CN104659280B - A kind of organic electroluminescence device and preparation method thereof - Google Patents
A kind of organic electroluminescence device and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of organic electroluminescence device, comprising a pair of electrodes and the luminescent layer being arranged between the electrode pair, and the luminescent layer includes the first material of main part, the second material of main part and dopant dye, wherein：（a）First material of main part is a kind of and quinoline；（b）Second material of main part is a kind of with formula as follows（I）The indole derivativeses of structure.Present applicant proposes a kind of organic electroluminescence device, solves the problems, such as that double main body device efficiencies decline, while improving can device voltage reduction, life-span, efficiency gets a promotion.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device, more specifically, is related to a kind of efficient organic electroluminescence and sends out
Optical device.
Technical background
Display of organic electroluminescence（Hereinafter referred to as OLED）With from main light emission, low-voltage direct-current driving, all solidstate, regard
The a series of advantages such as angular width, lightweight, composition and process is simple, compared with liquid crystal display, display of organic electroluminescence
Backlight is not needed, visual angle is big, and power is low, 1000 times up to liquid crystal display of its response speed, and its manufacturing cost is but less than
The liquid crystal display of equal resolution, therefore, display of organic electroluminescence has broad application prospects.
Organic electroluminescent LED（OLED）It was developed so far from 1987, device performance has obtained significantly being lifted, and
The lifting of device performance, in addition to the constantly bringing forth new ideas of material, is exactly the constantly improve of device architecture therewith accordingly.OLED devices
Part structure is developed to present multiple structure from initial single layer structure after double-decker, three-decker.It is more common at present
Structure be multiple structure：Anode/hole injection layer（HIL）/ hole transmission layer（HTL）/ luminescent layer（EML）（Generally main body
Host doping luminescent dye dopant）/ electron transfer layer（ETL）/ electron injecting layer（EIL）/ negative electrode, it is every in this device architecture
The characteristics of layer of material all has respective and function so that hole and electronics can preferably inject and be combined, so as to improve device
The efficiency of part.But if per layer of material for using is different, then be equivalent to hetero-junctions between layers, for hetero-junctions OLED
For device, have a disadvantage that：There is potential barrier in the energy level between layers of material, so the voltage of device is higher；Further, since electric
Son and hole mobility inject the inconsistent of number, and often at HTL/EML interfaces, or EML/ETL interfaces produce hole
Or the accumulation of electronics, some unstable cations or anion can be so formed, so as to cause the decay of device lifetime.Pin
To these shortcomings, researchers contemplate various methods and go to solve.Such as, go to eliminate as far as possible or obscure hetero-junctions.Such as, pass through
Method of the luminescent layer using double main bodys（See document：Appl.phys.lett.,86,103506(2005)；
Appl.phys.lett.,89,163511(2006)；Appl.phys.lett.,80,725(2002)；Appl.phys.lett.,
80,3641(2002)；Jour.Appl.phys.,93,1108(2003)；）, and the first main body using and HTL identical materials
Material, the second main body using with ETL identical materials, the two is steamed as main body altogether, it is possible to so that HTL/EML, or EML/ETL
Interface obscure, so as to eliminate hetero-junctions to a certain extent so that the voltage of device declines, life-span upgrading, but it is this double
Main body device, is accompanied by another drawback, that is, the decline of device efficiency again.
A kind of problem that the application declines for double main body phosphorescent devices efficiency, it is proposed that method, can make device voltage
While reduction, life-span improve, efficiency gets a promotion.
The content of the invention
A kind of problem that the application declines for double main body device efficiencies, it is proposed that organic electroluminescence device, can make device
Voltage is reduced, and while the life-span improves, efficiency gets a promotion.
For this purpose, the technical scheme that the present invention takes is：
A kind of organic electroluminescence device, comprising a pair of electrodes and the luminescent layer being arranged between the electrode pair, and should
Luminescent layer includes the first material of main part, the second material of main part and dopant dye, wherein：
（a）First material of main part is a kind of and quinoline；
（b）Second material of main part is a kind of with formula as follows（I）The indole derivativeses of structure,
Wherein：
R1One of aromatic group of acyclic straight or branched hydrocarbyl or C6～C30 selected from C1～C20；
R2The substituted or non-substituted carbazyl of substituted or non-substituted arylamine group, C4～C40 selected from C4～C40
Group, the substituted or non-substituted dibenzothiophenes group of C4～C40, the substituted or non-substituted indolyl radical of C4～C40, C4～
One of the replacement of C40 or non-substituted dibenzofurans group；
L is bridge linkage group, is taken selected from singly-bound, the substituted aromatic amines of C4～C40, the substituted carbazole of C4～C40, C4～C40
For indole, C4～C40 substituted diphenylamine and furan, the substituted diphenylamine bithiophene of C4～C40, substituted or unsubstituted diphenyl ether,
One of oxygen atom, nitrogen-atoms or sulphur atom；
R3-R6Independently selected from the aromatic series base of H atom, the acyclic straight of C1～C20 or branched hydrocarbyl or C6～C30
Group, or, two neighboring group connects cyclization, forms benzindole derivant；
Integers of the n selected from 2-5.
Preferably, formula（I）In R1May be selected from methyl, ethyl, propyl group, isopropyl, butyl, normal-butyl, amyl group, second
Any one in base, phenyl, xenyl, naphthyl, anthryl.
Preferably, formula（I）In R2May be selected from the N- aryl carbazole bases of C4～C40, carbazyl aromatic radical, N- alkyl
Carbazyl, carbazyl, alkyl-substituted carbazyl aromatic radical, triarylamine, diaryl-amine base, benzothienyl, dibenzothiophenes
One of benzothienyl, benzofuranyl or dibenzofuran group that base, aromatic radical replace.
First material of main part is containing aromatic amine and quinoline.
Preferably, the general structure of first material of main part（Ⅱ）It is as follows：
Wherein：
Ar1And Ar2The substituted or unsubstituted aromatic group of C6-C40 is respectively and independently selected from, or can connect to form C3-C40
Substituted or unsubstituted fused-aryl.
Preferably, formula（Ⅱ）Described in Ar1And Ar2Be respectively and independently selected from phenyl, xenyl, terphenyl, naphthyl,
Anthryl, phenanthryl, fluoranthene base, benzo anthryl, fluorenyl, pyrenyl, carbazyl, benzo carbazole base, N- phenyl carbazole bases, N- alkyl carbazoles
Base, hexichol amido, benzo triarylamine, 9,9- dimethyl fluorenyls, diphenylethyllene phenyl, benzo fluorenyl, indeno fluorenyl or indenes
Base.
The dyestuff adulterated in organic electroluminescence device luminescent layer be phosphorescent coloring, the triplet state energy of the phosphorescent coloring
Triplet of the level less than the second material of main part.
The shared weight ratio in luminescent layer of second material of main part is 5%-80%, preferably 10%-50%.
In order to become apparent from illustrating present invention, the first material of main part that lower mask body is described in luminescent layer of the present invention is related to
The preferred structure of the compound for arriving：
In order to become apparent from illustrating present invention, the second material of main part that lower mask body is described in luminescent layer of the present invention is related to
The preferred structure of the compound for arriving：
The application also proposed a kind of method for preparing organic electroluminescence device, is included on substrate and is sequentially depositing each other
The anode of stacking, hole transmission layer, luminescent layer, electron transfer layer and negative electrode, then encapsulate, and specifically, emitting layer material is by one
Plant and quinoline is used as the first material of main part, a kind of formula as follows（I）The indole derivativeses of structure are used as the second master
Body material and dopant dye composition, are deposited with hole transmission layer in the way of three sources are steamed altogether, it is preferred that we select phosphorescence
Dyestuff is doped.
Description of the drawings：
In order to present disclosure is more likely to be clearly understood, below according to specific embodiment of the invention and with reference to attached
Figure, the present invention is further detailed explanation, wherein,
Fig. 1 is the structural representation of organic electroluminescence device of the present invention.
Wherein, reference is：
1st, substrate；2nd, anode layer；3rd, hole injection layer；4th, hole transmission layer；5th, luminescent layer；6th, electron transfer layer；7th, electricity
Sub- implanted layer;8th, cathode layer.
Specific embodiment
Unless otherwise indicated, in the present invention, raw materials used, intermediate is commercial goods；In the present invention, mass spectrum adopts ZAB-
HS types mass spectrograph is determined（Micromass companies of Britain manufacture）, elementary analysiss are using vario EL types elemental analyser measure（English
Elementar Analysensysteme GmbH companies of state manufacture）.
Preparation embodiment of the embodiment of the present invention 1 for the intermediate M1
Embodiment 1
The present embodiment is to prepare intermediate formula M1：
List of references（Angew.Chem.Int.Ed.Engl., 1987,26,460.）Middle method synthesizes the 4,9- dichloros of M1
And quinoline midbody.
Its synthetic route is as follows：
Embodiment 2- embodiment 11 is the embodiment of prepare compound S1-S10.
Embodiment 2
The synthesis of compound S1, synthetic route are as follows：
Under Ar gas shieldeds, diphenylamines 4.04g is added in 100ml reaction bulbs（Molecular weight 169,0.024mol）, it is anhydrous
THF40ml, is cooled to 0 DEG C, by the n-BuLi of 11ml（2.4M, 0.026mol）It is slowly added thereto.30min is stirred at room temperature,
Its colour changed into yellow.At 0 DEG C, by the solution with 30 minutes, S13.0g is slowly added（Molecular weight 299.15,0.01mol）'s
In 50mlTHF solution, stir 4 hours at 35 DEG C, stir 8 hours in 500C, cooling, mixture is poured in water, with 50ml bis-
Chloromethanes are extracted, and organic faciess are dried with anhydrous MgSO4, and organic faciess are evaporated, the solid pillar layer separation for obtaining, and obtain 4.0g yellow
Color solid, molecular weight 565, yield 70%.
Product MS（m/e）：565, elementary analysiss（C40H28N4）：Theoretical value C：85.08%, H：5.00%, N：9.92%；It is real
Measured value C：85.00%, H：5.06%, N：9.94%.
Embodiment 3
The synthesis of compound S2, synthetic route are as follows：
Under Ar gas shieldeds, 5.11g NaH（Content 55%, 0.117mol）In 90mlDMF, Deca carbazole 16.7g（Point
Son amount 167,0.1mol）The solution being dissolved in dry DMF 90ml, 20 minutes used times, stirs 1 hour, then by S113.46g（Point
Son amount 299.15,0.045mol）（Molecular weight 299.15,0.045mol）The solution being dissolved in 90mlDMF, adds which with 20min
In, to stir 3 hours, be poured in water 500ml, filter precipitation, vacuum drying, product silica column purification obtain 20.2g targets point
Son（0.036mol）, molecular weight 561, yield 75%.
Product MS（m/e）：561, elementary analysiss（C40H24N4）：Theoretical value C：85.69%, H：4.31%, N：9.99%；It is real
Measured value C：85.60%, H：4.34%, N：10.05%.
Embodiment 4
The synthesis of compound S3, synthetic route are as follows：
The first step：The synthesis of S3-1
Under nitrogen protection, 25.7g is added in 500ml three neck round bottom flask（0.1mol）9- bromine anthracenes, 10.3g
（0.11mol）Aniline, 0.57g（1.0mol%）Pd(dba)2,2.0ml（1.0mol%）P(t-Bu)310% cyclohexane solution and
19.2g (0.2mol) NaO (t-Bu), is subsequently adding the toluene of 250ml Jing Non-aqueous processings, obtains reactant liquor.By above-mentioned reactant liquor
110 DEG C of oil baths under magnetic stirring flow back 2h, cooling, reactant liquor are carried out a point liquid Jing after appropriate water washing 2-3 time then, by institute
Obtain the anhydrous MgSO of organic faciess4After drying, rotary evaporation removes organic solvent and obtains crude product.By crude on silica gel（200-
300 mesh, Haiyang Chemical Plant, Qingdao）Pillar layer separation obtains product 22.1g, yield 81.6%.
Second step：Implementation process simply changes diphenylamines into S3-1 with embodiment 2, synthesizes product.
Product MS（m/e）：765, elementary analysiss（C56H36N4）：Theoretical value C：87.93%, H：4.74%, N：7.32%；It is real
Measured value C：88.01%, H：4.76%, N：7.38%.
Embodiment 5
The synthesis of compound S4, synthetic route are as follows：
The first step：The synthesis of S4-1
Synthesis of the method with S3-1, simply changes 9- bromine anthracenes into 1- bromo- 3,5 diphenyl benzenes, and pillar layer separation obtains white product
Thing 22.6g, yield 70.3%.
Second step：Implementation process simply changes diphenylamines into S4-1 with embodiment 2, synthesizes product.
Product MS（m/e）：869, elementary analysiss（C64H44N4）：Theoretical value C：88.45%, H：5.10%, N：6.45%；It is real
Measured value C：88.37%, H：5.12%, N：6.51%.
Embodiment 6
The synthesis of compound S5, synthetic route are as follows：
The first step：The synthesis of S5-1
Synthesis of the method with S3-1, simply changes 9- bromine anthracenes into 9- (4- bromophenyls) carbazole, and pillar layer separation obtains white product
Thing.
Second step：Implementation process simply changes diphenylamines into S5-1 with embodiment 2, synthesizes product.
Product MS（m/e）：895, elementary analysiss（C64H42N6）：Theoretical value C：85.88%, H：4.73%, N：9.39%；
Measured value C：85.76%, H：4.76%, N：9.47%.
Embodiment 7
The synthesis of compound s 6, synthetic route are as follows：
The first step：The synthesis of S6-1
Synthesis of the method with S3-1, simply changes 9- bromine anthracenes into 9- (4- bromophenyls) carbazole, and aniline changes 9- (4- aminobenzenes into
Base) carbazole, pillar layer separation obtains white product.
Second step：Implementation process simply changes diphenylamines into S6-1 with embodiment 2, synthesizes product.
Product MS（m/e）：1225, elementary analysiss（C88H56N8）：Theoretical value C：86.25%, H：4.61%, N：
9.14%；Measured value C：86.15%, H：4.66%, N：9.19%.
Embodiment 8
The synthesis of compound S7, synthetic route are as follows：
The first step：The synthesis of S7-1
Synthesis of the method with S3-1, simply changes 3,5- dimethylanilines, bromobenzene into aniline, 3- bromine fluoranthene, post color respectively
Spectrum separates to obtain white product 24.0g, yield 81.8%.
Second step：Implementation process simply changes diphenylamines into S7-1 with embodiment 2, synthesizes product.
Product MS（m/e）：813, elementary analysiss（C60H36N4）：Theoretical value C：88.64%, H：4.46%, N：6.89%；It is real
Measured value C：88.51%, H：4.56%, N：6.92%.
Embodiment 9
The synthesis of compound S8, synthetic route are as follows：
The first step：The synthesis of S8-1
Synthesis of the method with S3-1, simply changes 3,5- dimethylanilines, bromobenzene into aniline, 4- bromine triphenylamines, post respectively
Chromatographic isolation obtains white product 24.2g, yield 71.9%.
Second step：Implementation process simply changes diphenylamines into S8-1 with embodiment 2, synthesizes product.
Product MS（m/e）：899, elementary analysiss（C64H46N6）：Theoretical value C：85.50%, H：5.16%, N：9.35%；It is real
Measured value C：85.30%, H：5.26%, N：9.45%.
Embodiment 10
The synthesis of compound S9, synthetic route are as follows：
The first step：The synthesis of S9-1
Synthesis of the method with S3-1, simply changes 3,5- dimethylanilines, bromobenzene into aniline, N- phenyl-N (1- naphthalenes respectively
Base) -4- bromanilines, pillar layer separation obtains white product 24.4g, yield 65.3%.
Second step：Implementation process simply changes diphenylamines into S9-1 with embodiment 2, synthesizes product.
Product MS（m/e）：1101, elementary analysiss（C80H56N6）：Theoretical value C：87.24%, H：5.13%, N：7.63%；
Measured value C：87.04%, H：5.25%, N：7.71%.
Embodiment 11
The synthesis of compound S10, synthetic route are as follows：
The first step：The synthesis of S10-1
Synthesis of the method with S3-1, simply by 3,5- dimethylanilines, bromobenzene change into respectively aniline, 2- (4- bromophenyls)-
1，1-diphenylethylene, pillar layer separation obtain white product 22.6g, yield 64.0%.
Second step：Implementation process simply changes diphenylamines into S10-1 with embodiment 2, synthesizes product.
Product MS（m/e）：923, elementary analysiss（C68H50N4）：Theoretical value C：88.47%, H：5.46%, N：6.07%；It is real
Measured value C：88.66%, H：5.55%, N：6.17%.
Device Application Example：
Embodiment 12
A kind of organic electroluminescence device, including anode layer 2, organic function layer and cathode layer 8, specifically, in device
Organic function layer, including luminescent layer 5, electron transfer layer 6, can also include the functional layers such as hole transmission layer 4.
Fig. 1 is the structural representation of the organic electroluminescence device of the present invention, and the organic electroluminescence device includes base
Plate 1, anode layer 2, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, cathode layer 8.
The substrate 1 is transparent base, can be glass substrate or flexible base board, and flexible base board is using polyesters, poly-
A kind of material in imide analog compounds, substrate 1 carry anode layer 2 above.The present invention uses glass substrate.
The anode layer 2 can adopt inorganic material or organic conductive polymer, inorganic material to be generally tin indium oxide
（ITO）, Zinc Oxide, the higher metal of the work function such as metal-oxide or gold, copper, silver such as zinc tin oxide, optimized selection is
ITO, organic conductive polymer are preferably polythiophene/polyvinylbenzenesulfonic acid sodium（Hereinafter referred to as PEDOT:PSS）, polyaniline（With
Lower abbreviation PANI）In a kind of material.Preferably ITO of the invention（Tin indium oxide）Do anode material.
The cathode layer 8 typically using the relatively low metals of work function such as lithium, magnesium, calcium, strontium, aluminum, indium or they with copper, gold,
The alloy of silver, or the electrode layer that metal and metal fluoride are alternatively formed, e.g., Mg successively:Ag alloy-layers and Ag layers, successively
Lithium fluoride or nitridation lithium layer and Ag layers, lithium fluoride successively or nitridation lithium layer and Al layers, select aluminum in the present invention.
The application luminescent layer 5 includes dopant dye, and dopant dye is phosphorescent coloring, and the phosphorescent coloring uses Ir
(ppy)3Or Ir (piq)3。
The electron transfer layer（ETL）6 can adopt Alq3, it would however also be possible to employ TPBI.
The hole transmission layer（HTL）4 materials for using generally arylamine class and branch polymer same clan low molecule material, such as N,
N '-two-（1- naphthyls）- N, N '-diphenyl -1,1- xenyl -4,4- diamidogen（NPB）, N, N '-diphenyl-N, N '-bis-（Between first
Base phenyl）- 1,1 '-xenyl -4,4 '-diamidogen（TPD）Deng, the present invention 4 material therefor of hole transmission layer select NPB（N,N'-
Two (naphthalene -2- bases)-N, N'- bis- (phenyl) biphenyl -4,4'- diamidogen）.
The structural formula of the chemical substance mentioned in embodiment in the present invention is as follows：
Particularly, a kind of organic function layer of organic electroluminescence device, can also include that electron injecting layer 7 and hole are noted
Enter layer 3.
Some embodiments, specific explanations technical scheme is presented below.It should be noted that the following examples
It is only used for help and understands invention, rather than limitation of the present invention.
Embodiment 13
It is below device Application Example of the present invention
In the present embodiment structure adopted by organic electroluminescence device for：
Substrate/anode/hole transmission layer（HTL）/ organic luminous layer（EL）/ electron transfer layer (ETL)/negative electrode
The preparation method of the organic electroluminescence device of the present invention is as follows：
（1）Process substrate 1
The glass plate of the transparent conductive layer supersound process in commercial detergent will be coated with, be rinsed in deionized water,
In acetone：Alcohol mixed solvent（Volume ratio 1：1）Middle ultrasonic oil removing, is baked under clean environment and completely removes moisture content, then
With ultraviolet light and ozone clean, and with mental retardation cation beam bombarded surface, so that glass plate carries anode layer 2；
（2）Evaporation organic luminescence function layer
The above-mentioned glass substrate with anode 2 is placed in vacuum intracavity, 1 × 10 is evacuated to-6To 2 × 10-4Pa, upper
, used as hole transmission layer 4, evaporation rate is 0.1nm/s to state vacuum evaporation NPB on anode tunic, and evaporation thickness is 40nm；
In hole transmission layer（HTL）Luminescent layer 5 is deposited with 4, luminescent layer 5 is by the first material of main part and the second material of main part
Doping phosphorescent coloring composition.Specifically preparation method is：First material of main part and the of the vacuum evaporation present invention in the way of common steaming
Two material of main parts are deposited with material C BP of the prior art sending out as device as the material of main part in luminescent layer 5 in comparative example
Material of main part in photosphere 5, while co-evaporation phosphorescence luminescent dye Ir (ppy)3Or Ir (piq)3, when luminescent dye selects Ir
(ppy)3When, its doping ratio is the 15% of the first host thickness（Comparative example is then the 15% of CBP thickness）；Work as luminescent dye
From Ir (piq)3When, its doping ratio is the 7% of the first host thickness（Comparative example is then the 7% of CBP thickness）.Second master
The doping content of body material is the 5%-50% of the first host thickness, during evaporation, CBP or the first material of main part evaporation rate
For 0.1nm/s, evaporation total film thickness is 30nm；
Electron transfer layers 6 of the one layer of Bphen of vacuum evaporation for device on the luminescent layer 5, its evaporation rate are 0.1nm/
S, evaporation total film thickness are 20nm；
On electron transfer layer 6, Al layers of the LiF of vacuum evaporation 0.5nm as electron injecting layer and thickness for 150nm is made
For the negative electrode 8 of device.
Method as described above prepares following device, and device embodiments 1-24 is the first material of main part of checking and the
Performance under the collocation of two material of main parts, wherein the doping content of the second material of main part is the 20% of the first main body.
Comparative example 1：
ITO/NPB(40nm)/CBP:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Comparative example 2：
ITO/NPB(40nm)/CBP:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 1：
ITO/NPB(40nm)/S1:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 2：
ITO/NPB(40nm)/S1:20%M5:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 3：
ITO/NPB(40nm)/S2:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 4：
ITO/NPB(40nm)/S2:20%M5:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 5：
ITO/NPB(40nm)/S5:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 6：
ITO/NPB(40nm)/S5:20%M5:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 7：
ITO/NPB(40nm)/S6:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 8：
ITO/NPB(40nm)/S6:20%M5:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 9：
ITO/NPB(40nm)/S8:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 10：
ITO/NPB(40nm)/S8:20%M5:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 11：
ITO/NPB(40nm)/S5:20%M6:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 12：
ITO/NPB(40nm)/S5:20%M8:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 13：
ITO/NPB(40nm)/S5:20%M9:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 14：
ITO/NPB(40nm)/S5:20%M25:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 15：
ITO/NPB(40nm)/S5:20%M39:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 16：
ITO/NPB(40nm)/S5:20%M53:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 17：
ITO/NPB(40nm)/S6:20%M6:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 18：
ITO/NPB(40nm)/S6:20%M9:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 19：
ITO/NPB(40nm)/S6:20%M27:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 20：
ITO/NPB(40nm)/S6:20%M29:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 21：
ITO/NPB(40nm)/S6:20%M46:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 22：
ITO/NPB(40nm)/S6:20%M47:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 23：
ITO/NPB(40nm)/S6:20%M52:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 24：
ITO/NPB(40nm)/S6:20%M53:15%Ir(ppy)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 25：
ITO/NPB(40nm)/S3:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 26：
ITO/NPB(40nm)/S3:20%M6:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 27：
ITO/NPB(40nm)/S4:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 28：
ITO/NPB(40nm)/S4:20%M8:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
Device embodiments 29：
ITO/NPB(40nm)/S7:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Device embodiments 28：
ITO/NPB(40nm)/S7:20%M9:7%Ir(piq)3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al
(150nm)
The device performance data that table 1 is obtained by above device architecture
| Device | Brightness cd/m2 | Voltage V | Current efficiency cd/A | Chromaticity coordinates（X, y） |
| Comparative example 1 | 1000 | 3.9 | 36.2 | （0.301,0.640） |
| Comparative example 2 | 1000 | 5.2 | 3.0 | (0.662,0.321) |
| Device embodiments 1 | 1000 | 3.7 | 38.0 | （0.295,0.643） |
| Device embodiments 2 | 1000 | 3.4 | 40.1 | （0.297,0.644） |
| Device embodiments 3 | 1000 | 3.7 | 38.3 | （0.302,0.648） |
| Device embodiments 4 | 1000 | 3.4 | 40.3 | （0.296,0.647） |
| Device embodiments 5 | 1000 | 3.7 | 37.7 | （0.297,0.644） |
| Device embodiments 6 | 1000 | 3.5 | 39.9 | （0.299,0.641） |
| Device embodiments 7 | 1000 | 3.7 | 38.1 | （0.297,0.642） |
| Device embodiments 8 | 1000 | 3.4 | 40.5 | （0.307,0.654） |
| Device embodiments 9 | 1000 | 3.7 | 38.2 | （0.301,0.648） |
| Device embodiments 10 | 1000 | 3.4 | 40.4 | （0.298,0.642） |
| Device embodiments 11 | 1000 | 3.1 | 43.0 | （0.297,0.641） |
| Device embodiments 12 | 1000 | 3.4 | 40.5 | （0.295,0.648） |
| Device embodiments 13 | 1000 | 3.1 | 43.3 | （0.298,0.647） |
| Device embodiments 14 | 1000 | 3.4 | 40.7 | （0.299,0.649） |
| Device embodiments 15 | 1000 | 3.3 | 40.6 | （0.301,0.648） |
| Device embodiments 16 | 1000 | 3.4 | 40.6 | （0.297,0.644） |
| Device embodiments 17 | 1000 | 3.1 | 42.9 | （0.298,0.654） |
| Device embodiments 18 | 1000 | 3.1 | 43.0 | （0.299,0.647） |
| Device embodiments 19 | 1000 | 3.4 | 41.6 | （0.302,0.648） |
| Device embodiments 20 | 1000 | 3.3 | 41.4 | （0.303,0.644） |
| Device embodiments 21 | 1000 | 3.3 | 42.0 | （0.304,0.648） |
| Device embodiments 22 | 1000 | 3.3 | 42.1 | （0.298,0.645） |
| Device embodiments 23 | 1000 | 3.2 | 42.0 | （0.299,0.646） |
| Device embodiments 24 | 1000 | 3.2 | 42.1 | （0.295,0.641） |
| Device embodiments 25 | 1000 | 5.0 | 3.5 | (0.661,0.327) |
| Device embodiments 26 | 1000 | 4.7 | 4.0 | (0.662,0.326) |
| Device embodiments 27 | 1000 | 5.0 | 3.6 | (0.663,0.327) |
| Device embodiments 28 | 1000 | 4.6 | 4.2 | (0.662,0.324) |
| Device embodiments 29 | 1000 | 5.0 | 3.6 | (0.663,0.328) |
| Device embodiments 30 | 1000 | 4.7 | 4.1 | (0.664,0.325) |
Device embodiments 1-24 of the present invention is compared with comparative example 1, while device embodiments 25-30 is adopted compared with comparative example 2
The green glow or red device prepared with the present invention obtains the higher current efficiency of hinge structure, while effectively reducing
Driving voltage, this is that have bipolarity due to first main body of the present invention, can make the preferably injection and compound of hole and electronics,
The accumulation of hole and electronics is reduced, while the second main body is cavity type again, this further balances the note in electronics and hole
Enter quantity, also reduce the potential barrier between HTL and EML, expand recombination region, so as to reduce voltage, improve efficiency and
Life-span.
Claims (12)
1. a kind of organic electroluminescence device, comprising a pair of electrodes and the luminescent layer being arranged between the electrode pair, and this
Photosphere includes the first material of main part, the second material of main part and dopant dye, wherein：
A () first material of main part is a kind of and quinoline；
B () second material of main part is a kind of indole derivativeses with logical formula (I) structure as follows,
Wherein：
R1One of aromatic group of acyclic straight or branched hydrocarbyl or C6～C30 selected from C1～C20；
R2Substituted or non-substituted arylamine group, the substituted or non-substituted carbazole group of C4～C40, C4 selected from C4～C40～
The substituted or non-substituted dibenzothiophenes group of C40, the substituted or non-substituted indolyl radical of C4～C40, C4～C40 take
One of generation or non-substituted dibenzofurans group；
L is bridge linkage group, selected from singly-bound, the substituted aromatic amines of C4～C40, the substituted carbazole of C4～C40, C4～C40 replacement Yin
Diindyl, the substituted diphenylamine of C4～C40 furan, the substituted diphenylamine bithiophene of C4～C40, substituted or unsubstituted diphenyl ether, oxygen original
One of son, nitrogen-atoms or sulphur atom；
R3-R6Independently selected from the aromatic group of H atom, the acyclic straight of C1～C20 or branched hydrocarbyl or C6～C30, or
Person, two neighboring group connect cyclization, form benzindole derivant；
Integers of the n selected from 2-5.
2. organic electroluminescence device according to claim 1, it is characterised in that the R1Selected from methyl, ethyl, propyl group,
Isopropyl, butyl, normal-butyl, amyl group, phenyl, xenyl, naphthyl, anthryl；
The R2N- aryl carbazole bases, carbazyl aromatic radical selected from C4～C40, N- alkyl carbazole bases, carbazyl, alkyl take
The benzo thiophene that the carbazyl aromatic radical in generation, triarylamine, diaryl-amine base, benzothienyl, dibenzothiophenes base, aromatic radical replace
One of fen base, benzofuranyl or dibenzofuran group.
3. organic electroluminescence device according to claim 1, it is characterised in that first material of main part is containing fragrance
The simultaneously quinoline of race's amine.
4. organic electroluminescence device according to claim 3, it is characterised in that the structure of first material of main part is led to
Formula II is as follows：
Wherein：
Ar1And Ar2The substituted or unsubstituted aromatic group of C6-C40 is respectively and independently selected from, or can be connected and to be formed taking for C3-C40
Generation or unsubstituted fused-aryl.
5. organic electroluminescence device according to claim 4, it is characterised in that the Ar1And Ar2It is respectively and independently selected from
Phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthene base, benzo anthryl, fluorenyl, pyrenyl, carbazyl, benzo carbazole
Base, N- phenyl carbazole bases, N- alkyl carbazole bases, hexichol amido, benzo triarylamine, 9,9- dimethyl fluorenyls, diphenylethyllene
Phenyl, benzo fluorenyl, indeno fluorenyl or indenyl.
6. organic electroluminescence device according to claim 1, it is characterised in that the dopant dye is phosphorescent coloring.
7. organic electroluminescence device according to claim 6, it is characterised in that the triplet of the phosphorescent coloring
Less than the triplet of the second material of main part.
8. organic electroluminescence device according to claim 1, it is characterised in that second material of main part is in luminescent layer
In shared weight ratio be 5%-80%.
9. organic electroluminescence device according to claim 8, it is characterised in that second material of main part is in luminescent layer
In shared weight ratio be 10%-50%.
10. organic electroluminescence device according to claim 4, it is characterised in that the first main body in the luminescent layer
The structural formula of material is selected from following formula：
11. organic electroluminescence devices according to claim 1, it is characterised in that the second main body in the luminescent layer
Material is selected from following compounds：
A kind of 12. methods for preparing organic electroluminescence device, are included on substrate and are sequentially depositing anode, the hole being stacked on one another
Transport layer, luminescent layer, electron transfer layer and negative electrode, then encapsulate, it is characterised in that：Luminescent layer is made by a kind of and quinoline
Be the first material of main part, a kind of indole derivativeses of logical formula (I) structure as follows as the second material of main part and doping dye
Material composition；
Wherein：
R1One of aromatic group of acyclic straight or branched hydrocarbyl or C6～C30 selected from C1～C20；
R2Substituted or non-substituted arylamine group, the substituted or non-substituted carbazole group of C4～C40, C4 selected from C4～C40～
The substituted or non-substituted dibenzothiophenes group of C40, the substituted or non-substituted indolyl radical of C4～C40, C4～C40 take
One of generation or non-substituted dibenzofurans group；
L is bridge linkage group, selected from singly-bound, the substituted aromatic amines of C4～C40, the substituted carbazole of C4～C40, C4～C40 replacement Yin
Diindyl, the substituted diphenylamine of C4～C40 furan, the substituted diphenylamine bithiophene of C4～C40, substituted or unsubstituted diphenyl ether, oxygen original
One of son, nitrogen-atoms or sulphur atom；
R3-R6Independently selected from the aromatic group of H atom, the acyclic straight of C1～C20 or branched hydrocarbyl or C6～C30, or
Person, two neighboring group connect cyclization, form benzindole derivant；
Integers of the n selected from 2-5.
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