CN109994640A

CN109994640A - A kind of organic electroluminescence device containing multichannel carrier transmission material

Info

Publication number: CN109994640A
Application number: CN201910282357.6A
Authority: CN
Inventors: 徐凯; 李崇; 谢丹丹; 张兆超
Original assignee: Jiangsu Sanyue Optoelectronic Technology Co Ltd
Current assignee: Jiangsu Sunera Technology Co Ltd; Jiangsu Sanyue Optoelectronic Technology Co Ltd
Priority date: 2019-04-09
Filing date: 2019-04-09
Publication date: 2019-07-09
Anticipated expiration: 2039-04-09
Also published as: CN109994640B

Abstract

The present invention relates to a kind of organic electroluminescence devices, it successively includes substrate, first electrode, organic functional material layer and second electrode from the bottom to top, the organic functional material layer successively includes hole transporting zone, luminescent layer and electron transporting zone from the bottom to top, wherein the hole transporting zone includes multichannel carrier transmission material as noted in the discussion, wherein, the multichannel carrier transmission material includes more than two carrier conduction pathways, and the absolute value differences of the HOMO energy level of two of them carrier conduction pathway are between 0.01-0.8eV.The present invention can be achieved have high efficiency and the organic electroluminescence device of long life.

Description

A kind of organic electroluminescence device containing multichannel carrier transmission material

Technical field

The present invention relates to technical field of semiconductors.Specifically, the present invention relates to one kind to contain multichannel carrier transport The organic electroluminescence device of material.

Background technique

Organic electroluminescent (OLED:Organic Light Emitting Diodes) device technology can both be used to make New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is very extensive.In general, by the organic electroluminescence device that several layers are constituted include anode, cathode, hole injection layer, Hole transmission layer, organic luminous layer, electron transfer layer and electron injecting layer.Organic electroluminescence device as current device, When applying voltage to its two end electrodes, make the hole from anode and the electronics from cathode in organic hair by electric field action Exciton is compounded to form in photosphere, excitonic relaxation to ground state releases energy and generates organic electroluminescent.

It include: at present the driving voltage for reducing device, the hair for improving device to the performance study of organic electroluminescence device Light efficiency, the service life for improving device etc..In order to realize organic electroluminescence device performance continuous promotion, not only need The innovation of the structure and preparation process of organic electroluminescence device, with greater need for organic electroluminescent functional material it is continuous research and Innovation, to produce the organic electroluminescence device with higher performance.

Carrier (hole and electronics) in organic electroluminescence device is under the driving of electric field respectively by two of device Electrode injection is into device, and the recombination luminescence that meets in organic luminous layer.High performance organic electroluminescence device, it is desirable that each Kind organic functional material has good photoelectric characteristic, for example, as charge transport materials, it is desirable that there is good carrier to move Shifting rate.The injection and transmission characteristic phase of hole injection layer used in existing organic electroluminescence device and hole transmission layer To weaker, hole injection and transmission rate and electron injection and transmission rate are mismatched, and cause recombination region to deviate larger, unfavorable In the stability of device.In addition hole injection layer material and the reasonable level-density parameter of hole transport layer material are to improve device efficiency And an important factor for device lifetime, therefore driving voltage of the injection in hole with transmission for reduction device is improved, and improve device The luminous efficiency and service life of part are of great significance.

Carrier conducting material mainstream type used in OLED luminescent device so far includes single triphen amine material Material, carbazoles material, double triphenylamine materials, three triphenylamine materials and more phenyl amines conductive materials.For example, traditional β- TTA belongs to typical single triphenylamine material, and α-NPD and TAPC belong to typical double triphenylamine materials, and TDATA belongs to typical three A triphenylamine material, TCTA belong to single triphenylamine in conjunction with three carbazoles materials.But all these typical hole mobile materials It is full symmetrical configuration.Full symmetrical configuration, only has single carrier transport channel due to molecule fragment structure, carries It is lower to flow sub- efficiency of transmission.Therefore, it is necessary to continually develop for organic electroluminescence device hole injection with transmission rate more Excellent material.

Summary of the invention

To solve the above-mentioned problems, the present inventor it has been investigated that, constitute the same carrier of organic electroluminescence device In conducting membrane layer, if carrier transmission material has different a variety of carrier conduction pathways, help to promote carrier Injection and laser propagation effect, be more conducive to interface between the film phase stability of this kind of material and different carrier conducting membrane layer Stability, so facilitate promoted organic electroluminescence device including luminous efficiency, driving voltage and driving the service life including it is comprehensive Close performance.

Further, for constituting the injection of holoe carrier of organic electroluminescence device transmission, no matter constitute What kind of overlaying structure the holoe carrier conducting membrane layer of luminescent device is, if constituting appointing for holoe carrier injection transmission In film layer of anticipating, the single molecule of any materials has two or more carrier conduction pathways, i.e., the HOMO in one of channel There is some difference for energy level and the HOMO energy level in another channel, then this species diversity causes carrier in injection and conductive process It is different from existing holohedral symmetry hole transport material, to help to promote device performance.

Therefore, the purpose of the present invention is to provide a kind of high performance electroluminescent organic device, organic electroluminescents of the present invention The injection and conduction of carrier in device, because of the presence of multichannel carrier transmission material, be more advantageous to tunnelling mode into Row is easy to promote the injection conduction efficiency of holoe carrier, achievees the effect that low voltage drive, simultaneously as holoe carrier can It is transmitted to luminescent layer with easier, the balance of carrier will be conducive to, is conducive to the promotion of device performance.

Organic electroluminescence device of the present invention from the bottom to top successively include substrate, first electrode, organic functional material layer and Second electrode, the organic functional material layer include:

Hole transporting zone is located on 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 that hole injection layer, hole transmission layer and hole transport are auxiliary from the bottom to top Layer is helped, the hole injection layer includes p-type dopant material,

Wherein the hole transporting zone includes the multichannel carrier transmission material of general formula (1),

The multichannel carrier transmission material includes more than two carrier conduction pathways, and the carrier conduction is logical Road carrier shown in general formula (A1) or general formula (A2) conduction segment is constituted,

Wherein carrier shown in the general formula (A1) conducts the conduction segment of carrier shown in segment and general formula (A2) For the absolute value differences of HOMO energy level between 0.01-0.8eV, the HOMO energy level of carrier conduction segment is located at 5.4-5.7eV Between.

Wherein, Ar₁、Ar₂、Ar₃、Ar₄、Ar₅And Ar₆Each independently represent substituted or unsubstituted phenyl, substitution or not Substituted dibiphenylyl, substituted or unsubstituted naphthalene, substituted or unsubstituted pyridyl group, substituted or unsubstituted naphthyridines base, Substituted or unsubstituted terphenyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzene And phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted azepine pyrenyl, replace or The structure of unsubstituted azepine phenanthryl or general formula (A3):

In general formula (A3), R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈In any one expression be connected with the N in general formula (1) Singly-bound, remaining Rn each independently represents hydrogen atom, D-atom, C₁-C₁₀Alkoxy, adamantyl, cyano, C₁-C₁₀Alkane Base, C₃-C₁₀Naphthenic base, substituted or unsubstituted naphthalene, substituted or unsubstituted naphthyridines base, takes substituted or unsubstituted phenyl Generation or unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substituted or unsubstituted terphenyl, n indicate 1 to 8 Integer；

X indicates O, S ,-C (R₉)(R₁₀)-or-N (R₁₁)-；

R₉、R₁₀And R₁₁Each independently represent C₁-C₁₀Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthalene, substituted or unsubstituted naphthyridines base, substituted or unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substitution or Unsubstituted terphenyl, wherein R₉With R₁₀Cyclization can be connected with each other；

Wherein in the substituted group, the substituent group is independently from each other D-atom, halogen atom, C₁-C₁₀ Alkoxy, adamantyl, cyano, C₁-C₁₀Alkyl, C₃-C₂₀Naphthenic base, C₆-C₃₀Aryl contains one or more heteroatomic 5- 30 unit's heteroaryls, wherein the hetero atom is optionally selected from one or more of oxygen atom, sulphur atom or nitrogen-atoms.

Core of the invention is the provision of a kind of hole transport area for being used to prepare high performance electroluminescent organic device The selection mode and advanced design theory of domain material.It is of the invention theoretical using meeting based on design concept provided by the present invention The cavity type material on basis can not only prepare high performance electroluminescent organic device, can also be by reason provided by the present invention The research and development for being further used for cavity type material are read, to excavate the superior hole transporting zone material of performance.

Compared with prior art, the beneficial effects of the invention are that:

The present invention using with two or more carriers by conducting in any film layer that carrier injects and transmits The material in channel, i.e., the absolute value differences of the HOMO energy level of the HOMO energy level and another channel in one of channel are in 0.01- Between 0.8eV, carrier can in injection and conductive process the common transport on these channels respectively, to improve current-carrying The injection and efficiency of transmission of son help to promote device performance.

Based on different groups to known to the affecting laws of energy level: the electron cloud of surrounding molecules distribution is subdivided into not according to energy With the molecular orbit of energy level, the difference of general formula (A1) and general formula (A2) electron donation makes molecule HOMO energy level be subdivided into difference The molecular orbit of energy level, molecule HOMO segment shallower energy level and are conducive to hole from hole transmission layer injection, reduce interface Potential barrier and gather charge；And molecule HOMO segment deeper energy level be conducive to hole be injected into from hole auxiliary transmission layer it is luminous Layer reduces interface potential barrier and gathers charge, facilitates the interface between the film phase stability and conducting membrane layer of hole class material Stability.

In hole transporting zone, carrier forms electron exchange in different conduction pathways, and along a variety of carriers Channel is conducted, therefore the organic electroluminescence device as made by multichannel carrier transmission material of the invention can be kept High holoe carrier injection and transmission characteristic effectively promote the photoelectric properties and organic electroluminescence hair of organic electroluminescence device The service life of optical device.

Detailed description of the invention

Fig. 1 is the structural schematic diagram of organic electroluminescence device of the present invention.

Description of symbols: 1-substrate；2-first electrodes；3-hole injection layers；4-hole transmission layers；5-holes Transmit auxiliary layer；6-luminescent layers；7-hole barriers/electron transfer layer；8-electron injecting layers；9-second electrodes.

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.

In the present invention, as without opposite explanation, then all operations are implemented in room temperature, condition of normal pressure.

In the present invention, unless otherwise indicated, HOMO means that the highest occupied molecular orbital of molecule, LUMO mean the minimum of molecule Unoccupied orbital.In addition, " difference of HOMO energy level " and " difference of lumo energy " involved in this specification mean each energy The difference of the absolute value of value.In addition, in the present invention, HOMO and lumo energy absolute value representation, and the ratio between energy level It is also relatively the size for comparing its absolute value, the absolute value of energy level is bigger as known to those skilled in the art, then the energy of the energy level is got over It is low.

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.

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.

In the present invention, used when describing electrode and organic electroluminescence device and other structures body "upper", "lower", "top" and "bottom" etc. indicate the word in orientation, are merely represented in the orientation of certain particular state, are not intended to relevant Structure can only only be existed by the orientation；On the contrary, if structural body can shift one's position, such as it is inverted, then the orientation of structural body Make corresponding change.Specifically, in the present invention, "bottom", the "lower" side of electrode refer to electrode during the preparation process close to substrate Side, and far from substrate opposite side be "top", "upper" side.

The present invention provides a kind of organic electroluminescence device with improved luminous efficiency and service life, by down toward On include successively substrate, first electrode, organic functional material layer and second electrode, the organic functional material layer includes:

Hole transporting zone is located on first electrode；

Electron transporting zone is located on the luminescent layer；

Wherein carrier shown in the general formula (A1) conducts the conduction segment of carrier shown in segment and general formula (A2) The absolute value differences of HOMO energy level between 0.01-0.8eV,

X indicates O, S ,-C (R₉)(R₁₀)-or-N (R₁₁)-；

In a preferred embodiment in accordance with this invention, the conduction segment of carrier shown in general formula (A1) and general formula (A2) Shown in carrier conduction segment HOMO energy level absolute value differences between 0.02-0.5eV, more preferable 0.02-0.2eV Between.

In one embodiment of the invention, in the conduction of the carrier shown in general formula (A1) segment, group Ar₁And base Group Ar₂It is identical.In another embodiment of the present invention, in the conduction of the carrier shown in general formula (A1) segment, group Ar₁ With group Ar₂It is different.

In one embodiment of the invention, in the conduction of the carrier shown in general formula (A2) segment, group-NAr₃Ar₄ With group-NAr₅Ar₆It is identical.In another embodiment of the present invention, the carrier shown in general formula (A2) conducts segment In, group-NAr₃Ar₄With group-NAr₅Ar₆It is different.

In one embodiment of the invention, the multichannel carrier transmission material of general formula (1) can indicate following general formula (2) to any structure shown in general formula (11):

Wherein, A, B, C, D, E and F each independently represent substituted or unsubstituted phenyl, substituted or unsubstituted bigeminy Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted naphthyridines base, replaces or does not take substituted or unsubstituted naphthalene The terphenyl in generation, phenanthryl substituted or unsubstituted, substituted or unsubstituted benzo phenanthryl, replaces substituted or unsubstituted anthryl Or unsubstituted pyrenyl, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted azepine pyrenyl, substituted or unsubstituted nitrogen The structure of miscellaneous phenanthryl or general formula (A4)

In general formula (A4), R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈In any one expression be connected with the N in general formula (1) Singly-bound, remaining Rn each independently represents hydrogen atom, D-atom, C₁-C₁₀Alkoxy, adamantyl, cyano, C₁-C₁₀Alkane Base, C₃-C₁₀Naphthenic base, substituted or unsubstituted naphthalene, substituted or unsubstituted naphthyridines base, takes substituted or unsubstituted phenyl Generation or unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substituted or unsubstituted terphenyl, n indicate 1 to 8 Integer；

X indicates O, S ,-C (R₉)(R₁₀)-or-N (R₁₁)-；

Wherein in the substituted group, the substituent group is independently from each other D-atom, halogen atom, C₁-C₁₀Alkane Oxygroup, adamantyl, cyano, C₁-C₁₀Alkyl, C₃-C₂₀Naphthenic base, C₆-C₃₀Aryl contains one or more heteroatomic 5-30 Unit's heteroaryl, wherein the hetero atom is optionally selected from one or more of oxygen atom, sulphur atom or nitrogen-atoms.

In a preferred embodiment in accordance with this invention, the multichannel carrier transmission material of general formula (1) can be selected from down State any one of compound:

The compound of above-mentioned formula (I-1) to formula (I-310) is commercially available, or can be according to those skilled in the art Known method synthesis, such as the method being recorded in patent application CN 1458141A, JP 2010-280635 A.

In one embodiment of the invention, the luminescent layer includes at least one compound, and structure is represented by Any structure shown in general formula (12) to general formula (15):

The wherein Ar₇-Ar₁₃Being expressed as singly-bound, substituted or unsubstituted C6-C30 arlydene, containing one independently A or multiple substituted or unsubstituted 5-30 member inferior heteroaryls of hetero atom；Ar₁₄It is sub- to be expressed as hydrogen, substituted or unsubstituted C6-C30 Aryl contains the substituted or unsubstituted 5-30 member inferior heteroaryl of one or more hetero atoms；

The Q1-Q7 independently be expressed as substituted or unsubstituted C6-C30 aryl, containing one or more miscellaneous originals The substituted or unsubstituted 5-30 unit's heteroaryl of son；

The substituent group that may replace group optionally from D-atom, halogen atom, alkoxy, adamantyl, cyano, C1~ The alkyl of C10, C6-C30 aryl, contains one in one or more heteroatomic 5-30 unit's heteroaryls at the naphthenic base of C3~C20 Kind is several；

The hetero atom is optionally from one or more of oxygen atom, sulphur atom or nitrogen-atoms.

In one embodiment of the invention, the luminescent layer also includes to be represented by structure shown in general formula (16):

The wherein R₁₂-R₁₆Independently be expressed as substituted or unsubstituted C6-C30 arlydene, containing one or more A substituted or unsubstituted 5-30 member inferior heteroaryl of hetero atom；

R₁₂、R₁₃Structure shown in selection hydrogen independently, general formula (17) or general formula (18)；

A isX2, X3 are expressed as oxygen atom, sulphur atom, C1-10 linear or branched alkyl group and replace Alkylidene, one of the amido that replaces of the aryl alkylidene, the alkyl or aryl that replace；

Structure shown in general formula (17) or general formula (18) passes through C_L1-C_L2Key, C_L2-C_L3Key, C_L3-C_L4Key connection is in chemical formula 6 On.

In a preferred embodiment in accordance with this invention, the emitting layer material of general formula (12) to general formula (15) can be selected from down State any one of compound:

In a preferred embodiment in accordance with this invention, the emitting layer material of general formula (16) can be selected from following compounds It is any: material shown in general formula (16) can be led with material shown in general formula (12) to general formula (15) together as luminescent layer jointly Body material.

In a further preferred embodiment of the invention, the multichannel carrier transmission material of general formula (1) be can be selected from Any one of following compounds:

Multichannel carrier transmission material of the invention can significantly improve the injection and transmission rate in hole.Herein In, the holoe carrier conductive group that can be enumerated includes carbazole group, aniline group, carbazole and cyclic group etc..Based on this hair Bright principle, to realize the conduction of multiple level carrier, the carrier conductive group for constituting hole mobile material must not be one It is a, but have the presence of multiple hole class groups, for example molecular characterization of two aniline, an aniline and carbazole Molecular characterization, molecular characterization, two aniline and the molecular characterization of a carbazole of three aniline etc..While this Class hole transport material is not centainly full symmetrical configuration, and only non-full symmetrical configuration can just cause each hole-conductive segment The difference of HOMO energy level could obtain with good performance.

One of hole mobile material of the present invention is essentially characterized in that the hole current-carrying for constituting hole mobile material There is two or more energy levels in son conduction segment, and the difference of this various energy level is between 0.01-0.8eV, It is preferred that between 0.02-0.5eV.

Cavity type carrier conducting material is divided into asymmetric and two kinds of features of holohedral symmetry by we, and so-called holohedral symmetry material is Refer to that it is split based on its molecular structure, is only capable of splitting into a kind of structure fragment of feature, unsymmetric structure that is, of the present invention Multiple carrier conduction pathway material, it is characterised in that split based on its molecular structure, the removable various structures for separating different characteristic Segment.

The full symmetrical configuration material that we can enumerate herein includes all list fluorine-triphenylamine structure materials, α-NPD etc., Specific molecular structural formula can be listed below:

Deng,

Wherein, the material of above structure 1 and structure 2 can not be disassembled further because being single triphenylamine material, and Structure 3, though double fluorine-triphenylamine structures, it, which conducts segment and is only capable of disassembling, becomesA kind of feature, so should Molecular structure is still the holoe carrier conductive material of holohedral symmetry feature.

As example, the hole transport material of general formula

Based on the principle of the present invention, for its structure feature, R1-R6 must cannot be identical group；Such as Fruit is identical group, then entire molecule has reformed into full symmetrical configuration, and the carrier of the molecule of this configuration characteristic passes Pathway just only has a single seed type, has a kind of feature, and does not meet principle set forth in the present invention, so that prepared The performance of organic electroluminescence device be difficult to biggish breakthrough.Based on the above principles, the hole-conductive of above-mentioned general formula structure Material can further decompose into the material of general formula feature

Deng.

Specifically, the hole transport material of following feature can be enumerated:

Based on the principle of the present invention, judge a molecule whether have the hole conduction channel of a variety of energy levels method be by Molecular structure is disassembled at different hole-conductive segments, the HOMO energy level of the molecular structure after dismantling is carried out practical Measurement calculates, and judges the similarities and differences of the holoe carrier conduction pathway of disassembled material, to judge the superiority and inferiority of molecule With physical property quality.The exemplary approach disassembled to molecule is as follows:

It is disassembled to becomeTwo kinds of structures；

It is disassembled to becomeTwo kinds of structures.

For electroluminescent organic material HOMO energy level direct test method include for example CV method, UPS method, IPS method and AC method etc..Further, it is also possible to by way of quantum chemical method to the HOMO energy level of electroluminescent organic material into Row prediction.In above-mentioned various test methods, CV method influenced by the method for solvent and operation it is bigger, measurement numerical value it is past It is larger toward otherness；When being measured using AC method, sample needs to be placed in the environment of dry air, works as high-energy Ultraviolet monochromatic light action when sample surfaces, runaway electron need and air in oxygen combine, detector could obtain Signal, therefore, specimen material are affected by oxygen element in environment, material (for example P doping for some depth HOMO energy levels Material) HOMO energy level test inaccuracy.However, UPS method and IPS method can be under high vacuum environments to Organic Electricity The photoelectron spectroscopy of electroluminescent material is tested, and can thus exclude the influence of poor environment to the maximum extent, close to have The preparation environment of organic electro luminescent luminescent device, to greatest extent close to the theory of in situ measurement.Therefore from measurement method For upper, compared to other measurement methods, UPS method and IPS method numerical accuracy with higher.Nonetheless, still , it is emphasized that the test of the HOMO energy level of different materials, has only accomplished the consistency of equipment and the consistency of method, has advised simultaneously The influence of test environment is kept away, the HOMO energy level between material just has the meaning absolutely compared.

In the present invention, it is passed in the multichannel carrier transmission material dismantling of mutual-through type (1) at the carrier of general formula (A1) After the carrier of guide card section and general formula (A2) conducts segment, mutual-through type (A1) and general formula can be distinguished by IPS mensuration (A2) the HOMO energy level of carrier conduction segment measures, and calculates the absolute value differences of the HOMO energy level, wherein having The measuring condition of body is known to the skilled in the art.

The present invention is not the substrate collocation principle of negative conventional hole class material, but in the physical property ginseng of traditional material screening Further superposition on the basis of number, that is, recognize HOMO energy level, carrier mobility, film phase stability, material it is heat-resisting steady The qualitative equal impact effect for organic electroluminescence device hole injection efficiency.On this basis, material is further increased Screening conditions, and then high property is prepared with improving in the collocation of device by selecting superior electroluminescent organic material The material of energy organic electroluminescence device selects precision.

The device that electroluminescent organic material based on the principle of the present invention selection is constituted can achieve more preferably performance, Its advanced physical model can be described as follows:

1. hole-conductive film layer is selected based on appropriate HOMO energy level, formation is collocated with each other, under electric field action, carrier Transmission is formed between different hole-conductive film layers.

2. carrier enters the hole-conductive film layer of feature of the present invention, and during forming conduction, based on following Physical features:

When 2.1 carriers import the conducting membrane layer from adjacent electroluminescent organic material film layer band, along a variety of current-carrying In sub- conduction pathway, relatively low channel enters the hole-conductive film layer.

2.2 in the hole-conductive film layer, and carrier forms electron exchange in different conduction pathways, and along a variety of loads It flows in sub- conduction pathway, flow out the hole-conductive film layer in relatively high channel, and enters next layer of adjacent organic electroluminescence hair Luminescent material film layer.

It should be noted that constituting the HOMO energy level of the hole transport material of feature of the present invention and material itself possesses A variety of carrier conduction pathways there is certain connection, it is generally recognized that based on material HOMO energy level measured by existing evaluation and test means Numerical value the median of segment and shallow HOMO energy level conduction segment is conducted between deep HOMO energy level, while the conduction of a variety of carriers is logical Shallow carrier conduction pathway in road is different from shallow HOMO energy level segment numerical value, the list that different HOMO energy level conduction segments are constituted One molecule there will necessarily be between two kinds of difference HOMO segments and influence each other.

As organic semiconductor device, carrier is transmitted to luminescent layer from electrode, needs to cross certain energy rank, this energy The differential driving voltage to organic electroluminescence device constitutes adverse effect.Specific influence factor has very much, is current-carrying first Son is injected into the process of electroluminescent organic material film layer from electrode interface, this process is injected there are thermocurrent and tunneling injection Both of which.So-called thermocurrent injection, carrier need to skip the energy level difference between electrode and organic material, only reach certain Electric field strength, carrier can just be injected into organic material film laye, form the transmission of carrier.So-called tunneling injection, then can be with It is interpreted as being Ohmic contact between organic material and electrode, the injection of carrier does not depend on electric field strength.It is organic for constituting For the hole class material of electroluminescent device, both modes be it is simultaneous, only according to the difference of the characteristic of material, The ratio of the two accounting is different.If the HOMO energy level of electroluminescent organic material and the working function of electrode connect very much Closely, then be conducive to tunneling injection, undoubtedly, adversely affected caused by the thermocurrent injection bigger driving voltage device of ratio It is bigger.Further, flowing of the carrier between the electroluminescent organic material of different energy levels injects problem there is also mutual, Inject it is ineffective if, the driving voltage that will lead to device is excessively high.In general, it influences between different energy level organic materials The biggest factor of injection obstacle is equally the conduction energy level difference of different materials.For the class material of hole, that is, HOMO energy level difference, Energy level difference is bigger, adversely affects caused by the driving voltage of device bigger.The organic electroluminescence material of feature of the present invention Material, there are two types of the carrier conduction pathways of different energy levels for tool, and what carrier conducted in film layer of the present invention When, the conversion between low-lying level conduction pathway and high level conduction pathway is not also just deposited because not needing the effect of field energy It is entirely the electron exchange inside molecular structure, it can be understood as complete tunneling conduction in the adverse effect to driving voltage Mode.Meanwhile if the conduction pathway (molecular structure segment) of low-lying level and adjacent existing fringing field side organic electroluminescence material The HOMO energy level of material is close, the organic electroluminescence material of high level conduction pathway (molecular structure segment) and adjacent high electric field side The HOMO energy level of material is close, and under electric field action, carrier is transmitted to material membrane of the present invention from shallow HOMO energy level film layer Layer, so conduct to deep HOMO energy level adjacent material film layer when, then the injection Yu conduction of carrier can be more with tunnels Mode progress is worn, is easy for promoting the injection conduction efficiency of holoe carrier, achievees the effect that low voltage drive, simultaneously as empty Cave carrier easier can be transmitted to luminescent layer, will be conducive to the balance of carrier, be conducive to the promotion of device performance.

Organic electroluminescence device of the invention can be bottom light-emitting organic electroluminescent device, push up the organic electroluminescence hair that shines Optical device and laminated organic electroluminescent device do not do specific limitation to this.

As the substrate of organic electroluminescence device of the invention, can be used any commonly employed in organic electroluminescence device Substrate.Example is transparent substrate, such as glass or transparent plastic substrate；Opaque substrate, such as silicon substrate；Flexible PI ilm substrate.No There is different mechanical strengths, thermal stability, the transparency, surface flatness, waterproofness with substrate.Not according to the property of substrate Together, use direction is different.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, can be used Transparent metal oxide is formed, such as 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, 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, and usually 50-500nm, excellent It is selected as 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 hole transport auxiliary layer.For example, referring to Fig. 1, hole transporting zone may include setting gradually from the bottom to top Hole injection layer, hole transmission layer and hole transport auxiliary layer on first electrode.

Here, for the organic electroluminescence device of feature of the present invention, for electronics conducting membrane layer material and knot Structure does not do specific limitation.Simultaneously for the selection of emitting layer material, it can be the various monochromatic luminescent materials such as RGB, can also be The combination for having the secondary colour luminescent material of multispectral characteristic.Core of the invention technology is to select to have multiple carrier conduction The material in channel and the hole-conductive film layer for being used for organic electroluminescence device, which includes foregoing hole Implanted layer, hole transmission layer, hole transport auxiliary layer.

In organic electroluminescence device of the invention, the multi-pass of hole injection layer and hole transmission layer comprising general formula (1) The absolute value differences of road carrier transmission material, i.e., the HOMO energy level of the HOMO energy level and another channel in one of channel exist Between 0.01-0.8eV, allow the holoe carrier common transport on these channels respectively, to improve carrier Injection and efficiency of transmission help to promote device performance.

In one embodiment of the invention, in hole injection layer and hole transmission layer, the multichannel of general formula (1) is carried It flows sub- transmission material and is selected from least one of following formula: formula (I-1), formula (I-32), formula (I-58), formula (I-61), formula (I- 114), formula (I-129), formula (I-134), formula (I-146), formula (I-242) and formula (I-265).In another implementation of the invention In scheme, in hole injection layer and hole transmission layer, the HOMO energy level of the multichannel carrier transmission material of general formula (1) is located at Between 5.40-5.60eV, preferably 5.43-5.55eV, more preferable 5.47-5.52eV.

Herein, the hole-conductive film layer for being covered in anode surface had both been properly termed as anodic interface buffer layer, can also be with Referred to as hole injection layer can also be known as the hole transmission layer adulterated containing P.Either which kind of appellation, this film material All there is an essential characteristic, being exactly can be with the main body organic material of conduction hole comprising one, while also including a depth The p-type dopant material of HOMO energy level (corresponding lumo energy also can be very deep).Based on empirical summary, in order to realize hole from sun Smoothly injection of the pole to organic film, the HOMO energy of the main body organic material of conduction hole used in anodic interface buffer layer Grade must have certain feature with P dopant material, just be expected to the charge transfer state between realization body material and dopant material Occur, realize the Ohmic contact between buffer layer and anode, realize the efficient injection for injecting conduction from electrode to hole, this is special Sign is summarized are as follows: material of main part HOMO energy level-P dopant material lumo energy≤0.4eV.

In view of above-mentioned empirical summary, therefore for the hole human subject material of different HOMO energy levels, need to select Different P dopant materials is matching, is just able to achieve the Ohmic contact at interface, promotes hole and injects effect.

Therefore, in one embodiment of the invention, in order to inject hole preferably, hole injection layer also includes choosing From the p-type dopant material below with charge-conduction: quinone derivative, such as four cyano quinone bismethane (TCNQ) and 2,3,5,6- Four fluoro- four cyano -1,4- benzoquinones bismethanes (F4-TCNQ)；Or six azepine Sanya benzene derivatives, such as 2,3,6,7,10,11- six cyanogen Six azepine triphenylene (HAT-CN) of base -1,4,5,8,9,12-；Or cyclopropane derivative, such as 4,4', 4 "-((E of 1E, 1'E, 1 ")- Cyclopropane -1,2,3- trimethylene three (cyano formyl subunit)) three (2,3,5,6- ptfe benzyls)；Or metal oxide, such as oxygen Change tungsten and molybdenum oxide, but not limited to this.Preferred p-type dopant material is selected from least one of following P1-P10:

In hole injection layer of the invention, the doping ratio of used first organic material and P-type material is 99:1- 95:5, preferably 99:1-93:3, based on quality.

In the present invention, device is made of first electrode, organic functional material, second electrode；Device architecture can example It lifts are as follows:

(1) hole injection layer, hole transmission layer, hole transport auxiliary layer, luminescent layer, electronics are sequentially formed on anode Transport layer, electron injecting layer, eventually form cathode layer；

(2) hole injection layer, hole transmission layer, hole transport auxiliary layer, luminescent layer, hole are sequentially formed on anode Barrier layer, electron transfer layer, electron injecting layer, eventually form cathode layer；

Hole transport auxiliary layer can be single compound and constitute, and be also possible to from bottom to top by two different organic Material is constituted.

In one embodiment of the invention, the hole transport auxiliary layer includes general formula of the present invention (1) Multichannel carrier transmission material.In one embodiment of the invention, the hole transport auxiliary layer includes at least one Multichannel carrier transmission material in following formula: formula (I-2), formula (I-15), formula (I-156), formula (I-292) and formula (I- 310).In another embodiment of the present invention, the HOMO energy level of the hole transport auxiliary layer be located at 5.50-5.75eV it Between, between preferably 5.55-5.65eV, more preferable 5.55-5.57eV, triplet (T1) >=2.4eV.

In another embodiment of the present invention, the HOMO energy level of the hole transport auxiliary layer of at least one pixel unit With absolute value differences≤0.3eV of the HOMO energy level of hole transmission layer.

The thickness of hole injection layer of the invention can be 5-100nm, preferably 5-50nm and more preferably 5-20nm, but Thickness is not limited to this range.

The thickness of hole transmission layer of the invention can be 5-200nm, preferably 10-150nm and more preferably 20- 100nm, but thickness is not limited to this range.

The thickness of hole transport auxiliary layer of the present invention can be 1-200nm, preferably 10-100nm, but thickness is not limited to this Range.

Luminescent layer may include material of main part and guest materials.Master as organic electroluminescence device luminescent layer of the present invention The emitting layer material commonly known in the art for organic electroluminescence device can be used in body material and guest materials, The material of main part can be such as thiazole, benzimidizole derivatives, poly-diakyl fluorene derivative or bis- (the 9- clicks of 4,4'- Oxazolyl) biphenyl (CBP)；The guest materials can be such as quinacridone, cumarin, rubrene and its derivative, benzopyrene It mutters derivative, Rhodamine Derivatives or aminostyrl derivative.In a preferred embodiment of the invention, used Luminescent layer material of main part is selected from combination one or more shown in general formula (12) to general formula (16):

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 [(the 2- phenyl of fac- tri- of Ir (ppy) 3 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-25:

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.

When using vacuum deposition process, using shadow mask version subtly patterning organic materials functional layer and cathode layer, But when being handled using spin coating proceeding or laser induced thermal imaging, it is not necessary to the composition by way of shadow mask.

The thickness of adjustable luminescent layer is with optimized emission efficiency and driving voltage.Preferred thickness range be 5nm extremely 50nm, but thickness is not limited to this range.

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.It is supreme that hole blocking layer of the invention may be provided at 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, 9,9'- (5- (6- ([1,1'- biphenyl] -4- base) -2- phenyl pyrimidine -4- base) -1,3- phenylene) bis- (9H- clicks Azoles) pyrimidine derivatives such as (No. CAS: 1345338-69-3) etc..The thickness of hole blocking layer of the invention can be 2-200nm, excellent It is selected as 5-150nm and more preferably 10-100nm, but thickness is not limited to this range.

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, using Alq3, BAlq as the metal network of the 8-hydroxyquinoline derivative of representative Object, various metal complexes, triazole derivative, bis- (9,9- dimethyl -9H- fluorenes -2- the base) -6- (naphthalene -2- base) -1,3 of 2,4- are closed, The pyrrolotriazine derivatives such as 5- triazine (No. CAS: 1459162-51-6), 2- (4- (9,10- bis- (naphthalene -2- base) anthracene -2- base) phenyl) -1- Imdazole derivatives, oxadiazole derivatives, the thiophenes such as phenyl -1H- benzo [d] imidazoles (No. CAS: 561064-11-7 is commonly called as LG201) Oxadiazole derivative, carbodiimide derivative, quinoxaline derivant, phenanthroline derivative, silicon base compound derivative etc..This hair The thickness of bright electron transfer layer can be 10-80nm, preferably 20-60nm and more preferably 25-45nm, but thickness is not limited to This range.

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 function material layer.Electron injecting layer as organic electroluminescence device of the present invention The electron injecting layer material commonly known in the art for organic electroluminescence device can be used, for example, lithium in material；Lithium Salt, such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or Lithium Azide；Or cesium salt, cesium fluoride, cesium carbonate or cesium azide.This hair The thickness of bright electron injecting layer can be 0.1-5nm, preferably 0.5-3nm and more preferably 0.8-1.5nm, but thickness is unlimited In this range.

Second electrode may be provided on electron transporting zone.Second electrode can be cathode.Second electrode can be Radio pole, half transmitting electrode or reflecting electrode.When second electrode is transmission electrode, second electrode may include such as Li, Yb, Ca, LiF/Ca, LiF/Al, Al, Mg, BaF, Ba, Ag or its compound or mixture；When second electrode is semi-transparent radio When pole 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.

During preparing organic electroluminescence device, such as can be by being laminated anode, function material in succession on substrate The bed of material and cathode prepare organic electroluminescence device of the invention.About this point, physical gas-phase deposite method can be used, such as splash Method or Electron Beam Vapor method or vacuum vapour deposition are penetrated, but not limited to this.Also, it can be steamed for example, by vacuum deposition method, vacuum Above compound is used to form function material layer by plating method or solution coating process.About this point, solution coating process mean spin-coating method, Dip coating, jet printing method, screen printing method, spray-on process and rolling method, but not limited to this.Vacuum evaporation means in vacuum environment In, material is heated and is plated on substrate.In the present invention, it is preferred to form each layer using vacuum vapour deposition.

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.

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.Unless otherwise Illustrate, can be used alone in conjunction with feature, characteristic and/or the element that specific embodiment describes or is retouched in conjunction with other embodiments Feature, characteristic and/or the element stated are applied in combination.

Embodiment

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

In order to which the present invention is more clearly understood, the embodiment of the present invention is only described each electroluminescence cell, but It will be appreciated by those skilled in the art that phase can be used when forming tandem organic electroluminescence device in each pixel light emission unit Same hole injection layer and hole transmission layer.

A variety of materials used in embodiment and comparative example are commercially available, or can pass through those skilled in the art Method known to member obtains.

The preparation of structure shown in chemical formula 1

Embodiment 1: the synthesis of compound I-1

The raw material B- of 0.01mol raw material A -1,0.012mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml 1,0.03mol potassium tert-butoxide, 1 × 10^-4molPd₂(dba)₃, 1 × 10^-4Mol tri-tert-butylphosphine, 150ml toluene, is heated to reflux 12 Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, obtain intermediate D-1；Elemental analysis Structure (molecular formula C₄₂H₃₁BrN₂): theoretical value C, 78.38；H,4.85；N,4.35；Br,12.41；Test value: C, 78.36；H, 4.86；N,4.34；Br,12.43.ESI-MS(m/z)(M⁺): theoretical value 642.17, measured value 642.23.

The raw material of 0.01mol intermediate B -1,0.012mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml C-1,0.03mol potassium tert-butoxide, 1 × 10^-4molPd₂(dba)₃, 1 × 10^-4Mol tri-tert-butylphosphine, 150ml toluene, is heated to reflux 12 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, obtain target compound I-6；Member Element analysis structure (molecular formula C₅₄H₄₁N₃): theoretical value C, 88.61；H,5.65；N,5.74；Test value: C, 88.60；H,5.65；N, 5.75。ESI-MS(m/z)(M⁺): theoretical value 731.33, measured value 731.66.

Following compounds (raw materials used to have middle energy saving ten thousand profit to provide), synthesis are prepared in the same manner as in Example 1 Raw material is as shown in table 6 below；

Table 6

Detection method

HOMO energy level: being measured by IPS mensuration, and specific measuring process is as follows:

It is 1.0E in vacuum degree using vacuum evaporation equipment^-5Under the pressure of Pa, control evaporation rate isBy sample It is deposited on ito substrate, film thickness 60-80nm；Then IPS-3 measuring device is utilized, to the HOMO energy level of sample film It measures.

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

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

Triplet T1: being tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2*10^-5Toluene Solution.

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

Table 1 shows hole mobile material, p-type dopant material, hole transport auxiliary layer material and light emitting host material (A9 And EMH-9) and guest materials (EMD-13) each energy level test result.

Table 1

As shown in above-mentioned table 1, hole mobile material can be divided into two different segments, wherein each segment is equal With respectively different HOMO energy levels, and the difference of HOMO energy level is between 0.01-0.2eV.Hole transport layer material HOMO energy level is located at 5.43-5.50eV；The HOMO energy level of hole transport auxiliary layer material is located at 5.55-5.57eV, and triplet state Energy level (T1) >=2.62eV.

Prepare organic electroluminescence device

The molecular structural formula of associated materials is as follows:

Embodiment 1

Organic electroluminescence device is prepared according to the following steps:

A) use transparent glass as substrate, coating thickness is then the I TO of 150nm divides as anode layer on it It is not cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate, is then handled 2 minutes in plasma cleaner；

B) in washed first electrode layer, hole mobile material I-1 and p-type dopant material P1 are placed on two respectively In evaporation source, under vacuum degree 1.0E-5Pa pressure, control I-1 evaporation rate isControl p-type dopant material vapor deposition speed Rate isCommon mixed steam forms hole injection layer, with a thickness of 10nm；

C) on hole injection layer, hole transmission layer, hole transport layer material I- are deposited by way of vacuum evaporation 1, with a thickness of 60nm；

D) on the hole transport layer, hole transport auxiliary layer I-2 is deposited by way of vacuum evaporation, with a thickness of 40nm；

E) on hole transport auxiliary layer, be deposited emitting layer material by way of vacuum evaporation, material of main part be A9 and D5, guest materials EMD-13, mass ratio 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 electron transfer layer, LiF is deposited by vacuum evaporation mode, with a thickness of 1nm, the layer is as electron injection Layer；

H) on electron injecting layer, vacuum evaporation Al, with a thickness of 80nm, which is cathode layer.

Embodiment 2-20

It is carried out according to the process of device preparation embodiment 1, the difference is that by hole mobile material I-1 in step b) Change appointing in hole hole mobile material I-32, I-58, I-61, I-114, I-129, I-134, I-146, I-242, I-265 into Meaning one；Hole mobile material is changed into I-1 in step c) changes hole hole mobile material I-32, I-58, I-61, I- into 114, any one in I-129, I-134, I-146, I-242, I-265；Hole transport is assisted into layer material in step d) I-2 changes any one in hole mobile material I-15, I-156, I-292, I-310 or any combination with EB1 material into, Specific device architecture such as table 2.E) in material of main part change into A1, A5, A9, A16, A25, A27, B1, B5, B10, B16, B30, Any one in B40 and the combination of any one in D1, D5, D11, D15, D20.

Embodiment 21

It is carried out according to the process of device preparation embodiment 1, the difference is that material of main part is C25, visitor in step e) Body material is EMD-8, and C25 and EMD-8 mass ratio is 96:4, with a thickness of 40nm.

Embodiment 22-40

It is carried out according to the process of device preparation embodiment 21, the difference is that by hole mobile material I- in step b) 1 changes appointing in hole hole mobile material I-32, I-58, I-61, I-114, I-129, I-134, I-146, I-242, I-265 into Meaning one；Hole mobile material is changed into I-1 in step c) changes hole hole mobile material I-32, I-58, I-61, I- into 114, any one in I-129, I-134, I-146, I-242, I-265；Hole transport is assisted into layer material in step d) I-2 changes any one in hole mobile material I-15, I-156, I-292, I-310 or any combination with EB1 material into, Specific device architecture such as table 4.E) in material of main part change into C1, C2, C5, C8, C11, C14, C17, C19, C23, C25, D1, D5, Any one in D11, D15, D20 or several combinations.

Comparative example 1-4

It is carried out according to the process of device preparation embodiment 1, the difference is that material is injected in the hole used in step b) Material is HT-1；C) hole-transporting layer material is HT-1；D) hole transport auxiliary layer material I-2 is changed into hole transport auxiliary in The combination of layer material EB-1, EB-2, I-15 or EB-1 and I-15；E) luminescent layer material of main part is CBP in；Specific device architecture Such as table 4.

Comparative example 5-8

It is carried out according to the process of device preparation comparing embodiment 1-4, the difference is that material of main part is CBP, visitor in e) Body material is EMD-8, and CBP and EMD-8 mass ratio is 96:4, with a thickness of 40nm.Specific device architecture such as table 4.

Table 2

The results are shown in Table 3 for the device measurement performance of embodiment 1-20 and comparative example 1-4.

Table 3

Note: LT97 refers to that device brightness decays to the time used in the 97% of original brightness；

Life-span test system is owner of the present invention and the organic electro-luminescence device lifetime that Shanghai University is studied jointly Tester.The annotation is also applied for following table 5.

Table 4

The results are shown in Table 5 for the device measurement performance of embodiment 21-40 and comparative example 5-8.

Table 5

It can be seen from the result of table 3 compared with comparative example, the organic matter of carrier multichannel is used to pass as hole Defeated, hole injection layer assists device prepared by layer material as hole transport, and device is prepared obtained by embodiment 1-20 The driving voltage of device be substantially reduced, and luminous efficiency and service life are significantly increased.

It can be seen from the result of table 5 compared with comparative example, the organic matter of carrier multichannel is used to pass as hole Defeated, hole injection layer assists device prepared by layer material as hole transport, and device is prepared obtained by embodiment 21-40 The driving voltage of device be substantially reduced, and luminous efficiency and service life are significantly increased.

As described above, OLED light emitting device according to the present invention, which has used multichannel hole mobile material that can provide, to be had The brightness of raising, luminous efficiency, service life organic electroluminescence device.

Claims

It from the bottom to top successively include substrate, first electrode, organic functional material layer and the 1. a kind of organic electroluminescence device Two electrodes, the organic functional material layer include:

Hole transporting zone is located on 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 hole transport auxiliary from the bottom to top Layer, the hole injection layer include p-type dopant material,

Wherein the hole transporting zone includes the multichannel carrier transmission material of general formula (1),

The multichannel carrier transmission material include more than two carrier conduction pathways, the carrier conduction pathway by Carrier shown in general formula (A1) or general formula (A2) conducts segment and constitutes,

Wherein carrier shown in the general formula (A1) conducts the HOMO of the conduction segment of carrier shown in segment and general formula (A2) The absolute value differences of energy level between 0.01-0.8eV,

Wherein,

Ar₁、Ar₂、Ar₃、Ar₄、Ar₅And Ar₆Each independently represent substituted or unsubstituted phenyl, substituted or unsubstituted bigeminy Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted naphthyridines base, replaces or does not take substituted or unsubstituted naphthalene The terphenyl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzo phenanthryl, takes substituted or unsubstituted anthryl Generation or unsubstituted pyrenyl, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted azepine pyrenyl, substituted or unsubstituted nitrogen The structure of miscellaneous phenanthryl or general formula (A3):

In general formula (A3), R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈In any one indicate the list that is connected with the N in general formula (1) Key, remaining Rn each independently represent hydrogen atom, D-atom, C₁-C₁₀Alkoxy, adamantyl, cyano, C₁-C₁₀Alkyl, C₃-C₁₀Naphthenic base, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted naphthyridines base, replace or Unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substituted or unsubstituted terphenyl, n indicate 1 to 8 integer；

X indicates O, S ,-C (R₉)(R₁₀)-or-N (R₁₁)-；

R₉、R₁₀And R₁₁Each independently represent C₁-C₁₀Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, It is substituted or unsubstituted naphthyridines base, substituted or unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substituted or unsubstituted Terphenyl, wherein R₉With R₁₀Cyclization can be connected with each other；

Wherein in the substituted group, the substituent group is independently from each other D-atom, halogen atom, C₁-C₁₀Alcoxyl Base, adamantyl, cyano, C₁-C₁₀Alkyl, C₃-C₂₀Naphthenic base, C₆-C₃₀Aryl contains one or more heteroatomic 5-30 members Heteroaryl, wherein the hetero atom is optionally selected from one or more of oxygen atom, sulphur atom or nitrogen-atoms.
2. organic electroluminescence device according to claim 1, it is characterised in that: carrier shown in the general formula (A1) Conduction segment and general formula (A2) shown in carrier conduction segment HOMO energy level absolute value differences be located at 0.02-0.5eV it Between, it is more preferably located between 0.02-0.2eV.
3. organic electroluminescence device according to claim 1 or 2, it is characterised in that: the multichannel of the general formula (1) carries Any structure shown in general formula (2) to general formula (11) can be indicated by flowing sub- transmission material:

Wherein, A, B, C, D, E and F each independently represent substituted or unsubstituted phenyl, substituted or unsubstituted dibiphenylyl, Substituted or unsubstituted naphthalene, substituted or unsubstituted pyridyl group, substituted or unsubstituted naphthyridines base, substituted or unsubstituted three Xenyl, phenanthryl substituted or unsubstituted, substituted or unsubstituted benzo phenanthryl, replaces or does not take substituted or unsubstituted anthryl The pyrenyl in generation, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted azepine pyrenyl, substituted or unsubstituted aza-phenanthrenes The structure of base or general formula (A4)

In general formula (A4), R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈In any one indicate the list that is connected with the N in general formula (1) Key, remaining Rn each independently represent hydrogen atom, D-atom, C₁-C₁₀Alkoxy, adamantyl, cyano, C₁-C₁₀Alkyl, C₃-C₁₀Naphthenic base, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted naphthyridines base, replace or Unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substituted or unsubstituted terphenyl, n indicate 1 to 8 integer；

X indicates O, S ,-C (R₉)(R₁₀)-or-N (R₁₁)-；

R₉、R₁₀And R₁₁Each independently represent C₁-C₁₀Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, It is substituted or unsubstituted naphthyridines base, substituted or unsubstituted pyridyl group, substituted or unsubstituted dibiphenylyl, substituted or unsubstituted Terphenyl, wherein R₉With R₁₀Cyclization can be connected with each other；

Wherein in the substituted group, the substituent group is independently from each other D-atom, halogen atom, C₁-C₁₀Alkoxy, Adamantyl, cyano, C₁-C₁₀Alkyl, C₃-C₂₀Naphthenic base, C₆-C₃₀It is aryl, miscellaneous containing one or more heteroatomic 5-30 members Aryl, wherein the hetero atom is optionally selected from one or more of oxygen atom, sulphur atom or nitrogen-atoms.
4. organic electroluminescence device according to claim 1 or 2, it is characterised in that: the multichannel of the general formula (1) carries It flows sub- transmission material and is selected from any one of following compounds:
5. organic electroluminescence device according to claim 1 or 2, it is characterised in that: the luminescent layer includes at least one Kind compound, structure are represented by any structure shown in general formula (12) to general formula (15):

The wherein Ar₇-Ar₁₃Independently be expressed as singly-bound, substituted or unsubstituted C6-C30 arlydene, containing one or Multiple substituted or unsubstituted 5-30 member inferior heteroaryls of hetero atom；Ar₁₄It is expressed as the sub- virtue of hydrogen, substituted or unsubstituted C6-C30 Base contains the substituted or unsubstituted 5-30 member inferior heteroaryl of one or more hetero atoms；

The Q1-Q7 being expressed as substituted or unsubstituted C6-C30 aryl, being taken containing one or more hetero atoms independently Generation or unsubstituted 5-30 unit's heteroaryl；

The substituent group that may replace group is optionally from D-atom, halogen atom, alkoxy, adamantyl, cyano, C1~C10 Alkyl, the naphthenic base of C3~C20, C6-C30 aryl, contain one of one or more heteroatomic 5-30 unit's heteroaryls Or it is several；

The hetero atom is optionally from one or more of oxygen atom, sulphur atom or nitrogen-atoms.
6. organic electroluminescence device according to claim 5, it is characterised in that: the luminescent layer also includes to be represented by Structure shown in general formula (16):

The wherein R₁₂-R₁₆Independently be expressed as substituted or unsubstituted C6-C30 arlydene, containing one or more miscellaneous The substituted or unsubstituted 5-30 member inferior heteroaryl of atom；

R₁₂、R₁₃Structure shown in selection hydrogen independently, general formula (17) or general formula (18)；

A isX2, X3 are expressed as the Asia that oxygen atom, sulphur atom, C1-10 linear or branched alkyl group replace One of the amido that alkyl, the alkylidene of aryl substitution, alkyl or aryl replace；

Structure shown in general formula (17) or general formula (18) passes through C_L1-C_L2Key, C_L2-C_L3Key, C_L3-C_L4Key connection is on chemical formula 6.
7. organic electroluminescence device according to claim 5, it is characterised in that: the general formula (12) to general formula (15) Emitting layer material is selected from any one of following compounds:
8. organic electroluminescence device according to claim 6, it is characterised in that: the emitting layer material of the general formula (16) Selected from any one of following compounds:
9. organic electroluminescence device according to claim 1 or 2, it is characterised in that: the hole injection layer and described Hole transmission layer includes the multichannel carrier transmission material of general formula (1).
10. organic electroluminescence device according to claim 8, it is characterised in that: the HOMO energy of the hole transmission layer Grade is between 5.40-5.60eV, between preferably 5.43-5.55eV, between more preferable 5.47-5.52eV.
11. organic electroluminescence device according to claim 1 or 2, it is characterised in that: the hole transport auxiliary layer by Under supreme include one or two kinds of conventional hole mobile materials.
12. organic electroluminescence device according to claim 10, it is characterised in that: the hole transport auxiliary layer includes The multichannel carrier transmission material of general formula (1).
13. organic electroluminescence device according to claim 11, it is characterised in that: the hole transport auxiliary layer HOMO energy level is between 5.50eV-5.75eV, preferably triplet (T1) >=2.4eV.
14. organic electroluminescence device shown in 1 according to claim 1, it is characterised in that: the hole transport auxiliary layer Absolute value differences≤0.3eV of the HOMO energy level of HOMO energy level and hole transmission layer.