CN108976166A - A kind of compound and its preparation method and application - Google Patents

A kind of compound and its preparation method and application Download PDF

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CN108976166A
CN108976166A CN201810598646.2A CN201810598646A CN108976166A CN 108976166 A CN108976166 A CN 108976166A CN 201810598646 A CN201810598646 A CN 201810598646A CN 108976166 A CN108976166 A CN 108976166A
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phenyl
formula
propyl
butyl
tert
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王辉
李文军
李猛
刘志远
刘福全
于丹阳
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The present invention provides a kind of compounds and its preparation method and application, the experimental results showed that, compound provided by the invention can significantly improve luminous efficiency and the service life of organic electroluminescence device as the CPL layer in organic electroluminescence device.

Description

A kind of compound and its preparation method and application
Technical field
The present invention relates to organic photoelectrical material technical fields, more particularly, to a kind of compound and preparation method thereof and answer With.
Background technique
The correlative study of organic electroluminescence device is initiated at the sixties in 19th century, until the end of the eighties OLED just vigorously send out Exhibition is got up.There is OLED all solid state, low-voltage driving, active to shine, response quickly, wide viewing angle, light-emitting area are big, emission wavelength covers Cover entire visible region and it is rich in color the advantages that, realizing that panchromatic large-area displays field has very big advantage, becoming The flat-panel display device of great prospect.The light emission luminance of organic electroluminescence device is proportional to the concentration and exciton of hole and electronics The probability of recombination product, it is desirable to obtain higher luminous efficiency, not only need hole and electronics that can be efficiently injected into, transmit and It is compound and hole and electron injection is required to reach balance.Therefore, in organic electroluminescence device, between organic layer and organic layer It is matched with the energy band of two electrodes extremely important to device recombination luminescence.
In order to optimize the properties with balancing device, people introduce the functional layer of a variety of different roles, such as hole Implanted layer, hole blocking layer etc..The effect that hole injection layer is added between ito anode and hole transmission layer is mainly manifested in drop Low interface potential barrier, the Adhering capacity for increasing hole transmission layer and ITO electrode improve its stability and balance electronic and hole note Enter etc..
Further, since greatly being constrained between the external quantum efficiency and internal quantum efficiency of OLED there are huge gap The development of OLED, therefore, the light extraction efficiency for how improving OLED also have become a hot topic of research.Ito thin film and glass substrate The interface of interface and glass substrate and air can be totally reflected, and be accounted for about before being emitted to OLED device to the light of exterior space The 20% of organic material film EL total amount, it is thin that remaining about 80% light is mainly limited in organic material film, ITO in the form of guided wave In film and glass substrate, the development and application of OLED are seriously constrained, the total reflection effect in OLED device how is reduced, improves The performance drawn optically coupling to before device to the ratio of exterior space, and then improve device has played the extensive concern of people.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of compound and preparation method thereof and answer With CPL layer of the compound provided by the invention as OLED device can be improved the efficiency of luminescent device.
The present invention provides a kind of compounds, have structure shown in formula (I),
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20 Base；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn extremely Rare 1 is nitrogen；
The A is formula (A-1), formula (A-2) or formula (A-3),
The R1、R2、R3、R4、R5、R6The independent aryl selected from hydrogen, the alkyl of C1~C3 or C6~C10,
Or the R1And R2The condensed ring radical of C10~C20 is formed with the carbon where it.
Preferably, the Ar1Selected from hydrogen, the alkyl of C1~C5, phenyl, the alkyl-substituted phenyl of C1~C5, C10~C20 Fused ring aryl, the sulfur-bearing heteroaryl of C3~C15 or the nitrogenous heteroaryl of C3~C15；
The Ar2Selected from hydrogen, the alkyl of C1~C5, phenyl, the alkyl-substituted phenyl of C1~C5, C10~20 condensed ring The nitrogenous heteroaryl of aryl, the sulfur-bearing heteroaryl of C3~C15 or C3~C15.
Preferably, the Ar1Selected from hydrogen, methyl, ethyl, propyl, normal-butyl, tert-butyl, amyl, trifluoromethyl, phenyl, Anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- methylbenzene Base, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl, 4- aminomethyl phenyl, 3,5- diformazan Base phenyl, 2- thienyl, pyridyl group, pyridazinyl, pyrazinyl, triazine radical or acridinyl；
The Ar2Selected from hydrogen, methyl, ethyl, propyl, normal-butyl, tert-butyl, amyl, trifluoromethyl, phenyl, anthryl, naphthalene Base, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, uncle 4- Butyl phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl, 4- aminomethyl phenyl, 3,5- 3,5-dimethylphenyl, 2- thienyl, pyridyl group, pyridazinyl, pyrazinyl, triazine radical or acridinyl.
Preferably, the X1-a、X1-b、X1-c、X1-d、X1-eIn at most have 3 for nitrogen.
Preferably, the R1、R2It is independent to be selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthrene Base, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl Phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl；
Or the R1And R2Fluorenyl is formed with the carbon where it.
Preferably, the R3、R4、R5、R6It is independent selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, Naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- Tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl.
Preferably, formula (I) compound represented is formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5) Or formula (I-6),
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20 Base；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn extremely Rare 1 is nitrogen.
Preferably, formula (I) compound represented is formula (001)~formula (162).
The present invention also provides a kind of preparation methods of formula (I) compound, comprising: by the chemical combination of A-Br and formula (II) structure Object reaction, obtains the compound of formula (I) structure；
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20 Base；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn extremely Rare 1 is nitrogen:
The A is formula (A-1), formula (A-2) or formula (A-3),
The R1、R2、R3、R4、R5、R6The independent aryl selected from hydrogen, the alkyl of C1~C3 or C6~C10,
Or the R1And R2The condensed ring radical of C10~C20 is formed with the carbon where it.
The present invention also provides a kind of formula (I) compounds represented of the present invention as CPL layers is preparing Organic Electricity Application in electroluminescence device.
Compared with prior art, the present invention provides a kind of compounds and its preparation method and application, the experimental results showed that, Compound provided by the invention can significantly improve organic electroluminescence as the CPL layer in organic electroluminescence device The luminous efficiency of part and service life.
Specific embodiment
A kind of compound has structure shown in formula (I),
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20 Base；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn extremely Rare 1 is nitrogen；
The A is formula (A-1), formula (A-2) or formula (A-3),
The R1、R2、R3、R4、R5、R6The independent aryl selected from hydrogen, the alkyl of C1~C3 or C6~C10,
Or the R1And R2The condensed ring radical of C10~C20 is formed with the carbon where it.
According to the present invention, the Ar1Preferably hydrogen, the alkyl of C1~C5, phenyl, the alkyl-substituted phenyl of C1~C5, C10 The nitrogenous heteroaryl of~20 fused ring aryl, the sulfur-bearing heteroaryl of C3~C15 or C3~C15；More preferably hydrogen, methyl, ethyl, Propyl, normal-butyl, tert-butyl, amyl, trifluoromethyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl Phenyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- positive third Base phenyl, 4- isopropyl phenyl, 4- aminomethyl phenyl, 3,5- 3,5-dimethylphenyl, 2- thienyl, pyridyl group, pyridazinyl, pyrazinyl, Triazine radical or acridinyl；The Ar2Preferably hydrogen, the alkyl of C1~C5, phenyl, the alkyl-substituted phenyl of C1~C5, C10~20 Fused ring aryl, the sulfur-bearing heteroaryl of C3~C15 or the nitrogenous heteroaryl of C3~C15；More preferably hydrogen, methyl, ethyl, third Base, normal-butyl, tert-butyl, amyl, trifluoromethyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethylbenzene Base, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl Phenyl, 4- isopropyl phenyl, 4- aminomethyl phenyl, 3,5- 3,5-dimethylphenyl, 2- thienyl, pyridyl group, pyridazinyl, pyrazinyl, three Piperazine base or acridinyl.
According to the present invention, X1-a、X1-b、X1-c、X1-d、X1-eIn preferably have one be nitrogen, two be nitrogen or three are nitrogen.
According to the present invention, the R1 is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthrene Base, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl Phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl；The R2Preferably hydrogen, first Base, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- positive third Base phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- are different Propyl phenyl or 4- aminomethyl phenyl；Or R described in person1Fluorenyl is formed with the carbon where R2 and its.
The R3Preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl benzene Base, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- fluoroform Base phenyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl.
The R4Preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl benzene Base, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- fluoroform Base phenyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl.
The R5Preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl benzene Base, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- fluoroform Base phenyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl.
The R6Preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl benzene Base, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- fluoroform Base phenyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- aminomethyl phenyl.
Specifically, formula (I) compound represented is formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I- 5) or formula (I-6),
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20 Base；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn extremely Rare 1 is nitrogen.
More specifically, formula (I) compound represented is formula (001)~formula (161),
The present invention also provides a kind of preparation methods of formula (I) compound, comprising: by the chemical combination of A-Br and formula (II) structure Object reaction, obtains the compound of formula (I) structure；
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20 Base；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn extremely Rare 1 is nitrogen；
The A is formula (A-1), formula (A-2) or formula (A-3),
The R1、R2、R3、R4、R5、R6The independent aryl selected from hydrogen, the alkyl of C1~C3 or C6~C10,
Or the R1And R2The condensed ring radical of C10~C20 is formed with the carbon where it.
Wherein, the present invention does not have particular/special requirement to the condition of reaction, and those skilled in the art can select according to common knowledge It selects suitable reaction condition and product is prepared, and the restriction of group is identical as aforesaid compound.
The present invention also provides a kind of formula (I) compounds represented of the present invention as CPL layers is preparing Organic Electricity Application in electroluminescence device.
The present invention provides a kind of compound and its preparation method and application, compound provided by the invention is as Organic Electricity CPL layer in electroluminescence device, can significantly improve luminous efficiency and the service life of organic electroluminescence device.And preparation side Method is simple, and raw material sources are extensive, is suitable for industrialized production.
In addition, in the present inventionRepresent the connecting key of group；In-N represent the key can be in any one of aryl Position.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Embodiment 1
The synthesis of compound 001
Under condition of nitrogen gas, N- phenylpyridine -4- amine (110mmol), bromo- 9, the 9- dimethyl -9H- fluorenes (100mmol) of 2-, neighbour Phenanthroline (1.98g), cuprous iodide (1.90g), the substances such as cesium carbonate (38.6g, 2eq) are dissolved in heating in toluene (300mL) It 110 DEG C, reacts 7 hours, cooling, room temperature filtering removes metallics, evaporates solvent with revolving, obtain solid 001 (76mmolg, 76%).
With identical mole ratio It replaces in the synthesis of compound 001 'sWith chemical formulaReaction, is prepared shown in general formula 1
Compound.
Embodiment 2
Organic compound of the invention has high Tg (glass transition temperature) as the CPL layer material in luminescent device, High refractive index, the test of hot property and refractive index is carried out to the compound of embodiment preparation respectively, and testing result is as shown in table 1.
Table 1
Embodiment 3
It is applied to the preparation of OLED device using formula of the present invention (I) compound as CPL layers, in the present embodiment OLED device is top radiation organic EL part, and structure includes: substrate 1, and on substrate 1 successively plating formed it is anti- Penetrate layer 2, anode 3, hole injection layer (HIL) 4, hole transmission layer (HTL) 5, luminescent layer (EML) 6, electron transfer layer (ETL) 7, Electron injecting layer (EIL) 8, cathode 9 and coating 10.
Wherein, substrate 1 is glass substrate, quartz base plate or flexible macromolecule substrate (plastics or polyimides etc.)；
Reflecting layer 2 can be metallic silver or silver alloy, metal aluminum or aluminum alloy layer, for reflecting the light of incident orientation substrate Line；
Anode layer 3 can be ITO (tin indium oxide), IZO (indium zinc oxide), high-work-function metal or alloy, C60 etc. organic half Conductor material；
Hole injection layer 4 selects 4,4 ', 4 "-three (N-3- methylphenyl-N-phenyl amino) triphenylamines (MTDATA) and 2, The mixture of 3,5,6- tetrafluoro Kui bismethanes (F4TCNQ), the mass ratio of the two are 25: 1.
Hole transmission layer 5 is N, N '-two-(1- naphthalene)-N, diphenyl -1 N ' -, 1 '-xenyl -4,4 '-diamines (NPB).
Luminescent layer 6 can be feux rouges, green light or blue light.Wherein, the main body RH of feux rouges is Bebq2 (bis- (10- hydroxy benzos [h] quinoline) beryllium), doping RD be Ir (piq) 2 (acac), the main body GH of green light is CBP (4,4 '-bis- (N- carbazoles) -1,1 '-connection Benzene), doping GD be Ir (ppy) 3, blue light main body BH be ADN, doping BD be DPAVB (Isosorbide-5-Nitrae-two-[4- (diformazan aminophenyl) benzene second Alkenyl] benzene).
Electron transfer layer 7 is Bphen.Electron injecting layer 8 can be inorganic alkali metal compounds or organic alkali metal complex. Preferred as alkali is that inorganic alkali metal compounds are LiF, and organic alkali metal complex is 8-hydroxy-quinoline lithium.
The method for specifically preparing device is as follows:
Blue-light device
Substrate 1 is glass substrate, and sputtering sedimentation Ag sputters 10nm's as reflecting layer 2 with a thickness of 150nm on substrate 1 Anode 3 of the ITO as device, and required figure is etched, use O3Plasma treatment 3 minutes.Gained substrate 1 is placed in vacuum In, by the mixture of the total MTDATA and F4TCNQ for steaming deposition 130nm as hole injection layer (HIL) 4, wherein F4TCNQ weight Amount is the 4% of MTDATA weight.Then the NPB of 10nm is deposited as hole transmission layer (HTL) 5.Steam the ADN of deposition 30nm altogether again Mixture with DPAVB is as luminescent layer 6, and wherein the molar ratio of DPAVB and ADN is 1: 20.Then the Bphen for depositing 20nm makees For electron transfer layer (ETL) 7.The LiF of 1nm is deposited again as electron injecting layer 8.Cathode 9 is the alloy-layer of co-evaporation K and Ag 10nm, wherein K passes through KBH4The mode that (400 DEG C of temperature) is decomposed during vapor deposition is deposited, K and Ag molar ratio is 8: 1, then Deposit the Ag of 25nm.The compounds of this invention 001 that 30nm is deposited is used as CPL layers.
Green device
It is consistent with the preparation method of blue-light device, the thickness of HIL is only changed to 170nm, the material of luminescent layer is changed to CBP With the mixture of Ir (ppy) 3, the wherein molar ratio 1: 10 of Ir (ppy) 3 and CBP.
Red device
It is consistent with the preparation method of blue-light device, the thickness of HIL is only changed to 60nm, the material of luminescent layer is changed to BeBq2With Ir (piq)2(acac) mixture, wherein Ir (piq)2(acac) and BeBq2Molar ratio be 1: 10.
Embodiment 4
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: K and Ag alloy-layer, molar ratio 2: 1 are thick Degree is 7nm；Ag layers are 25nm；CPL layers prepare red device for the compounds of this invention 037 with a thickness of 50nm.
Embodiment 5
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 4: 1 are thick Degree is 5nm；Ag layers are 20nm；CPL layers are the compounds of this invention 061, with a thickness of 60nm, prepare green device.
Embodiment 6
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 6: 1 are thick Degree is 7nm；Ag layers are 25nm；CPL layers prepare red device for the compounds of this invention 085 with a thickness of 30nm.
Embodiment 7
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Li and Ag alloy-layer, molar ratio 8: 1 are thick Degree is 9nm；Ag layers are 30nm；CPL layers are the compounds of this invention 109, with a thickness of 50nm, prepare green device.
Embodiment 8
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 4: 1 are thick Degree is 11nm；Ag layers are 20nm；CPL layers prepare blue-light device for the compounds of this invention 139 with a thickness of 45nm.
Embodiment 9
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 4: 1 are thick Degree is 11nm；Ag layers are 20nm；CPL layers prepare blue-light device for the compounds of this invention 013 with a thickness of 45nm.
Embodiment 10
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 4: 1 are thick Degree is 3nm；Ag layers are 15nm；CPL layers prepare blue-light device for the compounds of this invention 049 with a thickness of 100nm.
11~embodiment of embodiment 15
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 6: 1 are thick Degree is 7nm；Ag layers are 25nm；CPL layers are the compounds of this invention 002,015,028,041,054, with a thickness of 30nm, prepare feux rouges Device.
16~embodiment of embodiment 19
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Li and Ag alloy-layer, molar ratio 8: 1 are thick Degree is 9nm；Ag layers are 30nm；CPL layers prepare green light device for the compounds of this invention 067,080,093,106 with a thickness of 50nm Part.
20~embodiment of embodiment 23
Specific implementation step is unique the difference is that cathode 9 with embodiment 3 are as follows: Mg and Ag alloy-layer, molar ratio 4: 1 are thick Degree is 3nm；Ag layers are 15nm；CPL layers prepare blue light device for the compounds of this invention 119,132,145,158 with a thickness of 100nm Part.
Comparative example 1
This comparative example is OLED device preparation embodiment, and specific steps are as described in Example 3, unique the difference is that described The transparent composite cathode 9 of OLED only includes the alloy-layer of the low workfunction metal and Ag that set gradually, Ag layers, does not include CPL layers, system Standby red device, green device and blue-light device.
Comparative example 2
OLED device preparation step is with embodiment 3 in this comparative example, the difference is that the cathode 9 is a kind of compound yin of OLED Pole structure, the OLED composite cathode structure include the alloy-layer of the low workfunction metal and Ag set gradually, Ag layers.Specific step It is rapid as follows: under vacuum conditions, using hot evaporation technology, Mg/Ag alloy material to be deposited as the alloy-layer, Mg/Ag's rubs You than be 1: 1, the alloy-layer with a thickness of 10nm；Under vacuum conditions, using hot evaporation technology, in the alloy-layer Top be deposited one layer Ag layers, with a thickness of 10nm, prepare red device, green device and blue-light device.
Embodiment 24
The performance for the OLED device that embodiment 3~23 and comparative example 1~2 obtain is tested, the results are shown in Table 2.
Table 2
As can be seen from the above table, the device of same type, the device in embodiment are imitated than the electric current of the device in comparative example Rate, brightness service life are more preferable.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims (10)

1. a kind of compound has structure shown in formula (I),
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn at least 1 is nitrogen；
The A is formula (A-1), formula (A-2) or formula (A-3),
The R1、R2、R3、R4、R5、R6The independent aryl selected from hydrogen, the alkyl of C1~C3 or C6~C10,
Or the R1And R2The condensed ring radical of C10~C20 is formed with the carbon where it.
2. compound according to claim 1, which is characterized in that the Ar1Selected from hydrogen, the alkyl of C1~C5, phenyl, C1 The alkyl-substituted phenyl of~C5, the fused ring aryl of C10~C20, the nitrogenous heteroaryl of the sulfur-bearing heteroaryl of C3~C15 or C3~C15 Base；
The Ar2Selected from hydrogen, the alkyl of C1~C5, phenyl, the alkyl-substituted phenyl of C1~C5, C10~20 fused ring aryl, The sulfur-bearing heteroaryl of C3~C15 or the nitrogenous heteroaryl of C3~C15.
3. compound according to claim 1, which is characterized in that the Ar1Selected from hydrogen, methyl, ethyl, propyl, positive fourth Base, tert-butyl, amyl, trifluoromethyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- are just Propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- Isopropyl phenyl, 4- aminomethyl phenyl, 3,5- 3,5-dimethylphenyl, 2- thienyl, pyridyl group, pyridazinyl, pyrazinyl, triazine radical or a word used for translation Piperidinyl；
The Ar2Selected from hydrogen, methyl, ethyl, propyl, normal-butyl, tert-butyl, amyl, trifluoromethyl, phenyl, anthryl, naphthalene, phenanthrene Base, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl Phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl, 4- aminomethyl phenyl, 3,5- 3,5-dimethylphenyl, 2- thiophene Pheno base, pyridyl group, pyridazinyl, pyrazinyl, triazine radical or acridinyl.
4. compound according to claim 1, which is characterized in that the X1-a、X1-b、X1-c、X1-d、X1-eIn at most have 3 For nitrogen.
5. compound according to claim 1, which is characterized in that the R1、R2It is independent selected from hydrogen, methyl, ethyl, just Propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propyl phenyl, 3- are different Propyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl phenyl or 4- Aminomethyl phenyl；
Or the R1And R2Fluorenyl is formed with the carbon where it.
6. compound according to claim 1, which is characterized in that the R3、R4、R5、R6It is independent to be selected from hydrogen, methyl, second Base, n-propyl, isopropyl, phenyl, anthryl, naphthalene, phenanthryl, 3- tert-butyl-phenyl, 3- trifluoromethyl, 3- n-propylbenzene Base, 3- isopropyl phenyl, 3- aminomethyl phenyl, 4- tert-butyl-phenyl, 4- trifluoromethyl, 4- n-propyl phenyl, 4- isopropyl Phenyl or 4- aminomethyl phenyl.
7. compound according to claim 1, which is characterized in that formula (I) compound represented is formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5) or formula (I-6)
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn at least 1 is nitrogen.
8. compound according to claim 1, which is characterized in that formula (I) compound represented is formula (001)~formula (162),
9. a kind of preparation method of formula (I) compound, comprising: react A-Br with the compound of formula (II) structure, obtain formula (I) The compound of structure；
Wherein, the Ar1、Ar2The independent heteroaryl selected from hydrogen, the alkyl of C1~C8, the aryl of C6~C25 or C2~C20；
The X1-a、X1-b、X1-c、X1-d、X1-eIt is independent to be selected from nitrogen or carbon, and the X1-a、X1-b、X1-c、X1-d、X1-eIn at least 1 is nitrogen；
The A is formula (A-1), formula (A-2) or formula (A-3),
The R1、R2、R3、R4、R5、R6The independent aryl selected from hydrogen, the alkyl of C1~C3 or C6~C10,
Or the R1And R2The condensed ring radical of C10~C20 is formed with the carbon where it.
10. formula (I) compound represented described in a kind of 1~claim 8 of claim any one is being prepared as CPL layers Application in organic electroluminescence device.
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