CN107611284B - A kind of organic electroluminescence device - Google Patents

A kind of organic electroluminescence device Download PDF

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CN107611284B
CN107611284B CN201710826719.4A CN201710826719A CN107611284B CN 107611284 B CN107611284 B CN 107611284B CN 201710826719 A CN201710826719 A CN 201710826719A CN 107611284 B CN107611284 B CN 107611284B
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phenyl
carbazole
anthryl
phenanthryl
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CN107611284A (en
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赵东敏
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Hainan Shineng Technology Co., Ltd.
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • 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
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-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
    • H10K85/649—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

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Abstract

The invention discloses a kind of 6- hydrogen iso-indoles simultaneously [2,1-a] Benzazole compounds, have the structural formula as shown in formula (1).The compound can be used as the fluorescent light-emitting layer of organic electroluminescence device and the material of main part of phosphorescence luminescent layer, the brightness of organic electroluminescence device and luminous efficiency can be made to improve, and reduce its driving voltage.

Description

A kind of organic electroluminescence device
The application is divisional application.Original application is Chinese patent application, application number: 201310455696.2, the applying date: On September 29th, 2013, denomination of invention: 6- hydrogen iso-indoles simultaneously [2,1-a] Benzazole compounds and its application.
Technical field
The present invention relates to a kind of organic compound, more particularly, to organic electroluminescence device luminescent layer material of main part Compound；The invention further relates to application of the compound in organic electroluminescence device.
Background technique
Electro optical phenomenon most early in 20th century the '30s be found, initial luminescent material be ZnS powder, thus send out LED technology has been put on display, has been widely applied on energy-conserving light source now.And organic electroluminescent phenomenon is Pope in 1963 et al. It finds earliest, they have found that the single layer crystal of anthracene under the driving of 100V or more voltage, can issue faint blue light.Until Bi-layer devices are made in organic fluorescent dye by doctor Deng Qingyun of Kodak in 1987 et al. in a manner of vacuum evaporation, are being driven Under voltage of the voltage less than 10 volts, external quantum efficiency has reached 1%, so that electroluminescent organic material and device are provided with reality With the possibility of property, the research of OLED material and device has been pushed significantly from this.
Relative to phosphor, electroluminescent organic material has the advantage that 1. organic material processing performances are good, It can be formed a film on any substrate by vapor deposition or the method for spin coating；2. the diversity of organic molecular structure can make can To adjust thermal stability, the engineering properties, luminous and electric conductivity of organic material by the method for Molecular Design and modification Can, the space so that material is significantly improved.
The principle of luminosity of organic electroluminescent diode is similar with inorganic light-emitting diode.When element is spread out by direct current When raw forward bias voltage drop, voltage energy will drive electronics (Electron) and hole (Hole) respectively by cathode and anode in addition outside Injection element forms the compound exciton of so-called electron-hole, exciton is by shining when the two meets in luminescent layer, combines The form of relaxation returns to ground state, to achieve the purpose that luminous.
What the generation of organic electroluminescent was leaned on is the carrier (electrons and holes) transmitted in organic semiconducting materials Recombination, it is well known that the electric conductivity of organic material is very poor, unlike inorganic semiconductor, does not continue in organic semiconductor Energy band, the transmission of carrier commonly uses jump theory and describes, i.e., under the driving of an electric field, electronics is being excited or is being injected into In the lumo energy of molecule, achieve the purpose that charge is transmitted via the lumo energy for jumping to another molecule.In order to make Organic electroluminescence device reaches breakthrough in application aspect, it is necessary to overcome organic material charge inject and transmittability difference it is tired It is difficult.Scientists are by the adjustment of device architecture, such as increase the number of device organic material layer, and make different organic layers Play the part of different roles, such as the functional material having helps electronics to inject from cathode and hole from anode, some materials help The transmission of charge, the material played the role of, which then plays, stops electronics and hole transport, most important certainly in organic electroluminescent The luminescent material of various colors also to achieve the purpose that match with adjacent functional material, an excellent in efficiency service life long organic Electroluminescent device is usually the optimization collocation of device architecture and various organic materials as a result, this is just that chemists design The functionalization material for developing various structures provides greatly opportunities and challenges.
Common functionalization organic material has: hole-injecting material, hole mobile material, hole barrier materials, electronics note Enter material, electron transport material, electron-blocking materials and light emitting host material and light-emitting guest (dyestuff) etc..
Hole-injecting material (HIM) requires its HOMO energy level between anode and hole transmission layer, is conducive to increase boundary Hole injection between face.
Hole mobile material (HTM), it is desirable that there is high thermal stability (high Tg), with anode or hole-injecting material There is lesser potential barrier, higher cavity transmission ability can vacuum evaporation formation pin-hole free films.Common HTM is that fragrance is more Aminated compounds, mainly derivative of tri-arylamine group.
It is reversible and sufficiently high that electron transport material (Electron transport Material, ETM) requires ETM to have Electrochemical reduction current potential, suitable HOMO and LUMO can rank value electronics is preferably injected, and be preferably provided with sky Cave blocking capability；Higher electron transport ability, the film forming and thermal stability having had.ETM is typically electron deficient knot The aromatic compound of the conjugate planes of structure.
Luminescent layer material of main part (host) needs to have following characteristics: reversible electrochemical redox current potential, and adjacent Hole and the electron transfer layer HOMO that matches and LUMO can rank, the good and hole to match and electron transport ability, it is good Good high thermal stability and film forming, and suitable singlet or triplet state energy gap are used to control exciton in luminescent layer, There are also the good energy transfers between corresponding fluorescent dye or phosphorescent coloring.
The luminescent material needs of luminescent layer have the special feature that: having high fluorescence or phosphorescence quantum efficiency；Dyestuff Absorption spectrum has had overlapping with the emission spectrum of main body, i.e., main body is adapted to dyestuff energy, can be effectively from main body to dyestuff Energy transmission；Emission peak red, green, blue is as narrow as possible, with the excitation purity obtained；Stability is good, is able to carry out vapor deposition etc..
Up to the present, new electroluminescent organic material is still among continuous research and development, it has been found that Yi Leixin Organic material, as shown in general formula (1):
It was found that this material may be used as material of main part in organic electroluminescence device, with more excellent efficiency and bright Degree.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a new class of different Yin of 6- hydrogen for organic electroluminescent Diindyl simultaneously [2,1-a] Benzazole compounds, this compound is as shown in general formula (1):
Wherein, R1 is selected from C6-C50 aromatic radical, replaces C6-C50 aromatic radical, and X is selected from C1-C20 alkyl, the fragrance of C6-C20 Base replaces the aromatic radical of C6-C20.
It is preferred:
The substitution C6-C50 aromatic radical is replaced alkyl of the C6-C50 aromatic radical by C1-C12；
The substitution C6-C20 aromatic radical is replaced alkyl of the C6-C20 aromatic radical by C1-C12；
The alkyl that the straight chained alkyl, branched alkyl or naphthenic base that the C1-C20 alkyl is C1-C20 replace.
It is further:
The R1Selected from C6-C24Aromatic radical replaces C6-C24Aromatic radical, X are selected from C1-C10Alkyl, phenyl, C1-C8Alkyl Substituted phenyl.
Further selection:
The R1 is selected from: phenyl, alkyl-substituted phenyl, the phenyl that phenyl replaces, the phenyl of naphthyl substituted, and anthryl takes The phenyl in generation, the phenyl that fluorenyl replaces, the phenyl that carbazole N- replaces, the phenyl that carbazole 3- replaces, the phenyl that phenanthryl replaces, naphthalene Base, alkyl-substituted naphthalene, the naphthalene that phenyl replaces, the naphthalene of naphthyl substituted, the naphthalene that anthryl replaces, the naphthalene that fluorenyl replaces Base, the naphthalene that carbazole N- replaces, the naphthalene that carbazole 3- replaces, the naphthalene that phenanthryl replaces, anthryl, alkyl-substituted anthryl, phenyl Substituted anthryl, the anthryl of naphthyl substituted, the anthryl that anthryl replaces, the anthryl that fluorenyl replaces, the anthryl that carbazole N- replaces, carbazole The anthryl that 3- replaces, the anthryl that phenanthryl replaces, phenanthryl, alkyl-substituted phenanthryl, the phenanthryl that phenyl replaces, the phenanthrene of naphthyl substituted Base, the phenanthryl that anthryl replaces, the phenanthryl that fluorenyl replaces, the phenanthryl that carbazole N- replaces, the phenanthryl that carbazole 3- replaces, what phenanthryl replaced Phenanthryl, fluorenyl, alkyl-substituted fluorenyl, the fluorenyl that phenyl replaces, the fluorenyl of naphthyl substituted, the fluorenyl that anthryl replaces, phenanthryl take The fluorenyl in generation, the fluorenyl that carbazole N- replaces, the fluorenyl that carbazole 3- replaces, the fluorenyl that fluorenyl replaces, carbazole, alkyl-substituted click Azoles, the carbazole that phenyl replaces, the carbazole of naphthyl substituted, the carbazole that anthryl replaces, the carbazole that phenanthryl replaces, the click that carbazole N- replaces Azoles, the carbazole that carbazole 3- replaces, terphenyl, alkyl-substituted terphenyl, the xenyl of naphthyl substituted, the connection that anthryl replaces Phenyl, the xenyl that phenanthryl replaces, the xenyl that fluorenyl replaces, the xenyl that carbazole replaces, the phenyl that diphenyl replaces, phenyl The phenyl of naphthyl substituted, the phenyl that phenyl carbazole base replaces, the phenyl that diaryl replaces, the naphthalene that xenyl replaces, biphenyl take The fluorenyl in generation, the carbazyl that biphenyl replaces, the phenyl that binaphthyl replaces, the binaphthyl that phenyl replaces, the anthryl that diphenyl replaces, The anthryl that phenyl napthyl replaces, the anthryl that dinaphthyl replaces, the anthryl that triaryl replaces, 4- (2,2- diaryl bases-vinyl) Phenyl, it is Spirofluorene-based；
The X is selected from: methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, amyl, isopentyl, cyclopenta, alkane The cyclopenta that base replaces, n-hexyl, cyclohexyl, alkyl-substituted cyclohexyl, phenyl, alkyl-substituted phenyl, benzyl.
It is furthermore preferred that simultaneously [2,1-a] Benzazole compounds are selected from flowering structure the 6- hydrogen iso-indoles:
A kind of luminescent layer of organic electroluminescence device, including material of main part and dyestuff: it is characterized in that, the main body Simultaneously prepared by [2,1-a] Benzazole compounds using 6- hydrogen iso-indoles of the present invention for material.
Simultaneously [2,1-a] Benzazole compounds can be used for blue light main body, feux rouges main body to 6- hydrogen iso-indoles of the present invention With green light main body.
A kind of organic electroluminescence device, including substrate, and sequentially form anode layer on the substrate, several Luminescence unit layer and cathode layer；
The luminescence unit layer includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the sky Cave implanted layer is formed on the anode layer, and the hole transmission layer is formed on the hole injection layer, described Cathode layer is formed on the electron transfer layer, is luminous between the hole transmission layer and the electron transfer layer Layer；The luminescent layer body material and dyestuff, material of main part are 6- hydrogen iso-indoles of the present invention simultaneously [2,1-a] indoles Close object.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism figure of the compound (M1) of the embodiment of the present invention 1.
Fig. 2 is the nuclear-magnetism figure of the compound (M7) of the embodiment of the present invention 7.
Fig. 3 is the nuclear-magnetism figure of the compound (P1) of the embodiment of the present invention 10.
Fig. 4 is the nuclear-magnetism figure of the compound (P28) of the embodiment of the present invention 35.
Fig. 5 is the nuclear-magnetism figure of the compound (P39) of the embodiment of the present invention 37.
Specific embodiment
It below will the invention will be further described by specific embodiment.
Embodiment 1
Intermediate shown in the present embodiment preparation formula (M1):
Synthetic method is as follows:
(1) synthesis of 1- (2- iodine benzyl) -3- Methyl-1H-indole
700 milliliters of dimethyl sulfoxides, 52 grams of potassium hydroxide, 26.2 grams of 3- are added under nitrogen protection for 1000 milliliters of there-necked flasks After 30 points of kinds are stirred at room temperature, 50.5 grams of adjacent iodine benzyl chlorides are added in methyl indol.Then it is stirred at room temperature 3 hours, is poured into 2000 milliliters of water In, ethyl acetate extracts, and is washed to neutrality, silica gel post separation, petroleum ether: ethyl acetate volume ratio=10:1 elution is produced 55.1 grams of product, MS (m/e): 347.
(2) synthesis of 11- methyl -6H- iso-indoles simultaneously [2,1-a] indoles
34.7 grams of 1- (2- iodine benzyl) -3- methyl-1 H- Yin is added in 1000 milliliters of there-necked flasks, nitrogen protection, mechanical stirring Diindyl, 1 gram of copper powder, 30 grams of potassium carbonate, 600 milliliters of PEG400 (polyethylene glycol 400) are to slowly warm up to 180 degree, react 24 hours, Cooling, is poured into 2000 milliliters of water, and methylene chloride extracts, after dichloromethane layer magnesium sulfate drying, silica gel column chromatography separation, and stone Oily ether: ethyl acetate: the elution of methylene chloride volume ratio=10:1:1 obtains 10.2 grams of product, and MS (m/e): 219.
(3) synthesis of M1
500 milliliters of there-necked flasks, are added 9 grams of 11- methyl -6H- iso-indoles simultaneously [2,1-a] indoles, 300 milliliters of methylene chloride, It is cooled to 0-5 DEG C, is slowly added dropwise 20 milliliters of dichloromethane solutions of 14.5 grams of bromines, drop finishes that be to slowly warm up to 20 DEG C of reactions 2 small When, solution of sodium bisulfite washing, washing, dichloromethane layer silica gel post separation, petroleum ether: ethyl acetate: methylene chloride is added The elution of volume ratio=10:1:1, obtains 12.1 grams of product, and MS (m/e): 377, the nuclear magnetic spectrogram (1H) of product M1 is shown in 1 institute of attached drawing Show.
Embodiment 2
Intermediate shown in the present embodiment preparation formula (M2):
Synthetic method is as follows:
Under nitrogen protection, 3.8 grams of M1 are added, 300 milliliters of DMSO are slowly added to 1.6 grams of contents in 500 milliliters of there-necked flasks 4.3 grams of iodomethane are added after stirring 30 minutes in 60% sodium hydride, react at room temperature 12 hours, it is not anti-that a small amount of Methanol Decomposition is added After the sodium hydride answered, reaction solution is poured into 900 milliliters of water, methylene chloride extracts, washing, dichloromethane layer silica gel post separation, Petroleum ether: ethyl acetate: the elution of methylene chloride volume ratio=10:1:1 obtains 3.0g grams of product, and MS (m/e): 405.
3-embodiment of embodiment 6
Referring to the method for embodiment 2, intermediate M3-M6 totally 4 intermediates are prepared for, specific data are as follows:
Embodiment 7
Intermediate shown in the present embodiment preparation formula (M7):
Synthetic method is as follows:
3.8 grams of M1 are added in 500 milliliters of there-necked flasks, nitrogen protection, and 300 milliliters of DMSO are slowly added to 1.6 grams of contents 60% After stirring 30 minutes, 6.0 grams of iodobenzenes are added in sodium hydride, and 0.6 gram of Pd (dppp) Cl2 is to slowly warm up to 50 DEG C, are reacted 24 hours, After the unreacted sodium hydride of a small amount of Methanol Decomposition is added, reaction solution is poured into 900 milliliters of water, methylene chloride extracts, washing, and two Chloromethanes layer silica gel post separation, petroleum ether: ethyl acetate: methylene chloride volume ratio=10:1:1 elution obtains 1.5g grams of product, The nuclear magnetic spectrogram (1H) of MS (m/e): 529, product M7 are as shown in attached drawing 2.
8-embodiment of embodiment 9
According to the method for embodiment 7, intermediate M8 and M9 totally 2 intermediates are prepared for, specific data are as follows:
Embodiment 10
Compound manufactured in the present embodiment compound as shown in formula (P1):
Synthetic method is as follows:
4.0g M2,2.8g phenyl boric acid, 0.6g tetra-triphenylphosphine palladium, 9.1g potassium carbonate, 80 millis are added in 250 milliliters of there-necked flasks Toluene, 50 milliliters of ethyl alcohol are risen, 30 milliliters of water under nitrogen protection, heating reflux reaction 8 hours, cool down, filtering, after solid is dry, Silica gel column chromatography separation, petroleum ether: ethyl acetate: methylene chloride volume ratio=10:1:1 elution obtains 3.6g grams of product, MS (m/e): the nuclear magnetic spectrogram (1H) of 399, compound P1 are as shown in attached drawing 3.
11-embodiment of embodiment 34
According to the method for embodiment 10, using intermediate M2 and corresponding acid reaction, following 24 products have been synthesized, Specific data are as follows:
Embodiment 35
Compound manufactured in the present embodiment compound as shown in formula (P28):
Synthetic method is as follows:
4.0g M2,4.0g carbazole, 300 milliliters of dimethylbenzene, 2.88g sodium tert-butoxide, 0.06g is added in 500 milliliters of there-necked flasks Pd(dba)2, the toluene solution of the tri-tert-butylphosphine of 0.2g 10%, under nitrogen protection, heating reflux reaction 8 hours, cooling, mistake Filter, after solid is dry, silica gel column chromatography separation, petroleum ether: ethyl acetate: methylene chloride volume ratio=10:1:1 elution is obtained 4.6g grams of product, MS (m/e): 577, the nuclear magnetic spectrogram (1H) of compound P28 is as shown in attached drawing 4.
Embodiment 36
Compound manufactured in the present embodiment compound as shown in formula (P30):
The same P28 of synthetic method, only changes carbazole into 3- phenyl carbazole, obtains 3.6g grams of product, and MS (m/e): 729.
Embodiment 37
Compound manufactured in the present embodiment compound as shown in formula (P39):
Synthetic method is as follows:
500 milliliters of there-necked flasks, addition 5.3g M7,2.8g phenyl boric acid, 0.6g tetra-triphenylphosphine palladium, 9.1g potassium carbonate, 200 Milliliter toluene, 150 milliliters of ethyl alcohol, 30 milliliters of water under nitrogen protection, heating reflux reaction 8 hours, cool down, filtering, and solid is dry Afterwards, silica gel column chromatography separates, petroleum ether: ethyl acetate: methylene chloride volume ratio=10:1:1 elution obtains 4.8 grams of product, MS (m/e): the nuclear magnetic spectrogram (1H) of 523, compound P39 are as shown in attached drawing 5.
Embodiment 38-39
According to the method for embodiment 37, using intermediate M7 and corresponding acid reaction, following 2 products have been synthesized, Specific data are as follows:
Embodiment 40
Compound manufactured in the present embodiment compound as shown in formula (P49):
The same P28 of synthetic method, only changes M2 into M7, obtains 2.8g grams of product, and MS (m/e): 701.
Embodiment 41
Compound manufactured in the present embodiment compound as shown in formula (P50):
The same P49 of synthetic method, only changes 3- phenyl carbazole for carbazole, obtains 2.7g grams of product, and MS (m/e): 853.
Embodiment 42
Compound manufactured in the present embodiment compound as shown in formula (P51):
The same P28 of synthetic method, only changes M2 into M3, obtains 1.8g grams of product, and MS (m/e): 713.
Embodiment 43
Compound manufactured in the present embodiment compound as shown in formula (P53):
The same P45 of synthetic method, only changes M7 into M3, obtains 6.2g grams of product, and MS (m/e): 865.
Embodiment 44-48
According to the method for embodiment 11, the intermediate M4, M5, M6, M8, M9 using 2- naphthalene boronic acids and corresponding this patent are anti- It answers, has synthesized following 5 products, specific data are as follows:
It is the Application Example of the compounds of this invention below:
The typical structure of OLED organic electroluminescence device are as follows:
Substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/cathode
The substrate in conventional organic luminescence organic electroluminescence device can be used in substrate, such as: glass or plastics.Anode Material can use transparent high conductivity material, such as indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), oxygen Change zinc (ZnO) etc..Glass substrate is selected in organic electroluminescence device production of the invention, ITO makees anode material.
Hole transmission layer can use N, N '-two (3- tolyl)-N, N '-diphenyl-[1,1- xenyl] -4,4 '-two The tri-arylamine groups material such as amine (TPD) or N, N '-diphenyl-N, N '-two (1- naphthalene)-(1,1 '-xenyl) -4,4 '-diamines (NPB) Material.Wherein NPB is common hole mobile material, and selected hole passes in organic electroluminescence device production of the invention Defeated material selection NPB.
Organic electroluminescence device structure can be also possible to multi-luminescent layer structure for single-shot photosphere.
Electron transfer layer uses Alq3 or TAZ or TPBi or any two kinds of the collocation for being derived from these three materials.
Selected cathode material is LiF/Al in organic electroluminescence device production of the invention.
Different materials specific structure used in the present invention is seen below:
Embodiment 49:
The compound of the present invention is as the material of main part in blue-fluorescence OLED organic electroluminescence device:
13 organic electroluminescence devices, organic electroluminescence device structure are prepared altogether are as follows:
ITO/NPB (40nm)/Blue-light emitting host material (30nm): DPAVBi [5%]/Alq3 (20nm)/LiF (0.5nm)/Al (150nm)。
One of them is comparison organic electroluminescence device, and Blue-light emitting host material selects ADN, other 12 organic electroluminescences hairs Optical device selects material of the invention.
Organic electroluminescence device preparation process is as follows: the glass plate for being coated with transparent conductive layer is cleaned in commercialization It is ultrasonically treated in agent, rinses in deionized water, in acetone: ultrasonic oil removing in alcohol mixed solvent is toasted under clean environment To completely removing moisture content, with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10-5~9 × 10-3Pa is evacuated to, Vacuum evaporation NPB is as hole transmission layer on above-mentioned anode tunic, and evaporation rate 0.1nm/s, vapor deposition film thickness is 40nm；
The vacuum evaporation Blue-light emitting host material on hole transmission layer: DPAVBi [5%] is used as organic electroluminescence device Luminescent layer, evaporation rate 0.1nm/s, vapor deposition total film thickness be 30nm；Wherein " DPAVBi [5%] " refers to mixing for blue light dyestuff The weight part ratio of miscellaneous ratio, i.e. Blue-light emitting host material and DPAVBi is 100:5.
Electron transfer layer of the vacuum evaporation Alq3 as organic electroluminescence device, evaporation rate are on luminescent layer 0.1nm/s, vapor deposition total film thickness are 20nm；
The Al of the LiF of vacuum evaporation 0.5nm on the electron transport layer, Al 150nm are as cathode.
Organic electroluminescence device performance see the table below:
It can see by upper table, generally made in the industry using the organic electroluminescence device of the compounds of this invention relative to use The organic electroluminescence device of ADN obtains preferable effect, obtains higher current efficiency and lower driving electricity Pressure.
Embodiment 50:
The compound of the present invention is as the material of main part in red phosphorescent OLED organic electroluminescence device:
10 organic electroluminescence devices, organic electroluminescence device structure are prepared altogether are as follows:
ITO/NPB (20nm)/feux rouges material of main part (30nm): Ir (piq) 3 [5%]/TPBI (10nm)/Alq3 (15nm)/ LiF(0.5nm)/Al(150nm)。
One of them is comparison organic electroluminescence device, and feux rouges material of main part selects CBP, other 9 organic electroluminescences hairs Optical device selects material of the invention.
Organic electroluminescence device preparation process is as follows: the glass plate for being coated with transparent conductive layer is cleaned in commercialization It is ultrasonically treated in agent, rinses in deionized water, in acetone: ultrasonic oil removing in alcohol mixed solvent is toasted under clean environment To completely removing moisture content, with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10-5~9 × 10-3Pa is evacuated to, Vacuum evaporation hole transmission layer NPB on above-mentioned anode tunic, evaporation rate 0.1nm/s, vapor deposition film thickness are 20nm；
Vacuum evaporation light emitting host material and dyestuff on hole transmission layer, as shining for organic electroluminescence device Layer, evaporation rate 0.1nm/s, vapor deposition total film thickness are 30nm；
Successively vacuum evaporation electron transfer layer TPBI and Alq3, evaporation rate are 0.1nm/s on luminescent layer, are steamed Plating film thickness is respectively 10nm and 15nm；
The Al of the LiF of vacuum evaporation 0.5nm on the electron transport layer, 150nm are as cathode.
Organic electroluminescence device performance see the table below:
Can see by upper table, using chemical combination of the present invention as phosphorescence host organic electroluminescence device relative to use CBP obtains preferable effect as the organic electroluminescence device of main body, obtains higher current efficiency and lower drive Dynamic voltage.
Embodiment 51:
The compound of the present invention is as the material of main part in green phosphorescent OLED organic electroluminescence device:
6 organic electroluminescence devices, organic electroluminescence device structure are prepared altogether are as follows:
ITO/NPB (20nm)/green light material of main part (30nm): Ir (ppy) 3 [7%]/TPBI (10nm)/Alq3 (15nm)/ LiF(0.5nm)/Al(150nm)。
One of them is comparison organic electroluminescence device, and green light material of main part selects CBP, other 5 organic electroluminescences hairs Optical device selects material of the invention.
Organic electroluminescence device preparation process is as follows: the glass plate for being coated with transparent conductive layer is cleaned in commercialization It is ultrasonically treated in agent, rinses in deionized water, in acetone: ultrasonic oil removing in alcohol mixed solvent is toasted under clean environment To completely removing moisture content, with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10-5~9 × 10-3Pa is evacuated to, Vacuum evaporation hole transmission layer NPB on above-mentioned anode tunic, evaporation rate 0.1nm/s, vapor deposition film thickness are 20nm；
Vacuum evaporation light emitting host material and dyestuff on hole transmission layer, as shining for organic electroluminescence device Layer, evaporation rate 0.1nm/s, vapor deposition total film thickness are 30nm；
Successively vacuum evaporation electron transfer layer TPBI and Alq3, evaporation rate are 0.1nm/s on luminescent layer, are steamed Plating film thickness is respectively 10nm and 15nm；
The Al of the LiF of vacuum evaporation 0.5nm on the electron transport layer, 150nm are as electron injecting layer and cathode.
Organic electroluminescence device performance see the table below:
Can see by upper table, using chemical combination of the present invention as phosphorescence host organic electroluminescence device relative to use CBP obtains preferable effect as the organic electroluminescence device of main body, obtains higher current efficiency and lower drive Dynamic voltage.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (4)

1. a kind of organic electroluminescence device, containing luminescent layer, the luminescent layer is green light emitting layer, the green light emitting layer packet Material of main part and dyestuff are included, the material of main part is selected from formula (1) described compound:
Wherein, R1Selected from phenyl, alkyl-substituted phenyl, the phenyl that phenyl replaces, the phenyl of naphthyl substituted, the benzene that anthryl replaces Base, the phenyl that fluorenyl replaces, the phenyl that carbazole N- replaces, the phenyl that carbazole 3- replaces, the phenyl that phenanthryl replaces, naphthalene, alkyl Substituted naphthalene, the naphthalene that phenyl replaces, the naphthalene of naphthyl substituted, the naphthalene that anthryl replaces, the naphthalene that fluorenyl replaces, carbazole N- Substituted naphthalene, the naphthalene that carbazole 3- replaces, the naphthalene that phenanthryl replaces, anthryl, phenanthryl, alkyl-substituted anthryl, phenyl replace Anthryl, the anthryl of naphthyl substituted, the anthryl that anthryl replaces, the anthryl that fluorenyl replaces, the anthryl that carbazole N- replaces, carbazole 3- takes The anthryl in generation, the anthryl that phenanthryl replaces, alkyl-substituted phenanthryl, the phenanthryl that phenyl replaces, the phenanthryl of naphthyl substituted, anthryl replace Phenanthryl, fluorenyl replace phenanthryl, carbazole N- replace phenanthryl, carbazole 3- replace phenanthryl, phenanthryl replace phenanthryl, fluorenyl, Alkyl-substituted fluorenyl, the fluorenyl that phenyl replaces, the fluorenyl of naphthyl substituted, the fluorenyl that anthryl replaces, the fluorenyl that phenanthryl replaces, click The fluorenyl that azoles N- replaces, the fluorenyl that carbazole 3- replaces, the fluorenyl that fluorenyl replaces, carbazole, alkyl-substituted carbazole, what phenyl replaced Carbazole, the carbazole of naphthyl substituted, the carbazole that anthryl replaces, the carbazole that phenanthryl replaces, the carbazole that carbazole N- replaces, carbazole 3- replace Carbazole, terphenyl, alkyl-substituted terphenyl, the xenyl of naphthyl substituted, anthryl replace xenyl, phenanthryl replace Xenyl, fluorenyl replace xenyl, carbazole replace xenyl, phenyl napthyl replace phenyl, phenyl carbazole base replace Phenyl, diphenyl replace phenyl, xenyl replace naphthalene, biphenyl replace fluorenyl, biphenyl replace carbazyl, dinaphthalene The phenyl that base replaces, the binaphthyl that phenyl replaces, the anthryl that diphenyl replaces, the anthryl that phenyl napthyl replaces, dinaphthyl replace Anthryl, 4- (2,2- Diphenyl-vinyl) phenyl is Spirofluorene-based；
X is selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, amyl, isopentyl, cyclopenta, alkyl-substituted ring Amyl, n-hexyl, cyclohexyl, alkyl-substituted cyclohexyl, phenyl, alkyl-substituted phenyl, benzyl.
2. organic electroluminescence device according to claim 1, the green light emitting layer includes material of main part and dyestuff, It is characterized in that, the material of main part is selected from flowering structure:
3. organic electroluminescence device according to claim 1, which is characterized in that the wherein main body of the green light emitting layer Material is selected from flowering structure:
4. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, several hairs on the substrate Light unit layer and cathode layer；
The luminescence unit layer includes hole transmission layer, luminescent layer, electron transfer layer, and the hole transmission layer is formed in institute On the anode layer stated, the cathode layer is formed on the electron transfer layer, the hole transmission layer and the electricity It is luminescent layer between sub- transport layer, the luminescent layer is green light emitting layer, it is characterised in that:
The green light emitting layer includes material of main part and dyestuff, and the material of main part is selected from compound shown in formula (1)；
Wherein, R1Selected from phenyl, alkyl-substituted phenyl, the phenyl that phenyl replaces, the phenyl of naphthyl substituted, the benzene that anthryl replaces Base, the phenyl that fluorenyl replaces, the phenyl that carbazole N- replaces, the phenyl that carbazole 3- replaces, the phenyl that phenanthryl replaces, naphthalene, alkyl Substituted naphthalene, the naphthalene that phenyl replaces, the naphthalene of naphthyl substituted, the naphthalene that anthryl replaces, the naphthalene that fluorenyl replaces, carbazole N- Substituted naphthalene, the naphthalene that carbazole 3- replaces, the naphthalene that phenanthryl replaces, anthryl, alkyl-substituted anthryl, the anthracene that phenyl replaces Base, the anthryl of naphthyl substituted, the anthryl that anthryl replaces, the anthryl that fluorenyl replaces, the anthryl that carbazole N- replaces, what carbazole 3- replaced Anthryl, the anthryl that phenanthryl replaces, phenanthryl, alkyl-substituted phenanthryl, the phenanthryl that phenyl replaces, the phenanthryl of naphthyl substituted, anthryl take The phenanthryl in generation, the phenanthryl that fluorenyl replaces, the phenanthryl that carbazole N- replaces, the phenanthryl that carbazole 3- replaces, the phenanthryl that phenanthryl replaces, fluorenes Base, alkyl-substituted fluorenyl, the fluorenyl that phenyl replaces, the fluorenyl of naphthyl substituted, the fluorenyl that anthryl replaces, the fluorenes that phenanthryl replaces Base, the fluorenyl that carbazole N- replaces, the fluorenyl that carbazole 3- replaces, the fluorenyl that fluorenyl replaces, carbazole, alkyl-substituted carbazole, phenyl Substituted carbazole, the carbazole of naphthyl substituted, the carbazole that anthryl replaces, the carbazole that phenanthryl replaces, the carbazole that carbazole N- replaces, carbazole The carbazole that 3- replaces, terphenyl, alkyl-substituted terphenyl, the xenyl of naphthyl substituted, the xenyl that anthryl replaces are luxuriant and rich with fragrance The xenyl that base replaces, the xenyl that fluorenyl replaces, the xenyl that carbazole replaces, the phenyl that phenyl napthyl replaces, phenyl carbazole The phenyl that base replaces, the phenyl that diphenyl replaces, the naphthalene that xenyl replaces, the fluorenyl that biphenyl replaces, the carbazole that biphenyl replaces Base, the phenyl that binaphthyl replaces, the binaphthyl that phenyl replaces, the anthryl that diphenyl replaces, the anthryl that phenyl napthyl replaces, dinaphthyl The anthryl that base replaces, 4- (2,2- Diphenyl-vinyl) phenyl are Spirofluorene-based；
X is selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, amyl, isopentyl, cyclopenta, alkyl-substituted ring Amyl, n-hexyl, cyclohexyl, alkyl-substituted cyclohexyl, phenyl, alkyl-substituted phenyl, benzyl.
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