CN104513192B - A kind of benzo anthra [9,1-bc] carbazole derivates and its application - Google Patents
A kind of benzo anthra [9,1-bc] carbazole derivates and its application Download PDFInfo
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Abstract
The present invention relates to a kind of benzo anthra [9,1-bc] carbazole derivates benzo anthra [9,1-bc] carbazole derivates as shown in the formula (I), in which: Ar1‑Ar8It is independently selected from the substituted or non-substituted aromatic hydrocarbon group of H, C6~C30, the substituted or non-substituted condensed-nuclei aromatics group of C6~C30, the substituted or non-substituted condensed hetero ring group of C6~C30, five yuan, hexa-atomic heterocycle or substituted heterocycle, triarylamine group, aryl oxide group base group, one of substituted or non-substituted aliphatic alkyl group of C1~C12.The present invention also protects application of such compound in organic electroluminescence device, especially as hole-injecting material, hole transport layer material, fluorescent host material or the luminescent material in OLED device.
Description
Technical field
The present invention relates to a kind of novel organic compound more particularly to a kind of compounds for organic electroluminescence device
And the application in organic electroluminescence device.
Background technique
Display of organic electroluminescence (hereinafter referred to as OLED) has from main light emission, low-voltage direct-current driving, all solidstate, view
The a series of advantages such as angular width, light-weight, composition and simple process, compared with liquid crystal display, display of organic electroluminescence
Backlight is not needed, visual angle is big, and power is low, and up to 1000 times of liquid crystal display, manufacturing cost is but lower than response speed
The liquid crystal display of same resolution ratio, therefore, organic electroluminescence device has broad application prospects.
What the generation of organic electroluminescent was leaned on is the weight of the carrier (electrons and holes) transmitted in organic electroluminescence material
Group, it is well known that the electric conductivity of organic material is very poor, does not have continuity unlike inorganic semiconductor, in organic semiconductor
Energy band, the transmission of carrier is commonly used jump theory and is described, i.e., under the driving of an electric field, electronics is being excited or is injected into point
In the lumo energy of son, achieve the purpose that charge is transmitted via the lumo energy for jumping to another molecule.In order to make have
Organic electroluminescence devices reach breakthrough in application aspect, it is necessary to overcome the difficulty of the injection of organic material charge and transmittability difference.
Scientists are by the adjustment of device architecture, such as increase the number of device organic material layer, and play the part of different organic layers
Different roles is drilled, such as the functional material having helps electronics to inject from cathode and hole from anode, some materials help electricity
The transmission of lotus, 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 will also achieve the purpose that match with adjacent functional material, the Organic Electricity of excellent in efficiency service life length
Electroluminescence device is usually the optimization collocation of device architecture and various organic materials as a result, this is just that chemists design out
The functionalization material for sending out structure various provides great opportunities and challenges.
The hole injection used always in organic electroluminescent device and transmission material are usually derivative of tri-arylamine group (example
Such as go out light patent: publication number CN1152607C, publication date 2004,6,2), it is general to be structurally characterized in that, as injection material,
Its triaryl amine structural unit is at least at three or more in a molecule, and is separated between two N with a phenyl ring, sees formula 1；Make
For transmission material, its triaryl amine structural unit is usually two in a molecule, and is separated between two N with biphenyl, at this
In class material, typical example is NPB, and structure is shown in formula 2.
In recent years, the research of this kind of material has some new progresses, introduces one or more thienyls in the molecule, or
Person introduces one or more benzothienyls, sees that formula 3 and formula 4(go out light patent: publication number CN101506191A, publication date 2009,
8,12), the result is that considerably increasing the Hole injection capacity of material；As transmission material, when by a triaryl amine in material
When structural unit carbazole or dibenzofurans replace, the transmittability of material all has a more substantial increase.See that formula 5 and formula 6(go out
Light patent: publication number CN102334210A, the applying date 2012,1,25；Publication number: WO2010/114017A1, publication date 2010,
10,7).
Summary of the invention
The purpose of the present invention is to provide a kind of new compound, i.e. benzo anthra [9,1-bc] carbazole derivates, such
Compound can be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
For this purpose, the technical scheme adopted by the invention is as follows:
A kind of benzo anthra [9,1-bc] carbazole derivates have structure as shown in the formula (I):
Wherein:
Ar1-Ar8Be independently selected from the substituted or non-substituted aromatic hydrocarbon group of H, C6~C30, C6~C30 it is substituted or non-substituted
Condensed-nuclei aromatics group, C6~C30 substituted or non-substituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, three
One of aryl amine group, aryl oxide group base group, substituted or non-substituted aliphatic alkyl group of C1~C12.
The condensed-nuclei aromatics group be naphthalene, substituted naphthyl, anthryl, replace anthryl, phenanthryl, replace phenanthryl, benzo naphthalene,
Replace benzo naphthalene, benzo phenanthryl, replaces benzo phenanthryl, pyrenyl, replaces pyrenyl, Qu Ji, triphenylene, benzo phenanthryl.
The condensed hetero ring group is carbazyl, substituted carbazole base, dibenzo thiophene base, substituted diphenylamine thienyl, dibenzo furan
It mutters base, substituted diphenylamine and furyl.
Illustrate the content of present invention to become apparent from, the narration of lower mask body the present invention relates to compound preferred structure:
The present invention provides benzo anthra [9,1-bc] carbazole derivates described in one kind, are applied to organic electroluminescence
In part.
The present invention also provides a kind of organic electroluminescence devices, including substrate, and sequentially form on the substrate
Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, and feature exists
In:
The host material of the hole transmission layer contains described benzo anthra [9, the 1-bc] carbazole derivates.
The present invention also provides a kind of organic electroluminescence devices, including substrate, and sequentially form on the substrate
Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, and feature exists
In:
The host material of the organic luminous layer contains described benzo anthra [9, the 1-bc] carbazole derivates.
For the convenience of description, hole mobile material signified in the application subsequent content is the matrix material of hole transmission layer
Material, material of main part is the host material of organic luminous layer.
Compared with prior art, the present invention has the advantage that
(1) in the present invention, we have proposed this new materials of benzo anthra [9,1-bc] carbazole derivates, if benzo
If only connecting condensed-nuclei aromatics on [5,10] anthra [9,1-bc] carbazole precursor structure, for example, carbazole group, dibenzo thiophene group,
Dibenzofurans group etc., such material are suitable as light emitting host material, device light emitting efficiency are made to improve a lot, device
It lasts a long time.And it is connected with triaryl amine or condensed hetero ring aromatic hydrocarbons on benzo [5,10] anthra [9,1-bc] carbazole precursor structure, example
Such as carbazole group, dibenzothiophenes group, dibenzofurans group etc., such material is suitable as hole mobile material.
(2) preparation is simple for the compounds of this invention, and these compounds have good thermal stability, high
Hole mobility, the electroluminescent device made of the material, the bright voltage that opens of device substantially reduce, and luminous efficiency is mentioned
Height, while the service life of device is dramatically increased can be used as hole mobile material and organic in organic electroluminescence device
The material of main part of luminescent layer.
Detailed description of the invention
In order to be more easily understood the contents of the present invention, Gaussian03B3LYP/6-31G(d is used in the present invention) method
The highest occupied molecular orbital(HOMO) (HOMO), lowest unoccupied molecular orbital (LUMO) and triplet (T1) of compound are acquired respectively.
Fig. 1 is the highest occupied molecular orbital(HOMO) of compound 13 in the embodiment of the present invention 14, and HOMO energy level is -4.792ev, three
Line state energy level T1=1.5176ev；
Fig. 2 is the lowest unoccupied molecular orbital of compound 13 in the embodiment of the present invention 14, and lumo energy is -1.903ev；
Fig. 3 be in the embodiment of the present invention 14 compound 13 through Gaussian03B3LYP/6-31G(d) method optimization after it is each
The three-dimensional distribution map of atom and group；
Fig. 4 is the highest occupied molecular orbital(HOMO) of 8 compound 7 of the embodiment of the present invention, and HOMO energy level is -4.790ev, triplet state
Energy level T1=1.5198ev；
Fig. 5 is the lowest unoccupied molecular orbital of 8 compound 7 of the embodiment of the present invention, and lumo energy is -1.902ev；
Specific embodiment
Basic raw material used in the present invention, 3- bromine, 3,9- dibromos, 2- bromo nitrobenzene, 2,4- bis- bromo nitrobenzenes,
2,5- bis- bromo nitrobenzenes and bromo carbazole derivative, bromo dibenzofurans, bromo dibenzothiophenes, bromo Chrysene,
Bromo triphenylene, bromo pyrene etc. major industrial chemicals can be commercially available at home.It closes in 5- bromine benzophenanthrene system this laboratory oneself
At.
Embodiment 1
For the preparation embodiment of intermediate of the present invention:
The synthesis of main intermediate -3- boric acid
The 3- bromine (molecular weight 330,0.02mol) of 6.0g is dissolved in the dry THF of 100ml, -80 DEG C are added dropwise positive fourth
Basis mechanism 10ml(2.5M, 0.025mol), 15min is stirred, then triisopropyl borate 18ml is added dropwise.Hydrolysis adjusts pH to neutrality
White boronic acid derivatives 5.92g, yield intimate 100% is precipitated.
Embodiment 2
The synthesis of compound 1
(1) first step
1000 milliliters of a bite bottles match magnetic agitation, addition -3- boric acid 5.92g(molecular weight 296,0.02mol), 2,4-
Two bromo nitrobenzene 5.28g(molecular weight 278,0.019mol), 4 usage amount 1.3g(molecular weight 1154 of Pd (PPh3),
0.001265mol), sodium carbonate 140ml(2M), toluene 140ml, ethyl alcohol 140ml.After argon gas displacement, reflux is monitored anti-with TLC
It answers, fully reacting after 3 hours, cools down, separated base, be evaporated, carried out post separation with 1/10 ethyl acetate/petroleum ether, obtain
To 7.9g product, molecular weight 451, yield 92%.
(2) second step
150 milliliters of a bite bottles match magnetic agitation, the final product 7.9g(molecular weight 451 of the first step are added,
0.0175mol), triphenylphosphine 10.4g(molecular weight 262,0.0395mol), o-dichlorohenzene 70ml.Mixture is heated to 1750C,
Stirring is reacted 15 hours and is completed with TCL board monitoring reaction process.It is cooling, solvent is evaporated in vacuo, washes, it is dry, use column chromatography
Separation, ethyl acetate and petroleum ether mixtures elution, obtain target molecule 6.2g, molecular weight 419, yield 84.5%
(3) third step
150 milliliters of a bite bottles match magnetic agitation, and second step final product 6.2g(molecular weight 419,0.0148mol is added),
2- iodonaphthalene 5.1g(molecular weight 254,0.02mol), cuprous iodide 0.4g(molecular weight 190,0.0021mol), potassium carbonate 7.0g
(138,0.05mol), DMPU solvent 60ml.Mixture is heated to 1750C, stirring, with TCL board monitoring reaction process, reaction 10
Hour completes.It is cooling, it is poured into water, filters out, dry, with pillar layer separation, ethyl acetate and petroleum ether mixtures elution are obtained
Target molecule 7.22g, molecular weight 545, yield 89.5%
(4) the 4th steps
1000 milliliters of a bite bottles match magnetic agitation, above-mentioned third step final product 7.22g(molecular weight 545 are added,
0.0132mol), 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid 5.1g(molecular weight 339,0.015mol), Pd (PPh3) 4
Usage amount 1.3g(molecular weight 1154,0.001126mol), sodium carbonate 140ml(2M), toluene 140ml, ethyl alcohol 140ml.Argon gas is set
After changing, reflux is monitored with TLC and is reacted, fully reacting after 4 hours, cooling, and product solid is largely precipitated, filtering, with recrystallization
Methods For Purification (can also use post separation Methods For Purification) when necessary, obtain 8.26g product, yield 82%.
Embodiment 3
The synthesis of compound 2
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 4-(N, N- diphenylamino) phenyl boric acid, obtain compound 2.
Embodiment 4
The synthesis of compound 3
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 4-(carbazole -9- base) phenyl boric acid, obtain compound 3.
Embodiment 5
The synthesis of compound 4
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 4-(3- phenyl-carbazole -9- base) phenyl boric acid, obtain compound 4.
Embodiment 6
The synthesis of compound 5
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into N- phenyl carbazole -3- boric acid, obtain compound 5.
Embodiment 7
The synthesis of compound 6
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 6,9- diphenyl-carbazole -3- boric acid, obtain compound 6.
Embodiment 8
The synthesis of compound 7
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into dibenzothiophenes -4- boric acid, obtain compound 7.
Embodiment 9
The synthesis of compound 8
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into dibenzothiophenes -2- boric acid, obtain compound 8.
Embodiment 10
The synthesis of compound 9
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 8- phenyl dibenzothiophenes -2- boric acid, obtain compound 9.
Embodiment 11
The synthesis of compound 10
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into dibenzofurans -4- boric acid, obtain compound 10.
Embodiment 12
The synthesis of compound 11
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into dibenzofurans -2- boric acid, obtain compound 11.
Embodiment 13
The synthesis of compound 12
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 8- phenyl dibenzofurans -2- boric acid, obtain compound 12.
Embodiment 14
The synthesis of compound 13
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 10-(2- naphthalene) anthracene -9- boric acid, obtain compound 13.
Embodiment 15
The synthesis of compound 14
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 4-(10- phenylanthracene -9- base) phenyl boric acid, obtain compound 14.
Embodiment 16
The synthesis of compound 15
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into pyrene -1- boric acid, obtain compound 15.
Embodiment 17
The synthesis of compound 16
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into 6- phenyl pyrene -1- boric acid, obtain compound 16.
Embodiment 18
The synthesis of compound 17
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into -1- boric acid in the wrong, obtain compound 17.
Embodiment 19
The synthesis of compound 18
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into -6- boric acid in the wrong, obtain compound 18.
Embodiment 20
The synthesis of compound 19
Synthesis step is same as the four-step reaction in embodiment 2, only in the 4th step, 4-(N- phenyl-N-(1- naphthalene) ammonia
Base) phenyl boric acid changes into benzophenanthrene -5- boric acid, obtain compound 19.
Embodiment 21
The synthesis of compound 20
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 4-(N, N- diphenylamino)
Phenyl boric acid obtains compound 20.
Embodiment 22
The synthesis of compound 21
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into N- phenyl carbazole -3- boron
Acid obtains compound 21.
Embodiment 23
The synthesis of compound 22
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 6,9- diphenyl-carbazole-
3- boric acid obtains compound 22.
Embodiment 24
The synthesis of compound 23
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into dibenzofurans -2- boron
Acid obtains compound 23.
Embodiment 25
The synthesis of compound 24
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 8- phenyl dibenzofurans-
2- boric acid obtains compound 24.
Embodiment 26
The synthesis of compound 25
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into dibenzofurans -4- boron
Acid obtains compound 25.
Embodiment 27
The synthesis of compound 26
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into dibenzothiophenes -4- boron
Acid obtains compound 26.
Embodiment 28
The synthesis of compound 27
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into dibenzothiophenes -2- boron
Acid obtains compound 27.
Embodiment 29
The synthesis of compound 28
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 8- phenyl dibenzothiophenes-
2- boric acid obtains compound 28.
Embodiment 30
The synthesis of compound 29
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 10- phenylanthracene -9- boric acid,
Obtain compound 29.
Embodiment 31
The synthesis of compound 30
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 10-(2- naphthalene) anthracene -9-
Boric acid obtains compound 30.
Embodiment 32
The synthesis of compound 31
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 4-(10-(2- naphthalene) anthracene-
9- yl) phenyl boric acid, obtain compound 31.
Embodiment 33
The synthesis of compound 32
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into pyrene -1- boric acid, changed
Close object 32.
Embodiment 34
The synthesis of compound 33
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into 6- phenyl pyrene -1- boric acid,
Obtain compound 33.
Embodiment 35
The synthesis of compound 34
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into triphenylene -2- boric acid, it obtains
To compound 34.
Embodiment 36
The synthesis of compound 35
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into benzophenanthrene -5- boric acid, it obtains
To compound 35.
Embodiment 37
The synthesis of compound 36
Synthesis step is same as the four-step reaction in embodiment 2, and 2,4-, bis- bromo nitrobenzene is only changed into 2 in the first step,
Bis- bromo nitrobenzene of 5-；In the 4th step by 4-(N- phenyl-N-(1- naphthalene) amino) phenyl boric acid changes into -6- boric acid in the wrong, changed
Close object 36.
See Table 1 for details for the Mass Spectrometer Method data and Elemental analysis data of gained compound 1-36.
It is mass spectrum and Elemental analysis data of the compound of the present invention 1 to compound 36 below:
Embodiment 38
The Application Example of each compound of the present invention
Compare the performance of these hole mobile materials and fluorescent host material for convenience, the present invention devises a simple electricity
Luminescent device, we select HAT to hole injection layer material, and material is compared in hole mobile material NPB conduct.Organic luminous layer is by sending out
Light main body and dopant material composition, we use traditional light emitting host material EM1 as material, EM2 is compared and mix as shining
Miscellaneous material, wherein the structure of HAT, NPB, EM1, EM2 are respectively as follows:
The structure of organic electroluminescence device in the embodiment of the present invention are as follows:
Substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer
(ETL)/cathode.
The substrate in conventional organic luminescence device can be used in substrate, such as: glass or plastics.In Organic Electricity of the invention
Glass substrate is selected in electroluminescence device production, ITO makees anode material.
The various more arylamine for easily providing electronics can be used in hole-injecting material, it is possible to use more cyano of extreme electron deficient
Class material, such molecule usually use its lowest unoccupied molecular orbital (LUMO) to transmit electronics.The note of hole used in the present invention
Entering material is HAT.
Hole transmission layer can use various tri-arylamine group materials.The material stated in the present invention is in electroluminescence device
It can be used as hole mobile material, be compared with traditional hole mobile material NPB.
There are many kinds for emitting layer material.The material stated in the present invention can be used as light emitting host material in electroluminescence device
Material, luminescent dopant material is EM2.
There are many kinds for electron transport layer materials.In order to characterize the material stated in the present invention, we are used common here
AlQ3 as electron transport material, it is therefore an objective to material property in more of the invention, do not lie in pursue device performance it is excellent.
Cathode can use metal and its mixture structure, such as Mg:Ag, Ca:Ag, be also possible to electron injecting layer/gold
Belong to layer structure, such as LiF/Al, Li2O/Al common cathode structure.It is selected in organic electroluminescence device production of the invention
Cathode material is LiF/Al.
Embodiment 39
Compound in the present embodiment is prepared for multiple having altogether as the hole mobile material in organic electroluminescence device
Organic electroluminescence devices, structure are as follows: ITO/HAT(5nm)/hole mobile material (40nm)/EM1:EM2 (30nm)/Alq3
(20nm)/LiF(0.5nm)/Al(150nm)；
One comparison organic electroluminescence device, hole mobile material select NPB, remaining organic electroluminescence device is selected
Material of the invention.
Organic electroluminescence device preparation process is as follows in the present embodiment:
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, is rinsed in deionized water,
In acetone: ultrasonic oil removing in alcohol mixed solvent is baked under clean environment and completely removes moisture content, clear with ultraviolet light and ozone
It washes, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned
Vacuum evaporation HAT is as hole injection layer on anode tunic, and evaporation rate 0.1nm/s, vapor deposition film thickness is 40nm；
Be deposited again on hole injection layer compound 1 in one layer of present invention, 2,3,4,5,6,7,8,9,10,12,20,
21,22,23,24,25,26,27,28 or NPB is as hole transmission layer, and evaporation rate 0.1nm/s, vapor deposition film thickness is 40nm；
The vacuum evaporation luminescent layer EM1 and EM2(ratio 95%:5% on hole transmission layer), evaporation rate 0.1nm/s,
Vapor deposition total film thickness is 30nm；
One layer of AlQ3 of vacuum evaporation is distinguished on luminescent layer as electron transport material, evaporation rate 0.1nm/s,
Vapor deposition total film thickness is 20nm；
On the electron transport layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of 150nm
Cathode of the Al layer as device.
Organic electroluminescence device performance see the table below:
| Compound number | It is required that brightness cd/m2 | Voltage V | Current efficiency cd/A |
| NPB | 5000.00 | 6.8 | 25.1 |
| 1 | 5000.00 | 6.2 | 26.4 |
| 2 | 5000.00 | 6.0 | 26.9 |
| 3 | 5000.00 | 6.1 | 27.5 |
| 4 | 5000.00 | 6.4 | 27.7 |
| 5 | 5000.00 | 6.5 | 28.2 |
| 6 | 5000.00 | 6.2 | 27.9 |
| 7 | 5000.00 | 6.1 | 26.3 |
| 8 | 5000.00 | 6.1 | 26.5 |
| 9 | 5000.00 | 6.0 | 28.4 |
| 10 | 5000.00 | 5.9 | 27.3 |
| 12 | 5000.00 | 6.1 | 26.3 |
| 20 | 5000.00 | 6.3 | 26.4 |
| 21 | 5000.00 | 6.3 | 27.4 |
| 22 | 5000.00 | 6.4 | 27.9 |
| 23 | 5000.00 | 6.2 | 26.3 |
| 24 | 5000.00 | 6.0 | 26.8 |
| 25 | 5000.00 | 6.5 | 27.1 |
| 26 | 5000.00 | 6.3 | 28.1 |
| 27 | 5000.00 | 6.1 | 26.3 |
| 28 | 5000.00 | 6.0 | 26.5 |
Embodiment 40
Compound in the present embodiment is prepared for multiple Organic Electricities as the material of main part in organic electroluminescence device altogether
Electroluminescence device, structure are as follows: ITO/HAT(5nm)/NPB(40nm)/light emitting host material: EM2 (95%:5%, 30nm)/Alq3
(20nm)/LiF(0.5nm)/Al(150nm)；
One comparison organic electroluminescence device, light emitting host material selection EM1, remaining organic electroluminescence device are selected
Material of the invention.
Organic electroluminescence device preparation process is as follows in the present embodiment:
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, is rinsed in deionized water,
In acetone: ultrasonic oil removing in alcohol mixed solvent is baked under clean environment and completely removes moisture content, clear with ultraviolet light and ozone
It washes, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10- is evacuated to5~9×10-3Pa, above-mentioned
Vacuum evaporation HAT is as hole injection layer on anode tunic, and evaporation rate 0.1nm/s, vapor deposition film thickness is 40nm；
One layer of NPB is deposited again on hole injection layer as hole transmission layer, evaporation rate 0.1nm/s, evaporation film
Thickness is 40nm；
Compound 13 on the hole transmission layer in the vacuum evaporation luminescent layer present invention, 14,15,16,17,18,19,
29,30,31,32,33,34,35,36 or EM1, doping vapor deposition EM2(ratio 85%:15%), evaporation rate 0.1nm/s, vapor deposition
Total film thickness is 30nm；
One layer of AlQ3 of vacuum evaporation is distinguished on luminescent layer as electron transport material, evaporation rate 0.1nm/s,
Vapor deposition total film thickness is 20nm；
On the electron transport layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of 150nm
Cathode of the Al layer as device.
Luminescent device performance see the table below:
| Compound number | It is required that brightness cd/m2 | Voltage V | Current efficiency cd/A |
| EM1 | 5000.00 | 6.8 | 25.1 |
| 13 | 5000.00 | 6.4 | 27.8 |
| 14 | 5000.00 | 6.3 | 27.4 |
| 15 | 5000.00 | 6.5 | 27.0 |
| 16 | 5000.00 | 6.1 | 27.8 |
| 17 | 5000.00 | 6.2 | 26.9 |
| 18 | 5000.00 | 6.1 | 26.4 |
| 19 | 5000.00 | 6.0 | 26.8 |
| 29 | 5000.00 | 6.3 | 27.1 |
| 30 | 5000.00 | 6.2 | 27.3 |
| 31 | 5000.00 | 6.4 | 27.7 |
| 32 | 5000.00 | 6.2 | 26.7 |
| 33 | 5000.00 | 6.3 | 28.0 |
| 34 | 5000.00 | 6.3 | 28.3 |
| 35 | 5000.00 | 6.1 | 27.4 |
| 36 | 5000.00 | 5.9 | 27.3 |
The above result shows that new organic materials of the invention are used for organic electroluminescence device, can effectively reduce
Landing voltage improves current efficiency, is hole mobile material and light emitting host material of good performance.
Although the present invention is described in conjunction with the embodiments, the present invention is not limited to the above embodiments, should manage
Solution, under the guidance of present inventive concept, those skilled in the art can carry out various modifications and improve, and appended claims summarise
The scope of the present invention.
Claims (4)
1. a kind of benzo anthra [9,1-bc] carbazole derivates, which is characterized in that the compound is selected from following structural formula:
2. application of benzo anthra [9, the 1-bc] carbazole derivates described in claim 1 in organic electroluminescence device.
3. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；
The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, it is characterised in that:
The host material of the hole transmission layer contains benzo anthra [9,1-bc] carbazole derivates described in claim 1.
4. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；
The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, it is characterised in that:
The host material of the organic luminous layer contains benzo anthra [9,1-bc] carbazole derivates described in claim 1.
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