CN109713142A - Composition and its organic electroluminescence device - Google Patents
Composition and its organic electroluminescence device Download PDFInfo
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- CN109713142A CN109713142A CN201711012308.8A CN201711012308A CN109713142A CN 109713142 A CN109713142 A CN 109713142A CN 201711012308 A CN201711012308 A CN 201711012308A CN 109713142 A CN109713142 A CN 109713142A
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Abstract
The present invention relates to a kind of compositions, and it includes the first electron transport materials and the second electron transport material.First electron transport material and the second electron transport material can be total to the modes such as molten by physical grinding, altogether distillation or solvent and carry out preparatory mixing.The composition of the premix is used as the electron transport layer materials of organic electroluminescence device, it is possible to reduce the use of evaporation source reduces material evaporating temperature, improves device photoelectric and life performance.
Description
Technical field
The present invention relates to a kind of composition and its organic electroluminescence devices.
Background technique
From the 1960s, organic electroluminescent technology and its application are just widely studied and show diversification
Application prospect.Wherein, carrier of the OLED device technology as OLED technology development and application, lead always OLED technology into
Step.Wherein, doctor Deng Qingyun be successfully prepared for the first time within 1987 have many advantages, such as low-voltage, high brightness, low-power consumption amorphous
OLED device, the road for having guided OLED technology to develop and apply.
Based on the studies above, it is the multilayer films device with multiple functional layers that OLED device, which gradually develops, wherein
Hole transmission layer and electron transfer layer close the voltage of device, efficiency, service life etc. respectively as the prevailing transmission channel of carrier
Keyness can have decisive impact.Since the lagging in development of electron transport material is in hole mobile material, electronics is passed
Research and development of defeated material and using being above focusing only in the MOLECULE DESIGN of material.
Compared to traditional Alq3, Bphen etc., although the new materials such as N003 are in the side such as electron mobility, stability of material
Face is improved, but still needs, for the large area volume production stability of OLED, to still remain in such a way that Liq is adulterated
Large effect.
Summary of the invention
The present invention provides a kind of composition, is asked with improving existing electron transport material using what constraint device performance improved
Topic.
For this purpose, it includes the first electron transport materials and the second electron transport material the present invention provides a kind of composition
Mixture,
Wherein the band gap Eg of first electron transport material is greater than 2.5eV, and triplet T1 is greater than 2.0eV；
The electron mobility μ of second electron transport materialeGreater than 1.0*10-5(cm2/ Vs), HOMO is greater than 5.5eV,
LUMO is greater than 2.5eV.
Using broad-band gap, the first electron transport material of high triplet energy level, electron transfer layer can be enhanced, exciton is expanded
Scattered blocking improves the compound and service efficiency of carrier, plays the role of reducing device voltage and improves device efficiency；Gao Qian
The second shifting rate, HOMO/LUMO shallow electron transport material can enhance the electron-transport efficiency of electron transfer layer, reduce current-carrying
Sub (electronics) transmits potential barrier, stops the diffusion in hole, plays the role of reducing device voltage and improves device efficiency.
To in the description of HOMO, LUMO and T1 energy level of material in the present invention, the energy level of " being higher than " or " being greater than " refer to absolutely
It is higher than the energy level of benchmark energy level absolute value to value；To in the description of material Eg (band gap), which is the LUMO energy of material
The difference of grade and HOMO energy level.
Specifically, first electron transport material is selected from general formula (1) compound represented:
Ar1、Ar2、Ar3In at least two groups be selected from 5~30 carbon atoms containing pyridine ring aromatic group, remain
Remaining group is selected from hydrogen atom, the alkyl with 1~30 carbon atom, the aromatic group with 5~30 carbon atoms, has
The nitrogen-containing heterocycle of 5~30 carbon atoms；N is 1 or 2.
Second electron transport material is selected from general formula (2) or general formula (3) compound represented:
X1~X8It is respectively and independently selected from CR ' or N, R ' indicates hydrogen, the alkyl with 1~4 carbon atom, has 6~30
The aromatic group of carbon atom, nitrogen-containing heterocycle group, halogen and/or nitro with 3~30 carbon atoms；Ar4Selected from have 6~
The aromatic group of 30 carbon atoms, or selected from the nitrogen-containing heterocycle group with 3~30 carbon atoms；
Two Ar4It is same or different, as two Ar4When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference.
Ar5、Ar6It is respectively and independently selected from substituted or unsubstituted C6~C20Aryl, substituted or unsubstituted C4~C20It is nitrogenous
Heteroaryl；
The C6~C20Aryl, C4~C20Nitrogenous heteroaryl substituent group be selected from C6~C20Aryl, C4~C20It is nitrogenous
Heteroaryl, C1~C4Alkyl, halogen, nitro, cyano；
Two R are independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano；
Two Ar5It is same or different, as two Ar5When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference；
Two Ar6It is same or different, as two Ar6When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference.
The C6~C20Aryl, C4~C20Heteroaryl can be monocycle, condensed ring or the ring of covalent linkage.
As a kind of preferred embodiment of general formula (3), Ar5Selected from phenyl, xenyl, naphthalene or phenanthryl, Ar6Selected from by C4~
C20Nitrogenous heteroaryl replace phenyl；
As another preferred embodiment of general formula (3), Ar5Selected from by C4~C20Nitrogenous heteroaryl replace phenyl, Ar2
Selected from phenyl, xenyl, naphthalene or phenanthryl；
In general formula (3), the C4~C20Nitrogenous heteroaryl can enumerate
Further, compound shown in above-mentioned general formula (1), the preferably structure of general formula (A-1) and general formula (A-2):
First electron transport material of structure shown in general formula (1) can enumerate the compound of following concrete structure formula:
Second electron transport material of structure shown in general formula (2) can enumerate following particular compound
Second electron transport material of structure shown in general formula (3) can enumerate following particular compound:
As a kind of preferred embodiment of the present composition, the band gap Eg of first electron transport material is greater than
3.0eV, triplet T1 are greater than 2.5eV；The electron mobility μ of second electron transport materialeGreater than 1.0*10-4
(cm2/ Vs), HOMO is greater than 5.7eV, and LUMO is greater than 3.0eV.
According to the material that level-density parameter relationship matched combined object uses, the potential barrier in energy transfer process is effectively reduced；Compared with
Deep T1 energy level and wider band gap can effectively improve the utilization efficiency of exciton, play the work of hole barrier (HB)
With reducing the use of hole blocking layer, fluorescence and phosphorescence system (TADF) can be met simultaneously.
As another preferred embodiment of the present composition, the evaporating temperature and second of first electron transport material
Less than 20 DEG C of the absolute value of the evaporating temperature difference of electron transport material (preferably smaller than 10 DEG C, more preferably less than 5 DEG C), the first electricity
Sub- transmission material and the second electron transport material can by physical grinding, altogether distillation and/or solvent altogether the modes such as molten carry out it is pre-
It is mixed；In special circumstances, the hybrid mode of first electron transport material and the second electron transport material includes that solvent is total to molten, object
Two or three in reason grinding and the three kinds of modes that distil altogether.
As another preferred embodiment of the present composition, the first electron transport material solubility is in 2~9g/
100ml toluene, the second electron transport material solubility in 2~9g/100ml toluene, first electron transport material with
Second electron transport material can be used the total molten mode of solvent and be mixed.As a further preferred solution, institute
The first electron transport material solubility is stated in 2~5g/100ml toluene, the second electron transport material solubility is in 2~5g/
100ml toluene.
The hybrid mode of multiplicity, can satisfy the different electron transport material of physical property and is premixed.First electricity
Sub- transmission material and the mixed proportion of the second electron transport material are 1:100~100:1, and preferred mixed proportion is 1:9~9:
1；Specific mixed proportion can reach higher evaporation rate under lower evaporating temperature, reduce the speed of material thermal decomposition
Rate improves device lifetime.
Invention additionally discloses a kind of organic electroluminescence devices, it includes first electrode, second electrode and are located at the first electricity
Organic layer between pole and second electrode, the organic layer include the mixed of the first electron transport material and the second electron transport material
Object is closed,
Wherein the band gap Eg of first electron transport material is greater than 2.5eV, and triplet T1 is greater than 2.0eV；
The electron mobility μ of second electron transport materialeGreater than 1.0*10-5(cm2/ Vs), HOMO is greater than 5.5eV, and LUMO is greater than
2.5eV。
Preferably, the band gap Eg of first electron transport material is greater than 3.0eV, and triplet T1 is greater than
2.5eV；The electron mobility μ of second electron transport materialeGreater than 1.0*10-4(cm2/ Vs), HOMO is greater than 5.7eV,
LUMO is greater than 3.0eV.
Specifically, in organic electroluminescence device disclosed by the invention, first electron transport material is selected from general formula (1)
Compound represented:
Ar1、Ar2、Ar3In at least there are two group be selected from 5~30 carbon atoms containing pyridine ring aromatic group, remain
Remaining group is selected from hydrogen atom, the alkyl with 1~30 carbon atom, the aromatic group with 5~30 carbon atoms, has
The nitrogen-containing heterocycle of 5~30 carbon atoms；N is 1 or 2.
Second electron transport material is selected from general formula (2), general formula (3) compound represented:
X1~X8It is respectively and independently selected from CR ' or N, R ' indicates hydrogen, the alkyl with 1~4 carbon atom, has 6~30
The aromatic group of carbon atom, nitrogen-containing heterocycle group, halogen and/or nitro with 3~30 carbon atoms；Ar4Selected from have 6~
The aromatic group of 30 carbon atoms, or selected from the nitrogen-containing heterocycle group with 3~30 carbon atoms.
Ar5、Ar6It is respectively and independently selected from substituted or unsubstituted C6~C20Aryl, substituted or unsubstituted C4~C20It is nitrogenous
Heteroaryl；
The C6~C20Aryl, C4~C20Nitrogenous heteroaryl substituent group be selected from C6~C20Aryl, C4~C20It is nitrogenous
Heteroaryl, C1~C4Alkyl, halogen, nitro, cyano；
Two R are independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano；
Two Ar5It is same or different, as two Ar5When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference；
Two Ar6It is same or different, as two Ar6When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference.
In organic electroluminescence device disclosed by the invention, when the evaporating temperature and second of first electron transport material
When the absolute value of the evaporating temperature difference of electron transport material is less than 20 DEG C (preferably smaller than 10 DEG C, more preferably less than 5 DEG C), first
Electron transport material can be total to the modes such as molten by physical grinding, altogether distillation and/or solvent with the second electron transport material and carry out
Premix.
Particularly, when the first electron transport material solubility is 2~9g/100ml toluene, second electron transport material
When solubility is 2~9g/100ml toluene, first electron transport material can be used with second electron transport material
The total molten mode of solvent is premixed.As a further preferred solution, the first electron transport material solubility 2~
5g/100ml toluene, the second electron transport material solubility is in 2~5g/100ml toluene.
First electron transport material and the second electron transport material carry out preparatory mixing by the way of premix, without mixing
Miscellaneous Liq can effectively reduce the technology difficulty of device preparation to reduce the use of evaporation source, improve technology stability.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment to skill of the invention
Art scheme carries out clear, complete description.Obviously, described embodiment is a part of the embodiments of the present invention, rather than this
Invention whole embodiments.Based on described embodiment, those skilled in the art are obtained under the premise of being not necessarily to creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
The synthetic example of compound
The synthesis of compound 1-15
Nitrogen protection, 3,6- dibromo carbazoles (100mmol) and 4- (4- boric acid phenyl)-pyridine (2.30eq), potassium carbonate
(5eq), Pd2 (dba) 3 (2%eq) toluene 1000mL+ ethyl alcohol 500ml+ water 300ml open stirring, are heated to 100 DEG C of reflux,
12h is reacted, reaction solution washing, organic phase is dry, crosses silicagel column, and concentration is boiled with petroleum ether and washed, obtains intermediate 1-15a
(31.2g, yield 85.4%).
Nitrogen protection, intermediate 1-15a (100mmol) and 4- (4- bromophenyl)-pyridine (1.20eq), sodium tert-butoxide
(3eq), 3 (2%eq) toluene 1000mL of Pd2 (dba), tri-tert-butylphosphine (2%eq) open stirring, are heated to 100 DEG C of reflux,
12h is reacted, reaction solution washing, organic phase is dry, crosses silicagel column, and concentration is boiled with petroleum ether and washed, obtains product 1-15.
The synthesis of general formula (1) other compounds can refer to the description of Chinese patent disclosure CN102372694B.
The synthesis of compound 2-2
Nitrogen protection, 10,10 ,-dibromo dianthranide (100mmol) and 4- (4- boric acid phenyl)-pyridine (2.30eq), potassium carbonate
(5eq), Pd2 (dba) 3 (2%eq) toluene 1000mL+ ethyl alcohol 500ml+ water 300ml open stirring, are heated to 100 DEG C of reflux,
12h is reacted, reaction solution washing, organic phase is dry, crosses silicagel column, and concentration is boiled with petroleum ether and washed, and obtaining product 2-2, (43.6g is received
Rate 89.7%).
The synthesis of compound 2-6
Nitrogen protection, 10,10,-dibromo dianthranide (100mmol) and 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole
(2.30eq), potassium carbonate (5eq), Pd2 (dba) 3 (2%eq) toluene 1000mL+ ethyl alcohol 500ml+ water 300ml open stirring, add
Heat reacts 12h, reaction solution washing, organic phase is dry, crosses silicagel column, is concentrated, is boiled and washed with petroleum ether, produced to 100 DEG C of reflux
Product 2-6 (39.7g, yield 81.3%).
The synthesis of compound 3-10
Nitrogen protection, 2,6- dibromo-anthraquinones (36.5g, 100mmol) and 2- naphthalene boronic acids (2.30eq), potassium carbonate (5eq),
Pd2 (dba) 3 (2%eq) toluene 1000mL+ ethyl alcohol 500ml+ water 300ml opens stirring, is heated to 100 DEG C of reflux, reaction
12h, reaction solution washing, organic phase is dry, crosses silicagel column, and concentration is boiled with petroleum ether and washed, and obtaining intermediate 3-10a, (30.9g is received
Rate 82.4%).
Under nitrogen protection, to mechanical stirring is equipped with, 2- phenyl -5- bromopyridine is added in the 10L there-necked flask of low-reading thermometer
(2.5eq.), tetrahydrofuran 200ml open stirring, and ice ethyl alcohol cryostat, to -90 DEG C to -80 DEG C, 30min is interior to be added dropwise liquid nitrogen cooling
N-BuLi (2.45eq.), -90 DEG C to -80 DEG C of temperature control during dropwise addition are added intermediate 3-11b (3.62g, 10mmol), add
Bi Ziran heating, removes cryostat, continues stirring 8 hours.Aqueous ammonium chloride solution is added, separates organic phase, dry, first is used in concentration
Benzene recrystallization, obtains intermediate 3-10b (4.0g, 90.8%)
Acetic acid 100ml is added into 250ml reaction flask for nitrogen protection, opens stirring, heating, and reaction solution is warming up to 60 DEG C
Intermediate 3-10b (5.2g, 10mmol) is added when left and right, KI (5eq.), NaHPO2.H2O (8eq.) flow back (120 DEG C or so)
Reaction 5 hours.Filtering, with acetic acid, water, ethyl alcohol washes much filtrate.Re crystallization from toluene obtains 3-10 (4.9g, 90.3%).
The synthesis of compound 3-11
Nitrogen protection, 2,6- dibromo-anthraquinones (36.5g, 100mmol) and 1- (4- boric acid phenyl) -2- phenyl -1H- benzo miaow
Azoles (2.30eq), potassium carbonate (5eq), Pd2 (dba) 3 (2%eq) toluene 1000mL+ ethyl alcohol 500ml+ water 300ml open stirring,
100 DEG C of reflux are heated to, 12h is reacted, reaction solution washing, organic phase is dry, crosses silicagel column, and concentration is boiled with petroleum ether and washed, obtained
Intermediate 3-11b (31.2g, yield 85.4%).
Under nitrogen protection, to mechanical stirring is equipped with, 4- bromo biphenyl is added in the 10L there-necked flask of low-reading thermometer
(2.5eq.), tetrahydrofuran 200ml open stirring, and ice ethyl alcohol cryostat, to -90 DEG C to -80 DEG C, 30min is interior to be added dropwise liquid nitrogen cooling
N-BuLi (2.45eq.), -90 DEG C to -80 DEG C of temperature control during dropwise addition are added intermediate 3-11b (3.62g, 10mmol), add
Bi Ziran heating, removes cryostat, continues stirring 8 hours.Aqueous ammonium chloride solution is added, separates organic phase, dry, first is used in concentration
Benzene recrystallization, obtains intermediate 3-11c (4.8g, 92.3%)
Acetic acid 100ml is added into 250ml reaction flask for nitrogen protection, opens stirring, heating, and reaction solution is warming up to 60 DEG C
Intermediate 3-11c (5.2g, 10mmol) is added when left and right, KI (5eq.), NaHPO2.H2O (8eq.) flow back (120 DEG C or so)
Reaction 5 hours.Filtering, with acetic acid, water, ethyl alcohol washes much filtrate.Re crystallization from toluene obtains 3-11 (4.2g, 87.5%).
The physical-chemical parameters of compound
(1) evaporation rate
Using the evaporation rate of film thickness monitor detection material, detector is located at 20~30cm of top of corresponding evaporation source,
Crystal oscillator frequency 6MHz.When test in advance in film thickness monitor the setting means factor be 15, under the present conditions withSteaming
Sending out rate evaporation thickness isFilm (vacuum degree < 2.0*10-4Pa), using step instrument or ellipsometer to film sample
Thickness carry out test and according to test result adjust film thickness monitor Tooling factor, reuse corrected Tooling factor
Re-start film thickness calibration, the display thickness such as film thickness monitor is identical with actual measurement thickness, mark film terminate, otherwise repeatedly into
The above-mentioned work of row, until film thickness gauge show value is identical as true value, at this point, being by the evaporation rate that film thickness monitor is shown
The actual evaporation rate of material.
(2) evaporating temperature
Film thickness is demarcated using target material first, resets the Tooling factor of film thickness monitor.Then, it is steamed using vacuum
Coating apparatus is in 2.0*10-4Rate generation has been warming up under Pa vacuum degree, keep the temperature and continue evaporation after ten minutes, continue with
The frequency of 20 DEG C/min increases temperature, when evaporation rate is closeHeating rate is adjusted to 2 DEG C/min, reaches the evaporation
Current Temperatures are kept after rate, steady-state evaporation records Current Temperatures after five minutes, then repeats warming temperature and searches simultaneously recording rate
?When evaporating temperature.Hygrosensor is located at the bottom of cylindrical crucible.
(3) triplet (T1)
It is tested using Fluorescence Spectrometer.Sample is dissolved in dimethyl-tetrahydrofuran or methylene chloride or toluene and is used
Low-temperature accessory carries out liquid nitrogen cooling, and Fluorescence Spectrometer excitation wavelength is the material strongest absorption peak pair in ultra-violet absorption spectrum
The wavelength answered, sweep speed 240nm/min, Photomultiplier tube voltage 250V.
(4)HOMO&LUMO
Cyclic voltammetry test is carried out to sample using electrochemical workstation, work station uses three-electrode system, platinum electrode
For working electrode, platinum electrode is to electrode, and Ag electrodes are reference electrode.Sample is dissolved in 10mL dry dichloromethane or super dry
In tetrahydrofuran, electrolytic salt is pressed using tetra-n-butyl perchloric acid or tetra-n-butyl ammonium hexafluorophosphate, and test sample leads to argon gas guarantor
Shield, voltage range -2~2V, 50~200mV/s of scanning speed, scanning circle number 2~50.
(5) electron mobility
In ITO with a thickness of the detected materials film of 1000~3000nm of vapor deposition on the glass substrate of 150nm, then it is deposited
The Ag electrode of 200nm is connected on test equipment after device encapsulation obtained, applies the deflection voltage of 20~120V, open and swash
Light device excitation material generates photo-generated carrier；Carrier meeting directed movement under the action of electric field, and drifted about by oscillograph recording
Simultaneously carrier mobility is finally calculated in the relationship of electric current and time.
It is biased at V outside, the time that hole passes through thin layer experience is t (flight time), and thickness of thin layer d is then migrated
Rate can be expressed as:
μ=d2/Vt
The physical-chemical parameters of compound see the table below 1:
Table 1
As a kind of embodiment of organic electroluminescence device of the invention, it includes anode, hole injection layer, holes
Transport layer, luminescent layer, electron transfer layer, electron injecting layer and cathode, other function layer such as hole blocking layer etc. can be as needed
Design is cancelled.The following are specific device designs:
(1) substrate
Substrate is the carrier of organic electroluminescence device, is surface smooth, homogeneous plate or film, and shape can be
Regular polygon or abnormal shape, light transmittance are higher than 75%, and preferably transmitance is higher than 90%.Its material can for quartz or glass plate,
Metal plate or metal foil, polymer sheet or film etc., preferably glass plate, the polymeric materials such as poly- intelligence, polycarbonate, polyimides
Resin plate or film.
(2) anode
Anode is set on substrate, plays the role of injecting holes into hole injection layer.Its material be aluminium, silver, nickel, gold,
The metal oxides or carbon black, polythiophene, polypyrrole, polyaniline etc. such as the metals such as platinum or indium/tin-oxide, indium/zinc oxide are led
Electric polymer.The preparation of anode can be carried out by magnetron sputtering method, vacuum vapour deposition, spin coating or cladding process, chemical deposition etc.
Preparation.The translucency of anode can be as needed, and the thickness by adjusting anode material is adjusted, for there is the device of light transmission demand
Part, the light transmittance of anode is generally greater than 50%, preferably 85% or more.The thickness of anode is usually 10~2000nm, preferably
20~500nm, pole in special circumstances, thickness and the higher anode of intensity can replace substrate.
(3) hole injection layer
Hole injection layer (HIL) is set on anode, and playing will be through the work of the incoming hole transport of anode to hole transmission layer
With usually organic materials such as the metal oxides such as MoO3 or 2T-NATA.Thickness is usually 0.5~50nm, preferably 1~
10nm。
(4) hole transmission layer
Hole transmission layer (HTL) is set on hole injection layer, is played the role of to luminescent layer transporting holes.It is passed as hole
The material of defeated layer, it is desirable that the hole mobility height and stability and high efficiency of material, simultaneously as contacted with luminescent layer, therefore it is required that its
With high transparency, the luminescent layer that will not decay go out light and have chemical stability, will not be formed between luminescent layer swash base answer
Object is closed, meanwhile, have thermal stability, Tg > 90 DEG C.
(5) luminescent layer
Luminescent layer (EML) is set on electronic barrier layer.Luminescent layer can be made of single luminescent layer, can also there is multiple luminescent layers
Directly superposition is constituted, and can be also made up of multiple luminescent layers articulamentum superposition.Luminescent layer is made of main body and dyestuff, and dyestuff can
For fluorescence luminescent material or phosphorescent light-emitting materials, the dyestuff of each luminescent layer can be used simultaneously one or two kinds of same types
Dyestuff.
(6) hole blocking layer
Hole barrier city (HBL) is set between luminescent layer and electron transfer layer, for stopping hole through luminescent layer outflow, mentioning
The effect for the efficiency that high electronics is passed to through electron transfer layer.The general HOMO of hole barrier layer material is not less than 5.6eV, and LUMO exists
Between 2.5eV~3.5eV, T1 energy level is not less than 2.5eV, and the thicknesses of layers of vapor deposition is in 0.5~10nm, preferably 2~8nm.With
When the ET material of this layer connection can satisfy above-mentioned requirements, it is preferable that HB layers can not used in the device structure.
(7) electron transfer layer
Electron transfer layer (ETL) plays the role of electronics being transferred to hole blocking layer from electron injecting layer.Of the invention
Electron transfer layer includes the mixture of the first electron transport material and the second electron transport material, first electron transport material
Band gap Eg be greater than 2.5eV, triplet T1 be greater than 2.0eV；The electron mobility of second electron transport material
μeGreater than 1.0*10-5(cm2/ Vs), HOMO is greater than 5.5eV, and LUMO is greater than 2.5eV.
Preferably, the evaporating temperature of first electron transport material is 250~360 DEG C of (@), second electronics
The evaporating temperature of transmission material be 220~390 DEG C ()；It is highly preferred that the evaporation temperature of first electron transport material
Degree for 270~340 DEG C (), the evaporating temperature of second electron transport material be 280~340 DEG C ()。
When first electron transport material has close evaporating temperature with the second electron transport material under identical evaporation rate, pass through
Physical grinding, one or both of modes such as distillation carry out preparatory mixing altogether, particularly, when two class materials are in same solvent
In solubility it is identical when, in addition to above two hybrid mode, can also individually or simultaneously using solvent altogether molten mode into
Row mixing.
First electron transport material is mixed with the second electron transport material according to mass ratio, mixed proportion 1:100
~100:1, preferably mixed proportion are 1:9~9:1.
(8) electron injecting layer
Electron injecting layer (EIL) is set on electron transfer layer, is played enhancing from cathode and is injected electrons into electron transfer layer
Effect, this layer of optional metal, metallic compound or metal-doped mode are prepared, are determined by material properties, generally
Using sputtering or vacuum evaporation, 0.1~10nm of thicknesses of layers, preferably 0.2~5nm.
(9) cathode
Cathode plays the role of injecting electrons into electron injecting layer, and cathode material is metal or alloy material, to guarantee
The efficient injection of electronics, the preferably metal or alloy of low work function, such as magnesium, aluminium, silver, magnesium-silver alloy.Cathode is by material properties
It determines, generally uses sputtering or vacuum evaporation, 5~500nm of thicknesses of layers, preferably 10~300nm.
The embodiment of following composition is provided, formula is as shown in table 2:
Table 2
1. composition ET1 of material mix embodiment
It the first electron transport material 1-15 of quality such as weighs and the second electron transport material 2-2 powder is placed in crucible,
Sublimation purification is carried out in 350 DEG C of sublimation apparatus after mortar grinder 15 minutes, then by mixture, the product grinding after distillation
To 2000 mesh.
2. composition ET2 of material mix embodiment
It the first electron transport material 1-15 of quality such as weighs and the second electron transport material 2-6 powder is placed in crucible,
It is mixed 25 minutes with mortar grinder, until material color is uniform, granularity reaches 2000 mesh.
3. composition ET3 of material mix embodiment
The the first electron transport material 1-15 (5g) and the second electron transport material 3-10 (5g) for the quality such as weighing are placed in burning
In cup, the toluene of 250ml is added, be heated to reflux and stirs until material is completely dissolved, resulting solution left standstill cools down 7 hours
It to crystalline solid, then is to reach 2000 mesh with mortar grinder to granularity.
4. composition ET4 of material mix embodiment
It weighs the first electron transport material 1-15 (5g) and the second electron transport material 3-11 (5g) is placed in a beaker, be added
250ml toluene is heated to reflux and stirs until material is completely dissolved, and resulting solution left standstill cooling obtains crystalline solid in 7 hours,
It is to reach 2000 mesh with mortar grinder to granularity again.
5. composition ET5 of material mix embodiment
It weighs the first electron transport material 1-23 (5g) and second electron transport material 2-2 (5g) powder is placed in a beaker,
The toluene for pouring into 300ml is heated to reflux and stirs until material is completely dissolved, and resulting solution left standstill cooling is tied for 8 hours
Brilliant solid.Sample is placed in sublimation apparatus at 360 DEG C through simple grinding and carries out sublimation purification, and product uses mortar grinder extremely
2000 mesh.
6. composition ET6 of material mix embodiment
The the first electron transport material 1-23 (5g) and the second electron transport material 2-6 (5g) for the quality such as weighing are placed in distillation
It in equipment, distils under 340 degrees Celsius, obtained sample is dissolved in 100 DEG C of toluene solution (200ml), is stood
The sample being precipitated after 6 hours cooling uses mortar grinder to 2000 mesh.
In addition, a variety of different material hybrid modes of the invention can also carry out any combination according to the property of material,
As long as it does not violate the idea of the present invention, it should also be regarded as the disclosure of the present invention.
Device embodiments 1
On the ito thin film substrate of anode thickness 150nm, using the method for vacuum evaporation in vacuum degree 2*10-4It is steamed under Pa
Plate each layer.The 2-TNATA of deposition thickness 2nm is as hole injection layer first on ITO；Then the NPB conduct of 50nm thickness is formed
Hole transmission layer.Next, use two evaporation sources that TCTA is deposited respectively as main body and BCZVB as dyestuff, formed with a thickness of
The luminescent layer of 20nm, dyestuff doping concentration (5%).Then, the TPBi of 2nm is formed as HBL.Further, in hole blocking layer
The Alq3 of upper deposition 20nm is as electron transfer layer.Next the LiF of deposition 5nm is as electron injecting layer.Finally, deposition
Organic electroluminescence device is made as cathode in the Al of 100nm.
Device embodiments 2~23
Preparation method identical with device embodiments 1, difference are only that device embodiments 2~23 use compound 1- respectively
15, organic electroluminescence is equally made as electron transport layer materials in 1-23,2-2,2-6,3-10,3-11, ET1~ET16
Part.
Device embodiments 24
On the ito thin film substrate of anode thickness 150nm, using the method for vacuum evaporation in vacuum degree 2*10-4It is steamed under Pa
Plate each layer.The 2-TNATA of deposition thickness 2nm is as hole injection layer first on ITO；Then the NPB conduct of 50nm thickness is formed
Hole transmission layer.Next, use two evaporation sources that TCTA is deposited respectively as main body and BCZVB as dyestuff, formed with a thickness of
The luminescent layer of 20nm, dyestuff doping concentration (5%).Then, on the light-emitting layer the ET3 of Direct precipitation 22nm as electron-transport
Layer.Next the LiF of deposition 5nm is as electron injecting layer.Finally, organic electroluminescence hair is made as cathode in the Al of deposition 100nm
Optical device.
Device embodiments 25
On the ito thin film substrate of anode thickness 150nm, steamed at vacuum degree 2*10-4Pa using the method for vacuum evaporation
Plate each layer.The HAT of deposition thickness 5nm is as hole injection layer first on ITO,；Then the NPB of 80nm thickness is formed as hole
Transport layer.Next, using two evaporation sources that mCP is deposited respectively as main body and C545T as dyestuff, formed with a thickness of 30nm's
Luminescent layer, dyestuff doping concentration (10%).Then, the TPBi of 3nm is formed as HBL.Further, it deposits on the hole blocking layer
The Bphen of 25nm is as electron transfer layer.Next the LiF of deposition 4nm is as electron injecting layer.Finally, the Al of deposition 150nm
As cathode, organic electroluminescence device is made.
Device embodiments 26~28
Preparation process identical with device embodiments 25, difference be only that device embodiments 26~28 respectively using 1-15,
Organic electroluminescence device is equally made as electron transport layer materials in 2-2 and ET1.
Device embodiments 29
On the ito thin film substrate of anode thickness 150nm, using the method for vacuum evaporation in vacuum degree 2*10-4It is steamed under Pa
Plate each layer.The HAT of deposition thickness 5nm is as hole injection layer first on ITO,；Then the NPB of 80nm thickness is formed as hole
Transport layer.Next, using two evaporation sources that mCP is deposited respectively as main body and C545T as dyestuff, formed with a thickness of 30nm's
Luminescent layer, dyestuff doping concentration (10%).Then, the ET1 of 30nm is deposited on the light-emitting layer as electron transfer layer.Next heavy
The LiF of product 4nm is as electron injecting layer.Finally, organic electroluminescence device is made as cathode in the Al of deposition 150nm.
Device embodiments 30
On the ito thin film substrate of anode thickness 150nm, using the method for vacuum evaporation in vacuum degree 2*10-4It is steamed under Pa
Plate each layer.First on ITO then the HAT of deposition thickness 10nm forms the NPB of 110nm thickness as empty as hole injection layer
Cave transport layer.Next, using two evaporation sources that CBP is deposited respectively as main body and Ir (piq) 2acac as dyestuff, formed thick
Degree is the luminescent layer of 36nm, dyestuff doping concentration (3%).Then, the TPBi of 5nm is formed as HBL.Further, it is hindered in hole
The Bphen of 30nm is deposited in barrier as electron transfer layer.Next the LiF of deposition 6nm is as electron injecting layer.Finally, heavy
Organic electroluminescence device is made as cathode in the Al of product 80nm.
Device embodiments 31~33
Identical with device embodiments 30, device embodiments 31~33 use 1-15,3-11 and ET4 as ETL material respectively
Organic electroluminescence device is equally made in material.
Device embodiments 34
On the ito thin film substrate of anode thickness 150nm, steamed at vacuum degree 2*10-4Pa using the method for vacuum evaporation
Plate each layer.First on ITO then the HAT of deposition thickness 10nm forms the NPB of 110nm thickness as empty as hole injection layer
Cave transport layer.Next, using two evaporation sources that CBP is deposited respectively as main body and Ir (piq) 2acac as dyestuff, formed thick
Degree is the luminescent layer of 36nm, dyestuff doping concentration (3%).Then, the ET4 of Direct precipitation 35nm is passed as electronics on the light-emitting layer
Defeated layer.Next the LiF of deposition 6nm is as electron injecting layer.Finally, organic electroluminescence is made as cathode in the Al of deposition 80nm
Luminescent device.
Each layer is as follows using material structure formula in the device embodiments that the present invention enumerates:
The structure design of the above device embodiments is summarized in table 3；Brightness, voltage, efficiency and the test data in service life are shown in Table
4。
Table 3
Table 4
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within the scope of the present invention.In addition, various embodiments of the present invention can be combined randomly, as long as
It is without prejudice to thought of the invention, and it should also be regarded as the disclosure of the present invention.
Claims (15)
1. a kind of composition, it includes the mixtures of the first electron transport material and the second electron transport material, wherein described
The band gap Eg of one electron transport material is greater than 2.5eV, and triplet T1 is greater than 2.0eV；
The electron mobility μ of second electron transport materialeGreater than 1.0*10-5(cm2/ Vs), HOMO is greater than 5.5eV, and LUMO is big
In 2.5eV.
2. composition according to claim 1, wherein first electron transport material is selected from chemical combination shown in general formula (1)
Object:
Ar1、Ar2、Ar3In at least there are two group be selected from 5~30 carbon atoms containing pyridine ring aromatic group, it is remaining
Group be selected from hydrogen atom, the alkyl with 1~30 carbon atom, the aromatic group with 5~30 carbon atoms, have 5~
The nitrogen-containing heterocycle of 30 carbon atoms；N is 1 or 2；
Second electron transport material is selected from general formula (2) or general formula (3) compound represented:
In general formula (2), X1~X8It is respectively and independently selected from CR ' or N, R ' indicates hydrogen, the alkyl with 1~4 carbon atom, has 6
The aromatic group of~30 carbon atoms, nitrogen-containing heterocycle group, halogen and/or nitro with 3~30 carbon atoms；Ar4It is selected from
Aromatic group with 6~30 carbon atoms, or selected from the nitrogen-containing heterocycle group with 3~30 carbon atoms；
In general formula (3), Ar5、Ar6It is respectively and independently selected from substituted or unsubstituted C6~C20Aryl, substituted or unsubstituted C4~C20
Nitrogenous heteroaryl；Two R are independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano.
3. composition according to claim 1, wherein the band gap Eg of first electron transport material is greater than
3.0eV, triplet T1 are greater than 2.5eV；The electron mobility μ of second electron transport materialeGreater than 1.0*10-4
(cm2/ Vs), HOMO is greater than 5.7eV, and LUMO is greater than 3.0eV.
4. composition according to claim 1, which is characterized in that first electron transport material and the second electron-transport
The mixed proportion of material is 1:100~100:1, and preferably mixed proportion is 1:9~9:1.
5. composition according to claim 1, which is characterized in that first electron transport material and the second electron-transport
For the absolute value of the evaporating temperature difference of material less than 20 DEG C, the first electron transport material and the second electron transport material pass through physics
Grinding, altogether distillation and/or the total molten mode of solvent are mixed.
6. composition according to claim 5, which is characterized in that the first electron transport material solubility is in 2~9g/
100ml toluene, the second electron transport material solubility in 2~9g/100ml toluene, first electron transport material with
Second electron transport material is mixed in such a way that solvent is molten altogether.
7. a kind of electron transport material, it includes compositions according to any one of claims 1 to 6.
8. a kind of organic electroluminescence device comprising first electrode, second electrode and be located at first electrode and second electrode
Between electron transfer layer, the electron transfer layer include the first electron transport material and the second electron transport material mixing
Object, which is characterized in that the band gap Eg of first electron transport material is greater than 2.5eV, and triplet T1 is greater than
2.0eV；
The electron mobility μ of second electron transport materialeGreater than 1.0*10-5(cm2/ Vs), HOMO is greater than 5.5eV, and LUMO is big
In 2.5eV.
9. organic electroluminescence device according to claim 8, which is characterized in that first electron transport material is selected from
General formula (1) compound represented:
Ar1、Ar2、Ar3In at least there are two group be selected from 5~60 carbon atoms containing pyridine ring aromatic group, it is remaining
Group be selected from hydrogen atom, the alkyl with 1~40 carbon atom, the aromatic group with 5~50 carbon atoms, have 5~
The nitrogen-containing heterocycle of 50 carbon atoms；N is 1 or 2；
Second electron transport material is selected from general formula (2) or general formula (3) compound represented:
In general formula (2), X1~X8It is respectively and independently selected from CR ' or N, R ' indicates hydrogen, the alkyl with 1~4 carbon atom, has 6
The aromatic group of~30 carbon atoms, nitrogen-containing heterocycle group, halogen and/or nitro with 3~30 carbon atoms；Ar4It is selected from
Aromatic group with 6~30 carbon atoms, or selected from the nitrogen-containing heterocycle group with 3~30 carbon atoms；
In general formula (3), Ar5、Ar6It is respectively and independently selected from substituted or unsubstituted C6~C20Aryl, substituted or unsubstituted C4~C20
Heteroaryl；Two R are independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano.
10. organic electroluminescence device according to claim 9, it is characterised in that: the first electron transport material choosing
From the compound of structure shown in following formula 1-1 to 1-23,
Second electron transport material is selected from the compound of structure shown in following formula 2-1 to 2-8,3-1 to 3-19,
11. organic electroluminescence device according to claim 8, which is characterized in that first electron transport material with
The mixed proportion of second electron transport material is 1:100~100:1, and preferably mixed proportion is 1:9~9:1.
12. organic electroluminescence device according to claim 8, which is characterized in that first electron transport material with
The absolute value of the evaporating temperature difference of second electron transport material is less than 20 DEG C, the first electron transport material and the second electron-transport
Material is mixed by the total molten mode of physical grinding, altogether distillation and/or solvent.
13. organic electroluminescence device according to claim 12, which is characterized in that first electron transport material is molten
Xie Du is in 2~9g/100ml toluene, and the second electron transport material solubility is in 2~9g/100ml toluene, first electricity
Sub- transmission material is mixed in such a way that solvent is molten altogether with second electron transport material.
14. successively there is anode, hole injection according to the described in any item organic electroluminescence devices of claim 8 to 13
Layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and cathode.
15. successively there is anode, hole injection according to the described in any item organic electroluminescence devices of claim 8 to 13
Layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode.
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