CN103904225A - Organic light emitting device with barrier layer - Google Patents

Organic light emitting device with barrier layer Download PDF

Info

Publication number
CN103904225A
CN103904225A CN201210371943.6A CN201210371943A CN103904225A CN 103904225 A CN103904225 A CN 103904225A CN 201210371943 A CN201210371943 A CN 201210371943A CN 103904225 A CN103904225 A CN 103904225A
Authority
CN
China
Prior art keywords
layer
barrier layer
formula
luminescent layer
organic electroluminescence
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201210371943.6A
Other languages
Chinese (zh)
Other versions
CN103904225B (en
Inventor
邱勇
段炼
李艳蕊
张嵩
李建仁
张国辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Guan Yeolight Technology Co Ltd
Original Assignee
Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University, Beijing Visionox Technology Co Ltd, Kunshan Visionox Display Co Ltd filed Critical Tsinghua University
Priority to CN201210371943.6A priority Critical patent/CN103904225B/en
Publication of CN103904225A publication Critical patent/CN103904225A/en
Application granted granted Critical
Publication of CN103904225B publication Critical patent/CN103904225B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • 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

Abstract

The invention relates to a barrier layer and an organic light emitting device with a barrier layer. The organic light emitting device comprises a substrate, and an anode layer, a light emitting unit layer and a cathode layer which are sequentially formed on the substrate. The light emitting unit layer includes a hole injection layer, a hole transport layer, light emitting layers and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, the plurality of light emitting layers are arranged between the hole transport layer and the electron transport layer, the light emitting layers include a fluorescent light emitting layer and phosphorescent light emitting layers, and a barrier layer is arranged between the fluorescent light emitting layer and the phosphorescent light emitting layers. The main materials of the barrier layer include an electron transport material and a hole transport material which have the same mother nucleus. The electron transport efficiency and the hole transport efficiency of the organic light emitting device of the invention can be effectively adjusted, and the organic light emitting device has the advantage of high light emitting efficiency.

Description

A kind of organic electroluminescence device with barrier layer
Technical field
The present invention relates to the barrier layer of organic electroluminescence device technical field, particularly a kind of organic electroluminescence device, the invention still further relates to the organic electroluminescence device that is provided with this barrier layer.
Background technology
The mode that the luminescent layer of organic electroluminescent device OLED mainly adopts full fluorescent material, full phosphor material or fluorescent material and phosphor material to mix is made.The material of phosphorescence system can be realized higher luminous efficiency, but because the life-span is short and efficiency is low, also not applicable blue phosphorescent material is developed out.Although and there are stronger advantage in colourity and the life-span of full fluorescent material, mix the structure using with full phosphor material layer, efficiency is lower.At present generally adopt blue fluorescent material and red green phosphor material to be used in conjunction with the luminescent layer as OLED, but because the triplet of red green phosphorescence can be delivered to blue luminescence layer, and fluorescence radiation layer is forbidden from triplet to the transition of singlet energy level, people increase barrier layer and solve this problem between blue luminescence layer and red green phosphorescence luminescent layer.
The people such as Sun Yiru (Yiru Sun) report luminescent device as shown in Figure 1 at " singlet of efficient white light parts and triplet excitons management " (" Management of singlet and triplet excitons for efficient white organic light-emitting devices " is shown in 04645 page of " nature (nature) " magazine 440 13 phase of volume of April in 2006), comprise substrate, anode (ITO), hole injection layer (2-TNANA ), hole transmission layer (NPB
Figure BDA00002215473700012
luminescent layer, electron injecting layer (BPhen
Figure BDA00002215473700013
), negative electrode (LiF/Al
Figure BDA00002215473700014
), luminescent layer wherein comprises blue luminescence layer (CBP:BCzVBi (5%)), barrier layer (CBP (6nm)), green phosphorescent luminescent layer (CBP:Ir (ppy) 3 (5%)), red phosphorescent luminescent layer (CBP:PQIr (4%)), it has increased one deck barrier layer CBP between blue luminescence layer and redness and green phosphorescent luminescent layer, in order to stop singlet energy level in blue luminescence layer to the transmission of red phosphorescent luminescent layer, thus efficiency, brightness and the life-span of having improved device.The material that wherein barrier layer uses is CBP, because hole and the electron transport ability of CBP self are fixed, uncontrollable, thereby causes the luminous intensity of luminescent layer to adjust.
CN038207818 discloses a kind of the have spirobifluorene derivative of following general formula and the radical anion being represented by following general formula accordingly,
Figure BDA00002215473700021
Wherein, K, L, M and N are identical or different, are H or A-C=O independently of one another, collateral condition is never to make K=L=M=N=H, wherein A is aryl, may be selected from and be generally used for the substituent at least R ' group of organic chemistry and/or at least one R group, and wherein R=aliphatic group replaces.CN 2004800212480 discloses a kind of organic electroluminescence device, comprise anode, negative electrode and at least one emission layer, described emission layer comprises at least one host material doped with at least one phosphorescent emitters, is characterised in that and between emission layer and negative electrode, adds at least one to comprise the hole blocking layer of the compound of at least one following general formula
Figure BDA00002215473700022
As preferred scheme, hole blocking layer comprises at least 50% above-claimed cpd, most preferably 100% above-claimed cpd composition.Hole blocking layer is mainly used for blocking hole, cannot play a role for upper state exciton.
Summary of the invention
For this reason, technical problem to be solved by this invention is that in prior art, triplet easily occurring between blue luminescence layer and red green phosphorescence luminescent layer does not mate the problem that causes luminous efficiency low, and then a kind of barrier layer for organic electroluminescence device is provided;
Still a further object of the present invention is to provide a kind of organic electroluminescence device that is provided with above-mentioned barrier layer.
For solving the problems of the technologies described above, the material of main part of the barrier layer of organic electroluminescence device of the present invention comprises electron transport material and the hole mobile material with identical parent nucleus.
Preferably, described electron transport material accounts for the 10wt%-90wt% of barrier layer
Described hole mobile material accounts for the 10wt%-90wt% of barrier layer.
More preferably, described electron transport material accounts for the 30wt%-70wt% of barrier layer
Described hole mobile material accounts for the 30wt%-70wt% of barrier layer.
Described electron transport material is shown in formula ET-10 5, and 8-disubstituted benzenes is [c] phenanthrene derivative also:
Figure BDA00002215473700031
Wherein: R1 and R2 are the pyridine radicals phenyl shown in formula ET-11 independent of each other, or the aryl pyridyl shown in formula ET-12, formula ET-13;
Described Ar 1and Ar 2for independent of each other be hydrogen, or be the carbon number alkyl that is 1-20, aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,
Figure BDA00002215473700032
base, perylene base, benzophenanthrene, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl;
Described hole mobile material is triarylamine derivative shown in formula HTL-10:
Figure BDA00002215473700033
Wherein: the natural number that n is 1 ~ 4, A is sub-benzo shown in formula HTL-11 [c] phenanthrene-5,8-base; Described Ar 5and Ar 6independent of each other is hydrogen, the alkyl that carbon number is 1-20, and aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,
Figure BDA00002215473700034
base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals, or thienyl.
Described electron transport material is shown in formula ET-3 shown in two (9,9 '-spiral shell, two fluorenes-2-yl) ketone, formula ET-4 shown in pyridine, pyrimidine or the pyrrolotriazine derivatives of Spirofluorene-based replacement, formula ET-5 5,8-bis--4-(3-pyridine radicals) phenyl benzo [c] phenanthrene:
Figure BDA00002215473700035
Figure BDA00002215473700041
In its Chinese style ET-4: X, Y, the Z O that is selected from independent of each other, S, N;
Described Ar 3and Ar 4independent of each other is hydrogen, the alkyl that carbon number is 1-20, and aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl, base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals, or thienyl;
Described hole mobile material is triarylamine derivative shown in formula HTL-10:
Figure BDA00002215473700043
Wherein: the natural number that n is 1 ~ 4, A is shown in formula HTL-12 9,9 '-spiral shell, two fluorenes-2,2 ', 7,7 '-Ji, shown in formula HTL-13 9,9 '-spiral shell, two fluorenes-2,2 '-Ji, shown in formula HTL-14 9,9 '-spiral shell, two fluorenes-2, shown in 2 '-Ji or formula HTL-15 9,9 '-spiral shell, two fluorenes-2,7-base;
Described Ar 5and Ar 6independent of each other is hydrogen, the alkyl that carbon number is 1-20, and aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl, base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals, or thienyl.
The thickness of described barrier layer is 1-20nm.
A kind of organic electroluminescence device, comprises substrate, and is formed on successively anode layer, several luminescence unit layer and cathode layers on described substrate;
Described luminescence unit layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described hole injection layer is formed on described anode layer, described hole transmission layer is formed on described hole injection layer, described electron transfer layer is formed on described cathode layer, between described hole transmission layer and described electron transfer layer, be multiple luminescent layers, described luminescent layer comprises fluorescence radiation layer and phosphorescence luminescent layer
Between described fluorescence radiation layer and phosphorescence luminescent layer, be provided with the arbitrary described barrier layer of claim 1-7.
Described electron transport material in described barrier layer is compound shown in formula ET-5, and described hole mobile material is compound shown in formula HTL-1 and/or HTL-16:
Figure BDA00002215473700051
Described electron transport material in described barrier layer is compound shown in formula ET-3, and described hole mobile material is compound shown in formula HTL-2:
Figure BDA00002215473700052
Described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the green phosphorescent luminescent layer near blue luminescence layer, and away from described blue luminescence layer and the red phosphorescent luminescent layer adjacent with described green phosphorescent luminescent layer;
Described barrier layer is arranged between described blue luminescence layer and described green phosphorescent luminescent layer.
Alternatively, described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the red phosphorescent luminescent layer near blue luminescence layer, and away from described blue luminescence layer and the green phosphorescent luminescent layer adjacent with described red phosphorescent luminescent layer;
Described barrier layer is arranged between described blue luminescence layer and described red phosphorescent luminescent layer.
Alternatively, described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the green phosphorescent luminescent layer that is arranged on described blue luminescence layer one side and the red phosphorescent luminescent layer that is arranged on described blue luminescence layer opposite side;
Between described described blue luminescence layer and described green phosphorescent luminescent layer and red phosphorescent luminescent layer, be respectively arranged with described barrier layer.
The thickness of described blue luminescence layer is: 10-40nm;
The thickness of described green phosphorescent luminescent layer is: 10-40nm;
The thickness of described red phosphorescent luminescent layer is: 10-40nm;
The thickness of described barrier layer is 1-20nm.
Technique scheme of the present invention has the following advantages compared to existing technology:
What 1, use due to barrier material of the present invention is that electron transport material and the hole mobile material with same parent nucleus carries out co-doped evaporation, as blue luminescence layer and red, and the barrier layer between green phosphorescent luminescent layer.Owing to thering is the ability that can allocate flexibly this barrier layer transmission electronic and hole by the mode of doping between the electron transport material of identical parent nucleus and hole mobile material, thereby the triplet that prevents phosphorescence is delivered to fluorescence radiation layer, in guaranteeing device luminous efficiency, can control flexibly again the luminous intensity of each luminescent layer.
2, because can effectively preventing the triplet of phosphorescence, barrier layer of the present invention is delivered to fluorescence radiation layer, and can stop singlet energy level in fluorescence coating to the transmission of red phosphorescent luminescent layer, therefore be more prone to select blue fluorescent material and red, green phosphorescent material.Organic electroluminescent device OLED producer can be according to existing, or the blue fluorescent material that is easy to obtain and red, green phosphorescent material, rationally the electron transport material in adjustment barrier layer and the doping ratio of hole mobile material, prepare the high-performance white light parts more approaching with color in kind.
3, adopt after barrier material of the present invention, no matter be that green phosphorescent luminescent layer or red phosphorescent layer are adjacent with blue luminescence layer, can, by the doping ratio of hole transmission layer and electric transmission layer material in adjustment barrier layer, realize good luminous efficiency.
4, as shown in Figure 4, phosphor material is mainly to realize luminously by triplet transition, and fluorescence radiation layer is forbidden from triplet to the transition of singlet energy level.In addition, the singlet exciton life-span is short, be diffused as short-range diffusion, the triplet excitons life-span is long, be diffused as long-range diffusion, so in the time that fluorescence and phosphorescence material fit is used, adopt barrier layer of the present invention, can effectively allocate electric transmission efficiency and hole transport efficiency, thereby effectively stop that triplet excitons is to the transmission of phosphorescence luminescent layer.
5, can find out by embodiment 1-8 and comparative example 1-4 contrast, when CBP is during as barrier layer, it is very strong to the selectivity of luminescent layer, and the current efficiency of comparative example 1 and comparative example 3 is significantly better than comparative example 2 and comparative example 4, and wherein just green light luminescent material is changed.For barrier layer of the present invention, the device performance of embodiment 1 and embodiment 3 and CBP are suitable as the device of barrier material, and embodiment 2 and embodiment 4 show to change luminescent layer material does not have negative effect to device performance, and be all better than the level of comparative example 2 and comparative example 4.By above experiment, show to adopt the novel barrier layer of electric transmission shaped material and the material doped formation of hole-transporting type, can effectively allocate electric transmission efficiency and hole transport efficiency, thereby make luminescent layer material be easier to select collocation.Fig. 2 shows that replacing has occurred to work as luminescent layer, uses CBP can cause the luminous intensity of part luminescent layer to reduce as the device of barrier layer, thereby has affected the whole lighting efficiency of device.
6, by spin statistical theory take into account in advance experimental study, the ratio of triplet state and singlet exciton is 3:1.Because Triplet Excited State is prohibited to the transition spin of ground state, the triplet state of most of organic molecule swashs in luminous efficiency low, and the peak efficiency of organic electroluminescence device is limited in 25% (for the ideal situation of photoluminescence efficiency 100%).Luminous efficiency loss and the device inside of considering solid film reflect the optical loss causing, the efficiency upper limit of practical devices is greatly about 5%.The energy of triplet state shifts conventionally need to be flux matched to the energy between body and acceptor, for example give between the absorption spectrum of luminous and acceptor of body large overlapping, although easily determine for its energy level of most of fluorescence molecule and energy position, but the ground state transition intensity that triplet state phosphorescent molecules is relatively low, the data of its corresponding level of energy are difficult to measure, and this has increased great difficulty to the material system of further preferred energy coupling.And the electron transport material that barrier layer of the present invention adopts accounts for the material mixture ratio of barrier layer and can effectively address this problem.
Accompanying drawing explanation
For content of the present invention is more easily expressly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the luminescent device structural representation of prior art;
Fig. 2 is luminescent device structural representation of the present invention;
Fig. 3 is the structural representation of the luminescent device of the embodiment of the present invention 1;
Fig. 4 is exciton transition schematic diagram;
Fig. 5 is compd E T-5 mass spectrogram in the present invention;
Fig. 6 is compd E T-3 mass spectrogram in the present invention;
Fig. 7 be compd E T-5 in the present invention nuclear magnetic spectrogram ( 1h);
Fig. 8 be compound H TL-1 in the present invention nuclear magnetic spectrogram ( 1h);
Fig. 9 be compd E T-3 in the present invention nuclear magnetic spectrogram ( 1h);
Figure 10 be compound H TL-16 in the present invention nuclear magnetic spectrogram ( 1h).
Embodiment
Below will by specific embodiment, the invention will be further described.
As shown in Figures 2 and 3, be the structural representation of organic electroluminescence device of the present invention.
Described organic electroluminescence device comprises substrate, and be formed on successively anode layer (the first electrode layer), several luminescence unit layers and the cathode layer (the second electrode lay, metal level) on described substrate, between adjacent described luminescence unit layer, there is barrier layer.
Described substrate can be selected glass substrate or flexible substrate, above it with anode.
Described anode layer can adopt inorganic material or organic conductive polymer, inorganic material is generally the higher metals of work function such as the metal oxides such as tin indium oxide, zinc oxide, indium zinc oxide or gold, copper, silver, the optimized tin indium oxide (ITO) that is chosen as, organic conductive polymer is preferably a kind of material in polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS), polyaniline (hereinafter to be referred as PANI).
Described cathode layer generally adopts lower metal, metallic compound or the alloys of work function such as lithium, magnesium, calcium, strontium, aluminium, indium, the present invention is preferably the active metals such as electron transfer layer Li doped, K, Cs, and this active metal preferably adopts the method for evaporation alkali metal compound to obtain.
Described luminescence unit layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described hole injection layer is formed on described anode layer, described hole transmission layer is formed on described hole injection layer, described electron transfer layer is formed on described cathode layer, between described hole transmission layer and described electron transfer layer, is luminescent layer;
The preferred HAT of host material of described hole injection layer (HIL) or be 4,4 materials excellent three (N-3-aminomethyl phenyl-N-phenyl-amino)-triphenylamine (m-MTDATA), 4,4TDAT tri-(N-2-naphthyl-N-phenyl-amino)-triphenylamine (2-TNATA).
The host material of described hole transmission layer (HTL) can adopt the low molecular material of arylamine class and the branch polymer same clan, is preferably N, N matter material two-(1-naphthyl)-N, N material diphenyl-1,11 base xenyl-4,44 base diamines (NPB).
Described electric transmission layer material is selected from Alq 3, CBP, Bphen, BAlq, also optional from following material:
Figure BDA00002215473700081
Figure BDA00002215473700091
Described luminescent layer comprises blue luminescence layer, green phosphorescent luminescent layer, red phosphorescent luminescent layer and barrier layer; Between described blue luminescence layer and green phosphorescent luminescent layer, be provided with barrier layer, as selectable execution mode, also can blue luminescence layer and red phosphorescent luminescent layer be set to adjacent luminescent layer, barrier layer is arranged between described blue luminescence layer and red phosphorescent luminescent layer.Described blue luminescence layer thickness is:
The thickness of described blue luminescence layer is: 10-40nm;
The thickness of described green phosphorescent luminescent layer is: 10-40nm;
The thickness of described red phosphorescent luminescent layer is: 10-40nm.
Wherein the general material adopting of green phosphorescent luminescent layer is:
Ir (ppy) 3, Ir (ppy) 2or Ir (mppy) (acac) 3deng.
The general material adopting of red phosphorescent luminescent layer is:
Ir (piq) 3, Ir (piq) 2(acac), Btp 2ir (acac), Ir (MDQ) 2(acac), Ir (DBQ) 2(acac), Ir (fbi) 2(acac), Ir (2-phq) 3, Ir (2-phq) 2(acac), Ir (bt) 2or PtOEP etc. (acac).
The general material adopting of blue luminescence layer is:
Material of main part is selected from ADN and derivative thereof, and dyestuff is selected from shown in Alq3, CBP, Bphen, BAlq, formula (BD-1) or shown in formula (BD-2):
Figure BDA00002215473700092
The material that described barrier layer adopts must meet: have higher triplet, as 3eV, and be necessary for same parent nucleus material as hole mobile material and the electron transport material of barrier layer.In actual practical process, need to be by the electron transport material of identical parent nucleus and hole mobile material mixing evaporation, as barrier layer.In barrier layer, preferably, the mass ratio of electron transport material and hole mobile material is 3:7-7:3.
The invention provides the barrier material of following several structures.
1, electron transport material is shown below:
Figure BDA00002215473700101
Wherein ET-1 specifically elects ET-5 as
Figure BDA00002215473700102
Wherein Ar 1and Ar 2for the carbon number alkyl that is 1-20, aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,
Figure BDA00002215473700103
base, perylene base, benzophenanthrene, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl, can be also hydrogen, Ar 1and Ar 2can be identical, also can be different.
Figure BDA00002215473700104
Wherein X, Y, the Z O that is selected from independent of each other, S, N, can be identical, also can be different, quantity be 1-3 not etc.Ar 3and Ar 4for the carbon number alkyl that is 1-20, aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl, base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl, can be also hydrogen, Ar 3and Ar 4can be identical, also can be different.
Hole mobile material (formula HTL-10):
Figure BDA00002215473700106
The natural number that in base, n is 1-4,
Ar 5and Ar 6for the carbon number alkyl that is 1-20, aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,
Figure BDA00002215473700111
base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl, can be also hydrogen, Ar 3and Ar 4can be identical, also can be different.
A is selected from following group (formula HTL-11 is to formula HTL-15):
Figure BDA00002215473700112
Preferred hole mobile material is compound shown in formula HTL-1, formula HTL-2 or formula HTL-16:
Figure BDA00002215473700113
It should be noted that, the electron transport material using when barrier layer is during suc as formula compound shown in ET-1 or formula ET-2, and the A of the hole mobile material shown in the formula HTL-10 being used in conjunction with described electron transport material in being is selected from formula HTL-11; The electron transport material using when barrier layer is during suc as formula compound shown in ET-3 or formula ET-4, and the A of the hole mobile material shown in the formula HTL-10 being used in conjunction with described electron transport material in being is selected from shown in formula HTL-12 9,9 '-spiral shell, two fluorenes-2,2 ', 7,7 '-Ji, shown in formula HTL-13 9,9 '-spiral shell, two fluorenes-2,2 '-Ji, shown in formula HTL-14 9,9 '-spiral shell, two fluorenes-2, shown in 2 '-Ji or formula HTL-15 9,9 '-spiral shell, two fluorenes-2,7-base.Especially, the electron transport material that barrier layer of the present invention uses can be also the mixture of one or more in material shown in formula ET-1, formula ET-2, formula ET-3, formula ET-4, and described hole mobile material can be also the mixture of one or more in material shown in formula HTL-10.
The structural formula of the main chemical substance of the present invention is described as follows:
Figure BDA00002215473700121
Figure BDA00002215473700131
To provide some embodiment below, and specific explanations technical scheme of the present invention by reference to the accompanying drawings.It should be noted that the following examples are only for helping understanding invention, rather than limitation of the present invention.
Embodiment 1
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EMLR/EMLG-1/Spacer(10nm)/EML-B/BPhen(30nm)/LiF(3nm)/Al(150nm)
As shown in Figure 3, it is the section of structure of the embodiment of the present invention 1, and it comprises substrate 10, anode layer 20, hole injection layer 30, hole transmission layer 40, red phosphorescent luminescent layer 50, green phosphorescent luminescent layer 60, barrier layer 70, blue luminescence layer 80, electron transfer layer 90, cathode layer 100.
Preparation method is as follows for this organic light-emitting device:
1. the ito glass substrate that utilizes the ultrasonic method of ultrasonic detergent and deionized water to fix well figure to etching cleans, and is placed under infrared lamp and dries.
2. the above-mentioned glass substrate of handling well is placed in vacuum chamber, is evacuated to 1 × 10 -5pa continues evaporation hole injection layer (2-TNATA) on above-mentioned anode tunic, and this layer of rate of film build is 0.1nm/s, and thickness is 60nm.
3. on hole injection layer, evaporation NPB is as hole transmission layer, and evaporation speed is 0.1nm/s, and total film thickness is 20nm.
4. evaporation red phosphorescent luminescent layer (CBP:PQIr) on hole injection layer, and evaporation green phosphorescent luminescent layer (CBP:Ir (ppy) more thereon 3), evaporation speed is controlled at 0.1nm/s, and total film thickness is 20nm.
5. evaporation barrier layer on green phosphorescent luminescent layer, described hole mobile material accounts for the 50wt% of barrier layer, and electron transport material accounts for resistance layer 50wt%, and evaporation speed is 0.1nm/s, and total film thickness is 10nm.
Electron transport material is shown in formula ET-5, and hole mobile material is shown in formula HTL-16:
Figure BDA00002215473700141
6. evaporation blue luminescence layer (CBP:BczVBi) on barrier layer, evaporation speed is 0.1nm/s, total film thickness is 20nm.
7. evaporation electron transfer layer (BPhen) on blue luminescence layer, evaporation speed is 0.1nm/s, total film thickness is 30nm.
8. evaporation electron injecting layer (LiF) on electron transfer layer, evaporation speed is controlled at 0.01nm/s, and thickness is 3nm.
9. on above-mentioned electron injecting layer, continue the cathode layer of evaporating Al layer as device, the evaporation speed of Al layer is 1nm/s, and thickness is 150nm.
Embodiment 2
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-R/EMLG-2/Spacer(10nm)/EML-B/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 1, and difference is exactly that step green phosphorescent luminescent layer material is 4. changed.
Embodiment 3
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-B/Spacer(10nm)/EMLG-1/EMLR/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 1, and difference is exactly that 4. step changes in 6. enforcement afterwards of step, and the evaporation of green phosphorescent luminescent layer order is exchanged with red phosphorescent luminescent layer.
Embodiment 4
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-B/Spacer(10nm)/EMLG-2/EMLR/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 3, and difference is exactly that step green phosphorescent luminescent layer material is 4. changed.
Comparative example 1
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EMLR/EMLG-1/CBP(10nm)/EML-B/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 1, and difference is exactly that step barrier material 5. changes CBP into and is prepared.
Comparative example 2
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EMLR/EMLG-2/CBP(10nm)/EML-B/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 2, and difference is exactly that step barrier material 5. changes CBP into and is prepared.
Comparative example 3
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-B/CBP(10nm)/EMLG-1/EMLR/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 3, and difference is exactly that step barrier material 5. changes CBP into and is prepared.
Comparative example 4
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-B/CBP(10nm)/EMLG-2/EMLR/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 4, and difference is exactly that step barrier material 5. changes CBP into and is prepared.
Embodiment 5
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-R/EMLG-1/Spacer(10nm)/EML-B/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 1, difference is exactly that the electron transport material that uses of barrier layer 5. of step is for shown in formula ET-3, hole mobile material is shown in formula HTL-2, and described hole mobile material accounts for the 30wt% of barrier layer, and electron transport material accounts for and intercepts 70wt%.
Figure BDA00002215473700161
Embodiment 6
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-R/EMLG-2/Spacer(10nm)/EML-B/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 5, and difference is exactly that step green phosphorescent luminescent layer material is 4. changed.And described hole mobile material accounts for the 50wt% of barrier layer, electron transport material accounts for and intercepts 50wt%.
Embodiment 7
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-B/Spacer(10nm)/EMLG-1/EMLR/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 5, and difference is exactly that 4. step changes in 6. enforcement afterwards of step, and the evaporation of green phosphorescent luminescent layer order is exchanged with red phosphorescent luminescent layer.And described hole mobile material accounts for the 40wt% of barrier layer, electron transport material accounts for and intercepts 60wt%.
Embodiment 8
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-B/Spacer(10nm)/EMLG-2/EMLR/BPhen(30nm)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 7, and difference is exactly that step green phosphorescent luminescent layer material is 4. changed.And described hole mobile material accounts for the 70wt% of barrier layer, electron transport material accounts for and intercepts 30wt%.
Table 1
Figure BDA00002215473700171
Can find out by above embodiment and comparative example contrast, when CBP is during as barrier layer, it is very strong to the selectivity of luminescent layer, and the current efficiency of comparative example 1 and comparative example 3 is significantly better than comparative example 2 and comparative example 4, and wherein just green light luminescent material is changed.For novel barrier layer, the device performance of embodiment 1 and embodiment 3 and CBP are suitable as the device of barrier material, and embodiment 2 and embodiment 4 show to change luminescent layer material does not have negative effect to device performance, and be all better than the level of comparative example 2 and comparative example 4.By above experiment, show to adopt the novel barrier layer of electric transmission shaped material and the material doped formation of hole-transporting type, can effectively allocate electric transmission efficiency and hole transport efficiency, thereby make luminescent layer material be easier to select collocation.Fig. 2 shows that replacing has occurred to work as luminescent layer, uses CBP can cause the luminous intensity of part luminescent layer to reduce as the device of barrier layer, thereby has affected the whole lighting efficiency of device.
Embodiment 9
Organic electroluminescence device structure and preparation method are with embodiment 5
Difference be exactly the hole mobile material that uses of barrier layer 5. of step for shown in formula HTL-1, electron transport material is shown in formula ET-5, and described hole mobile material accounts for the 10wt% of barrier layer, electron transport material accounts for and intercepts 90wt%.
The thickness of described barrier layer is 20nm; The thickness of described blue luminescence layer is: 10nm; The thickness of described green phosphorescent luminescent layer is: 15nm; The thickness of described red phosphorescent luminescent layer is: 25nm.
Figure BDA00002215473700181
Embodiment 10
Organic electroluminescence device structure and preparation method are with embodiment 5
Difference be exactly the hole mobile material that uses of barrier layer 5. of step for shown in formula HTL-17, electron transport material is shown in formula ET-14, and described hole mobile material accounts for the 40wt% of barrier layer, electron transport material accounts for and intercepts 60wt%.The thickness of described barrier layer is 1nm; The thickness of described blue luminescence layer is: 25nm; The thickness of described green phosphorescent luminescent layer is: 40nm; The thickness of described red phosphorescent luminescent layer is: 15nm.
Figure BDA00002215473700182
Embodiment 11
Organic electroluminescence device structure and preparation method are with embodiment 6
Preparation method is with embodiment 6, difference is exactly that the hole mobile material that uses of barrier layer 5. of step is for shown in formula HTL-18, the electron transport material using is for shown in formula ET-15, and described hole mobile material accounts for the 45wt% of barrier layer, and electron transport material accounts for and intercepts 55wt%.The thickness of described barrier layer is 15nm; The thickness of described blue luminescence layer is: 40nm; The thickness of described green phosphorescent luminescent layer is: 25nm; The thickness of described red phosphorescent luminescent layer is: 10nm.
Figure BDA00002215473700191
Embodiment 12
Organic electroluminescence device structure and preparation method are with embodiment 8
Preparation method is with embodiment 8, difference is exactly that the hole mobile material that uses of barrier layer 5. of step is for shown in formula HTL-19, the electron transport material using is for shown in formula ET-16, and described hole mobile material accounts for the 60wt% of barrier layer, and electron transport material accounts for and intercepts 70wt%.The thickness of described barrier layer is 5nm; The thickness of described blue luminescence layer is: 15nm; The thickness of described green phosphorescent luminescent layer is: 10nm; The thickness of described red phosphorescent luminescent layer is: 40nm.
Figure BDA00002215473700192
Embodiment 13
Organic electroluminescence device structure and preparation method are with embodiment 5
Difference be exactly the hole mobile material that uses of barrier layer 5. of step for shown in formula HTL-20, the electron transport material of use is for shown in formula ET-3, and described hole mobile material accounts for the 20wt% of barrier layer, electron transport material accounts for and intercepts 80wt%.The thickness of described barrier layer is 10nm; The thickness of described blue luminescence layer is: 32nm; The thickness of described green phosphorescent luminescent layer is: 28nm; The thickness of described red phosphorescent luminescent layer is: 26nm.
Embodiment 14
Organic electroluminescence device structure and preparation method are with embodiment 6
Preparation method is with embodiment 6, difference be exactly the hole mobile material that uses of step barrier layer 5. for shown in formula HTL-21, the electron transport material of use is for shown in formula ET-3; And described hole mobile material accounts for the 25wt% of barrier layer, electron transport material accounts for and intercepts 75wt%.The thickness of described barrier layer is 18nm; The thickness of described blue luminescence layer is: 22nm; The thickness of described green phosphorescent luminescent layer is: 37nm; The thickness of described red phosphorescent luminescent layer is: 18nm.
Figure BDA00002215473700202
Embodiment 15
Organic electroluminescence device structure and preparation method are with embodiment 8
Preparation method is with embodiment 8, difference is exactly that the hole mobile material that uses of barrier layer 5. of step is for shown in formula HTL-22, the electron transport material using is for shown in formula ET-3, and described hole mobile material accounts for the 60wt% of barrier layer, and electron transport material accounts for and intercepts 70wt%.The thickness of described barrier layer is 6nm; The thickness of described blue luminescence layer is: 16nm; The thickness of described green phosphorescent luminescent layer is: 29nm; The thickness of described red phosphorescent luminescent layer is: 13nm.
Figure BDA00002215473700211
Embodiment 16-embodiment 23
The organic electroluminescence device structure of embodiment 16-embodiment 23 and preparation method are respectively with embodiment 5-12, wherein blue fluorescent material luminescent layer is arranged between described green phosphorescent luminous material layer and red phosphorescent luminous material layer, between blue-fluorescence luminescent material layer and green phosphorescent luminous material layer, it is barrier layer, the composition of barrier layer is respectively with embodiment 5-12, between blue-fluorescence luminescent material layer and red phosphorescent luminous material layer, be barrier layer, the composition of barrier layer is respectively with embodiment 5-12.
Embodiment 24
" same to parent nucleus " in the present invention refers to that electron transport material and hole mobile material have identical agent structure, for example: shown in electron transport material shown in formula ET-5 and formula HTL-16, hole mobile material is all based on 5,8-disubstituted benzenes also [c] phenanthrene derivative is body of material, adopt the synthetic material of different substituents, this bi-material is the material of " identical parent nucleus "
Figure BDA00002215473700212
Compound preparation process in the present invention is mainly divided three steps: (1) makes benzene [c] phenanthrene derivative by reactions such as coupling, cyclization, bromos; (2) by coupling reaction, aromatic ring and pyridine ring are coupled together, then become boric acid (Organic Syntheses2005, Vol.81, p.89); (3) boric acid of gained in 2 is reacted and gets final product to obtain target molecule with gained bromo-derivative in 1.
The preparation method of electron transport material of the present invention and hole mobile material is as follows:
(1) preparation of HTL-1:
Get 250 milliliters of there-necked flasks, dry after clean, add 7.4 grams of diphenylamines (44mmol), 7.7 gram 5, 8 two bromo-benzene [c] luxuriant and rich with fragrance (20, mmol), 4.8 grams of sodium tert-butoxides (50mmol), , vacuum nitrogen filling gas, add again 150 milliliters of toluene and 0.23 gram of two (dibenzalacetone) palladium (0.4mmol after bulging nitrogen, 10% toluene solution of 2%e.q.) He 1.6 milliliters of tri-butyl phosphines, heating reflux reaction 8 hours, be down to room temperature, slowly add the watery hydrochloric acid of 50 milliliter 5%, reactant mixture separatory, separate organic layer, anhydrous magnesium sulfate drying, drain solvent, thick product carries out silica gel column chromatography separation, obtain 9.2 grams of products, productive rate: 82%.MS(m/e): 562, elementary analysis (C42H30N2): theoretical value C:89.65%, H:5.37%, N:4.98%; Measured value C:89.60%, H:5.42%, N:4.95%.Nuclear magnetic spectrogram ( 1h) as shown in Figure 8.
(2) preparation of HTL-2:
Figure BDA00002215473700222
Get 250 milliliters of there-necked flasks, dry after clean, add 4.4 gram 9, 9-bis-(4-aminophenyl) fluorenes, 14.3 grams of 4-bromo biphenyls, 7.1 grams of sodium tert-butoxides, after 0.14 gram of two (dibenzalacetone) palladium, vacuumize and rush nitrogen, under nitrogen protection, add again 130 milliliters of toluene, 10% toluene solution of 0.5 milliliter of tri-butyl phosphine, heating reflux reaction 8 hours, be down to room temperature, slowly add the watery hydrochloric acid of 50 milliliter 5%, filter, wash obtained filter residue with water post-drying, then silica gel column chromatography separates, toluene is eluant, eluent, obtain white-yellowish solid 8.5g, yield 70.3%.Product MS(m/e): 956.7, elementary analysis (C 73h 52n 2): theoretical value C:91.60%, H:5.48%, N:2.93%; Measured value C:91.57%, H:5.51%, N:3.10%.
(3) preparation of HTL-16:
Figure BDA00002215473700231
Get 250 milliliters of there-necked flasks, dry after clean, add 14.1 grams of bigeminy aniline, 7.7 gram 5, 8 two bromo-benzene [c] luxuriant and rich with fragrance (20mmol), 4.8 grams of sodium tert-butoxides (50mmol), 0.23 gram of two (dibenzalacetone) palladium (0.4mmol, 2%e.q.), vacuum nitrogen filling gas, add again 10% toluene solution of 150 milliliters of toluene after bulging nitrogen and 1.6 milliliters of tri-butyl phosphines, heating reflux reaction 8 hours, be down to room temperature, slowly add the watery hydrochloric acid of 50 milliliter 5%, reactant mixture separatory, separate organic layer, anhydrous magnesium sulfate drying, drain solvent, thick product carries out silica gel column chromatography separation, obtain 13 grams of productive rates of product: 75%.MS(m/e): 867, elementary analysis (C66H46N2): theoretical value C:91.42%, H:5.35%, N:3.23%; Measured value C:91.66%, H:5.42%, N:3.19%.Nuclear magnetic spectrogram ( 1h) as shown in Figure 10.
(4) preparation of ET-5:
Figure BDA00002215473700232
In the there-necked flask of one 1000 milliliters, add 6.13 grams of 5,8-dibromo benzophenanthrenes, 4-(3-pyridine radicals) 6.9 grams of phenyl-boric acid, 1.8 grams of four (triphenylphosphine closes) palladiums, 300 milliliters of toluene, 150 milliliters of absolute ethyl alcohols, 120 milliliters of the aqueous sodium carbonates of 2M.Back flow reaction 2.5 hours under nitrogen protection, stops reaction.After cooling, extract organic substance, evaporate solvent, the solid obtaining is separated with silica gel column chromatography, the ethyl acetate that eluent is 1:3 by volume ratio: benzinum, obtains 8.2 grams of faint yellow products, productive rate: 71.16%.MS(m/e): Figure of description 5 between 535(mass spectrogram), elementary analysis (C 40h 26n 2): theoretical value C:89.86%, H:4.90%, N:5.24%; Measured value C:90.15%, H:4.88%, N:5.16%.Nuclear magnetic spectrogram ( 1h) as shown in Figure 7.
(5) preparation of ET-3:
Figure BDA00002215473700233
Under nitrogen protection, add successively 49.4 grams of 2-bromines 9 to being equipped with in churned mechanically 3 liters of there-necked flasks, 9 '-spiral shell, two fluorenes, 1300 milliliters of oxolanes; stirring and dissolving; be down to-78 ℃ with, slowly drip 50 milliliters of (2.4M) butyl lithiums, add rear continuation reaction 40 minutes.
Drip 3.7 grams of methyl formates to reactant mixture, naturally rise to room temperature, add 500 ml waters, 20 milliliters of concentrated hydrochloric acids, stir separatory, and water extracts with 150 milliliters of ethyl acetate, merges organic phase, uses anhydrous sodium sulfate drying.Solvent evaporated obtains 41 grams of white solids, the not treated the next step that is directly used in.
In churned mechanically 5 liters of there-necked flasks are housed, add successively 58 grams of upper step intermediates, 3.8 liters of carrene, stir room temperature and dissolve completely.Under room temperature, add 52 grams of PCC hydrochlorides in batches, add rear continuation and stir 20 minutes, then add hot reflux, react 3 hours.After cooling, reactant is crossed to silica gel sand filtration, filtrate evaporate to dryness, carrene and ethyl alcohol recrystallization for gained solid, obtain 38g white solid, yield: 64.6%.MS(m/e): 658.7(mass spectrogram is shown in Figure of description 6), elementary analysis (C 51h 30o): theoretical value C:92.98%, H:4.59%, O:2.43%; Measured value C:92.98%, H:4.59%, O:2.43%.Nuclear magnetic spectrogram ( 1h) as shown in Figure 9.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all execution modes.And the apparent variation of being extended out thus or variation are still among the protection range in the invention.

Claims (15)

1. a barrier layer for organic electroluminescence device, is characterized in that:
The material of main part of described barrier layer comprises electron transport material and the hole mobile material with identical parent nucleus.
2. the barrier layer of organic electroluminescence device according to claim 1, is characterized in that:
Described electron transport material accounts for the 10wt%-90wt% of barrier layer
Described hole mobile material accounts for the 10wt%-90wt% of barrier layer.
3. the barrier layer of organic electroluminescence device according to claim 1, is characterized in that:
Described electron transport material accounts for the 30wt%-70wt% of barrier layer
Described hole mobile material accounts for the 30wt%-70wt% of barrier layer.
4. according to the barrier layer of the arbitrary described organic electroluminescence device of claim 1-3, it is characterized in that:
Described electron transport material is shown in formula ET-10 5, and 8-disubstituted benzenes is [c] phenanthrene derivative also:
Figure FDA00002215473600011
Wherein: R1 and R2 are the pyridine radicals phenyl shown in formula ET-11 independent of each other, or the aryl pyridyl shown in formula ET-12, formula ET-13;
Described Ar 1and Ar 2for independent of each other be hydrogen, or be carbon number be 1-20 alkyl, aromatic radical or heteroaryl;
Described hole mobile material is triarylamine derivative shown in formula HTL-10:
Figure FDA00002215473600012
Wherein: the natural number that n is 1 ~ 4, A is sub-benzo shown in formula HTL-11 [c] phenanthrene-5,8-base;
Described Ar 5and Ar 6independent of each other is hydrogen, the alkyl that carbon number is 1-20, aromatic radical or heteroaryl.
5. according to the barrier layer of the arbitrary described organic electroluminescence device of claim 1-4, it is characterized in that:
Described electron transport material is two (9,9 '-spiral shell, two fluorenes-2-yl) ketone shown in formula ET-3, shown in pyridine, pyrimidine or the pyrrolotriazine derivatives of Spirofluorene-based replacement shown in formula ET-4 or formula ET-5 5, and 8-bis--4-(3-pyridine radicals) phenyl benzo [c] phenanthrene:
Figure FDA00002215473600021
In its Chinese style ET-4: X, Y, the Z O that is selected from independent of each other, S, N;
Described Ar 3and Ar 4independent of each other is hydrogen, the alkyl that carbon number is 1-20, aromatic radical or heteroaryl;
Described hole mobile material is triarylamine derivative shown in formula HTL-10:
Figure FDA00002215473600022
Wherein: the natural number that n is 1 ~ 4, A is shown in formula HTL-12 9,9 '-spiral shell, two fluorenes-2,2 ', 7,7 '-Ji, shown in formula HTL-13 9,9 '-spiral shell, two fluorenes-2,2 '-Ji, shown in formula HTL-14 9,9 '-spiral shell, two fluorenes-2, shown in 2 '-Ji or formula HTL-15 9,9 '-spiral shell, two fluorenes-2,7-base;
Described Ar 5and Ar 6independent of each other is hydrogen, the alkyl that carbon number is 1-20, aromatic radical or heteroaryl.
6. according to the barrier layer of the organic electroluminescence device described in claim 4 or 5, it is characterized in that:
Ar 1and Ar 2for cyclohexyl independent of each other, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,
Figure FDA00002215473600023
base, perylene base, benzophenanthrene, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl;
Ar 5and Ar 6cyclohexyl independent of each other, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,
Figure FDA00002215473600031
base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl.
7. the barrier layer of organic electroluminescence device according to claim 6, is characterized in that:
Described hole mobile material is the triarylamine derivative shown in formula HTL-1, formula HTL-2 or formula HTL-16:
Figure FDA00002215473600032
8. according to the barrier layer of the arbitrary described organic electroluminescence device of claim 1-7, it is characterized in that:
The thickness of described barrier layer is 1-20nm.
9. an organic electroluminescence device, comprises substrate, and is formed on successively anode layer, several luminescence unit layer and cathode layers on described substrate;
Described luminescence unit layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described hole injection layer is formed on described anode layer, described hole transmission layer is formed on described hole injection layer, described cathode layer is formed on described electron transfer layer, between described hole transmission layer and described electron transfer layer, be multiple luminescent layers, described luminescent layer comprises fluorescence radiation layer and phosphorescence luminescent layer
It is characterized in that:
Between described fluorescence radiation layer and phosphorescence luminescent layer, be provided with the arbitrary described barrier layer of claim 1-7.
10. organic electroluminescence device according to claim 9, is characterized in that:
Described electron transport material in described barrier layer is compound shown in formula ET-5, and described hole mobile material is compound shown in formula HTL-1 and/or HTL-16:
Figure FDA00002215473600041
11. organic electroluminescence devices according to claim 9, is characterized in that:
Described electron transport material in described barrier layer is compound shown in formula ET-3, and described hole mobile material is compound shown in formula HTL-2:
Figure FDA00002215473600042
12. according to the organic electroluminescence device described in claim 9-11, it is characterized in that:
Described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the green phosphorescent luminescent layer near blue luminescence layer, and away from described blue luminescence layer and the red phosphorescent luminescent layer adjacent with described green phosphorescent luminescent layer;
Described barrier layer is arranged between described blue luminescence layer and described green phosphorescent luminescent layer.
13. according to the organic electroluminescence device described in claim 9-11, it is characterized in that:
Described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the red phosphorescent luminescent layer near blue luminescence layer, and away from described blue luminescence layer and the green phosphorescent luminescent layer adjacent with described red phosphorescent luminescent layer;
Described barrier layer is arranged between described blue luminescence layer and described red phosphorescent luminescent layer.
14. according to the organic electroluminescence device described in claim 9-11, it is characterized in that:
Described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the green phosphorescent luminescent layer that is arranged on described blue luminescence layer one side and the red phosphorescent luminescent layer that is arranged on described blue luminescence layer opposite side;
Between described blue luminescence layer and described green phosphorescent luminescent layer and red phosphorescent luminescent layer, be respectively arranged with described barrier layer.
15. according to the organic electroluminescence device described in claim 9-14, it is characterized in that:
The thickness of described blue luminescence layer is: 10-40nm;
The thickness of described green phosphorescent luminescent layer is: 10-40nm;
The thickness of described red phosphorescent luminescent layer is: 10-40nm;
The thickness of described barrier layer is 1-20nm.
CN201210371943.6A 2011-12-31 2012-09-29 A kind of organic electroluminescence device with barrier layer Active CN103904225B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210371943.6A CN103904225B (en) 2011-12-31 2012-09-29 A kind of organic electroluminescence device with barrier layer

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN2011104594772 2011-12-31
CN201110459477 2011-12-31
CN201110459477.2 2011-12-31
CN201210371943.6A CN103904225B (en) 2011-12-31 2012-09-29 A kind of organic electroluminescence device with barrier layer

Publications (2)

Publication Number Publication Date
CN103904225A true CN103904225A (en) 2014-07-02
CN103904225B CN103904225B (en) 2016-05-25

Family

ID=50995458

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210371943.6A Active CN103904225B (en) 2011-12-31 2012-09-29 A kind of organic electroluminescence device with barrier layer

Country Status (1)

Country Link
CN (1) CN103904225B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538559A (en) * 2014-12-31 2015-04-22 北京维信诺科技有限公司 Organic electroluminescence device with RGB pixel region
CN109273615A (en) * 2018-09-11 2019-01-25 长春海谱润斯科技有限公司 A kind of organic luminescent device
JP2019029159A (en) * 2017-07-28 2019-02-21 セイコーエプソン株式会社 Light-emitting element, display device and electronic equipment
CN110048006A (en) * 2019-04-24 2019-07-23 上海钥熠电子科技有限公司 A kind of luminescent device of efficient stable and display device comprising it

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1790768A (en) * 2004-12-13 2006-06-21 株式会社丰田自动织机 Organic EL device
CN101055923A (en) * 2006-04-13 2007-10-17 Lg电子株式会社 Organic electroluminescence device and method for fabricating the same
CN101847692A (en) * 2009-03-26 2010-09-29 精工爱普生株式会社 Light-emitting component, light-emitting device, display unit and electronic equipment
WO2011141109A1 (en) * 2010-05-11 2011-11-17 Merck Patent Gmbh Organic electroluminescent devices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1790768A (en) * 2004-12-13 2006-06-21 株式会社丰田自动织机 Organic EL device
CN101055923A (en) * 2006-04-13 2007-10-17 Lg电子株式会社 Organic electroluminescence device and method for fabricating the same
CN101847692A (en) * 2009-03-26 2010-09-29 精工爱普生株式会社 Light-emitting component, light-emitting device, display unit and electronic equipment
WO2011141109A1 (en) * 2010-05-11 2011-11-17 Merck Patent Gmbh Organic electroluminescent devices

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538559A (en) * 2014-12-31 2015-04-22 北京维信诺科技有限公司 Organic electroluminescence device with RGB pixel region
US10693107B2 (en) 2014-12-31 2020-06-23 Beijing Visionox Technology Co., Ltd. Organic electroluminescence device having RGB pixel areas
JP2019029159A (en) * 2017-07-28 2019-02-21 セイコーエプソン株式会社 Light-emitting element, display device and electronic equipment
JP6999876B2 (en) 2017-07-28 2022-01-19 セイコーエプソン株式会社 Light emitting elements, display devices, and electronic devices
CN109273615A (en) * 2018-09-11 2019-01-25 长春海谱润斯科技有限公司 A kind of organic luminescent device
CN109273615B (en) * 2018-09-11 2020-09-25 长春海谱润斯科技有限公司 Organic light-emitting device
CN110048006A (en) * 2019-04-24 2019-07-23 上海钥熠电子科技有限公司 A kind of luminescent device of efficient stable and display device comprising it
CN110048006B (en) * 2019-04-24 2021-06-25 上海钥熠电子科技有限公司 High-efficiency stable light-emitting device and display device comprising same

Also Published As

Publication number Publication date
CN103904225B (en) 2016-05-25

Similar Documents

Publication Publication Date Title
CN103187537B (en) A kind of High-efficient white-light organic electroluminescence device
CN105895810B (en) A kind of thermal activation sensitized phosphorescence organic electroluminescence device
CN108675975A (en) Material for organic electroluminescence device
CN103153998B (en) Material for electronic device
CN106488917A (en) Material for organic electroluminescence device
CN106459747A (en) Compositions for electronic devices
CN112500410B (en) Spiro nitrogen-containing organic luminescent compound, and preparation method and application thereof
CN110799484B (en) Material for electronic devices
CN106831743A (en) A kind of electroluminescent organic material and organic photoelectric device
CN110724132B (en) Compound, display panel and display device
CN113150002B (en) Organic compound and organic electroluminescent device
CN109824671B (en) Quinazoline triazole derivative and application thereof in organic electroluminescence field
CN108276428A (en) Perimidine derivative and application
CN106831745A (en) A kind of electroluminescent organic material and organic photoelectric device
CN101510585A (en) Organic electroluminescence element
CN115745977B (en) Electron transport material, preparation method thereof and organic electroluminescent device
CN106831633A (en) A kind of electroluminescent organic material and organic photoelectric device
CN110078754A (en) Compound, display panel and display device
CN104649956B (en) A kind of fluorenes carbazole derivative and the application in organic electroluminescence device thereof
CN110003258A (en) Compound, display panel and display device
CN111116561B (en) Compound containing condensed ring structure, application thereof and organic electroluminescent device
CN103904225B (en) A kind of organic electroluminescence device with barrier layer
CN113169274A (en) Compounds for electronic devices
CN102503937A (en) Bipolar organic material containing pyridine and carbazole and preparation method and application thereof
CN109400585A (en) Bis- pyridine benzene analog derivative of 1,4- and organic electroluminescence device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20160128

Address after: 065500 Guan County, Hebei Province emerging industry demonstration park

Applicant after: GU'AN YEOLIGHT TECHNOLOGY CO., LTD.

Applicant after: Tsinghua University

Address before: 215300 Kunshan high tech Zone, Jiangsu Province, Feng Feng Road, No. 188, No.

Applicant before: Weixinnuo Display Tech Co., Ltd.

Applicant before: Tsinghua University

Applicant before: Weixinnuo Science and Technology Co., Ltd., Beijing

C14 Grant of patent or utility model
GR01 Patent grant