CN106898701B - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
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- CN106898701B CN106898701B CN201510956740.7A CN201510956740A CN106898701B CN 106898701 B CN106898701 B CN 106898701B CN 201510956740 A CN201510956740 A CN 201510956740A CN 106898701 B CN106898701 B CN 106898701B
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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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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Abstract
The present invention relates to a kind of organic electroluminescence devices, including first electrode layer, luminescent layer, electron injecting layer and the second electrode lay being superposed, the electron injecting layer and the second electrode lay physical contact setting.The electron injecting layer includes one or more in the dimer of benzimidazole organic material shown in benzimidazole neutral organic material and formula (III) shown in the organic ion salt of benzimidazole, formula (II) shown in formula (I), this kind of material makes the potential barrier between the second electrode lay and organic electron transport layer interface reduce, improve the transmittability of carrier, so as to so that electron injecting layer and the second electrode lay direct physical contact setting, it no longer needs that insulating buffer layer is arranged, has and improve device efficiency, extend the performances such as device lifetime.
Description
Technical field
The invention belongs to OLED device fields, 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；The organic light emission work(
Ergosphere includes hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and electron injecting layer.Due to cathode with have
There is larger electron injection barriers between the interface of machine electron transfer layer, in order to improve the balance between electrons and holes
Property, insulating buffer layer is introduced between electron injecting layer and cathode, such as LiF layers (0.5nm), after introducing, potential barrier reduces, electronics note
Enter ability to be obviously improved, driving voltage declines, and luminous efficiency improves.But LiF evaporating temperatures are high (620~640 DEG C), Li ions
Infiltration be easy to cause be quenched it is luminous, and then influence device stability.
Nowalt Publication Co., Ltd CN200710088908 disclose a kind of free radical of heterocycle and it is double from
By base, dimer, oligomer, polymer, dispiro compounds and polycyclic, shown in structure specific as follows：(same type, but point
Minor structure does not repeat, and can refer to and use)
Such compound is N-type dopant, is used as implanted layer and barrier layer, when being used as implanted layer, is adulterated with N-type
Agent mode uses, it is necessary to which carrier transport speed could be increased by being entrained in host material, and this material needs are light-initiated
It uses, technique is harsh.
Invention content
The Li ions infiltration that the present invention is directed in existing insulating buffer layer leads to that luminous problem is quenched, and providing one kind has
Organic electroluminescence devices, the material that electron injecting layer uses for benzimidazole organic material, this kind of material make the cathode with
Potential barrier reduces between the interface of organic electron transport layer, so as to so as to make electron injecting layer and the direct object of the second electrode lay
Reason contact setting, need not be arranged insulating buffer layer, have and improve device efficiency, extend the performances such as device lifetime.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of organic electroluminescence device, including be superposed first electrode layer, luminescent layer, electron injecting layer and second
Electrode layer, the electron injecting layer and the second electrode lay physical contact setting；
The electron injecting layer includes benzimidazole shown in the organic ion salt of benzimidazole, formula (II) shown in formula (I)
It is one or more in the dimer of benzimidazole organic material shown in neutral organic material and formula (III)：
Wherein：BI has structure shown in formula (IV) or formula (V)：
R1~R10It is identical or different, separately it is selected from methoxyl group, dimethylamino, substituted or unsubstituted indoles and click
Oxazolyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base, substitution
Or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
It is C for the substituent group in phenoxazine groups1-C6Alkyl, methoxyl group, dimethylamino, ethyoxyl and one kind or more in phenyl
Kind；
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 it is one or more in structure shown in formula (21)-formula (26), it is described
Benzimidazole neutral organic material has one or more, the benzimidazole in structure shown in formula (27)-formula (32)
The dimer of organic material has one or more in structure shown in formula (33)-formula (38)：
R1~R10It is identical or different, separately it is selected from methoxyl group, dimethylamino, substituted or unsubstituted indoles and click
Oxazolyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base, substitution
Or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
It is C for the substituent group in phenoxazine groups1-C6Alkyl, methoxyl group, dimethylamino, ethyoxyl and one kind or more in phenyl
Kind.
The organic ion salt of the benzimidazole has one or more, the institute in structure shown in formula (1-1)-formula (1-15)
Benzimidazole neutral organic material is stated with one or more, the benzo miaow in structure shown in formula (2-1)-formula (2-9)
The dimer of azole organic material has one or more in structure shown in formula (3-1)-formula (3-6)：
The thickness of the electron injecting layer is 1-10nm.
Preferably, it is provided with electron transfer layer between the luminescent layer and the electron injecting layer.
It is further preferred that being provided with the first organic function layer between the luminescent layer and the first electrode layer.
First organic function layer is hole injection layer and/or hole transmission layer.
Compared with prior art, the advantages of benzimidazole organic functional material of the invention, is：
(1) electron injecting layer in organic electroluminescence device of the present invention uses the organic material of benzimidazole
Material is because this kind of material makes potential barrier between the cathode and the interface of organic electron transport layer reduce, so as to so that electronics
Implanted layer and the second electrode lay direct physical contact setting avoid device because what Li ion permeable belts came is quenched luminous and device
The unstability of part has and improves the performances such as device efficiency and extension device lifetime.
(2) the benzimidazole organic material that the present invention uses stable in the air can exist, including contain benzimidazole
Halide anion organic salt, neutral organic molecule and dimeric molecule etc., after heating in vacuum, decompose generate it is active
Free radical realizes the effect of N doping.The substituent group that electron is introduced in organic molecule, improves the activity of free radical, makes it
HOMO energy levels are higher than -3.0eV.Due to common OLED electron transport materials lumo energy about -3.0eV, work as electron injection
Layer uses the organic salt of the halide anion of benzimidazole, neutral organic molecule and dimeric molecule etc. that can enhance electron injection,
Thin film electronic mobility and carrier concentration are improved, device current density is increased, improves device efficiency and stability.With low work content
The shortcomings that stability is poor in an atmosphere for several alkali and alkaline earth metal ions salts, and resistance to corrosion is bad, oxidizable or stripping is not
Equally, benzimidazole organic functional material presence stable in the air of the invention, convenient for long-term storage.
(3) the vapor deposition temperature of benzimidazole organic material of the invention is low, only 150 DEG C or so and common electronics injection
Material is suitable, and the vapor deposition temperature well below common alkaline metal salt or alkaline-earth metal salt N type dopant (is more than 600
DEG C), therefore may be implemented to be deposited in organic chamber, reduce cost.
(4) such in addition, compared to the n-type dopant based on alkali metal atom/alkaline earth metal atom that tradition uses
The benzimidazole material that low temperature can be deposited can to avoid being permeated because of metallic atom caused by shine quenching phenomenon, improve device
Efficiency extends device lifetime.
(5) organic electroluminescence of the invention reduces potential barrier between cathode and the interface of organic electron transport layer, and
Since the reduction of potential barrier causes carrier injection to increase, the transmittability of carrier is improved, so as to so that electron injecting layer
It is arranged with the second electrode lay direct physical contact, it is no longer necessary to insulating buffer layer be set, device efficiency is improved, extended
Device lifetime.
Description of the drawings
Fig. 1 is the organic electroluminescence device structural schematic diagram of the present invention；
Fig. 2 is comparative device 1, the current density voltage curve figure of comparative device 2 and device 1；
Fig. 3 is comparative device 1, the luminance vs. voltage graph of comparative device 2 and device 1；
Fig. 4 is comparative device 1, current density-brightness curve figure of comparative device 2 and device 1；
Fig. 5 is comparative device 1, power efficiency-brightness curve figure of comparative device 2 and device 1；
Fig. 6 is comparative device 1, current density-brightness curve figure of comparative device 2 and device 1~5；
Fig. 7 is comparative device 1, current efficiency-brightness curve figure of comparative device 2 and device 1~5；
Fig. 8 is comparative device 1, power efficiency-brightness curve figure of comparative device 2 and device 1~5.
Specific implementation mode
It 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 embodiment set forth herein.
On the contrary, providing these embodiments so that it will be thorough and complete that the present invention, which discloses, and the design of the present invention will fully be passed
Up to those skilled in the art, the present invention will only be defined by the appended claims.In the accompanying drawings, for clarity, layer can be exaggerated
With the size and relative size in region.It should be understood that when element such as layer, region or substrate be referred to as " being formed in " or
When " setting exists " another element "upper", which can be arranged directly on another element, or there may also be centres
Element.On the contrary, when element is referred to as on " being formed directly into " or " being set up directly on " another element, intermediary element is not present.
As shown in Figure 1, a kind of organic electroluminescence device, including substrate, and the first electricity for being superposed on substrate
Pole 01 (anode) of layer, luminescent layer 04, electron injecting layer 06 and the second electrode lay 07 (cathode), the electron injecting layer 06 and described
The physical contact setting of the second electrode lay 07.The first organic function layer is provided between the first electrode layer 01 and luminescent layer 04,
Electron transfer layer 05 is provided between the luminescent layer 04 and the electron injecting layer 06；First organic function layer is hole
Implanted layer 02 and/or hole transmission layer 03；
The electron injecting layer includes benzimidazole shown in the organic ion salt of benzimidazole, formula (II) shown in formula (I)
It is one or more in the dimer of benzimidazole organic material shown in neutral organic material or formula (III)：
Wherein：BI has structure shown in formula (IV) or formula (V)：
R1~R10It is identical or different, separately it is selected from methoxyl group, dimethylamino, substituted or unsubstituted indoles and click
Oxazolyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base, substitution
Or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
It is C for the substituent group in phenoxazine groups1-C6Alkyl, methoxyl group, dimethylamino, ethyoxyl and one kind or more in phenyl
Kind；
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 it is one or more in structure shown in formula (21)-formula (26), it is described
Benzimidazole neutral organic material has one or more, the benzimidazole in structure shown in formula (27)-formula (32)
The dimer of organic material has one or more in structure shown in formula (33)-formula (38)：
R1~R10It is identical or different, separately it is selected from methoxyl group, dimethylamino, substituted or unsubstituted indoles and click
Oxazolyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base, substitution
Or unsubstituted phenoxazine group；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
It is C for the substituent group in phenoxazine groups1-C6Alkyl, methoxyl group, dimethylamino, ethyoxyl and one kind or more in phenyl
Kind.
Preferably, the organic ion salt of the benzimidazole have one kind shown in formula (1-1)-formula (1-15) in structure or
It is a variety of, the benzimidazole neutral organic material have it is one or more in structure shown in formula (2-1)-formula (2-9), it is described
The dimer of benzimidazole organic material has one or more in structure shown in formula (3-1)-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：
Inorganic material or organic conductive polymer may be used in anode.Inorganic material is generally tin indium oxide (ITO), oxidation
The higher metal of the work functions such as metal oxides or gold, copper, silver such as zinc (ZnO), indium zinc oxide (IZO), preferably ITO；It is organic to lead
Electric polymer is preferably polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter referred to as PEDOT:PSS), polyaniline (hereinafter referred to as PANI)
In one kind.
Cathode generally uses the lower metals of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or the conjunction of they and copper, gold, silver
The electrode layer that gold or metal are alternatively formed with metal fluoride.Cathode is preferably Al electrodes in the present invention.
The material of hole transmission layer can be selected from arylamine class, carbazoles and branch polymer class low molecule material, preferably NPB and
TCTA。
The organic electroluminescence device of the present invention can also have hole injection layer between anode and hole transmission layer, described
Six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzophenanthrenes for example can be used in the material of hole injection layer
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.Hole injection layer material is preferably HATCN in the present invention.
The luminescent material of luminescent layer can be selected from Coumarins such as DMQA or C545T, or double pyrans such as DCJTB or DCM
Equal fluorescent dyes, or contain Ir, Pt, Os, Ru, Rh, Pd, group of the lanthanides, the metal complexs such as actinium series.
Doping concentration of the fluorescent dye in luminescent layer is not higher than 5wt%, doping concentration of the phosphorescent coloring in luminescent layer
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 can be selected from the material for being usually used in host material, such as 4,4 '-two (carbazyl -9-) biphenyl
CBP。
The material for being usually used in electron transfer layer can be used in the material of the electron transfer layer of the present invention, (such as such as aromatic condensed ring class
Pentacene) or o-phenanthroline class (such as Bphen, BCP) compound.
Substrate can be glass or flexible substrate, and polyesters, polyimide compound can be used in the flexible substrate
Material or foil.Any suitable method well known by persons skilled in the art can be used in the stacking and packaging method.
The specific preparation method of the organic electroluminescence device of the present invention is as follows：
First, glass substrate is cleaned using detergent and deionized water, and is placed under infrared lamp and dries, in glass
One layer of anode material, film thickness 150nm are sputtered on glass；
Then, the above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-4Pa, in above-mentioned anode
Continue to be deposited HATCN on tunic as hole injection layer, continues to be deposited NPB in HATCN film layers as hole transmission layer, film forming
Rate is 0.1nm/s, and vapor deposition film thickness is 40nm.
Luminescent layer is deposited on the hole transport layer, is carried out using the method that double source steams altogether, the quality of material of main part and dyestuff
Percentage is controlled by thickness monitoring instrument, adjustment rate of film build.Vapor deposition film thickness is 30nm.
On luminescent layer, continue to be deposited one layer of Bphen material as electron transfer layer, evaporation rate 0.1nm/s,
Vapor deposition total film thickness is 40nm；
On the electron transport layer, continue that one layer of electron transport layer materials are deposited, evaporation rate 0.1nm/s, vapor deposition is always
Film thickness is 0.5nm；
Finally, the second electrode lay of the evaporating Al layer as device on above-mentioned electron transfer layer, vapor deposition film thickness are
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]
1 structure of comparative device is as follows：
ITO/HATCN[5nm]/NPB[30nm]/TCTA[10nm]/CBP[30nm]:10wt%Ir (ppy)3/Bphen
[40nm]/Al[150nm]
2 structure of comparative device is as follows：
The structure of this comparative example is identical as comparative example 1, differs only in the material that electron injecting layer uses as 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 2 structure of comparative device, differ only in the electron injecting layer use of device 1
Material is o-MeO-DMBI-I shown in formula (1-3), and it is exhausted that comparative device 1 without electron injecting layer material and comparative device 2 uses LiF
Edge buffer layer, for comparative device 1 in addition to not having insulating buffer layer (control), structure is identical with comparative device 2 in table 1,
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 device 1 are (in figure
Radical curves) current density voltage curve figure see that Fig. 2, luminance vs. voltage graph are shown in Fig. 3, current density-brightness curve
Figure is shown in that Fig. 4, power efficiency-brightness curve figure are shown in Fig. 5.Fig. 1-Fig. 5 illustrates the benzimidazole material conduct that the present invention is protected
Electron injection material, where device 1 driving voltage and the comparative device 2 where LiF driving voltage it is slightly lower, but
35700cd/m2Under light emission luminance, the maximum current efficiency of device 1 is than comparative device 1 high 49%, than comparative device 2 high 25%,
Illustrate that the benzimidazole material that the present invention is protected can promote in more electron injections to device, improves carrier transport
Ability, and then the device efficiency improved, extend device lifetime.
Embodiment 2- embodiments 5
The structure of the device 2- devices 5 of embodiment 2- embodiments 5 is identical as device 1, differs only in electron injecting layer
Thickness, table 2 are its performance test results.
Table 2
Comparative device 1 (control device curves in figure), comparative device 2 (0.5 nanometer of curve of LiF in figure) and device
(radical 1nm, radical 2nm, radical 3nm, radical 4nm, radical 6nm are bent in figure for part 1- devices 5
Line) current density-brightness curve figure see that Fig. 6, current efficiency-brightness curve figure are shown in that Fig. 7, power efficiency-brightness curve figure are shown in
Fig. 8, Fig. 6-Fig. 8 explanations increase with electron injection layer thickness, and driving voltage gradually rises, in 35700cd/m2Light emission luminance
Under, maximum current efficiency first increases with electron injection layer thickness increase and subtracts afterwards, reaches maximum when electron injection layer thickness is 3nm
Value.
Embodiment 6
6 structure of device is identical as device 1, and the thickness of electron injecting layer is 3nm, and electron injecting layer is protected using the present invention
Different benzimidazole electron injection materials, table 3 be its performance test results.
Table 3
As the data in table 3 indicates, the benzimidazole material protected of the present invention is as electron injection material, where device
Part is in 35700cd/m2Under light emission luminance, there is larger current efficiency, and driving voltage is relatively low, so what the present invention was protected
Benzimidazole material is as electron injection material so that potential barrier reduces between cathode and the interface of organic electron transport layer, no
It needs that insulating buffer layer is arranged again, improves the transmittability of carrier, then improve the efficiency of device, extend device
Service life.
The preparation method of the compound of the present invention is as follows：
1, the synthetic route of formula (1-3)：
By 5.0g (23.85mmol) 2- (2- hydroxy phenyls) -1H- benzimidazoles (formula 4-1) be dissolved in 40mL 5N KOH and
In 10mL alcohol mixed solutions, then by 20mL (45.60g, 321.26mmol) CH3I is added dropwise in solution system.Reaction system
45 DEG C are kept in oil bath to stay overnight.Reaction finishes, the white depositions being obtained by filtration, and is then cleaned 2 times with ethyl alcohol, obtains formula
Compound shown in (1-3), yield 70%.1H NMR(400MHz,DMSO)δ/ppm:8.12 (dd, J=6.23,3.14Hz,2H),
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) is 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)
It 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) is formula (4-8) and CH3I reacts；Formula (1-15) be formula (4-9) with
CH3I reacts, the same formula of reaction condition (1-3).
2, formula (2-1) synthetic route
50mL 2- oxygen tolyl aldehydes (formula 5-1) and N, N '-dimethyl-o-PDA (formula 5-4) (136mg,
It 1.0mmol) is added in methanol (2mL), aromatic aldehyde appropriate (1.00mmol) is then added.A drop glacial acetic acid is then added,
Solution system is ultrasonic until there is solid precipitation at room temperature.Mixture system obtains crude product by vacuum filtration, this thick production
Object recrystallizes in methyl alcohol, obtains pure compound shown in formula (2-1).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 that formula (5-5) is reacted with formula (5-1)；Formula (2-3) is formula
(5-4) is reacted with formula (5-2)；Formula (2-4) is that formula (5-6) is reacted with formula (5-2)；Formula (2-5) is that formula (5-5) and formula (5-3) are anti-
It answers；Formula (2-6) is that formula (5-7) is reacted with formula (5-3)；Formula (2-7) is that formula (5-8) is reacted with formula (5-1)；Formula (2-8) is formula (5-
9) it is reacted with formula (5-2)；Formula (2-9) is that formula (5-10) is reacted with formula (5-3), the same formula of reaction condition (2-1).
3, formula (3-1) synthetic route
In glove box (a kind of device that anhydrous and oxygen-free synthesis is provided, Vacuum Atmospheres Co.Glovebox,
OMNI-LAB, VAC101975), dry Schlenk pipes are full of mercury (60g, 0.3mol), by the Na of fritter (600mg,
26mmol) it is added into Shrek bottle Schlenk pipes.2-Cyc-DMBI-PF6 (formula 6-1) (2.0g, 5.3mmol) is added and does
In the tetrahydrofuran THF (10mL) to pipe of dry anaerobic, it is ensured that sodium amalgam can be stirred evenly in liquid condition.Solution system exists
It is stirred at room temperature under dark state 12 hours.THF solution is removed from sodium amalgam system then, THF cleanings are then used for multiple times
Sodium amalgam.The THF solution being collected into is concentrated in the case where not heating.The solid matter being concentrated to give is suspended in anhydrous
Then the heptane (100mL) of anaerobic is washed by DMSO (3 × 30mL) and water (30mL) respectively.Finally removed using magnesium sulfate
Water in system carries out normal-temperature vacuum concentration, obtains white solid shown in formula (3-1), yield 57% after filtering.It can also pass through
It is recrystallized in -20 DEG C of saturation normal heptane, obtains 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 is (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/z473.4(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), formula (3-6)
Raw material is formula (6-2), formula (6-3), formula (6-4), formula (6-5), the same formula of formula (6-6) reaction condition (3-1) respectively.
Formula (3-2) synthetic route：Reactant is 2- phenyl-DMBI-PF shown in formula (6-2)6(2.0g, 5.43mmol), warp
The identical synthetic method with formula (3-1) is crossed, the formula (3-2) of white powder is obtained.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiments, should manage
Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improve, and appended claims summarise
The scope of the present invention.
Claims (7)
1. a kind of organic electroluminescence device, including the first electrode layer, luminescent layer, electron injecting layer and the second electricity that are superposed
Pole layer, it is characterised in that：
The electron injecting layer and the second electrode lay physical contact setting；
The material of the electron injecting layer is benzimidazole shown in the organic ion salt of benzimidazole, formula (II) shown in formula (I)
It is one or more in the dimer of benzimidazole organic material shown in neutral organic material and formula (III)：
Wherein：BI has structure shown in formula (IV) or formula (V)：
R1~R10It is identical or different, separately it is selected from hydrogen, methoxyl group or dimethylamino；
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, which is characterized in that the organic ion salt of the benzimidazole has
Have it is one or more in structure shown in formula (21)-formula (26), the benzimidazole neutral organic material have formula (27)-formula
(32) one or more in structure shown in, the dimer of the benzimidazole organic material has formula (33)-formula (38) institute
Show one or more in structure：
R1~R10It is identical or different, separately it is selected from hydrogen, methoxyl group or dimethylamino.
3. organic electroluminescence device according to claim 2, which is characterized in that the organic ion salt of the benzimidazole
With one or more in structure shown in formula (1-1)-formula (1-15), the benzimidazole neutral organic material has formula
One or more in structure shown in (2-1)-formula (2-9), the dimer of the benzimidazole organic material has formula (3-
1) one or more in structure shown in-formula (3-6)：
4. according to any one of the claim 1-3 organic electroluminescence devices, which is characterized in that the thickness of the electron injecting layer
Degree is 1-10nm.
5. organic electroluminescence device according to claim 4, which is characterized in that the luminescent layer and electronics note
Enter and is provided with electron transfer layer between layer.
6. organic electroluminescence device according to claim 5, which is characterized in that the luminescent layer and the first electrode
It is provided with the first organic function layer between layer.
7. organic electroluminescence device according to claim 6, which is characterized in that the first organic function layer injects for hole
Layer and/or hole transmission layer.
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| Zhengyang Bin等.Air Stable Organic Salt As an n‑Type Dopant for Efficient and Stable Organic Light-Emitting Diodes.《ACS Appl. Mater. Interfaces》.2015,第7卷(第12期),第6444-6450页. * |
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