CN106898701A - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
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- CN106898701A CN106898701A CN201510956740.7A CN201510956740A CN106898701A CN 106898701 A CN106898701 A CN 106898701A CN 201510956740 A CN201510956740 A CN 201510956740A CN 106898701 A CN106898701 A CN 106898701A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of organic electroluminescence device, including first electrode layer, luminescent layer, electron injecting layer and the second electrode lay that superposition is set, the electron injecting layer and the second electrode lay physical contact are set.The electron injecting layer include the organic ion salt of benzimidazole shown in formula (I), one or more in benzimidazole neutral organic material and the dimer of benzimidazole organic material shown in formula (III) shown in formula (II), this kind of material reduces the potential barrier between the second electrode lay and organic electron transport layer interface, improve the transmittability of carrier, such that it is able to set electron injecting layer and the second electrode lay direct physical contact, no longer need to set insulating buffer layer, with performances such as raising device efficiency, extension device lifetimes.
Description
Technical field
The invention belongs to OLED field, and in particular to a kind of organic electroluminescence device.
Background technology
Organic electroluminescence device includes anode layer, organic luminescence function layer and the second electrode lay；It is described to have
Machine light emitting functional layer includes hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and electricity
Sub- implanted layer.Due to there is larger electron injection gesture between negative electrode and the interface of organic electron transport layer
Build, in order to improve the balance between electronics and hole, insulation is introduced between electron injecting layer and negative electrode
Cushion, such as LiF layer (0.5nm), after introducing, potential barrier reduction, electron injection ability is obviously improved, and drives
Dynamic voltage declines, and luminous efficiency is improved.But LiF evaporating temperatures are (620~640 DEG C) high, and Li ions ooze
Thoroughly be easily caused be quenched it is luminous, and then influence device stability.
Nowalt Publication Co., Ltd discloses a kind of freedom of heterocycle in CN200710088908
Base and diradical, its dimer, oligomer, polymer, dispiro compounds and polycyclic are specific as follows
Shown in structure：(same type, but molecular structure is not repeated, and may be referred to use)
Such compound is N-type dopant, as implanted layer and barrier layer, when it is used as implanted layer, is
Used in N-type dopant mode, it is necessary to which being entrained in host material could increase carrier transport speed,
And this material need it is light-initiated use, technique is harsh.
The content of the invention
The present invention causes luminous problem is quenched for the Li ions infiltration in existing insulating buffer layer, carries
For a kind of organic electroluminescence device, the material that electron injecting layer is used is benzimidazole organic material,
This kind of material makes potential barrier reduction between the negative electrode and the interface of organic electron transport layer, such that it is able to make
Electron injecting layer and the second electrode lay direct physical contact are set, it is not necessary to set insulating buffer layer,
With performances such as raising device efficiency, extension device lifetimes.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of organic electroluminescence device, including first electrode layer, luminescent layer, the electronics note that superposition is set
Enter layer and the second electrode lay, the electron injecting layer and the second electrode lay physical contact are set；
The electron injecting layer includes the organic ion salt of benzimidazole shown in formula (I), formula (II) institute
In showing benzimidazole neutral organic material and the dimer of benzimidazole organic material shown in formula (III)
One or more：
Wherein：BI has formula (IV) or the structure shown in formula (V)：
R1~R10It is identical or different, separately selected from methoxyl group, dimethylamino, substitution or unsubstituted
Indolocarbazole base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substitution
Or unsubstituted triphenylamine base, substituted or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted three
Anilino-, the substitution base in substituted phenoxazine groups is C1-C6Alkyl, methoxyl group, dimethylamino, second
One or more in epoxide and phenyl；
Ar is 2- methoxybenzenes, 2,6- dimethoxy benzenes or 2,4,6- trimethoxy-benzenes；
X is halogen.
The organic ion salt of the benzimidazole have one kind in formula (21)-structure shown in formula (26) or
Various, the benzimidazole neutral organic material has in formula (27)-structure shown in formula (32)
Plant or various, the dimer of the benzimidazole organic material has knot shown in formula (33)-formula (38)
One or more in structure：
R1~R10It is identical or different, separately selected from methoxyl group, dimethylamino, substitution or unsubstituted
Indolocarbazole base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substitution
Or unsubstituted triphenylamine base, substituted or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted three
Anilino-, the substitution base in substituted phenoxazine groups is C1-C6Alkyl, methoxyl group, dimethylamino, second
One or more in epoxide and phenyl.
The organic ion salt of the benzimidazole has the one kind in formula (1-1)-structure shown in formula (1-15)
Or it is various, the benzimidazole neutral organic material has in formula (2-1)-structure shown in formula (2-9)
One or more, the dimer of the benzimidazole organic material has formula (3-1)-formula (3-6)
One or more in shown structure：
The thickness of the electron injecting layer is 1-10nm.
Preferably, it is provided with electron transfer layer between described luminescent layer and described electron injecting layer.
It is further preferred that being provided with first organic work(between described luminescent layer and the first electrode layer
Ergosphere.
First organic function layer is hole injection layer and/or hole transmission layer.
Compared with prior art, the advantage of benzimidazole organic functional material of the invention is：
(1) electron injecting layer in organic electroluminescence device of the present invention uses benzimidazole
Organic material, because potential barrier between the negative electrode and the interface of organic electron transport layer drops in this kind of material
It is low, such that it is able to set electron injecting layer and the second electrode lay direct physical contact, it is to avoid device
Because of the unstability that luminous and device is quenched that Li ions permeable belt comes, with raising device efficiency and extension
The performances such as device lifetime.
(2) the benzimidazole organic material that the present invention is used stable in the air can be present, including contain
The organic salt of the halide anion of benzimidazole, neutral organic molecule and dimeric molecule etc., by vacuum
After heating, decompose and produce active free radical, realize the effect of N doping.Introduced in organic molecule to
The substitution base of electronics, improves the activity of free radical, makes its HOMO energy level be higher than -3.0eV.Due to normal
OLED electron transport materials lumo energy about -3.0eV, therefore when electron injecting layer uses benzo
The organic salt of the halide anion of imidazoles, neutral organic molecule and dimeric molecule etc., can strengthen electronics note
Enter, improve thin film electronic mobility and carrier concentration, increase device current density, improve device efficiency
And stability.Stability is poor in an atmosphere with the alkali and alkaline earth metal ions salt of low work function, anticorrosive
Ability is bad, and shortcoming that is oxidizable or peeling off is different, benzimidazole organic functional material of the invention
Presence stable in the air, is easy to longer-term storage.
(3) the evaporation temperature of benzimidazole organic material of the invention is low, only 150 DEG C or so, and often
See electron injection material quite, and mixed well below conventional alkaline metal salt or alkaline-earth metal salt N-type
Miscellaneous dose of evaporation temperature (being more than 600 DEG C), therefore can realize being deposited with organic chamber, reduces cost.
(4) in addition, being adulterated compared to the n-type based on alkali metal atom/alkaline earth metal atom that tradition is used
Agent, the benzimidazole material that such low temperature can be deposited with can avoid luminous caused by metallic atom permeates
Quenching phenomenon, improves device efficiency, extends device lifetime.
(5) organic electroluminescence of the invention is reduced between negative electrode and the interface of organic electron transport layer
Potential barrier, and increase because the reduction of potential barrier causes carrier to inject, the transmittability of carrier is improve,
Such that it is able to set electron injecting layer and the second electrode lay direct physical contact, it is no longer necessary to set
Insulating buffer layer, improves device efficiency, extends device lifetime.
Brief description of the drawings
Fig. 1 is organic electroluminescence device structural representation of the invention；
Fig. 2 is the current density voltage curve figure of comparative device 1, comparative device 2 and device 1；
Fig. 3 is the luminance vs. voltage graph of comparative device 1, comparative device 2 and device 1；
Fig. 4 is the current density-brightness curve figure of comparative device 1, comparative device 2 and device 1；
Fig. 5 is the power efficiency-brightness curve figure of comparative device 1, comparative device 2 and device 1；
Fig. 6 is the current density-brightness curve figure of comparative device 1, comparative device 2 and device 1~5；
Fig. 7 is the current efficiency-brightness curve figure of comparative device 1, comparative device 2 and device 1~5；
Fig. 8 is the power efficiency-brightness curve figure of comparative device 1, comparative device 2 and device 1~5.
Specific embodiment
Below will the invention will be further described by specific embodiment.
The present invention can be embodied in many different forms, and should not be construed as limited to set forth herein
Embodiment.Conversely, there is provided these embodiments so as to disclose will be thorough and complete to the present invention, and
Design of the invention will be fully conveyed to those skilled in the art, the present invention will be limited only by claim
It is fixed.In the accompanying drawings, for clarity, the size and relative size in layer and region can be exaggerated.Should manage
Solution, when element such as layer, region or substrate are referred to as " being formed in " or " being arranged on " another unit
Part " on " when, the element can be arranged directly on another element, or can also there is centre
Element.Conversely, when element is referred to as on " being formed directly into " or " being set directly at " another element,
In the absence of intermediary element.
As shown in figure 1, a kind of organic electroluminescence device, including substrate, and it is superimposed on substrate and is set
First electrode layer 01 (anode), luminescent layer 04, electron injecting layer 06 and the second electrode lay 07 put are (cloudy
Pole), the electron injecting layer 06 and the physical contact of the second electrode lay 07 are set.The first electrode
The first organic function layer is provided between layer 01 and luminescent layer 04, the luminescent layer 04 is noted with the electronics
Enter and be provided with electron transfer layer 05 between layer 06；First organic function layer be hole injection layer 02 and/
Or hole transmission layer 03；
The electron injecting layer includes the organic ion salt of benzimidazole shown in formula (I), formula (II) institute
In showing benzimidazole neutral organic material or the dimer of benzimidazole organic material shown in formula (III)
One or more：
Wherein：BI has formula (IV) or the structure shown in formula (V)：
R1~R10It is identical or different, separately selected from methoxyl group, dimethylamino, substitution or unsubstituted
Indolocarbazole base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substitution
Or unsubstituted triphenylamine base, substituted or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted three
Anilino-, the substitution base in substituted phenoxazine groups is C1-C6Alkyl, methoxyl group, dimethylamino, second
One or more in epoxide and phenyl；
Ar is 2- methoxybenzenes, 2,6- dimethoxy benzenes or 2,4,6- trimethoxy-benzenes；
X is halogen.
The organic ion salt of the benzimidazole have one kind in formula (21)-structure shown in formula (26) or
Various, the benzimidazole neutral organic material has in formula (27)-structure shown in formula (32)
Plant or various, the dimer of the benzimidazole organic material has knot shown in formula (33)-formula (38)
One or more in structure：
R1~R10It is identical or different, separately selected from methoxyl group, dimethylamino, substitution or unsubstituted
Indolocarbazole base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substitution
Or unsubstituted triphenylamine base, substituted or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted three
Anilino-, the substitution base in substituted phenoxazine groups is C1-C6Alkyl, methoxyl group, dimethylamino, second
One or more in epoxide and phenyl.
Preferably, the organic ion salt of the benzimidazole has formula (1-1)-structure shown in formula (1-15)
In one or more, the benzimidazole neutral organic material has formula (2-1)-formula (2-9) institute
Show one or more in structure, the dimer of the benzimidazole organic material have formula (3-1)-
One or more in structure shown in formula (3-6)：
The thickness of the electron injecting layer is 1-10nm.
Unless otherwise instructed, the device layers in the present invention are as follows using material：
Anode can use inorganic material or organic conductive polymer.Inorganic material is generally tin indium oxide
(ITO), the work(such as metal oxide or gold, copper, silver such as zinc oxide (ZnO), indium zinc oxide (IZO)
Function metal higher, preferably ITO；Organic conductive polymer is preferably polythiophene/polyvinylbenzenesulfonic acid
Sodium (hereinafter referred to as PEDOT:PSS), one kind in polyaniline (hereinafter referred to as PANI).
Negative electrode typically using the relatively low metal of work function such as lithium, magnesium, calcium, strontium, aluminium, indium or they with copper,
The alloy of gold, silver, or the electrode layer that metal is alternatively formed with metal fluoride.Negative electrode is preferred in the present invention
It is Al electrodes.
The material of hole transmission layer can be selected from arylamine class, carbazoles and branch polymer class low molecule material, excellent
Select NPB and TCTA.
Organic electroluminescence device of the invention can also inject between anode and hole transmission layer with hole
Layer, the material of the hole injection layer can for example use 2,3,6,7,10,11- six cyano group-Isosorbide-5-Nitrae, 5,8,9,12- six nitrogen
Miscellaneous benzophenanthrene HATCN, 4,4', 4 "-three (3- aminomethyl phenyls aniline) triphen amino-group doping F4TCNQ, or
Using copper phthalocyanine (CuPc), or can be metal oxide-type, such as molybdenum oxide, rheium oxide.The present invention is hollow
Cave injection layer material is preferably HATCN.
The luminescent material of luminescent layer can be selected from Coumarins such as DMQA or C545T, or double pyrans are such as
The metal complexs such as fluorescent dyes such as DCJTB or DCM, or containing Ir, Pt, Os, Ru, Rh, Pd, group of the lanthanides, actinium series.
Doping concentration of the fluorescent dye in luminescent layer is not higher than 5wt%, phosphorescent coloring mixing in luminescent layer
Miscellaneous concentration is not higher than 30wt%.The doping concentration=dyestuff quality/(dyestuff quality+material of main part quality)
× 100%.
The material of main part of luminescent layer may be selected from being usually used in the material of host material, such as 4,4 '-two (carbazyl -9-)
Biphenyl CBP.
The material of electron transfer layer of the invention can be thick using the material for being usually used in electron transfer layer, such as fragrance
Ring class (such as Pentacene, perylenes) or o-phenanthroline class (such as Bphen, BCP) compound.
Substrate can be glass or flexible substrate, and the flexible substrate can use polyesters, polyimides
Class compound-material or foil.The stacking and method for packing can be using those skilled in the art
Any suitable method known.
The specific preparation method of organic electroluminescence device of the invention is as follows：
First, glass substrate is cleaned using detergent and deionized water, and is placed under infrared lamp
Drying, sputters one layer of anode material on glass, and thickness is 150nm；
Then, the above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-4Pa,
Continue to be deposited with HATCN on above-mentioned anode tunic as hole injection layer, continue in HATCN film layers
Used as hole transmission layer, rate of film build is 0.1nm/s to evaporation NPB, and evaporation thickness is 40nm.
Luminescent layer is deposited with hole transmission layer, the method steamed altogether using double source is carried out, material of main part with dye
The mass percent of material is controlled by thickness monitoring instrument, adjustment rate of film build.Evaporation thickness is 30nm.
On luminescent layer, continue to be deposited with one layer of Bphen material as electron transfer layer, its evaporation rate
It is 0.1nm/s, evaporation total film thickness is 40nm；
On the electron transport layer, continue to be deposited with one layer of electron transport layer materials, its evaporation rate is 0.1nm/s,
Evaporation total film thickness is 0.5nm；
Finally, on above-mentioned electron transfer layer evaporating Al layer as device the second electrode lay, evaporation film
Thickness is 150nm.
Embodiment 1
The structure of device 1：
ITO/HATCN[5nm]/NPB[30nm]/TCTA[10nm]/CBP[30nm]:10wt%Ir (ppy)3/ Bphen [40nm]/formula (1-3) [0.5nm]/Al [150nm]
The structure of comparative device 1 is as follows：
ITO/HATCN[5nm]/NPB[30nm]/TCTA[10nm]/CBP[30nm]:10wt%Ir (ppy)3/Bphen[40nm]/Al[150nm]
The structure of comparative device 2 is as follows：
The structure of this comparative example is identical with comparative example 1, differ only in material that electron injecting layer uses for
LiF:
ITO/HATCN[5nm]/NPB[30nm]/TCTA[10nm]/CBP[30nm]:10wt%Ir (ppy)3/
Bphen[40nm]/LiF[0.5nm]/Al[150nm]
Device 1, comparative device 1 are identical with the structure of comparative device 2, differ only in the electronics note of device 1
Enter material that layer the uses o-MeO-DMBI-I shown in formula (1-3), comparative device 1 is without electron injecting layer material
Material and comparative device 2 employ LiF insulating buffer layers, and comparative device 1 is except slow without insulation in table 1
Layer (control) is rushed, its structure is identical with comparative device 2, table 1 is its performance test results.
Table 1
Comparative device 1 (control device curves in figure), comparative device 2 (LiF curves in figure) and
The current density voltage curve figure of device 1 (radical curves in figure) is shown in Fig. 2, luminance vs. voltage graph
See Fig. 3, current density-brightness curve figure is shown in Fig. 4, and power efficiency-brightness curve figure is shown in Fig. 5.Fig. 1-Fig. 5
The benzimidazole material protected of the present invention is illustrated as electron injection material, the device 1 where it
Driving voltage is lower slightly with the driving voltage of the comparative device 2 where LiF, but in 35700cd/m2It is luminous
Under brightness, the maximum current efficiency of device 1 than comparative device 1 high 49%, than comparative device 2 high 25%,
Illustrate that the benzimidazole material protected of the present invention can promote more electron injections in device, carry
High carrier transport ability, and then the device efficiency for improving, extend device lifetime.
Embodiment 2- embodiments 5
The structure of the device 2- devices 5 of embodiment 2- embodiments 5 is identical with device 1, differs only in electricity
The thickness of sub- implanted layer, table 2 is its performance test results.
Table 2
Comparative device 1 (control device curves in figure), (the 0.5 nanometer of song of LiF in figure of comparative device 2
Line) and device 1- devices 5 (radical 1nm, radical 2nm, radical 3nm, radical 4nm in figure,
Radical 6nm curves) current density-brightness curve figure see that Fig. 6, current efficiency-brightness curve figure are shown in figure
7th, power efficiency-brightness curve figure is shown in Fig. 8, and Fig. 6-Fig. 8 explanations increase with electron injecting layer thickness, drive
Dynamic voltage gradually rises, in 35700cd/m2Under luminosity, maximum current efficiency is with electron injection thickness
Degree increases first to increase and subtracts afterwards, and maximum is reached when electron injecting layer thickness is 3nm.
Embodiment 6
The structure of device 6 is identical with device 1, and the thickness of electron injecting layer is 3nm, and electron injecting layer is used
The different benzimidazole electron injection material of present invention protection, table 3 is its performance test results.
Table 3
As the data in table 3 indicates, the benzimidazole material protected of the present invention is used as electron injection material,
Device where it is in 35700cd/m2Under luminosity, with larger current efficiency, and driving voltage
It is relatively low, so the benzimidazole material that the present invention is protected is used as electron injection material so that negative electrode with
Potential barrier reduction between the interface of organic electron transport layer, it is no longer necessary to insulating buffer layer is set, load is improve
The transmittability of son is flowed, the efficiency of device is then improve, the life-span of device is extended.
The preparation method of compound of the invention is as follows：
1st, the synthetic route of formula (1-3)：
5.0g (23.85mmol) 2- (2- hydroxy phenyls) -1H- benzimidazoles (formula 4-1) is dissolved in 40mL
In 5N KOH and 10mL alcohol mixed solutions, then by 20mL (45.60g, 321.26mmol) CH3I
In dropping to solution system.Reaction system keeps 45 DEG C overnight in oil bath.Reaction is finished, and is filtrated to get
White depositions, then cleaned with ethanol 2 times, obtain compound shown in formula (1-3), yield 70%.1H NMR(400MHz,DMSO)δ/ppm:8.12 (dd, J=6.23,3.14Hz,2), H 7.84 (t, J=
7.75Hz,1H), 7.45 (d, J=8.48Hz,1H), 7.32 (t, J=7.54Hz,1H),3.88(s,3H),3.85
(s,6H).
13C NMR(400MHz,DMSO)δ/ppm:167.20,157.76,144.88,141.58,
141.10,136.17,130.77,122.95,122.29,118.33,65.83,42.18.
When formula (1-1), formula (1-2) and formula (1-4) are to formula (1-15), wherein formula (1-1) and
Formula (1-2) be formula (4-1) respectively with CH3Cl and CH3Br reacts；Formula (1-4), formula (1-5),
Formula (1-6) be formula (4-2) respectively with CH3Cl, CH3Br and CH3I reacts；Formula (1-7), formula (1-8),
Formula (1-9) be formula (4-3) respectively with CH3Cl, CH3Br and CH3I reacts；Formula (1-10) is formula
(4-4) and CH3I reacts；Formula (1-11) is formula (4-5) and CH3Cl reacts；Formula (1-12) is
Formula (4-6) and CH3Br reacts；Formula (1-13) is formula (4-7) and CH3Cl reacts；Formula (1-14)
It is formula (4-8) and CH3I reacts；Formula (1-15) is formula (4-9) and CH3I reacts, and reaction condition is same
Formula (1-3).
2nd, formula (2-1) synthetic route
50mL 2- oxygen tolyl aldehyde (formula 5-1) and N, N '-dimethyl-o-PDA (formula 5-4)
(136mg, 1.0mmol) is added in methyl alcohol (2mL), is subsequently adding appropriate aromatic aldehyde (1.00mmol).
A drop glacial acetic acid is subsequently added, solution system is ultrasonic until there is solid to separate out at room temperature.Mixing object
System obtains crude product by vacuum filtration, and this crude product is recrystallized in methyl alcohol, obtains shown in formula (2-1)
Pure compound.1H NMR(D6-DMSO,300MHz):7.65(dd,1H),7.37(td,1H),7.12(d,1H),7.03(t,1H),6.59(dd,2H),6.41(dd,2H),5.47(s,1H),3.82(s,3H),2.48(s,6H)；13C{1H}NMR(D6-DMSO,300MHz):158.65,142.1,130.01,128.73,126.23,
120.79,118.88,111.27,105.61,84.65,55.66,33.19；ESI-MS=253.1335 (M-H+),
255.1491(M+H+)。
When formula (2-2) is to formula (2-9), wherein formula (2-2) is formula (5-5) and formula (5-1)
Reaction；Formula (2-3) is that formula (5-4) is reacted with formula (5-2)；Formula (2-4) is formula (5-6) and formula (5-2)
Reaction；Formula (2-5) is that formula (5-5) is reacted with formula (5-3)；Formula (2-6) is formula (5-7) and formula (5-3)
Reaction；Formula (2-7) is that formula (5-8) is reacted with formula (5-1)；Formula (2-8) is formula (5-9) and formula (5-2)
Reaction；Formula (2-9) is that formula (5-10) is reacted with formula (5-3), the same formula of reaction condition (2-1).
3rd, formula (3-1) synthetic route
(a kind of device that anhydrous and oxygen-free synthesis is provided, Vacuum Atmospheres in glove box
Co.Glovebox, OMNI-LAB, VAC101975), dry Schlenk pipes are full of mercury (60g, 0.3
Mol), the Na (600mg, 26mmol) of fritter is added into Shrek bottle Schlenk pipes.Add
2-Cyc-DMBI-PF6 (formula 6-1) (2.0g, 5.3mmol) and dry the tetrahydrofuran THF (10mL) of anaerobic
To in pipe, it is ensured that sodium amalgam can stir in liquid condition.Solution system room in the dark state
Temperature stirring 12 hours.Then THF solution is removed from sodium amalgam system, THF is then used for multiple times
Cleaning sodium amalgam.The THF solution that will be collected into is concentrated in the case where not heating.It is concentrated to give
Solid matter is suspended in the heptane (100mL) of anhydrous and oxygen-free, and DMSO (3 × 30mL) is then passed through respectively
Washed with water (30mL).The water in system is finally removed using magnesium sulfate, normal-temperature vacuum is carried out after filtering
Concentration, obtains white solid shown in formula (3-1), yield 57%.Can also be by the saturation at -20 DEG C just
Recrystallized in heptane, obtain the product of higher purity.1H NMR(D8-THF,500MHz)：δ6.43(dd,
J=5.4,3.2Hz,4H), 6.43 (dd, J=5.4,3.2Hz,4H), 3.04 (s,12H), 2.00 (m,2H),
1.58-1.10 (multiple broad peak,20H)。13C{1H}NMR(C6D6,500MHz):δ 143.24,
118.38,102.24,99.00,49.96,34.44,30.18,29.16,28.29；ESI-MS：m/z
473.4(Me+M+), 229.0 (Me/2+),
When formula (3-2) is to formula (3-6), wherein formula (3-2), formula (3-3), formula (3-4), formula
(3-5), the raw material of formula (3-6) is respectively formula (6-2), formula (6-3), formula (6-4), formula (6-5),
The same formula of formula (6-6) reaction condition (3-1).
Formula (3-2) synthetic route：Reactant is 2- phenyl-DMBI-PF shown in formula (6-2)6(2.0g,
5.43mmol), by with formula (3-1) identical synthetic method, obtain the formula (3-2) of white powder.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiment,
It should be appreciated that under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements,
Appended claims summarise the scope of the present invention.
Claims (7)
1. a kind of organic electroluminescence device, including first electrode layer, luminescent layer, the electronics that superposition is set
Implanted layer and the second electrode lay, it is characterised in that：
The electron injecting layer and the second electrode lay physical contact are set；
The electron injecting layer includes the organic ion salt of benzimidazole shown in formula (I), formula (II) institute
In showing benzimidazole neutral organic material and the dimer of benzimidazole organic material shown in formula (III)
One or more：
Wherein：BI has formula (IV) or the structure shown in formula (V)：
R1~R10It is identical or different, separately selected from methoxyl group, dimethylamino, substitution or unsubstituted
Indolocarbazole base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substitution
Or unsubstituted triphenylamine base, substituted or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted three
Anilino-, the substitution base in substituted phenoxazine groups is C1-C6Alkyl, methoxyl group, dimethylamino, second
One or more in epoxide and phenyl；
Ar is 2- methoxybenzenes, 2,6- dimethoxy benzenes or 2,4,6- trimethoxy-benzenes；
X is halogen.
2. organic electroluminescence device according to claim 1, it is characterised in that the benzimidazole
Have in formula (21)-structure shown in formula (26) one or more of organic ion salt, the benzo miaow
Azole neutral organic material has one or more in formula (27)-structure shown in formula (32), the benzene
And the dimer of imidazoles organic material has one or more in formula (33)-structure shown in formula (38)：
R1~R10It is identical or different, separately selected from methoxyl group, dimethylamino, substitution or unsubstituted
Indolocarbazole base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substitution
Or unsubstituted triphenylamine base, substituted or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted three
Anilino-, the substitution base in substituted phenoxazine groups is C1-C6Alkyl, methoxyl group, dimethylamino, second
One or more in epoxide and phenyl.
3. organic electroluminescence device according to claim 2, it is characterised in that the benzo miaow
The organic ion salt of azoles has one or more in formula (1-1)-structure shown in formula (1-15), the benzene
And imidazoles neutral organic material has one or more in formula (2-1)-structure shown in formula (2-9),
The dimer of the benzimidazole organic material has in formula (3-1)-structure shown in formula (3-6)
Plant or various：
4. the organic electroluminescence device according to claim any one of 1-3, it is characterised in that described
The thickness of electron injecting layer is 1-10nm.
5. organic electroluminescence device according to claim 4, it is characterised in that described luminescent layer
Electron transfer layer is provided with and described electron injecting layer between.
6. organic electroluminescence device according to claim 5, it is characterised in that described luminescent layer
The first organic function layer is provided with and the first electrode layer between.
7. organic electroluminescence device according to claim 6, it is characterised in that first organic work(
Ergosphere is hole injection layer and/or hole transmission layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101093874A (en) * | 2006-03-21 | 2007-12-26 | 诺瓦莱德公开股份有限公司 | Method of manufacturing compound including matrix material and doping material, and layer including doped organic material |
| US20110240980A1 (en) * | 2010-04-05 | 2011-10-06 | Peng Wei | n-Type Doped Organic Materials and Methods Therefor |
| US20120256296A1 (en) * | 2011-04-05 | 2012-10-11 | Peng Wei | Semiconductor materials, apparatuses and methods |
| US20140070178A1 (en) * | 2012-09-07 | 2014-03-13 | Postech Academy-Industry Foundation | Organic light-emitting device |
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| CN101093874A (en) * | 2006-03-21 | 2007-12-26 | 诺瓦莱德公开股份有限公司 | Method of manufacturing compound including matrix material and doping material, and layer including doped organic material |
| US20110240980A1 (en) * | 2010-04-05 | 2011-10-06 | Peng Wei | n-Type Doped Organic Materials and Methods Therefor |
| US20120256296A1 (en) * | 2011-04-05 | 2012-10-11 | Peng Wei | Semiconductor materials, apparatuses and methods |
| US20140070178A1 (en) * | 2012-09-07 | 2014-03-13 | Postech Academy-Industry Foundation | Organic light-emitting device |
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