CN103904225B - A kind of organic electroluminescence device with barrier layer - Google Patents
A kind of organic electroluminescence device with barrier layer Download PDFInfo
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- CN103904225B CN103904225B CN201210371943.6A CN201210371943A CN103904225B CN 103904225 B CN103904225 B CN 103904225B CN 201210371943 A CN201210371943 A CN 201210371943A CN 103904225 B CN103904225 B CN 103904225B
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K50/00—Organic light-emitting devices
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Abstract
The present invention relates to a kind of barrier layer and the organic electroluminescence device with this barrier layer, comprise substrate, and be formed on successively anode layer, luminescence unit layer and cathode layer 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, between described fluorescence radiation layer and phosphorescence luminescent layer, is provided with barrier layer. The material of main part of described barrier layer comprises electron transport material and the hole mobile material with identical parent nucleus. Luminescent device of the present invention can be allocated electric transmission efficiency and hole transport efficiency effectively, and has advantages of that luminous efficiency is high.
Description
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 luminescent layer of organic electroluminescent device OLED mainly adopt full fluorescent material, full phosphor material or fluorescent material andThe mode that phosphor material mixes is made. The material of phosphorescence system can be realized higher luminous efficiency, but due to the longevityOrder short and efficiency low, also not applicable blue phosphorescent material is developed out. Though and colourity and the life-span of full fluorescent materialSo have stronger advantage, but mix the structure using with full phosphor material layer, efficiency is lower. Generally adopt at present blueLook fluorescent material and red green phosphor material are used in conjunction with the luminescent layer as OLED, but due to three lines of red green phosphorescenceState energy level can be delivered to blue luminescence layer, and the transition of fluorescence radiation layer from triplet to singlet energy level byForbid, people increase barrier layer and solve this problem between blue luminescence layer and red green phosphorescence luminescent layer.
The people such as Sun Yiru (YiruSun) are in " singlet of efficient white light parts and triplet excitons management "（《Managementofsingletandtripletexcitonsforefficientwhiteorganiclight-emittingDevices " see 04645 page of " nature (nature) " magazine 440 13 phase of volume of April in 2006) report as Fig. 1 instituteShow luminescent device, comprise substrate, anode (ITO), hole injection layer (2-TNANA), hole transmission layer（NPBLuminescent layer, electron injecting layer (BPhen), negative electrode (LiF/Al), itsIn luminescent layer comprise blue luminescence layer (CBP:BCzVBi (5%)), barrier layer (CBP (6nm)), green phosphorescentLuminescent layer (CBP:Ir (ppy) 3 (5%)), red phosphorescent luminescent layer (CBP:PQIr (4%)), it is at blue luminescence layerAnd between redness and green phosphorescent luminescent layer, increase one deck barrier layer CBP, in order to stop the list in blue luminescence layerLine state energy level transmits to red phosphorescent luminescent layer, thus efficiency, brightness and the life-span of having improved device. Wherein barrier layer makesWith material be CBP, because hole and the electron transport ability of CBP self are fixed, uncontrollable, therebyCause the luminous intensity of luminescent layer to adjust.
CN038207818 discloses a kind ofly to be had the spirobifluorene derivative of following general formula and is represented by following general formula accordinglyRadical anion,
Wherein, K, L, M and N are identical or different, are H or A-C=O independently of one another, and collateral condition is alwaysDo not make K=L=M=N=H, wherein A is aryl, may be selected from and be generally used for the substituent at least R ' of organic chemistryGroup and/or at least one R group, wherein R=aliphatic group replaces. CN2004800212480 discloses one to be hadOrganic electroluminescence devices, comprises anode, negative electrode and at least one emission layer, and described emission layer comprises at least one dopingHave the host material of at least one phosphorescent emitters, be characterised in that between emission layer and negative electrode, add at least one comprise toThe hole blocking layer of the compound of few a kind of following general formula
As preferred scheme, hole blocking layer comprises at least 50% above-claimed cpd, most preferably on 100%State compound 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 in prior art that blue luminescence layer and red green phosphorescence are sent outBetween photosphere, easily there is triplet and do not mate the problem that causes luminous efficiency low, and then provide a kind of for Organic ElectricityThe barrier layer of electroluminescence device;
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 toolThere are electron transport material and the hole mobile material of 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:
Wherein: R1 and R2 are the pyridine radicals phenyl shown in formula ET-11 independent of each other, or formula ET-12, formula ET-13Shown aryl pyridyl;
Described Ar1And Ar2For independent of each other be hydrogen, or be carbon number be 1-20 alkyl, aromatic radical, assorted virtueThe groups such as base, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,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:
Wherein: the natural number that n is 1 ~ 4, A is sub-benzo shown in formula HTL-11 [c] phenanthrene-5,8-base;Described Ar5And Ar6Independent of each other is hydrogen, the alkyl that carbon number is 1-20, aromatic radical, the bases such as heteroarylGroup, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,Ji ， perylene base,Benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals, or thienyl.
Described electron transport material is spiral shell fluorenes shown in two (9,9 '-spiral shell, two fluorenes-2-yl) ketone, formula ET-4 shown in formula ET-3Shown in pyridine, pyrimidine or pyrrolotriazine derivatives, formula ET-5 that base replaces 5,8-bis--4-(3-pyridine radicals) phenyl benzo [c] phenanthrene:
In its Chinese style ET-4: X, Y, the Z O that is selected from independent of each other, S, N;
Described Ar3And Ar4Independent of each other is hydrogen, the alkyl that carbon number is 1-20, aromatic radical, the bases such as heteroarylGroup, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,Ji ， 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:
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, formula HTL-13Shown in 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 Ar5And Ar6Independent of each other is hydrogen, the alkyl that carbon number is 1-20, aromatic radical, the bases such as heteroarylGroup, preferably cyclohexyl, phenyl, substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl, pyrenyl,Ji ， 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 be formed on successively anode layer on described substrate, severalLuminescence unit layer and cathode layer;
Described luminescence unit layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described skyCave implanted layer is formed on described anode layer, and described hole transmission layer is formed on described hole injection layer, described inElectron transfer layer be formed on described cathode layer, between described hole transmission layer and described electron transfer layer, be manyIndividual luminescent layer, 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 formulaCompound shown in HTL-1 and/or HTL-16:
Described electron transport material in described barrier layer is compound shown in formula ET-3, and described hole mobile material is formulaCompound shown in HTL-2:
Described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the green phosphorescent luminescent layer near blue luminescence layer, and glimmering away from described bluenessLight luminescent 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 glimmering away from described bluenessLight luminescent 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 and the setting that are arranged on described blue luminescence layer one sideAt the red phosphorescent luminescent layer of described blue luminescence layer opposite side;
Between described described blue luminescence layer and described green phosphorescent luminescent layer and red phosphorescent luminescent layer, establish respectivelyBe equipped 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 electron transport material and the hole mobile material with same parent nucleusCarry out co-doped evaporation, as blue luminescence layer and red, the barrier layer between green phosphorescent luminescent layer. Due to toolHave between the electron transport material of identical parent nucleus and hole mobile material and can allocate flexibly this resistance by the mode of dopingThe ability in interlayer transmission electronic and hole, thus prevent that the triplet of phosphorescence is delivered to fluorescence radiation layer, ensureing deviceWhen part 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 canTo stop the singlet energy level in fluorescence coating to transmit to red phosphorescent luminescent layer, be therefore more prone to select blue fluorescent materialWith red, green phosphorescent material. Organic electroluminescent device OLED producer can be according to existing, or be easy to obtainBlue fluorescent material and red, green phosphorescent material, rationally adjust electron transport material and hole mobile material in barrier layerDoping ratio, prepare the high-performance white light parts more approaching with color in kind.
3, no matter adopt after barrier material of the present invention, be that green phosphorescent luminescent layer or red phosphorescent layer are glimmering with bluenessLight luminescent layer is adjacent, can be by the doping ratio of hole transmission layer and electric transmission layer material in adjustment barrier layer, in factExisting good luminous efficiency.
4, as shown in Figure 4, phosphor material is mainly to realize luminously by triplet transition, and fluorescence radiation layer is from threeLine state energy level is forbidden to the transition of singlet energy level. In addition, the singlet exciton life-span is short, is diffused as short-range diffusion,The triplet excitons life-span is long, is diffused as long-range diffusion, so in the time that fluorescence and phosphorescence material is used in conjunction with, adopt the present inventionDescribed barrier layer, can effectively allocate electric transmission efficiency and hole transport efficiency, thereby effectively stop threeLine state exciton transmits to 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 to luminousLayer selectively very strong, the current efficiency of comparative example 1 and comparative example 3 is significantly better than comparative example 2 and comparative example 4, and itsIn just green light luminescent material is changed. For barrier layer of the present invention, the device of embodiment 1 and embodiment 3Performance and CBP are suitable as the device of barrier material, and embodiment 2 and embodiment 4 show to change luminescent layer materialDevice performance is not had to negative effect, and be all better than the level of comparative example 2 and comparative example 4. By above experiment, tableThe novel barrier layer of bright employing electric transmission shaped material and the material doped formation of hole-transporting type, can effectively pass electronicsDefeated efficiency and hole transport efficiency are allocated, thereby make luminescent layer material be easier to select collocation. Fig. 2 shows when luminousHaving there is replacing in layer, uses CBP can cause the luminous intensity of part luminescent layer to reduce as the device of barrier layer, therebyAffect 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. Due toTriplet Excited State is prohibited to the transition spin of ground state, and the triplet state of most of organic molecule swashs in luminous efficiency low, hasThe peak efficiency of organic electroluminescence devices is limited in 25% (for the ideal situation of photoluminescence efficiency 100%). ExamineConsider to luminous efficiency loss and the device inside of solid film and reflect the optical loss causing, the efficiency upper limit of practical devices is largeAbout 5%. The energy of triplet state shifts conventionally need to be flux matched to the energy between body and acceptor, for example, give the luminous of body and be subject toLarge overlapping between the absorption spectrum of body, although easily determine for its energy level of most of fluorescence molecule and energy position,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 gives furtherThe material system of preferred energy coupling has increased great difficulty. And the electron transport material that barrier layer of the present invention adopts accounts for resistanceThe material mixture ratio of interlayer can effectively address this problem.
Brief description of the drawings
For content of the present invention is more easily expressly understood, below according to a particular embodiment of the invention and in conjunction with attachedFigure, 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）。
Detailed description of the invention
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 is formed on successively anode layer (the first electrode on described substrateLayer), several luminescence unit layers and cathode layer (the second electrode lay, metal level), between adjacent described luminescence unit layerThere 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, and inorganic material is generally tin indium oxide, oxidationThe higher metals of work function such as the metal oxide such as zinc, indium zinc oxide or gold, copper, silver, the optimized indium oxide that is chosen asTin (ITO), organic conductive polymer be preferably polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS),A kind of material in polyaniline (hereinafter to be referred as PANI).
Described cathode layer generally adopt metal that the work functions such as lithium, magnesium, calcium, strontium, aluminium, indium are lower, metallic compound orAlloy, the present invention is preferably the active metals such as electron transfer layer Li doped, K, Cs, and this active metal preferably adopts steamingThe method of plating alkali metal compound obtains.
Described luminescence unit layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described skyCave implanted layer is formed on described anode layer, and described hole transmission layer is formed on described hole injection layer, described inElectron transfer layer be formed on described cathode layer, between described hole transmission layer and described electron transfer layer forPhotosphere;
The preferred HAT of host material of described hole injection layer (HIL) or be excellent three (the N-3-methylbenzene of 4,4 materialsBase-N-phenyl-amino)-triphenylamine (m-MTDATA), 4,4TDAT tri-(N-2-naphthyl-N-phenyl-amino)-tri-Phenyl amine (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, excellentElect N as, 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 Alq3, CBP, Bphen, BAlq, also optional from following material:
Described luminescent layer comprises blue luminescence layer, green phosphorescent luminescent layer, red phosphorescent luminescent layer and barrier layer; InstituteBetween the blue luminescence layer of stating and green phosphorescent luminescent layer, be provided with barrier layer, as selectable embodiment, also canBe set to adjacent luminescent layer with blue luminescence layer and red phosphorescent luminescent layer, barrier layer is arranged on described bluenessBetween fluorescence radiation 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)、Btp2Ir(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 Alq3, CBP, Bphen, BAlq, formula (BD-1)Shown in or shown in formula (BD-2):
The material that described barrier layer adopts must meet: there is higher triplet, and as 3eV, and as barrier layerHole mobile material and electron transport material be necessary for same parent nucleus material. In actual practical process, need to be by identical motherThe electron transport material of core and hole mobile material mixing evaporation, as barrier layer. In barrier layer, preferably, electronics passesThe mass ratio of defeated 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:
Wherein ET-1 specifically elects ET-5 as
Wherein Ar1And Ar2For 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, benzophenanthrene, benzo anthryl,Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl, can be also hydrogen, Ar1And Ar2Can be identical, also canWith difference.
Wherein X, Y, the Z O that is selected from independent of each other, S, N, can be identical, also can be different, quantity is 1-3Not etc. Ar3And Ar4For carbon number be 1-20 alkyl, aromatic radical, the groups such as heteroaryl, preferably cyclohexyl, benzeneBase, 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, Ar3And Ar4Can be identical, also canWith difference.
Hole mobile material (formula HTL-10):
The natural number that in base, n is 1-4,
Ar5And Ar6For 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, threePhenylene, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl, can be also hydrogen, Ar3And Ar4Can be identical, also canDifferent.
A is selected from following group (formula HTL-11 is to formula HTL-15):
Preferred hole mobile material is compound shown in formula HTL-1, formula HTL-2 or formula HTL-16:
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,The A of hole mobile material shown in the formula HTL-10 being used in conjunction with described electron transport material in being is selected from formulaHTL-11; The electron transport material using when barrier layer is during suc as formula compound shown in ET-3 or formula ET-4, with described electricityThe A of hole mobile material shown in the formula HTL-10 that sub-transferring material is used in conjunction with 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 shellTwo fluorenes-2, shown in 2 '-Ji or formula HTL-15 9,9 '-spiral shell, two fluorenes-2,7-base. Especially, the electricity that barrier layer of the present invention usesSub-transferring material can be also the mixed of one or more in material shown in formula ET-1, formula ET-2, formula ET-3, formula ET-4Compound, 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:
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 downThe embodiment of face only understands invention for helping, instead of 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, skyCave implanted layer 30, hole transmission layer 40, red phosphorescent luminescent layer 50, green phosphorescent luminescent layer 60, barrier layer 70, indigo plantLook fluorescence radiation layer 80, electron transfer layer 90, cathode layer 100.
Preparation method is as follows for this organic light-emitting device:
1. utilize the ultrasonic method of ultrasonic detergent and deionized water etching to be fixed well to the ito glass substrate of figureClean, and be placed under infrared lamp and dry.
2. the above-mentioned glass substrate of handling well is placed in vacuum chamber, is evacuated to 1 × 10-5Pa, at above-mentioned anode tunicUpper continuation evaporation hole injection layer (2-TNATA), this layer of rate of film build is 0.1nm/s, 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 is luminous more thereonLayer (CBP:Ir (ppy)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, electronicsTransferring 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:
6. evaporation blue luminescence layer (CBP:BczVBi) on barrier layer, evaporation speed is 0.1nm/s, total film thickness is20nm。
7. evaporation electron transfer layer (BPhen) on blue luminescence layer, evaporation speed is 0.1nm/s, total film thickness is30nm。
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,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 green phosphorescent is luminousThe evaporation order of layer 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 be exactly the electron transport material that uses of step barrier layer be 5. formula ET-3Shown in, hole mobile material is shown in formula HTL-2, and described hole mobile material accounts for the 30wt% of barrier layer, electricitySub-transferring material accounts for and intercepts 70wt%.
Embodiment 6
Organic electroluminescence device structure:
ITO/2-TNATA(60nm)/NPB(20nm)/EML-R/EMLG-2/Spacer(10nm)/EML-B/BPhen(30n m)/LiF(3nm)/Al(150nm)
Preparation method is with embodiment 5, and difference is exactly that step green phosphorescent luminescent layer material is 4. changed. AndDescribed hole mobile material accounts for the 50wt% of barrier layer, and 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 green phosphorescent is luminousThe evaporation order of layer is exchanged with red phosphorescent luminescent layer. And described hole mobile material accounts for the 40wt% of barrier layer, electronicsTransferring 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. AndDescribed hole mobile material accounts for the 70wt% of barrier layer, and electron transport material accounts for and intercepts 30wt%.
Table 1
Can find out by the contrast of above embodiment and comparative example, when CBP is during as barrier layer, its choosing to luminescent layerSelecting property is very strong, and the current efficiency of comparative example 1 and comparative example 3 is significantly better than comparative example 2 and comparative example 4, and is whereinGreen light luminescent material is changed. For novel barrier layer, device performance and the CBP of embodiment 1 and embodiment 3Device as barrier material is suitable, and embodiment 2 and embodiment 4 show to change luminescent layer material device performance is not hadThere is negative effect, and be all better than the level of comparative example 2 and comparative example 4. By above experiment, show to adopt electronics to passThe novel barrier layer of defeated shaped material and the material doped formation of hole-transporting type, can be effectively to electric transmission efficiency and holeEfficiency of transmission is allocated, thereby makes luminescent layer material be easier to select collocation. Fig. 2 shows that replacing has occurred to work as luminescent layer,Use CBP can cause the luminous intensity of part luminescent layer to reduce as the device of barrier layer, thereby affected the whole of deviceBody luminous efficiency.
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 materialShown in formula ET-5, and described hole mobile material accounts for the 10wt% of barrier layer, and 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; Described green phosphorusThe thickness of light luminescent layer is: 15nm; The thickness of described red phosphorescent luminescent layer is: 25nm.
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, electric transmission materialMaterial is for shown in formula ET-14, and described hole mobile material accounts for the 40wt% of barrier layer, and electron transport material accounts for obstruct60wt%. The thickness of described barrier layer is 1nm; The thickness of described blue luminescence layer is: 25nm; Described greenThe thickness of phosphorescence luminescent layer is: 40nm; The thickness of described red phosphorescent luminescent layer is: 15nm.
Embodiment 11
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 be 5. formulaShown in HTL-18, the electron transport material of use is for shown in formula ET-15, and described hole mobile material accounts for barrier layer45wt%, electron transport material account for intercept 55wt%. The thickness of described barrier layer is 15nm; Described blue-fluorescenceThe thickness of luminescent layer is: 40nm; The thickness of described green phosphorescent luminescent layer is: 25nm; Described red phosphorescent luminescent layerThickness be: 10nm.
Embodiment 12
Organic electroluminescence device structure and preparation method are with embodiment 8
Preparation method is with embodiment 8, difference be exactly the hole mobile material that uses of step barrier layer be 5. formulaShown in HTL-19, the electron transport material of use is for shown in formula ET-16, and described hole mobile material accounts for barrier layer60wt%, electron transport material account for intercept 70wt%. The thickness of described barrier layer is 5nm; Described blue-fluorescence is sent outThe thickness of photosphere is: 15nm; The thickness of described green phosphorescent luminescent layer is: 10nm; Described red phosphorescent luminescent layerThickness is: 40nm.
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 electronics of useTransferring material is shown in formula ET-3, and described hole mobile material accounts for the 20wt% of barrier layer, and electron transport material accounts forIntercept 80wt%. The thickness of described barrier layer is 10nm; The thickness of described blue luminescence layer is: 32nm; InstituteThe thickness of stating 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 be 5. formulaShown in HTL-21, the electron transport material of use is for shown in formula ET-3; And described hole mobile material accounts for barrier layer25wt%, electron transport material accounts for and intercepts 75wt%. The thickness of described barrier layer is 18nm; Described blue-fluorescence is sent outThe thickness of photosphere is: 22nm; The thickness of described green phosphorescent luminescent layer is: 37nm; Described red phosphorescent luminescent layerThickness is: 18nm.
Embodiment 15
Organic electroluminescence device structure and preparation method are with embodiment 8
Preparation method is with embodiment 8, difference be exactly the hole mobile material that uses of step barrier layer be 5. formulaShown in HTL-22, the electron transport material of use is for shown in formula ET-3, and described hole mobile material accounts for barrier layer60wt%, electron transport material accounts for and intercepts 70wt%. The thickness of described barrier layer is 6nm; Described blue-fluorescence is sent outThe thickness of photosphere is: 16nm; The thickness of described green phosphorescent luminescent layer is: 29nm; Described red phosphorescent luminescent layerThickness is: 13nm.
Embodiment 16-embodiment 23
The organic electroluminescence device structure of embodiment 16-embodiment 23 and preparation method are respectively with embodiment 5-12, whereinBlue fluorescent material luminescent layer is arranged between described green phosphorescent luminous material layer and red phosphorescent luminous material layer, bluenessBetween fluorescence luminescent material layer and green phosphorescent luminous material layer, be 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 same embodiment respectively5-12。
Embodiment 24
" same to parent nucleus " in the present invention refers to that electron transport material and hole mobile material have identical agent structure, exampleAs: shown in electron transport material as 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 different substituents synthetic material, and this bi-material is " identical parent nucleus "Material
Compound preparation process in the present invention is mainly divided three steps: (1) makes benzene by reactions such as coupling, cyclization, bromos[c] phenanthrene derivative; (2) by coupling reaction, aromatic ring and pyridine ring are coupled together, then become boric acid (OrganicSyntheses2005, Vol.81, p.89); (3) boric acid of gained in 2 is reacted and gets final product to obtain target with gained bromo-derivative in 1Molecule.
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 is two bromo-Benzene [c] luxuriant and rich with fragrance (20, mmol), 4.8 grams of sodium tert-butoxides (50mmol),, vacuum nitrogen filling gas, then add 150 after bulging nitrogenMilliliter toluene and 0.23 gram of two (dibenzalacetone) palladium (0.4mmol, 2%e.q.) and 1.6 milliliters of tri-butyl phosphines10% toluene solution, heating reflux reaction 8 hours, is down to room temperature, slowly adds the watery hydrochloric acid of 50 milliliter 5%, anti-Answer mixture separatory, separate organic layer, anhydrous magnesium sulfate drying, drains solvent, and 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-magnetismSpectrogram (1H) as shown in Figure 8.
(2) preparation of HTL-2:
Get 250 milliliters of there-necked flasks, clean rear dry, add 4.4 gram 9,9-bis-(4-aminophenyl) fluorenes, 14.3 grams of 4-After bromo biphenyl, 7.1 grams of sodium tert-butoxides, 0.14 gram of two (dibenzalacetone) palladium, vacuumize and rush nitrogen, under nitrogen protection,Add again 10% toluene solution of 130 milliliters of toluene, 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, soRear silica gel column chromatography separates, and toluene is eluant, eluent, obtains white-yellowish solid 8.5g, yield 70.3%. Product MS(m/e):956.7, elementary analysis (C73H52N2): 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:
Get 250 milliliters of there-necked flasks, clean rear dry, add 14.1 grams of bigeminy aniline, 7.7 gram of 5,8 two bromo-benzene [c] luxuriant and rich with fragrance(20mmol), two (dibenzalacetone) palladiums (0.4mmol, 2%e.q.) of 4.8 grams of sodium tert-butoxides (50mmol), 0.23 gram,Vacuum nitrogen filling gas, then add 10% toluene solution of 150 milliliters of toluene after bulging nitrogen and 1.6 milliliters of tri-butyl phosphines,Heating reflux reaction 8 hours, is down to room temperature, slowly adds the watery hydrochloric acid of 50 milliliter 5%, reactant mixture separatory, pointFrom organic layer, anhydrous magnesium sulfate drying, drains solvent, and thick product carries out silica gel column chromatography separation, obtains 13 grams of productsProductive rate: 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 10, accompanying drawingShow.
(4) preparation of ET-5:
In the there-necked flask of one 1000 milliliters, add 6.13 grams of 5,8-dibromo benzophenanthrenes, 4-(3-pyridine radicals) phenyl-6.9 grams of boric acid, 1.8 grams of four (triphenylphosphine closes) palladiums, 300 milliliters of toluene, 150 milliliters of absolute ethyl alcohols, the carbon of 2M120 milliliters of acid sodium aqueous solutions. Back flow reaction 2.5 hours under nitrogen protection, stops reaction. After cooling, extract organicThing, evaporates solvent, and the solid obtaining is separated with silica gel column chromatography, the acetic acid second that eluent is 1:3 by volume ratioEster: benzinum, obtains 8.2 grams of faint yellow products, productive rate: 71.16%. MS(m/e): between 535(mass spectrogram, illustrateBook accompanying drawing 5), elementary analysis (C40H26N2): theoretical value C:89.86%, H:4.90%, N:5.24%; Actual measurementValue C:90.15%, H:4.88%, N:5.16%. Nuclear magnetic spectrogram (1H) as shown in Figure 7.
(5) preparation of ET-3:
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 DEG C with, slowly drip 50 milliliters of (2.4M) butyl lithiums, after addingContinue 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 dense saltAcid, stirs separatory, and water extracts with 150 milliliters of ethyl acetate, merges organic phase, uses anhydrous sodium sulfate drying. Evaporate to drynessSolvent 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, stirRoom temperature is dissolved completely. Under room temperature, add 52 grams of PCC hydrochlorides in batches, add rear continuation and stir 20 minutes, soAfter add hot reflux, react 3 hours. After cooling, reactant is crossed to silica gel sand filtration, filtrate evaporate to dryness, gained solid dichloroMethane and ethyl alcohol recrystallization, obtain 38g white solid, yield: 64.6%. MS(m/e): 658.7(mass spectrogram is shown in explanationBook accompanying drawing 6), elementary analysis (C51H30O): theoretical value C:92.98%, H:4.59%, O:2.43%; Actual measurementValue 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 embodiment. RightIn those of ordinary skill in the field, can also make on the basis of the above description other multi-form variationOr variation. Here without also giving exhaustive to all embodiments. And the apparent change of being extended out thusChange or variation still among the protection domain in the invention.
Claims (13)
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;
Described electron transport material is shown in formula ET-10 5, and 8-disubstituted benzenes is [c] phenanthrene derivative also:
Wherein: R1 and R2 are independent of each other is the pyridine radicals phenyl shown in formula ET-11, or formula ET-12, formula ET-13Shown aryl pyridyl;
Ar1And Ar2Independent of each other is hydrogen, or the carbon number alkyl that is 1-20, or aromatic radical or heteroaryl;
Described hole mobile material is triarylamine derivative shown in formula HTL-10:
Wherein: the natural number that n is 1～4, A is sub-benzo shown in formula HTL-11 [c] phenanthrene-5,8-base;
Ar5And Ar6Independent of each other is hydrogen, or the carbon number alkyl that is 1-20, or aromatic radical or heteroaryl.
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. the barrier layer of organic electroluminescence device according to claim 1, is characterized in that:
Described electron transport material is shown in formula ET-5 5,8-bis--4-(3-pyridine radicals) phenyl benzo [c] phenanthrene:
5. the barrier layer of organic electroluminescence device according to claim 1, is characterized in that:
Ar1And Ar2Independent of each other is cyclohexyl, phenyl, and substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl,Pyrenyl,Base, perylene base, benzophenanthrene, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl;
Ar5And Ar6Independent of each other is cyclohexyl, phenyl, and substituted-phenyl, naphthyl, xenyl, phenanthryl, anthryl,Pyrenyl,Base, perylene base, benzo phenanthryl, benzo anthryl, Sanya phenyl, Spirofluorene-based, fluorenyl, pyridine radicals or thienyl.
6. the barrier layer of organic electroluminescence device according to claim 5, is characterized in that:
Described hole mobile material is the triarylamine derivative shown in formula HTL-1 or formula HTL-16:
7. according to the barrier layer of the organic electroluminescence device described in claim 1-6 any one, it is characterized in that:
The thickness of described barrier layer is 1-20nm.
8. an organic electroluminescence device, comprises substrate, and if be formed on successively the anode layer on described substrateA dry luminescence unit layer and cathode layer;
Described luminescence unit layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described skyCave implanted layer is formed on described anode layer, and described hole transmission layer is formed on described hole injection layer, described inCathode layer be formed on described electron transfer layer, between described hole transmission layer and described electron transfer layer, be manyIndividual luminescent layer, 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 barrier layer described in claim 1-7 any one.
9. organic electroluminescence device according to claim 8, 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 formulaCompound shown in HTL-1 and/or HTL-16:
10. organic electroluminescence device according to claim 8, 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 glimmering away from described bluenessLight luminescent 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.
11. organic electroluminescence devices according to claim 8, 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 glimmering away from described bluenessLight luminescent 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.
12. organic electroluminescence devices according to claim 8, is characterized in that:
Described fluorescence radiation layer is blue luminescence layer;
Described phosphorescence luminescent layer comprises the green phosphorescent luminescent layer and the setting that are arranged on described blue luminescence layer one sideAt the red phosphorescent luminescent layer of 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 withDescribed barrier layer.
13. according to the organic electroluminescence device described in claim 10-12 any one, 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.
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| 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 |
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