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:
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,
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 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.
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:
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:
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:
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:
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.
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:
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):
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:
Wherein ET-1 specifically elects ET-5 as
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,
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.
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):
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,
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):
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, 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:
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:
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%.
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
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.
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.
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.
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.
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.
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.
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 "
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:
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:
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:
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:
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.