode or half transmitting electrode.In the case where organic electroluminescence device is bottom emission type, First electrode can be transmission electrode or half transmitting electrode, and second electrode can be reflecting electrode.

Organic electroluminescence device may also include encapsulating structure.The encapsulating structure can be to prevent external substance such as moisture Enter the protection structure of the organic layer of organic electroluminescence device with oxygen.The encapsulating structure can be such as tank, such as glass jar Or metal can；Or the film of covering organic layer whole surface.

During preparing organic electroluminescence device, such as can be by being laminated first electrode in succession on substrate, having Machine function material layer and second electrode prepare organic electroluminescence device of the invention.About this point, physical vapor can be used Deposition method, such as sputtering method or Electron Beam Vapor method or vacuum vapour deposition, but not limited to this.Also, it can be for example, by vacuum Above compound is used to form organic functional material layer by sedimentation, vacuum vapour deposition or solution coating process.About this point, solution Cladding process means spin-coating method, dip coating, jet printing method, screen printing method, spray-on process and rolling method, but not limited to this.Vacuum Vapor deposition means in vacuum environment, and material is heated and is plated on substrate.In the present invention, it is preferred to carry out shape using vacuum vapour deposition At each layer.

In addition, it is necessary to which explanation, the material of the present invention for being used to form each layer can individually form a film and make It for single layer use, forms a film after can also being mixed with other materials and is used as single layer, can also be between the layer individually to form a film Stepped construction, the stepped construction between the layer that forms a film after mixing or the layer that individually forms a film with mix after the stacking of layer that forms a film Structure.

In another aspect of this invention, it is related to a kind of display comprising one or more organic electroluminescence hairs of the invention Optical device, and in the case where including multiple devices, the device laterally or longitudinally stack combinations.

In a preferred embodiment, display may include organic light emission respectively with blue, green, red three kinds of colors One of device of material layer or a variety of combinations, and the hole transmission layer that the device is all the same with film thickness and material And electronic barrier layer.In another preferred embodiment, display is by may include respectively having blue, green, red three kinds of colors One of the device of organic light emitting material or a variety of combinations, and the device have material identical but film thickness respectively not Identical hole transmission layer and electronic barrier layer.

In another preferred embodiment, display may include organic hair respectively with blue, green, red three kinds of colors One of device of optical material layer or a variety of combinations, and the device have that film thickness is identical but its material at least there are two types of Combined hole transmission layer and electronic barrier layer.In still another preferred embodiment, display may include respectively have it is blue, One of device of organic light emitting material of green, red three kinds of colors or a variety of combinations, and the device has film thickness At least there are two types of combined hole transmission layers and electronic barrier layer for different and its material.

It should be noted that illustrative embodiment has been disclosed herein, although which use specific arts Language, but these terms are only used to and be interpreted only as generic and descriptive meaning, and not for purposes of limitation.In some feelings Under condition, as with submitting for the application and to apparent to those of ordinary skill in the art, unless specifically indicating, otherwise It can be used alone in conjunction with feature, characteristic and/or the element that specific embodiment describes or be retouched in conjunction with other embodiments Feature, characteristic and/or the element stated are applied in combination.Correspondingly, it will be understood by those skilled in the art that without departing substantially from essence of the invention Under the premise of mind and range, a variety of variations can be made in terms of form and details.

Following embodiment is intended to preferably explain the present invention, but the scope of the present invention is not limited thereto.

Embodiment

Detection method used herein is as follows:

Glass transition temperature Tg: pass through differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning Calorimeter) measurement, 10 DEG C/min of heating rate；

HOMO energy level: for organic optoelectronic material HOMO energy level test there are many method or instrument means, including CV (cyclic voltammetry), UPS (ultraviolet photoelectron spectroscopy), AC serial equipment (the atmosphere photoelectricity of Japanese Li Yan gauge company production Sub- power spectrum), the IPS serial equipment (vacuum photoelectron spectroscopy) etc. of heart Tian Yi company production other than above-mentioned means, may be used also To pass through Gaussian Computation, and semiempirical judgement is combined, determine the level of HOMO energy level, the accurate HOMO energy level that measures is for research OLED device structure matching is extremely important.In the means that above-mentioned all HOMO energy levels determine, for CV method by solvent effect, data are accurate Degree and reproducibility are poor, other include UPS method, and AC method, IPS method is all ultraviolet photoelectron spectroscopy for cardinal principle Measuring principle, wherein UPS measurement not only needs ultrahigh vacuum, and apparatus value is expensive, and because the people of measurement and instrument are set The difference set, there are larger differences for data parsing result.AC method in principle, needs for sample to be placed in aerobic dry sky There is certain influence to sample in compression ring border, oxygen element, data reproduction and consistency are all poor, and IPS method measures HOMO energy level, It is that membrane material is placed in vacuum environment, ultraviolet monochromatic light is applied directly to sample surfaces, by measuring photoelectricity electron current, from And determine the size of HOMO energy level, belong to direct measurement.Think that IPS mensuration is being surveyed based on the above analysis and practice, inventor When measuring the HOMO energy level of OLED material, reproducibility, consistency and accuracy also highest.The HOMO energy of the related to material of the present invention Grade is the measurement means of IPS.Specific measurement method is as follows:

Using vacuum evaporation equipment, in vacuum degree 1.0E^-5Under Pa pressure, control evaporation rate isMaterial is deposited Onto ito substrate, film thickness 60-80nm carries out the HOMO energy level of sample film then using IPS3 measuring device is used Measurement, measurement environment are 10-2Pa vacuum environment below；

Eg energy level: uv-spectrophotometric (UV absorption) baseline and the uplifted side picture of the first absorption peak based on material monofilm are cut Line intersects point value with tangent line and baseline and calculates.

Lumo energy: the difference based on aforementioned HOMO energy level and Eg energy level is calculated.

The work function of electrode material: it is tested under atmospheric environment using the surface work function tester that Shanghai University researches and develops.

Hole mobility: being fabricated to single charge devices for material, is measured with SCLC method.

Prepare hole transport layer material

I. the first organic material of hole transmission layer used in preparing:

Prepare compound HTI-1

In a nitrogen atmosphere, raw material II -1 0.01mol raw material I-1,0.03mol is added into 500ml there-necked flask, with mixing Solvent (90ml toluene, 45ml ethyl alcohol) dissolution, is then added 0.04mol Na₂CO₃Aqueous solution (2M).It is small to stir the mixture for 1 When, then it is added 1 × 10^-4mol Pd(PPh₃)₄, it is heated to reflux 15 hours.Using TLC observing response, until the reaction is complete.From So cooling, filtering rotates filtrate to no fraction.Obtained material is purified by silicagel column (petroleum ether is as eluant, eluent), is obtained Target product, purity 99.5%, yield 72.9%.

Elemental analysis structure (molecular formula C₄₂H₂₅NO₃): theoretical value: C, 85.26；H,4.26；N,2.37；Test value: C, 85.27；H,4.25；N,2.41.ESI-MS(m/z)(M⁺): theoretical value 591.18, measured value 591.34.

Prepare compound HT1-29

In a nitrogen atmosphere, into 500ml three-necked flask be added 0.01mol raw material I-2,0.03mol raw material II -2, 0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃With 5 × 10^-5Mol tri-tert phosphorus, 150ml toluene is then added will It is dissolved, and is heated to 100 DEG C, is flowed back 24 hours, using TLC observing response, until the reaction is complete.Cooled to room temperature, mistake Filter, filtrate is rotated to no fraction.Obtained material is purified by silicagel column (petroleum ether is as eluant, eluent), obtains target product, Purity 99.6%, yield 70.4%.

Elemental analysis structure (molecular formula C₆₀H₄₂N₄): theoretical value: C, 87.99；H,5.17；N,6.84；Test value: C, 87.96；H,5.19；N,6.86.ESI-MS(m/z)(M⁺): theoretical value 818.34, measured value 818.59.

Prepare compound HTI-31

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-3, with -3 generation of raw material II For raw material II -3, the purity of gained target product is 99.91%, yield 73.7%.

Elemental analysis structure (molecular formula C₅₂H₃₇N): theoretical value: C, 92.41；H,5.52；N,2.07；Test value: C, 92.40；H,5.51；N,2.09.ESI-MS(m/z)(M⁺): theoretical value 675.29, measured value 675.45.

Prepare compound HTI-34

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-4, with -3 generation of raw material II For raw material II -1, the purity of gained target product is 99.5%, yield 71.2%.

Elemental analysis structure (molecular formula C₅₄H₃₉N): theoretical value: C, 92.40；H,5.60；N,2.00；Test value: C, 92.41；H,5.59；N,2.02.ESI-MS(m/z)(M⁺): theoretical value 701.31, measured value 701.49.

Prepare compound HTI-66

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-5, with -3 generation of raw material II For raw material II -1, the purity of gained target product is 99.9%, yield 75.8%.

Elemental analysis structure (molecular formula C₅₅H₄₃N): theoretical value: C, 92.01；H,6.04；N,1.95；Test value: C, 92.00；H,6.05；N,1.97.ESI-MS(m/z)(M⁺): theoretical value 717.34, measured value 717.47.

Prepare compound HTI-92

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-6, with -6 generation of raw material II For raw material II -1, the purity of gained target product is 99.5%, yield 74.1%.

Elemental analysis structure (molecular formula C₆₀H₄₉N₃): theoretical value: C, 88.74；H,6.08；N,5.17；Test value: C, 88.76；H,6.07；N,5.19.ESI-MS(m/z)(M⁺): theoretical value 811.39, measured value 811.57.

Prepare compound HTI-104

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-7, with -6 generation of raw material II For raw material II -1, the purity of gained target product is 99.7%, yield 75.7%.

Elemental analysis structure (molecular formula C₄₉H₄₁N): theoretical value: C, 91.41；H,6.42；N,2.18；Test value: C, 91.43；H,6.41；N,2.16.ESI-MS(m/z)(M⁺): theoretical value 643.32, measured value 643.60.

II, prepares the second organic material of used hole transmission layer:

Prepare compound HTII-101

In a nitrogen atmosphere, into 500ml three-necked flask be added 0.03mol raw material II I-1,0.01mol raw material IV-1, 0.04mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃With 5 × 10^-5Mol tri-tert phosphorus, 150ml toluene is then added will It is dissolved, and is heated to 100 DEG C, is flowed back 24 hours, using TLC observing response, until the reaction is complete.Cooled to room temperature, mistake Filter, filtrate is rotated to no fraction.Obtained material is purified by silicagel column (petroleum ether is as eluant, eluent), obtains target product, Purity 99.5%, yield 76.3%.

Elemental analysis structure (molecular formula C₅₄H₃₅NO₂): theoretical value: C, 88.86；H,4.83；N,1.92；Test value: C, 88.88；H,4.81；N,1.95.ESI-MS(m/z)(M⁺): theoretical value 729.27, measured value 729.39.

Prepare compound HTII-148

It is prepared by the synthetic method of compound HTII-101, difference is to replace raw material II I-1 with raw material II I-2, with original Expect that IV-2 replaces raw material IV-1, the purity of gained target product is 99.6%, yield 74.1%.

Elemental analysis structure (molecular formula C₅₄H₃₉N): theoretical value: C, 92.40；H,5.60；N,2.00；Test value: C, 92.38；H,5.57；N,2.02.ESI-MS(m/z)(M⁺): theoretical value 701.31, measured value 701.49.

Prepare compound HTII-85

It is prepared by the synthetic method of compound HTII-101, difference is to replace raw material II I-1 with raw material II I-3, with original Expect that IV-3 replaces raw material IV-1, the purity of gained target product is 99.8%, yield 77.3%.

Elemental analysis structure (molecular formula C₅₂H₃₇N): theoretical value: C, 92.41；H,5.52；N,2.07；Test value: C, 92.44；H,5.55；N,2.02.ESI-MS(m/z)(M⁺): theoretical value 675.29, measured value 675.57.

Prepare compound HTII-37

It is prepared by the synthetic method of compound HTII-101, difference is to replace raw material II I-1 with raw material II I-4, with original Expect that IV-4 replaces raw material IV-1, the purity of gained target product is 99.2%, yield 73.2%.

Elemental analysis structure (molecular formula C₄₅H₃₂N₂O): theoretical value: C, 87.63；H,5.23；N,4.54；Test value: C, 87.65；H,5.21；N,4.56.ESI-MS(m/z)(M⁺): theoretical value 616.25, measured value 616.48.

Prepare compound HTII-27

It is prepared by the synthetic method of compound HTII-101, difference is to replace raw material II I-1 with raw material II I-5, with original Expect that IV-5 replaces raw material IV-1, the purity of gained target product is 99.6%, yield 75.9%.

Elemental analysis structure (molecular formula C₄₆H₃₁NO): theoretical value: C, 90.02；H,5.09；N,2.28；Test value: C, 90.04；H,5.11；N,2.25.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.47.

Prepare compound HTII-112

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-3, with -3 generation of raw material II For raw material II -3, the purity of gained target product is 99.91%, yield 73.7%.

Elemental analysis structure (molecular formula C₅₂H₃₇N): theoretical value: C, 92.41；H,5.52；N,2.07；Test value: C, 92.40；H,5.51；N,2.09.ESI-MS(m/z)(M⁺): theoretical value 675.29, measured value 675.45.

Prepare compound HTII-14

It is prepared by the synthetic method of compound HTII-101, difference is to replace raw material II I-1 with raw material II I-6, with original Expect that IV-6 replaces raw material IV-1, the purity of gained target product is 99.5%, yield 73.9%.

Elemental analysis structure (molecular formula C₄₆H₃₁NO₂): theoretical value: C, 87.73；H,4.96；N,2.22；Test value: C, 87.74；H,4.99；N,2.21.ESI-MS(m/z)(M⁺): theoretical value 629.24, measured value 629.47.

Prepare electronic blocking layer material

III, prepares the first organic material of used electronic barrier layer:

Prepare compound EBI-36

In a nitrogen atmosphere, 0.015mol raw material V -1,0.01mol raw material VI -1 are added into 500ml there-necked flask, with mixed Bonding solvent (90ml toluene, 45ml ethyl alcohol) dissolution, is then added 0.03mol Na₂CO₃Aqueous solution (2M).It is small to stir the mixture for 1 When, then it is added 1 × 10^-4mol Pd(PPh₃)₄, it is heated to reflux 15 hours.Using TLC observing response, until the reaction is complete.From So cooling, filtering rotates filtrate to no fraction.Obtained material is purified by silicagel column (petroleum ether is as eluant, eluent), is obtained Target product, purity 99.8%, yield 79.4%.

Elemental analysis structure (molecular formula C₄₈H₃₂N₂O₂): theoretical value: C, 86.20；H,4.82；N,4.19；Test value: C, 86.22；H,4.81；N,4.17.ESI-MS(m/z)(M⁺): theoretical value 668.25, measured value 668.44.

Prepare compound EBI-9

In a nitrogen atmosphere, 0.015mol raw material V -2,0.01mol raw material raw material II-are added into 500ml three-necked flask 3,0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃With 5 × 10^-5Then 150ml toluene is added in mol tri-tert phosphorus It is dissolved, is heated to 100 DEG C, flowed back 24 hours, using TLC observing response, until the reaction is complete.Cooled to room temperature, Filtering, filtrate is rotated to no fraction.Obtained material is purified by silicagel column (petroleum ether is as eluant, eluent), obtains target production Object, purity 99.7%, yield 76.5%.

Elemental analysis structure (molecular formula C₅₅H₄₅N): theoretical value: C, 91.75；H,6.30；N,1.95；Test value: C, 91.74；H,6.32；N,1.94.

Prepare compound EBI-83

It is prepared by the synthetic method of compound EBI-36, difference is to replace raw material V -1 with raw material V -3, with raw material original Expect that IV-6 replaces raw material II I-1, the purity of gained target product is 99.8%, yield 71.1%.

Elemental analysis structure (molecular formula C₄₆H₃₁NO): theoretical value: C, 90.02；H,5.09；N,2.28；Test value: C, 90.03；H,5.07；N,2.29.

ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.52.

Prepare compound EBI-118

It is prepared by the synthetic method of compound HTI-1, difference is to replace raw material I-1 with raw material I-3, with VI -2 generation of raw material For raw material VI -2, the purity of gained target product is 99.1%, yield 71.7%.

Elemental analysis structure (molecular formula C₅₅H₄₁N): theoretical value: C, 92.27；H,5.77；N,1.96；Test value: C, 92.28；H,5.75；N,1.98.ESI-MS(m/z)(M⁺): theoretical value 715.94, measured value 716.13.

Prepare compound EBI-136

It is prepared by the synthetic method of compound EBI-101, difference is to replace raw material V -1 with raw material V -4, uses raw material VI -4 replaces raw material VI -1, and the purity of gained target product is 99.8%, yield 76.1%.

Elemental analysis structure (molecular formula C₅₁H₃₇NO): theoretical value: C, 90.10；H,5.49；N,2.06；Test value: C, 90.11；H,5.47；N,2.07.ESI-MS(m/z)(M⁺): theoretical value 679.29, measured value 679.63.

Prepare compound EBI-96

It is prepared by the synthetic method of compound EBI-19, difference is to replace raw material V -1 with raw material V -5, with raw material VI - 5 replace raw material VI -1, and the purity of gained target product is 99.9%, yield 77.2%.

Elemental analysis structure (molecular formula C₄₈H₃₂N₂): theoretical value: C, 90.54；H,5.07；N,4.40；Test value: C, 90.55；H,5.06；N,4.39.ESI-MS(m/z)(M⁺): theoretical value 636.26, measured value 636.48.

Prepare compound EBI-99

It is prepared by the synthetic method of compound EBI-101, difference is to replace raw material V -1 with raw material V -6, with raw material original Expect that IV-6 replaces raw material VI -1, the purity of gained target product is 99.5%, yield 73.4%.

Elemental analysis structure (molecular formula C₄₆H₃₃NO): theoretical value: C, 89.73；H,5.40；N,2.27；Test value: C, 89.71；H,5.43；N,2.26.ESI-MS(m/z)(M⁺): theoretical value 615.26, measured value 615.55.

IV, prepares the second organic material of used electronic barrier layer:

Prepare compound EBII-99

In a nitrogen atmosphere, 0.01mol raw material VII -1 and 0.015mol raw material VIII -1 are added into 500mL there-necked flask, uses Mixed solvent (90ml toluene, 45ml ethyl alcohol) is dissolved.Then 0.03mol Na is added₂CO₃It is mixed to stir this for aqueous solution (2M) It closes object 1 hour.Then it is added 1 × 10^-4mol Pd(PPh₃)₄, 110 DEG C are heated to, is flowed back 15 hours.Using TLC observing response, Until the reaction is complete.Cooled to room temperature, filtering, filtrate is rotated to no fraction.Obtained material passes through silicagel column (petroleum ether As eluant, eluent) purifying, obtain target product, purity 99.7%, yield 73.7%.

Elemental analysis structure (molecular formula C₅₂H₃₇N): theoretical value: C, 92.41；H,5.52；N,2.07；Test value: C, 92.44；H,5.51；N,2.05.ESI-MS(m/z)(M⁺): theoretical value 675.29, measured value 675.59.

Prepare compound EBII-109

Step 1)

In a nitrogen atmosphere, 0.05mol raw material E-1,0.075mol raw material F-1 are added into 500mL there-necked flask, with mixing Solvent (90ml toluene, 45ml ethyl alcohol) is dissolved.Then 0.15mol Na is added₂CO₃Aqueous solution (2M) stirs the mixture 1 Hour.Then 5 × 10 are added^-4mol Pd(PPh₃)₄, 100 DEG C are heated to, is flowed back 15 hours.Using TLC observing response, until Fully reacting.Cooled to room temperature, filtering, filtrate is rotated to no fraction.Obtained material passes through silicagel column (petroleum ether conduct Eluant, eluent) purifying, obtain intermediate G-1, purity 99.4%, yield 76.3%.

Elemental analysis structure (molecular formula C₄₀H₂₇NO₂): theoretical value C, 86.78；H,4.92；N,2.53；Test value: C, 86.76；H,4.93；N,2.54.ESI-MS(m/z)(M⁺): theoretical value 553.20, measured value 553.44.

Step 2)

In a nitrogen atmosphere, intermediate G-1,0.036mol that 0.03mol comes from step 1) are added into 100mL there-necked flask Then triphenylphosphine is dissolved with 50ml o-dichlorohenzene.Heat the mixture to 170 DEG C, back flow reaction 15 hours.It utilizes TLC observing response, until the reaction is complete.Cooled to room temperature, filtering, filtrate is rotated to no fraction.Obtained material passes through Silicagel column (petroleum ether is as eluant, eluent) purifying, obtains intermediate H-1, purity 99.4%, yield 78.8%.

Elemental analysis structure (molecular formula C₄₀H₂₇N): theoretical value: C, 92.10；H,5.22；N,2.69；Test value: C, 92.11；H,5.23；N,2.66.ESI-MS(m/z)(M⁺): theoretical value 521.21, measured value 521.44.

Step 3)

In a nitrogen atmosphere, intermediate H-1,0.012mol that 0.01mol comes from step 2) are added into 500mL there-necked flask Bromobenzene, 0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃、5×10^-5Then mol tri-tert phosphorus uses 150ml toluene It is dissolved, is heated to 120 DEG C, back flow reaction 24 hours.Using TLC observing response, until the reaction is complete.Naturally cool to room Temperature, filtering, filtrate is rotated to no fraction.Obtained material is purified by silicagel column (petroleum ether is as eluant, eluent), obtains target Product, purity 99.7%, yield 75.6%.

Elemental analysis structure (molecular formula C₄₆H₃₁N): theoretical value C, 92.43；H,5.23；N,2.34；Test value: C, 92.45；H,5.22；N,2.33.ESI-MS (m/z) (M+): theoretical value 597.25, measured value 597.58.

Prepare compound EBII-67

It is prepared by the synthetic method of compound EBII-99, difference is to replace raw material VII -1 with raw material VII -2, is with original Material VIII -2 replaces raw material VII -1, and the purity of gained target product is 99.9%, yield 78.5%.

Elemental analysis structure (molecular formula C₄₆H₃₁NO): theoretical value: C, 90.02；H,5.09；N,2.28；Test value: C, 90.01；H,5.08；N,2.29.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.65.

Prepare compound EBII-66

It is prepared by the synthetic method of compound EBII-99, difference is to replace raw material VII -1 with raw material VII -3, is with original Material VIII -3 replaces raw material VII -1, and the purity of gained target product is 99.7%, yield 77.9%.

Elemental analysis structure (molecular formula C₄₆H₃₁NO): theoretical value: C, 90.02；H,5.09；N,2.28；Test value: C, 90.03；H,5.07；N,2.29.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.59.

Prepare compound EBII-39

It is prepared by the synthetic method of compound EBII-99, difference is to replace raw material VII -1 with raw material VII -4, is with original Material VIII -4 replaces raw material VII -1, and the purity of gained target product is 99.7%, yield 76.2%.

Elemental analysis structure (molecular formula C₅₆H₃₃NO): theoretical value: C, 91.40；H,4.52；N,1.90；Test value: C, 91.41；H,4.51；N,1.92.ESI-MS(m/z)(M⁺): theoretical value 735.26, measured value 735.64.

Prepare compound EBII-160

It is prepared by the synthetic method of compound EBII-99, difference is to replace raw material VII -1 with raw material VII -5, is with original Material VIII -5 replaces raw material VII -1, and the purity of gained target product is 99.9%, yield 76.8%.

Elemental analysis structure (molecular formula C₅₂H₃5NO): theoretical value: C, 90.54；H,5.11；N,2.03；Test value: C, 90.55；H,5.10；N,2.02.ESI-MS(m/z)(M⁺): theoretical value 689.27, measured value 689.47.

Prepare compound EBII-84

It is prepared by the synthetic method of compound EBII-99, difference is to replace raw material VII -1 with raw material VII -6, is with original Material VIII -6 replaces raw material VII -1, and the purity of gained target product is 99.8%, yield 78.1%.

Elemental analysis structure (molecular formula C₄₅H₃₁NO₂): theoretical value: C, 87.49；H,5.06；N,2.27；Test value: C, 87.47；H,5.07；N,2.26.ESI-MS(m/z)(M⁺): theoretical value 617.24, measured value 617.65.

The first and second organic material of hole transmission layer, the electronic barrier layer first and second that table 1 shows preparation are organic Material and luminescent material material of main part (EMH-1, EMH-7 and EMH-13), guest materials (EMD-1, EMD-8 and EMD-13) Each energy level test result.

Table 1

It can be seen from the result of table 1 the HOMO energy level of first organic material of hole transmission layer of the invention- Between 5.2eV to -5.6eV, and the HOMO energy level of the second organic material is in -5.4eV extremely -5.7eV, and ︱ HOMO_{First organic material}︱ < ︱ HOMO_{Second organic material}︱.

It can be seen from the result of table 1 the HOMO energy level of first organic material of electronic barrier layer of the invention- Between 5.4eV to -5.75eV, and the HOMO energy level of the second organic material is in -5.6eV extremely -6.0eV, and ︱ HOMO_{First organic material}︱ < ︱ HOMO_{Second organic material}︱；And the HOMO of electronic barrier layer second organic material and luminescent layer material of main part Absolute value≤0.4ev of difference between energy level.

Embodiment 1: using CIC evaporated device (long state industry manufactures), respectively by the first organic material of hole transmission layer HTI-1 and the second organic material HTII-14 are placed in two evaporation sources, in vacuum degree 1.0E^-5Under Pa pressure, control first is organic 1 evaporation rate of material isControlling 1 evaporation rate of the second organic material isCommon mixed steam obtains sky of the invention Transmit layer material 1 in cave.

Embodiment 2: the preparation process of embodiment 1 is repeated, the difference is that the evaporation rate of the first organic material HTI-1 ForThe evaporation rate of second organic material HTII-14 isObtain hole transport layer material 2.

Embodiment 3: the preparation process of embodiment 1 is repeated, the difference is that the evaporation rate of the first organic material HTI-1 ForThe evaporation rate of second organic material HTII-14 isObtain hole transport layer material 3.

Embodiment 4: the preparation process of embodiment 1 is repeated, the difference is that the evaporation rate of the first organic material HTI-1 ForThe evaporation rate of second organic material HTII-14 isObtain hole transport layer material 4.

Embodiment 5: the preparation process of embodiment 1 is repeated, the difference is that the evaporation rate of the first organic material HTI-1 ForThe evaporation rate of second organic material HTII-14 isObtain hole transport layer material 5.

Embodiment 6: repeating the preparation process of embodiment 1, the difference is that using the first organic material HTI-29 and the Two organic material HTII-27, obtain hole transport layer material 6.

Embodiment 7: repeating the preparation process of embodiment 2, the difference is that using the first organic material HTI-31 and the Two organic material HTII-37, obtain hole transport layer material 7.

Embodiment 8: repeating the preparation process of embodiment 3, the difference is that using the first organic material HTI-34 and the Two organic material HTII-85, obtain hole transport layer material 8.

Embodiment 9: repeating the preparation process of embodiment 4, the difference is that using the first organic material HTI-66 and the Two organic material HTII-148, obtain hole mobile material 9.

Embodiment 10: repeating the preparation process of embodiment 5, the difference is that using the first organic material HTI-92 and the Two organic material HTII-101, obtain hole transport layer material 10.

Embodiment 11: using CIC evaporated device (long state industry manufactures), respectively by the first organic material of hole transmission layer EBI-36 and the second organic material EBII-39 are placed in two evaporation sources, in vacuum degree 1.0E^-5Under Pa pressure, control first has 1 evaporation rate of machine material isControlling 1 evaporation rate of the second organic material isCommon mixed steaming obtains of the invention Electronic blocking layer material 1.

Embodiment 12: repeating the preparation process of embodiment 1, the difference is that the vapor deposition speed of the first organic material EBI-36 Rate isThe evaporation rate of second organic material EBII-39 isObtain electronic blocking layer material 2.

Embodiment 13: repeating the preparation process of embodiment 1, the difference is that the vapor deposition speed of the first organic material EBI-36 Rate isThe evaporation rate of second organic material EBII-39 isObtain electronic blocking layer material 3.

Embodiment 14: repeating the preparation process of embodiment 1, the difference is that the vapor deposition speed of the first organic material EBI-36 Rate isThe evaporation rate of second organic material EBII-39 isObtain electronic blocking layer material 4.

Embodiment 15: repeating the preparation process of embodiment 1, the difference is that the vapor deposition speed of the first organic material EBI-36 Rate isThe evaporation rate of second organic material EBII-39 isObtain electronic blocking layer material 5.

Embodiment 16: repeating the preparation process of embodiment 1, the difference is that using the first organic material EBI-9 and the Two organic material EBII-66, obtain electronic blocking layer material 6.

Embodiment 17: repeating the preparation process of embodiment 2, the difference is that using the first organic material EBI-83 and the Two organic material EBII-99, obtain electronic blocking layer material 7.

Embodiment 18: repeating the preparation process of embodiment 3, the difference is that using the first organic material EBI-96 and the Two organic material EBII-109, obtain electronic blocking layer material 8.

Embodiment 19: repeating the preparation process of embodiment 4, the difference is that using the first organic material EBI-99 and the Two organic material EBII-160, obtain electronic blocking layer material 9.

Embodiment 20: repeating the preparation process of embodiment 5, the difference is that using the first organic material HTI-136 and Second organic material HTI-84, obtains electronic blocking layer material 10.

Prepare organic electroluminescence device

It should be noted that vacuum evaporation carries out under the following conditions: CIC evaporated device (long state industry manufactures) is used, In vacuum degree 1.0E^-5Under Pa pressure, control evaporation rate is

Device prepares embodiment 1: it is carried out according to following procedure:

A) use transparent glass as substrate, coating thickness is then the ITO of 150nm distinguishes as anode layer on it It is cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate, is then handled 2 minutes in plasma cleaner；

B) in washed first electrode layer, HAT-CN is deposited by vacuum deposition method, with a thickness of 10nm, this layer is made For hole injection layer；

C) it on hole injection layer, is vaporized in the embodiment 1 for preparing hole transport layer material by vacuum evaporation mode The hole transport layer material 1 of acquisition, with a thickness of 90nm, which is hole transmission layer；

D) hole transport layer by layer on, the embodiment 1 for preparing electronic blocking layer material is vaporized on by vacuum evaporation mode The electronic blocking layer material 1 of middle acquisition, with a thickness of 20nm, which is electronic barrier layer；

E) on electronic barrier layer, emitting layer material is deposited by vacuum evaporation mode, material of main part is EMH-7 and EMH- 9, guest materials EMD-8, EMH-7, EMH-9 and EMD-8 mass ratio is 45:45:10, with a thickness of 40nm；

F) on the light-emitting layer, LG201 and Liq being deposited by vacuum evaporation mode, LG201 and Liq mass ratio is 50:50, With a thickness of 40nm, the layer is as electron transfer layer；

G) on the electron transport layer, LiF is deposited by vacuum evaporation mode, with a thickness of 1nm, which is electron injecting layer；

G) on electron injecting layer, vacuum evaporation Al, with a thickness of 100nm, which is the second electrode lay.

Device prepares embodiment 2-10:

It is carried out according to the process of device preparation embodiment 1, the difference is that respectively using coming from in step c) and d) The above-mentioned materials described below prepared in hole transport layer material and electronic barrier layer materials Example, shown in table 2 specific as follows:

Table 2

Device prepares embodiment 11: carrying out according to the process of device preparation embodiment 1, the difference is that in step c) The film thickness of hole transport layer by layer is 160nm；In step e) material of main part be EMH-13, guest materials EMD-8, EMH-13 and EMD-8 mass ratio is 96:4, with a thickness of 40nm.

Device prepares embodiment 12-16:

It is carried out according to the process of device preparation embodiment 11, the difference is that respectively using coming from in step c) and d) The above-mentioned materials described below prepared in hole transport layer material and electronic barrier layer materials Example, shown in table 3 specific as follows:

Table 3

Device prepares embodiment 17: carrying out according to the process of device preparation embodiment 1, the difference is that in step c) The film thickness of hole transmission layer is 50nm；Material of main part is EMH-1, guest materials EMD-1, EMH-1 and EMD-1 matter in step e) Amount is than being 95:5, with a thickness of 25nm.

Device prepares embodiment 18-23:

It is carried out according to the process of device preparation embodiment 17, the difference is that respectively using coming from in step c) and d) The above-mentioned materials described below prepared in hole transport layer material and electronic barrier layer materials Example, shown in table 4 specific as follows:

Table 4

Comparing embodiment 1-12: it is carried out according to the process of device preparation embodiment 1, the difference is that using in the following table 5 Listed material is as hole transmission layer and electronic blocking layer material.

Table 5

Comparing embodiment 13-20: it is carried out according to the process of device preparation embodiment 11, the difference is that using the following table 6 In listed material as hole transmission layer and electronic blocking layer material.

Table 6

Comparing embodiment 21-28: it is carried out according to the process of device preparation embodiment 17, the difference is that using the following table 7 In listed material as hole transmission layer and electronic blocking layer material.

Table 7

Table 8-10 is shown in 10mA/cm²The performance knot of made organic electroluminescence device is measured under current density Fruit.

Table 8: the results of property of organic electroluminescence device prepared by inventive embodiments 1-10 and comparing embodiment 1-12

Note: * represents comparing embodiment

LT95 refers to that in current density be 10mA/cm²In the case of, device brightness decay to 95% used in the time.

Life-span test system is owner of the present invention and the OLED device life-span tester that Shanghai University is studied jointly.

The annotation is also applied for the following table 9 and 10.

Table 9: the performance knot of organic electroluminescence device prepared by inventive embodiments 11-16 and comparing embodiment 13-20 Fruit

Table 10 is shown in 10mA/cm²The results of property of made organic electroluminescence device is measured under current density.

It can be seen from the result of table 8 and organic material is used alone as hole transmission layer or the ratio of electronic barrier layer It is compared compared with embodiment 1 to 12, the driving voltage of device obtained by device preparation embodiment 1 to 10 of the invention is substantially reduced, And light emission luminance, luminous efficiency (i.e. current efficiency) and service life are significantly increased.It can be seen from the result of table 9 compared with Embodiment 13 to 20 is compared, and the driving voltage of device obtained by device preparation embodiment 11 to 16 of the invention also obviously drops It is low, and light emission luminance, luminous efficiency (i.e. current efficiency) and service life are significantly increased.It can be seen from the result of table 10 with Comparing embodiment 21 to 28 is compared, and the driving voltage of device obtained by device preparation embodiment 17 to 23 of the invention is also obvious It reduces, and light emission luminance, luminous efficiency (i.e. current efficiency) and service life are significantly increased.

Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Art technology Personnel in the case where not departing from the objective and range of technical solution of the present invention, to technical solution of the present invention carry out modification or Person's equivalent replacement, is intended to be within the scope of the claims of the invention.

Claims (16)

1. a kind of organic electroluminescence device, be disposed with from the bottom to top substrate, first electrode, organic functional material layer and Second electrode, the organic functional material layer include:

Hole transporting zone is located on the first electrode；

Luminescent layer is located on the hole transporting zone comprising material of main part and guest materials；

Electron transporting zone is located on the luminescent layer；

It is characterized in that, the hole transporting zone successively includes hole injection layer, hole transmission layer and electronics resistance from the bottom to top Barrier,

The hole transmission layer includes the first and second organic materials, and the electronic barrier layer includes first and second organic materials Material,

First and second organic materials of its hole-transporting layer and electronic barrier layer are each independently selected from general formula (1), general formula (2) or one of general formula (3):

Wherein, in general formula (1):

X、X₁It is each independently selected from singly-bound, carbon atom, N- (R₅), sulphur atom, oxygen atom, ethenylidene, linear chain or branched chain C_1-20The C of alkyl-substituted alkylidene, linear chain or branched chain_1-20Alkyl-substituted silicylene, C_6-20In the alkylidene that aryl replaces One kind；

If there is R₅, then its may be the same or different selected from hydrogen atom, protium atom, D-atom, tritium atom, fluorine atom, phosphoric acid or The C of its salt, linear chain or branched chain_1-20The C of alkyl-substituted alkyl, linear chain or branched chain_1-20Alkyl-substituted silylation has 5 to 30 The aryl of a carbon atom, with 5 to 30 carbon atoms and at least one be selected from N, O and S heteroatomic heteroaryl, wherein rear In the case where the two, the group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；

Z represents nitrogen-atoms or C-R₆, wherein R₆It is former to be selected from hydrogen atom, protium atom, D-atom, tritium atom, fluorine with may be the same or different Son, cyano, phosphoric acid or its salt, linear chain or branched chain C_1-20The C of alkyl-substituted alkyl, linear chain or branched chain_1-20Alkyl-substituted silicon Alkyl, the aryl with 5 to 30 carbon atoms, with 5 to 30 carbon atoms and at least one be selected from N, O and S it is heteroatomic Heteroaryl, wherein the group can be optionally by the C of linear chain or branched chain in the case where rear the two_1-20Alkyl, C_6-20Aryl, C_5-20 Heteroaryl replaces, two of them or more R₆Group can be connected to each other and can form ring structure；

Ar₁、Ar₂、Ar₃、Ar₄It is independently represented each other the C of singly-bound, linear chain or branched chain_1-20The C of alkylidene, linear chain or branched chain_1-20Alkane Base replace silicylene, the arlydene with 5 to 30 carbon atoms, have 5 to 30 carbon atoms and at least one be selected from N, O With the heteroatomic inferior heteroaryl of S, wherein the group can be optionally by the C of linear chain or branched chain in the case where rear the two_1-20Alkane Base, C_6-20Aryl, C_5-20Heteroaryl replaces, wherein Ar₁、Ar₂Group can also be directly connected to cyclization or be connected by C, O, S, N Ring；

M, n, p, q, s and t are equal to 0 or 1；And m+n+p+q >=1 and m+n+s+t >=1；

R₁、R₂、R₃And R₄It is independently represented each other hydrogen atom, general formula (4), structure shown in general formula (5) or general formula (6), condition is R₁、R₂、R₃And R₄It is not simultaneously hydrogen atom；

Wherein, in general formula (4) and general formula (5):

X₂、X₃Be independently represented each other singly-bound, oxygen atom, sulphur atom, ethenylidene, linear chain or branched chain C_1-20It is alkyl-substituted The C of alkylidene, linear chain or branched chain_1-20Alkyl-substituted silylation, C_6-20Alkylidene, the C of aryl substitution_1-20Alkyl-substituted Asia Amido, C_6-20Imido grpup, the C of aryl substitution_5-20One of the imido grpup that heteroaryl replaces；

Y₁Represent N atom or C-R with may be the same or different₇, wherein R₇Represent hydrogen atom, protium atom, deuterium with may be the same or different former Son, tritium atom, fluorine atom, cyano, phosphoric acid or its salt, linear chain or branched chain C_1-20Alkyl-substituted alkyl, linear chain or branched chain C_1-20Alkane Base replace silylation, the aryl with 5 to 30 carbon atoms, have 5 to 30 carbon atoms and at least one be selected from N, O and S Heteroatomic heteroaryl, wherein the group can be optionally by the C of linear chain or branched chain in the case where rear the two_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Two of them or more R₇Group can be connected to each other and can form ring structure；

R₈、R₉It is independently represented each other hydrogen atom, protium atom, D-atom, tritium atom, fluorine atom, phosphoric acid or its salt, straight chain or branch The C of chain_1-20The C of alkyl-substituted alkyl, linear chain or branched chain_1-20Alkyl-substituted silylation, the virtue with 5 to 30 carbon atoms Base, with 5 to 30 carbon atoms and at least one be selected from shown in the heteroatomic heteroaryl of N, O and S, general formula (7) or general formula (6) Structure；Wherein in the case where aryl and heteroaryl, the group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；

Wherein, in general formula (7):

Y₂Represent N atom or C-R with may be the same or different₁₄, wherein R₁₄Represent hydrogen atom, protium atom, deuterium with may be the same or different Atom, tritium atom, fluorine atom, cyano, phosphoric acid or its salt, linear chain or branched chain C_1-20Alkyl-substituted alkyl, linear chain or branched chain C_1-20Alkyl-substituted silylation, the aryl with 5 to 30 carbon atoms, have 5 to 30 carbon atoms and at least one be selected from N, the heteroatomic heteroaryl of O and S, wherein the group can be optionally by the C of linear chain or branched chain in the case where rear the two_1-20 Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Two of them or more R₁₂Group can be connected to each other and can form ring knot Structure；

X₄、X₅Be independently represented each other singly-bound, oxygen atom, sulphur atom, ethenylidene, linear chain or branched chain C_1-20It is alkyl-substituted The C of alkylidene, linear chain or branched chain_1-20Alkyl-substituted silicylene, C_6-20Alkylidene, the C of aryl substitution_1-20It is alkyl-substituted Imido grpup, C_6-20Imido grpup, the C of aryl substitution_5-20One of the imido grpup that heteroaryl replaces；

General formula (7) is connected by simultaneously ring mode with general formula (4) or general formula (5), and * is expressed as connection site, when being connected, can only take phase Two adjacent sites, general formula (7) and general formula (4) or general formula (5) are when simultaneously ring connects, connection site Y₁It is expressed as carbon atom；

In general formula (8):

R₁₂、R₁₃It is independently represented each other the aryl with 5 to 30 carbon atoms, there are 5 to 30 carbon atoms and at least one choosing From the heteroatomic heteroaryl of N, O and S, the group can be optionally by the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20It is miscellaneous Aryl replaces；R₁₂、R₁₃Cyclization can also be connected；

In general formula (2):

L₁、L₂、L₃It is independently represented each other singly-bound, the arlydene with 5 to 30 carbon atoms, there are 5 to 30 carbon atoms and extremely Few one is selected from the heteroatomic inferior heteroaryl of N, O and S, wherein the group can be optionally by straight chain in the case where rear the two Or the C of branch_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；L₁、L₂、L₃It can be connected to each other two-by-two and ring knot can be formed Structure；

Ar₅、Ar₆、Ar₇It is independently represented each other arlydene with 5 to 30 carbon atoms, there are 5 to 30 carbon atoms and at least The imido grpup of one heteroatomic inferior heteroaryl selected from N, O and S, 5 to 30 carbon atoms, the group can optionally by straight chain or The C of branch_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Ar₅、Ar₆、Ar₇It can be connected to each other two-by-two and ring knot can be formed Structure；

Ar₅、Ar₆、Ar₇It is also denoted as general formula (4), general formula (5), one in general formula (6), wherein the base on the general formula Group X₂、X₃、Y₁、R₈、R₉、R₁₀、R₁₁There is meaning as described above with *；

In general formula (3):

D₁、D₂、D₃It is independently represented each other singly-bound, the arlydene with 5 to 30 carbon atoms, there are 5 to 30 carbon atoms and extremely Few one is selected from the heteroatomic inferior heteroaryl of N, O and S, wherein the group can be optionally by straight chain in the case where rear the two Or the C of branch_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；D₁、D₂、D₃It can be connected to each other two-by-two and ring knot can be formed Structure；

Ar₈、Ar₉、Ar₁₀It is independently represented each other hydrogen atom, the arlydene with 5 to 30 carbon atoms, there are 5 to 30 carbon originals Son and at least one be selected from the imido grpup of the heteroatomic inferior heteroaryl of N, O and S, 5 to 30 carbon atoms, the group can be optional By the C of linear chain or branched chain_1-20Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；Ar₈、Ar₉、Ar₁₀It can be connected to each other two-by-two and can Form ring structure；

Ar₈、Ar₉、Ar₁₀In at least one be general formula (4), general formula (5), one in general formula (6)；The wherein base on the general formula Group X₂、X₃、Y₁、R₈、R₉、R₁₀、R₁₁Respectively there is meaning as described above with *.

2. organic electroluminescence device according to claim 1, it is characterised in that it is extremely logical that general formula (2) is expressed as general formula (9) One of formula (12):

Wherein,

Ar₅To Ar₇Indicate arlydene with 5 to 30 carbon atoms, have 5 to 30 carbon atoms and at least one selected from N, O and The imido grpup of the heteroatomic inferior heteroaryl of S, 5 to 30 carbon atoms, the group can be optionally by the C of linear chain or branched chain_1-20Alkane Base, C_6-20Aryl, C_5-20Heteroaryl replaces；

And L₁-L₃、R₆-R₉、Y₁And X₂-X₃All have meaning described in claim 1.

3. organic electroluminescence device according to claim 1 or 2, it is characterised in that the general formula (3) is expressed as general formula (13) one of to general formula (16):

Wherein,

Ar₈And Ar₁₀Indicate arlydene with 5 to 30 carbon atoms, have 5 to 30 carbon atoms and at least one selected from N, O With the imido grpup of the heteroatomic inferior heteroaryl of S, 5 to 30 carbon atoms, the group can be optionally by the C of linear chain or branched chain_1-20 Alkyl, C_6-20Aryl, C_5-20Heteroaryl replaces；And

And D₁-D₃、R₆-R₉、Y₁And X₂-X₃All have meaning described in claim 1.

4. according to claim 1 to organic electroluminescence device described in one of 3, it is characterised in that in the general formula (1)Part is selected from one of the following:

And wherein Z, Ar₁、Ar₂And R₅With the meaning described in claim 1.

5. organic electroluminescence device according to any one of claim 1 to 4, it is characterised in that its hole-transporting layer The HOMO energy level of the first organic material be -5.2eV to -5.6eV, preferably -5.3eV to -5.5eV, and hole transmission layer the The HOMO energy level of two organic materials is -5.4eV to -5.7eV, preferably -5.4eV to -5.6eV, and ︱ HOMO_{The first organic material of hole transmission layer}︱ < ︱ HOMO_{The second organic material of hole transmission layer}︱；

Also, the HOMO energy level of the first organic material of the electronic barrier layer is -5.4eV extremely -5.75eV, preferably -5.5eV To -5.65eV, and the HOMO energy level of the second organic material of electronic barrier layer is -5.6eV to -6.0eV, preferably -5.6eV to - 5.9eV, and ︱ HOMO_{The first organic material of electronic barrier layer}︱ < ︱ HOMO_{The second organic material of electronic barrier layer}︱；And the first organic material of electronic barrier layer and electricity Lumo energy >=-2.6eV of sub- the second organic material of barrier layer.

6. organic electroluminescence device according to claim 1, it is characterised in that the organic material of the electronic barrier layer second Absolute value≤the 0.4ev, preferably≤0.3ev of difference between material and the HOMO energy level of luminescent layer material of main part.

7. according to claim 1 to organic electroluminescence device described in 6, it is characterised in that the first He of the hole transmission layer The ratio of second organic material is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 30:70 to 70:30, is based on matter Meter.

8. organic electroluminescence device according to any one of claim 1 to 6, it is characterised in that the electronic barrier layer The ratio of first and second organic materials be 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 30:70 to 70:30, Based on quality.

9. organic electroluminescence device according to any one of claim 1 to 8, it is characterised in that the hole transmission layer First organic material is selected from one of following compounds:

10. organic electroluminescence device according to claim 1 to 8, it is characterised in that the hole transmission layer Second organic material is selected from one of following compound:

11. organic electroluminescence device according to claim 1 to 8, it is characterised in that the electronic barrier layer First organic material is selected from one of following compound:

12. organic electroluminescence device according to claim 1 to 8, it is characterised in that the electronic barrier layer Second organic material is selected from one of following compound:

13. organic electroluminescence device described in any one of -12 according to claim 1, it is characterised in that the hole transport The first organic material and the second organic material of layer and electronic barrier layer make after can mixing for electroluminescent device, It can be mixed during making organic electroluminescence device.

14. organic electroluminescence device according to claim 1 to 13, it is characterised in that the device includes One of blue, green, red or yellow organic light emitting material or multiple combinations；Different organic light emitting materials laterally or Longitudinal stack combinations.

15. a kind of display, including one or more organic electroluminescence devices as described in any one of claim 1-14； And in the case where including multiple devices, the device laterally or longitudinally stack combinations.

16. display according to claim 15, it is characterised in that the display includes respectively having blue, green, red three One of device of organic light emitting material of kind color or multiple combinations, the device respectively have identical or different film thickness Hole transmission layer and electronic barrier layer, and the material of the hole transmission layer and electronic barrier layer is identical or different.