CN109037491A - A kind of organic electroluminescence device - Google Patents

A kind of organic electroluminescence device Download PDF

Info

Publication number
CN109037491A
CN109037491A CN201810763044.8A CN201810763044A CN109037491A CN 109037491 A CN109037491 A CN 109037491A CN 201810763044 A CN201810763044 A CN 201810763044A CN 109037491 A CN109037491 A CN 109037491A
Authority
CN
China
Prior art keywords
layer
organic electroluminescence
unsubstituted
compound
electroluminescence device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810763044.8A
Other languages
Chinese (zh)
Inventor
周雯庭
蔡辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Haipurunsi Technology Co Ltd
Original Assignee
Changchun Haipurunsi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Haipurunsi Technology Co Ltd filed Critical Changchun Haipurunsi Technology Co Ltd
Priority to CN201810763044.8A priority Critical patent/CN109037491A/en
Publication of CN109037491A publication Critical patent/CN109037491A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a kind of organic electroluminescence device, is related to technical field of organic electroluminescence.The device is by designing reasonable device architecture, and the excellent fluorene kind derivative of service performance and aromatic amino-derivative are as light removing layer, effectively overcome substrate mode loss, surface plasma loss and waveguiding effect, so as to improve the transmitance of half transmitting electrode, improve the external quantum efficiency of OLED device, transmitance in visible-range effectively increases the luminous efficiency of device up to 80% or more.

Description

A kind of organic electroluminescence device
Technical field
The invention belongs to technical field of organic electroluminescence, and in particular to a kind of organic electroluminescence device.
Background technique
In recent years, Organic Light Emitting Diode (OLED) by its self-luminous, body is thin, flexibility, high brightness, high-resolution The advantages such as rate, high efficiency, wide viewing angle, fast response time, low-power consumption become the current most display of application value and luminaire Part.
OLED device is a kind of Dual Implantations type luminescent device, and when applying voltage appropriate between the two poles of the earth, hole is from sun The injection of pole side, electronics are injected from cathode side, and the two reaches luminescent layer by charge transport layer, are formed and are swashed by interaction Sub (exciton), exciton return to stable ground state by excitation state and generate radioluminescence, are converted into luminous energy by electric energy to realize. General OLED device is made of anode, cathode and organic function layer between the two, and wherein organic function layer includes hole note Enter layer, hole transmission layer, luminous auxiliary layer, buffer layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electricity One of sub- implanted layer is a variety of.
After decades of development, the internal quantum efficiency of OLED device has reached close to 100%, but due to substrate mode Factors, most of light such as loss, surface plasma loss and waveguiding effect are still limited in the inside of luminescent device, cause big The loss of energy, external quantum efficiency is only 20% or so.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of organic electroluminescence device, including anode, yin Pole, the luminescent layer between the anode and the cathode, the hole transport between the anode and the luminescent layer Layer, the hole injection layer between the hole transmission layer and the anode, between the luminescent layer and the cathode Electron transfer layer, the hole blocking layer between the luminescent layer and the electron transfer layer, be located at the electron-transport Electron injecting layer between layer and the cathode, the light removing layer for deviating from the anode side positioned at the cathode, feature exists In the light removing layer includes aromatic amino-derivative shown in fluorene kind derivative shown in logical formula (I) and logical formula (II):
Wherein, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Alkane independently selected from substituted or unsubstituted C1~C12 One of base, the aryl of substituted or unsubstituted C6~C30, aryl amine of substituted or unsubstituted C12~C30；
The Ar1’、Ar2’、Ar3’、Ar4' aryl independently selected from substituted or unsubstituted C6~C60, replace or One of the heteroaryl of unsubstituted C3~C60；
The L ' be selected from the divalent aryls of substituted or unsubstituted C6~30, substituted or unsubstituted C3~C30 two One of valence heteroaryl.
Preferably, the light removing layer includes the first smooth removing layer and the second smooth removing layer；First light takes out Layer is located at the cathode and deviates from the anode side, with a thickness of 40~60nm；The smooth removing layer of described second is located at described first Light removing layer deviates from the cathode side, with a thickness of 50~70nm.
Preferably, the first smooth removing layer contains fluorene kind derivative shown in logical formula (I), and second light takes out Layer contains aromatic amino-derivative shown in logical formula (II).
Preferably, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Independently selected from methyl, ethyl, n-propyl, isopropyl, One of normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl or group as follows:
Preferably, the L ' is selected from one of group as follows:
Preferably, the Ar1’、Ar2’、Ar3’、Ar4' independently selected from one of group as follows:
Preferably, any one of the fluorene kind derivative in compound as follows:
Preferably, any one of the aromatic amino-derivative in compound as follows:
Beneficial effects of the present invention:
Organic electroluminescence device provided by the invention, by designing reasonable device architecture, in traditional OLED device In structure basis, the first smooth removing layer is increased away from anode side in cathode, meanwhile, deviate from cathode one in the first smooth removing layer Side increases the second smooth removing layer；First smooth removing layer is taken out using fluorene kind derivative shown in the logical formula (I) of the present invention, the second light Layer is using aromatic amino-derivative shown in the logical formula (II) of the present invention；The refractive index of first smooth removing layer is between 1.7~2.2, and The refractive index of two smooth removing layers is between 1.8~2.3.Under the collective effect of two light removing layers, substrate can be effectively overcome Mode losses, surface plasma loss and waveguiding effect improve the outer of OLED device so as to improve the transmitance of half transmitting electrode Quantum efficiency, transmitance improves the luminous efficiency of device up to 80% or more in visible-range.
Specific embodiment
The present invention provides a kind of organic electroluminescence device, including anode, cathode, be located at the anode and the cathode it Between luminescent layer, the hole transmission layer between the anode and the luminescent layer, be located at the hole transmission layer with it is described Hole injection layer between anode, is located at the luminescent layer at the electron transfer layer between the luminescent layer and the cathode Hole blocking layer between the electron transfer layer, the electron injection between the electron transfer layer and the cathode Layer, the light removing layer for deviating from the anode side positioned at the cathode, which is characterized in that the light removing layer includes general formula (I) aromatic amino-derivative shown in fluorene kind derivative shown in and logical formula (II):
Wherein, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Alkane independently selected from substituted or unsubstituted C1~C12 One of base, the aryl of substituted or unsubstituted C6~C30, aryl amine of substituted or unsubstituted C12~C30；
The Ar1’、Ar2’、Ar3’、Ar4' aryl independently selected from substituted or unsubstituted C6~C60, replace or One of the heteroaryl of unsubstituted C3~C60；
The L ' be selected from the divalent aryls of substituted or unsubstituted C6~30, substituted or unsubstituted C3~C30 two One of valence heteroaryl.
Alkyl of the present invention refers to alkyl made of minusing a hydrogen atom in alkane molecule, can be straight chain alkane Base, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refers to remove a hydrogen atom on an aromatic core carbon of aromatic hydrocarbon molecule after, remaining group General name, can be monocyclic aryl or fused ring aryl, such as can be selected from phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthrene Base, pyrenyl, fluorenyl or benzo phenanthryl etc., but not limited to this.
Aryl amine of the present invention refers to that the amino with an armaticity substituent, anilino- are in the aryl amine Simplest example, in addition to this, there are also hexichol amido, naphthylamine base, benzidion, dinaphthyl amido, N- phenyl -4- benzidions Deng, but not limited to this.
Heteroaryl of the present invention refers to the group that one or more aromatic core carbon in aryl are replaced by hetero atom General name, the hetero atom includes but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be miscellaneous for bicyclic heteroaryl or condensed ring Aryl, such as can be selected from pyridyl group, quinolyl, carbazyl, thienyl, benzothienyl, furyl, benzofuranyl, phonetic Piperidinyl, benzo pyrimidine radicals, imidazole radicals or benzimidazolyl etc., but not limited to this.
Divalent aryl of the present invention refers to respectively remove a hydrogen atom on two aromatic core carbon of aromatic hydrocarbon molecule after, be left Bivalent group general name, can be valentbivalent monocyclic aryl or divalent fused ring aryl, such as can be selected from phenylene, sub- biphenyl Base, sub- terphenyl, naphthylene, anthrylene, phenanthrylene, sub- pyrenyl, fluorenylidene or sub- benzo phenanthryl etc., but not limited to this.
Divalent heteroaryl radical of the present invention refers to that one or more aromatic core carbon in divalent aryl are replaced by hetero atom The general name of the group arrived, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the divalent heteroaryl radical can be divalent list Ring heteroaryl or divalent fused ring heteroaryl, such as can be selected from sub-pyridyl group, sub- quinolyl, sub- carbazyl, sub- thienyl, sub- benzene Bithiophene base, furylidene, sub- benzofuranyl, sub- pyrimidine radicals, sub- benzo pyrimidine radicals, sub- imidazole radicals or sub- benzimidazolyl Deng, but not limited to this.
The alkyl of substituted or unsubstituted C1~C12 of the present invention, substituted or unsubstituted C6~C30 aryl, The aryl amine of substituted or unsubstituted C12~C30 refer to be substituted before alkyl, aryl, aryl amine the total number of carbon atoms be respectively 1 ~12,6~30,12~30, and so on.
Preferably, the light removing layer includes the first smooth removing layer and the second smooth removing layer；First light takes out Layer is located at the cathode and deviates from the anode side, with a thickness of 40~60nm；The smooth removing layer of described second is located at described first Light removing layer deviates from the cathode side, with a thickness of 50~70nm.
Preferably, the first smooth removing layer contains fluorene kind derivative shown in logical formula (I), and second light takes out Layer contains aromatic amino-derivative shown in logical formula (II).
Preferably, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Independently selected from methyl, ethyl, n-propyl, isopropyl, One of normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl or group as follows:
Preferably, the L ' is selected from one of group as follows:
Preferably, the Ar1’、Ar2’、Ar3’、Ar4' independently selected from one of group as follows:
Preferably, any one of the fluorene kind derivative in compound as follows:
Some specific constructive forms of fluorene kind derivative shown in logical formula (I) of the present invention, but this is enumerated above Invention is not limited to these listed chemical structures, and all based on structure shown in formula (I), substituent group is as defined above Group should be all included.
Preferably, any one of the aromatic amino-derivative in compound as follows:
Some specific constructive forms of aromatic amino-derivative shown in logical formula (II) of the present invention are enumerated above, but The invention is not limited to these listed chemical structures, all based on structure shown in formula (II), substituent group is as above is limited Fixed group should be all included.
Fluorene kind derivative shown in logical formula (I) of the present invention can be prepared by following synthetic route:
It is reacted with trim,ethylchlorosilane for raw material with 1,3,5- tribromo-benzene first, obtains intermediate 1；Then, intermediate 1 By oxidative coupling reaction, intermediate 2 is obtained；Intermediate 2 and chlorination Iod R, obtain intermediate 3；Intermediate 3 again with contain Ar6And Ar3Compound reaction, obtain intermediate A；Then, intermediate A is reacted with methylchloroformate, obtains intermediate B；So Afterwards, intermediate B obtains intermediate C by reduction reaction；Intermediate C and contain Ar1And Ar2Iodo object reaction, obtain centre Body D；Intermediate D reacts with methylene bromide again, obtains intermediate E；Finally, intermediate E and containing Ar4And Ar5Compound It reacts, obtains target compound (I).
Wherein, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Alkane independently selected from substituted or unsubstituted C1~C12 One of base, the aryl of substituted or unsubstituted C6~C30, aryl amine of substituted or unsubstituted C12~C30；
Aromatic amine compounds shown in logical formula (II) of the present invention can be prepared by following synthetic route:
With compound Y ' for starting material, Buchwald-Hartwig coupling reaction occurs with aromatic amine compound M ' first, Obtain intermediate A '；Intermediate A ' Buchwald-Hartwig coupling reaction occurs with aromatic amine compound N ' again, mesh can be obtained It marks compound (II).
Wherein, the Ar1’、Ar2’、Ar3’、Ar4' aryl independently selected from substituted or unsubstituted C6~C60, take One of generation or the heteroaryl of unsubstituted C3~C60；
The L ' be selected from the divalent aryls of substituted or unsubstituted C6~30, substituted or unsubstituted C3~C30 two One of valence heteroaryl.
The present invention limitation not special to above-mentioned reaction be using popular response well-known to those skilled in the art It can.
Preferably, the specific structure of organic electroluminescence device of the invention can be with are as follows: anode/hole injection layer/hole Transport layer/luminescent layer/hole blocking layer/electron transfer layer/smooth removing layer of electron injecting layer/cathode/the first/second light takes out Layer.
Hole injection layer of the present invention can be the single layer structure of single substance composition, can also be different material and is formed Single layer structure or multilayered structure, can be selected from α-NPD, TDATA, TPD, TAPC, Spiro-TAD, CuPC, 2-TNATA etc..
Hole transmission layer of the present invention can be the single layer structure of single substance composition, be also possible to different material shape At single layer structure or multilayered structure, can be selected from NPB, β-NPB, α-NPD, TDATA, TPD, TAPC, Spiro-TAD, Spiro- NPB etc..
Luminescent layer of the present invention includes guest materials and material of main part, wherein guest materials can be single substance The single layer structure of composition, can also be the single layer structure or multilayered structure of different material formation, and the luminescent layer guest materials is optional From C545T, DPAP-DPPA, TPPDA, Ir (ppy)3、(piq)2Ir(acac)、FIrPic、DCJTB、DCJT、DCM、DCM2、 DMQA, DBQA, TMDBQA, HAT-CN, F4-TCNQ, BCzVBi, TBPe, DPAVBi etc.；Material of main part can be single substance structure At single layer structure, can also be the single layer structure or multilayered structure of different material formation, the luminescent layer material of main part can be selected from CBP, MCP, ADN, 3Ph-anthracene, α-ADN, 4P-NPB, DPVBI, BCBP etc..
Hole blocking layer of the present invention can be the single layer structure of single substance composition, can also be different material and is formed Single layer structure or multilayered structure, can be selected from BCP, TPBi, Alq3, Liq, BAlq, PBD, Bphen, TAZ, NTAZ etc..
Electron transfer layer of the present invention can be the single layer structure of single substance composition, can also be different material and is formed Single layer structure or multilayered structure, can be selected from BCP, TPBi, Alq3, Liq, BAlq, PBD, Bphen, TAZ, NTAZ etc..
Electron injecting layer of the present invention can be the single layer structure of single substance composition, can also be different material and is formed Single layer structure or multilayered structure, can be selected from LiF, CsF, Al, Cs2CO3、MoO3Deng.
First smooth removing layer of the present invention can be the single layer structure of single substance composition, can also be different material shape At single layer structure or multilayered structure, the fluorene kind derivative shown in the logical formula (I) of the present invention.
Second smooth removing layer of the present invention can be the single layer structure of single substance composition, can also be different material shape At single layer structure or multilayered structure, the aromatic amino-derivative shown in the logical formula (II) of the present invention.
A kind of organic electroluminescence device of the present invention can carry out selection and group according to parameter request and material property It closes, to manufacture the organic electroluminescence device of construction same as below: ITO/2-TNATA/NPB//CBP:(piq)2Ir (acac) or Ir (ppy)3/ BAlq/Liq or Alq3/ LiF/Mg:Ag/ the present invention leads to fluorene kind derivative/present invention shown in formula (I) Aromatic amino-derivative shown in logical formula (II).
Above-mentioned each layer structure can be used the modes such as vacuum evaporation, inkjet printing, coating, spin coating, laser transfer and prepare, But not limited to this.
The organic electroluminescence device can be used for the application neck such as flat-panel monitor, lighting source, direction board, signal lamp Domain.
Hereinafter, enumerating embodiment come to the compound used in organic electroluminescence device provided by the invention and organic The preparation of electroluminescent device is specifically described, but so as not to the limitation present invention.On the basis of the description, this field Those of ordinary skill will without creative efforts, in disclosed entire scope implement the present invention and Prepare other organic electroluminescence devices according to the present invention.
The present invention is not particularly limited the source of raw material employed in following embodiment, can for commercial product or It is prepared using preparation method well-known to those skilled in the art.
Synthetic example 1: the preparation of 1~intermediate of intermediate 3
(1) preparation of intermediate 1: first by 1,3,5- tribromo-benzene, n-BuLi, tetrahydrofuran/toluene solution at -78 DEG C Lower stirring 15 minutes, is then added the trim,ethylchlorosilane of distillation, is to slowly warm up to react at room temperature from -78 DEG C, filters, passes through column Intermediate 1 can be obtained in chromatographic purifying.
(2) preparation of intermediate 2: intermediate 1, lithium diisopropylamine and tetrahydrofuran are stirred at -78 DEG C first 45 minutes；Then cuprous cyanide and lithium chloride is added, continuation is reacted 2 hours at -78 DEG C；Benzoquinones is added, maintain the temperature at- It 78 DEG C, reacts 2 hours, filters solid, extract, it is organic phase is dry, can be obtained finally by column chromatographic purifying except solvent Intermediate 2.
(3) preparation of intermediate 3: by intermediate 2 and lodine chloride investment methylene chloride, temperature control is small in 0 DEG C of reaction 2 When, solid is filtered, is extracted, by organic phase drying, removes solvent, then by column chromatographic purifying, intermediate 3 can be obtained.
Synthetic example 2: the preparation of compound TM1
Under argon atmospher, intermediate 3 and diphenylamines are under conditions of sodium tert-butoxide, palladium acetate and triphenylphosphine, to be dehydrated first Benzene is solution, is reacted 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, organic solvent is then removed, with toluene weight Crystallization, it is dry, intermediate A -1 can be obtained；
Intermediate A -1 is under conditions of n-BuLi, in toluene solution, reacts to obtain intermediate B-with methylchloroformate 1；
Intermediate B -1, hydrazine hydrate and Raney Ni are back flow reaction 2 hours, then cold in the mixed solution of toluene and ethyl alcohol But, solvent is removed, then is recrystallized in chloroform, by column chromatographic purifying, is then carried out with the mixed solution of chloroform and ethyl alcohol secondary Recrystallization, it is dry, intermediate C-1 can be obtained；
Intermediate C-1 and iodobenzene are under conditions of sodium tert-butoxide, anti-at 90 DEG C using dry dimethyl sulfoxide as solvent It answers 1 hour, is subsequently poured into ice water and stirs 20 minutes, filter, solid distilled water and methanol successively wash, and it is dry, it can obtain To intermediate D-1；
Intermediate D-1 and methylene bromide are under conditions of tris(dibenzylideneacetone) dipalladium and sodium tert-butoxide, with toluene Solvent reacts 18 hours at 65 DEG C, and filtering, organic phase is washed with water, and removes solvent, dry by column chromatographic purifying Obtain intermediate E -1；
Under argon atmospher, intermediate E -1, carbazole, sodium tert-butoxide, palladium acetate and triphenylphosphine are put into dehydrated toluene, It is reacted 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, then remove organic solvent, with re crystallization from toluene, done It is dry, compound TM1 can be obtained.
Synthetic example 3: the preparation of compound TM42
Compound TM42 can be prepared according to the method for synthetic example 2.
Synthetic example 4: the preparation of compound HT45
Compound TM45 can be prepared according to the method for synthetic example 2.
Synthetic example 5: the preparation of compound TM51
Compound TM51 can be prepared according to the method for synthetic example 2.
Synthetic example 6: the preparation of compound TM68
Compound TM68 can be prepared according to the method for synthetic example 2.
Synthetic example 7: the preparation of compound TM79
Compound TM79 can be prepared according to the method for synthetic example 2.
The FD-MS value of above-mentioned fluorene kind derivative is as shown in table 1.
[table 1]
Other fluorene kind derivatives shown in logical formula (I) are synthesized referring to the synthetic method of above-mentioned synthetic example 1~8.
Synthetic example 8: the preparation of compound A1
Under argon atmospher, compound a -1 and compound b-1 are with dehydrated toluene under conditions of palladium acetate and triphenylphosphine Solution reacts 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, then removes organic solvent, tied again with toluene Crystalline substance, it is dry, intermediate M ' -1 can be obtained；
Under argon atmospher, to bromo-iodobenzene and intermediate M ' -1 under conditions of palladium acetate and triphenylphosphine, it is with dehydrated toluene Solution reacts 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, then removes organic solvent, tied again with toluene Crystalline substance, dry, intermediate A can be obtained ' -1；
Under argon atmospher, intermediate A ' -1 and compound N ' -1 are under conditions of palladium acetate and triphenylphosphine, with dehydrated toluene It for solution, is reacted 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, then remove organic solvent, tied again with toluene Crystalline substance, it is dry, compound A1 can be obtained.
Synthetic example 9: the preparation of compound A16
Compound A16 can be prepared according to the method for synthetic example 8.
Synthetic example 10: the preparation of compound A23
Compound A23 can be prepared according to the method for synthetic example 8.
Synthetic example 11: the preparation of compound A-13 7
Compound A-13 7 can be prepared according to the method for synthetic example 6.
Synthetic example 12: the preparation of compound A48
Compound A48 can be prepared according to the method for synthetic example 8.
Synthetic example 13: the preparation of compound A61
Compound A61 can be prepared according to the method for synthetic example 8.
Synthetic example 14: the preparation of compound A69
Under argon atmospher, compound a -7 and compound b-7 are with dehydrated toluene under conditions of palladium acetate and triphenylphosphine Solution reacts 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, then removes organic solvent, tied again with toluene Crystalline substance, it is dry, intermediate M ' -7 can be obtained；
Under argon atmospher, 2,7- bis- bromo- 9,9- diphenylfluorenes and intermediate M ' -7 under conditions of palladium acetate and triphenylphosphine, It using dehydrated toluene as solution, is reacted 8 hours at 80 DEG C, after cooling, cross diatomite/silica gel funnel, then remove organic solvent, It is dry with re crystallization from toluene, compound A69 can be obtained.
Synthetic example 15: the preparation of compound A76
Compound A76 can be prepared according to the method for synthetic example 14.
The FD-MS value of above-mentioned aromatic amino-derivative is as shown in table 2.
[table 2]
Synthetic example FD-MS
Synthetic example 8 M/z=732.07 (C54H38N2O=730.91)
Synthetic example 9 M/z=858.01 (C62H38N2OS=859.06)
Synthetic example 10 M/z=845.98 (C63H46N2O=847.07)
Synthetic example 11 M/z=895.04 (C66H45N3O=896.11)
Synthetic example 12 M/z=967.35 (C69H47N3OS=966.22)
Synthetic example 13 M/z=965.22 (C69H45N3O3=964.14)
Synthetic example 14 M/z=831.69 (C61H40N2O2=833.00)
Synthetic example 15 M/z=853.07 (C61H38N2S2=863.11)
Other aromatic amino-derivatives shown in logical formula (II) are synthesized referring to the synthetic method of above-mentioned synthetic example 8~15.
Comparative device embodiment: the preparation of comparative device
Firstly, carrying out shape in the ITO layer (anode) for being formed in organic substrate with the thickness vacuum deposition 2-TNATA of 60nm At hole injection layer；On above-mentioned hole injection layer, hole transmission layer is formed with the thickness vacuum evaporation NPB of 60nm；Then, It is the CBP and Ir (ppy) of 90:10 with weight ratio on above-mentioned hole transmission layer3Vacuum deposition is as luminescent layer, thickness 30nm；Then, hole blocking layer is formed with the thickness vacuum deposition BAlq of 10nm on above-mentioned luminescent layer；Again in above-mentioned hole With the thickness vacuum deposition Alq of 40nm on barrier layer3To form electron transfer layer；Then, made with the thickness deposition LiF of 0.2nm For electron injecting layer；Finally, forming cathode with the thickness of 13nm deposition weight ratio for the Mg/Ag alloy of 3:7.
Device embodiments 1: the preparation of luminescent device 1
Firstly, being formed with the thickness vacuum deposition 2-TNATA of 60nm in the ITO layer (anode) for being formed in organic substrate Hole injection layer；Hole transmission layer is formed with the thickness vacuum evaporation NPB of 60nm on above-mentioned hole injection layer；Then upper It states on hole transmission layer, is the CBP and Ir (ppy) of 90:10 with weight ratio3Vacuum deposition is as luminescent layer, with a thickness of 30nm；It connects , hole blocking layer is formed with the thickness vacuum deposition BAlq of 10nm on above-mentioned luminescent layer；On above-mentioned hole blocking layer With the thickness vacuum deposition Alq of 40nm3To form electron transfer layer；Then, LiF is deposited as electronics using the thickness of 0.2nm to infuse Enter layer；Later, cathode is formed for the Mg/Ag alloy of 3:7 with the thickness vacuum deposition weight ratio of 13nm；Then, in above-mentioned yin The toluene solution of extremely upper 1.6 weight % compound TM1 of spin coating, to form the first smooth removing layer with a thickness of 45nm；Finally, upper Vacuum evaporation compound A1 on the first smooth removing layer is stated, to form the second smooth removing layer with a thickness of 60nm.
Device embodiments 2: the preparation of luminescent device 2
Compound TM1 is replaced with compound TM42, compound A1 is replaced with compound A16, other steps with Device embodiments 1 are identical.
Device embodiments 3: the preparation of luminescent device 3
Firstly, being formed with the thickness vacuum deposition 2-TNATA of 60nm in the ITO layer (anode) for being formed in organic substrate Hole injection layer；Hole transmission layer is formed with the thickness vacuum evaporation NPB of 60nm on above-mentioned hole injection layer；Then upper It states on hole transmission layer, is the CBP and Ir (ppy) of 90:10 with weight ratio3Vacuum deposition is as luminescent layer, with a thickness of 30nm；It connects , hole blocking layer is formed with the thickness vacuum deposition BAlq of 10nm on above-mentioned luminescent layer；On above-mentioned hole blocking layer With the thickness vacuum deposition Alq of 40nm3To form electron transfer layer；Then, LiF is deposited as electronics using the thickness of 0.2nm to infuse Enter layer；Later, cathode is formed for the Mg/Ag alloy of 3:7 with the thickness vacuum deposition weight ratio of 13nm；Then, in above-mentioned yin Extremely upper vacuum evaporation compound TM45, to form the first smooth removing layer with a thickness of 45nm；Finally, in the above-mentioned first smooth removing layer Upper vacuum evaporation compound A23, to form the second smooth removing layer with a thickness of 60nm.
Device embodiments 4: the preparation of luminescent device 4
Compound TM45 is replaced with compound TM51, compound A23 is replaced with compound A-13 7, other steps It is identical as device embodiments 3.
Device embodiments 5: the preparation of luminescent device 5
Compound TM45 is replaced with compound TM68, compound A23 is replaced with compound A48, other steps It is identical as device embodiments 3.
Device embodiments 6: the preparation of luminescent device 6
Compound TM45 is replaced with compound TM79, compound A23 is replaced with compound A61, other steps It is identical as device embodiments 3.
Device embodiments 7: the preparation of luminescent device 7
Compound A23 is replaced with compound A69, other steps are identical as device embodiments 3.
Device embodiments 8: the preparation of luminescent device 8
Compound TM45 is replaced with compound TM79, compound A23 is replaced with compound A76, other steps It is identical as device embodiments 3.
The luminescent properties for the organic electroluminescence device that device embodiments of the present invention are prepared are as shown in the table:
The above result shows that organic electroluminescence device provided by the invention, using fluorenes class shown in the logical formula (I) of the present invention Derivative as the first smooth removing layer, spread out between 1.7~2.2 using arylamine class shown in the logical formula (II) of the present invention by refractive index Biology is used as the second smooth removing layer, and refractive index is between 1.8~2.3.Under the collective effect of two light removing layers, half is improved The transmissivity of transmission electrode, to improve the external quantum efficiency of OLED device, the transmitance in visible-range is up to 80% More than, and then improve the luminous efficiency of device.
Obviously, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should refer to It out, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field Bright some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims (8)

1. a kind of organic electroluminescence device, including anode, cathode, the luminescent layer between the anode and the cathode, Hole transmission layer between the anode and the luminescent layer, the sky between the hole transmission layer and the anode Cave implanted layer, the electron transfer layer between the luminescent layer and the cathode are located at the luminescent layer and electronics biography Hole blocking layer between defeated layer, is located at the yin at the electron injecting layer between the electron transfer layer and the cathode Pole deviates from the light removing layer of the anode side, which is characterized in that the light removing layer includes that fluorenes class shown in logical formula (I) is spread out Aromatic amino-derivative shown in biological and logical formula (II):
Wherein, the Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Alkyl independently selected from substituted or unsubstituted C1~C12 takes One of the aryl of generation or unsubstituted C6~C30, aryl amine of substituted or unsubstituted C12~C30；
The Ar1’、Ar2’、Ar3’、Ar4' aryl independently selected from substituted or unsubstituted C6~C60, substituted or unsubstituted One of the heteroaryl of C3~C60；
It is miscellaneous that the L ' is selected from the divalent aryl of substituted or unsubstituted C6~30, the divalent of substituted or unsubstituted C3~C30 One of aryl.
2. organic electroluminescence device according to claim 1, which is characterized in that the light removing layer includes the first light Removing layer and the second smooth removing layer；The smooth removing layer of described first is located at the cathode away from the anode side, with a thickness of 40 ~60nm；The smooth removing layer of described second is located at the described first smooth removing layer away from the cathode side, with a thickness of 50~70nm.
3. organic electroluminescence device according to claim 2, which is characterized in that the smooth removing layer of described first contains logical Fluorene kind derivative shown in formula (I), the smooth removing layer of described second contain aromatic amino-derivative shown in logical formula (II).
4. organic electroluminescence device according to claim 1, which is characterized in that the Ar1、Ar2、Ar3、Ar4、Ar5、 Ar6Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl or as follows One of shown group:
5. organic electroluminescence device according to claim 1, which is characterized in that the L ' is selected from group as follows One of:
6. organic electroluminescence device according to claim 1, which is characterized in that the Ar1’、Ar2’、Ar3’、Ar4’ Independently selected from one of group as follows:
7. organic electroluminescence device according to claim 1, which is characterized in that the fluorene kind derivative is selected from as follows Any one in shown compound:
8. organic electroluminescence device according to claim 1, which is characterized in that the aromatic amino-derivative is selected from such as Descend any one in shown compound:
CN201810763044.8A 2018-07-12 2018-07-12 A kind of organic electroluminescence device Withdrawn CN109037491A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810763044.8A CN109037491A (en) 2018-07-12 2018-07-12 A kind of organic electroluminescence device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810763044.8A CN109037491A (en) 2018-07-12 2018-07-12 A kind of organic electroluminescence device

Publications (1)

Publication Number Publication Date
CN109037491A true CN109037491A (en) 2018-12-18

Family

ID=64642031

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810763044.8A Withdrawn CN109037491A (en) 2018-07-12 2018-07-12 A kind of organic electroluminescence device

Country Status (1)

Country Link
CN (1) CN109037491A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111933818A (en) * 2020-08-12 2020-11-13 长春海谱润斯科技有限公司 Organic light-emitting device
CN112038501A (en) * 2020-09-08 2020-12-04 长春海谱润斯科技股份有限公司 Top-emitting organic electroluminescent device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111933818A (en) * 2020-08-12 2020-11-13 长春海谱润斯科技有限公司 Organic light-emitting device
CN112038501A (en) * 2020-09-08 2020-12-04 长春海谱润斯科技股份有限公司 Top-emitting organic electroluminescent device
CN112038501B (en) * 2020-09-08 2021-08-10 长春海谱润斯科技股份有限公司 Top-emitting organic electroluminescent device

Similar Documents

Publication Publication Date Title
JP6506243B2 (en) Organic selenium material and its use in organic light emitting devices
EP2755253B1 (en) Material for organic light-emitting device, and organic light-emitting device using same
KR101153910B1 (en) Chemical Comprising Indole Derivatives and Organic Electronic Element using the same, Terminal thereof
US20140027741A1 (en) Heterocyclic compounds and organic light-emitting devices including the same
KR101219475B1 (en) Compound Containing Indoloacridine And Organic Electronic Element Using The Same, Terminal Thereof
TW201708209A (en) Novel compound and organic electroluminescent device comprising same
WO2014024880A1 (en) Organic electroluminescent element and electronic apparatus
CN107001930A (en) Organic photoelectric device constituent, organic photoelectric device and display device
CN108821985A (en) A kind of aromatic amine derivant and its organic electroluminescence device
CN108933198A (en) A kind of organic electroluminescence device containing aromatic amine compound
CN108863918A (en) A kind of aryl amine derivatives and its organic electroluminescence device
CN109037483A (en) A kind of organic electroluminescence device
KR101172053B1 (en) Chemical Comprising Indole Derivatives Substituded with two third Amines and Organic Electronic Element using the same, Terminal thereof
CN112538048B (en) Organic compound, electronic element containing organic compound and electronic device
CN109232492A (en) A kind of aromatic amine derivant and its organic electroluminescence device
CN103992232A (en) Compound and organic light-emitting diode including the same
KR101982749B1 (en) Chemical and Organic Electronic Element using the same, Electronic Device thereof
CN109422778B (en) Organometallic compound, organic light emitting device and diagnostic composition including the same
CN108847447A (en) A kind of top-emission organic electroluminescence device
CN108735911A (en) A kind of organic luminescent device
CN109360905A (en) A kind of organic electroluminescence device
CN109037491A (en) A kind of organic electroluminescence device
CN111556865A (en) Polycyclic compound and organic electronic device comprising same
WO2021135456A1 (en) Organic compound, electronic component and electronic device
CN109096277A (en) A kind of derivative of phenanthroline and its organic electroluminescence device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20181218

WW01 Invention patent application withdrawn after publication