CN110343073A - Benzimidazole n-type dopant and its application in organic electroluminescence device - Google Patents
Benzimidazole n-type dopant and its application in organic electroluminescence device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/20—Two benzimidazolyl-2 radicals linked together directly or via a hydrocarbon or substituted hydrocarbon radical
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H—ELECTRICITY
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract
The present invention relates to a kind of benzimidazole n-type dopants, the dimer class n-type doping material of structure shown in the neutral n-type doping material or formula (3) of structure shown in the organic ion salt of the halide anion containing benzimidazole with structure shown in formula (1), formula (2), it can enhance electron injection when being used as the dopant of electron transport material, improve thin film electronic mobility and carrier concentration, increase device current density, improves device efficiency and stability.
Description
The application is that " applying date 2015-07-02, application No. is 201510382456.3, entitled benzo miaows
The divisional application of azole n-type dopant and its application in organic electroluminescence device ".
Technical field
The invention belongs to field of organic electroluminescent materials, and in particular to a kind of organic electroluminescence device of can be applied to
Benzimidazole n-type dopant, and its application in field of organic electroluminescence.
Background technique
The luminescent layer of organic electroluminescent device OLED mainly use full fluorescent material, full phosphor material or fluorescent material and
The mode of phosphor material mixing is made.Requirement due to blue and green light, red device to hole transmission layer HTL is different, especially
It is that green light and feux rouges will have high triplet T to HTL material1, but there is high triplet T1HTL material
Material generally all has low mobility, and driving voltage is high, and the service life is short, so in order to meet the performance pair of RGB device simultaneously
HTL material should have high T1There is high mobility again, current this kind of material is difficult to find.
It is general to use precision Mask in order to reduce technology difficulty and production cost in OLED display device preparation process
The luminescent layer of vacuum evaporation red, green, blue sub-pixel respectively, and the hole injection layer, hole transmission layer, electronics except luminescent layer pass
The shared unified evaporation film-forming such as defeated layer, hole/exciton barrier-layer.The phosphorescent coloring used due to red and green subpixels luminescent layer
Triplet excitons last a long time, be easy to diffuse to electron transfer layer, Exciton quenching caused to inactivate, therefore in luminescent layer and electronics
One layer of exciton barrier-layer (HBL) is set between transport layer.Exciton blocking layer material generally requires higher triplet
And higher HOMO energy level, so that triplet excitons be stopped to enter electron transfer layer.
The HOMO energy level of n-type dopant must be on the lumo energy of material of main part, and HOMO energy level is excessively high can make to mix
Miscellaneous agent material is unstable in air.For the lumo energy of traditional electron transport material ETM in -3.0eV or so, this requires mix
Miscellaneous dose of HOMO energy level must be more than -3.0eV, and such dopant will be quickly oxidized in air.Containing n-type dopant
Organic evaporating layer conductivity it is not high.
It is adjacent luxuriant and rich with fragrance that CN200680050740.X discloses at least one organic semiconducting materials that can inversely restore being doped
Sieve quinoline derivant and at least one dopant (metal complex) (n- doping) improve conductivity (the height vapor deposition temperature of organic evaporating layer
Spend high conductivity).0.5~25wt% of doping concentration.The patent document dopant contains metallic atom, easily causes luminescence queenching.
CN200710089662.0 discloses at least one host material (electron transport material) and at least one is nonactive
The mixture of dopant steams altogether in the same evaporation source, through blue light illumination, so that conductivity improves.It needs to be additionally provided energy
Source, and can steam that blending material is few, and doping concentration is not easy to control altogether.
Summary of the invention
The purpose of the present invention is to provide a kind of benzimidazole n-type dopants, are used as electron transport material Shi Kezeng
Strong electron injection improves thin film electronic mobility and carrier concentration, increases device current density, improves device efficiency and stabilization
Property.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of benzimidazole n-type dopant, the halide anion containing benzimidazole with structure shown in formula (1) have
The dimer class n-type doping material of structure shown in the neutral n-type doping material or formula (3) of structure shown in machine ion salt, formula (2)
Material:
Wherein: BI has structure shown in formula (5),
R5~R10It is identical or different, separately it is selected from hydrogen, methoxyl group, dimethylamino, substituted or unsubstituted indoles
And carbazyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base,
Substituted or unsubstituted phenoxazine base；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
Substituent group in the phenoxazine base in generation is C1-C6Alkyl, methoxyl group, dimethylamino, it is a kind of in ethyoxyl or phenyl or in which
It is several；
Ar is 2- methoxybenzene, 2,6- dimethoxy benzene or 2,4,6- trimethoxy-benzene；
X is halogen.
Optionally, in benzimidazole n-type dopant, the organic ion salt containing benzimidazole has formula (24)-formula (26)
Shown structure, neutral n-type doping material have structure shown in formula (30)-formula (32), and dimer class n-type doping material has formula
(36) structure shown in-formula (38):
R1~R6It is identical or different, it is separately selected from hydrogen, methoxyl group, dimethylamino, substituted or unsubstituted indoles is simultaneously
Carbazyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base take
Generation or unsubstituted phenoxazine base；
Substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base are substituted
Substituent group in phenoxazine base is C1-C6Alkyl, methoxyl group, dimethylamino, it is a kind of in ethyoxyl or phenyl or in which it is several
Kind.
Optionally, in benzimidazole n-type dopant, the organic ion salt containing benzimidazole has formula (1-12)-formula
Structure shown in (1-15), neutral n-type doping material have structure shown in formula (2-7)-formula (2-19), dimer class n-type doping
Material has structure shown in formula (3-4)-formula (3-6):
Benzimidazole n-type dopant is used as the dopant material of electron transfer layer in organic electroluminescence device.
A kind of organic electroluminescence device, including substrate, and the anode layer, the organic light emission function that are sequentially formed on substrate
Ergosphere and cathode layer；Organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, electron transfer layer
In doped with aforementioned any benzimidazole n-type dopant.
Optionally, in organic electroluminescence device, benzimidazole n-type dopant accounts for the 0.5- of electron transfer layer
30wt%.
Compared with prior art, the advantages of benzimidizole derivatives of the invention, is:
(1) benzimidazole n-type dopant of the invention is that stable in the air existing can contain imidazole group, packet
The organic salt of the halide anion containing benzimidazole is included, neutral organic molecule and dimeric molecule etc. are divided after heating in vacuum
Solution generates active free radical, realizes the effect of N doping.Since dopant is organic molecule, and the inorganic base gold that tradition uses
Belong to class N type dopant to compare, doping effect can be adjusted by MOLECULE DESIGN (changing substituent group type and number etc.).Having
The upper substituent group for introducing electron, improves the activity of free radical in machine molecule, its HOMO energy level is made to be higher than -3.0eV.Due to normal
OLED electron transport material lumo energy about -3.0eV, therefore doped with benzimidazole n-type dopant of the invention
Electron transfer layer can enhance electron injection, improve thin film electronic mobility and carrier concentration, increase device current density, improve
Device efficiency and stability.Benzimidazole N dopant presence stable in the air of the invention, convenient for long-term storage.
(2) the vapor deposition temperature of benzimidazole n-type dopant of the invention is low, only 150 DEG C or so and common electronics biography
Defeated material is suitable, and well below the vapor deposition temperature of common alkaline metal salt N type dopant (be greater than 600 DEG C), therefore can be with
Realization is deposited in organic chamber with Organic Electron Transport Material altogether, reduces cost.
(3) in addition, compared to tradition use based on alkali metal atom/alkaline earth metal atom n-type dopant, it is such
Organic n-type dopant series that low temperature can be deposited can to avoid being permeated because of metallic atom caused by shine quenching phenomenon, improve
The performances such as device efficiency and extension service life.
Detailed description of the invention
Fig. 1 is the voltage and current density curve of the device of embodiment 1 and comparative example 1 and comparative example 2；
Fig. 2 is the brightness current efficiency curve graph of the device of embodiment 1 and comparative example 1 and comparative example 2；
Fig. 3 is the brightness power efficiency curve diagram of the device of embodiment 1 and comparative example 1 and comparative example 2；
Fig. 4 is the life curve figure of the device of embodiment 1 and comparative example 1 and comparative example 2；
Fig. 5 is the voltage brightness curve of the device of embodiment 1 and comparative example 1 and comparative example 2；
Fig. 6 is the structural schematic diagram of organic electroluminescence device；
Wherein 01- substrate, 02- anode layer, 03- cathode layer, 04- hole injection layer, 05- hole transmission layer, 06- shine
Layer, 07- electron transfer layer.
Specific embodiment
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 the disclosure will be thorough and complete, and design of the invention will be fully conveyed to
Those skilled in the art, the present invention will only be defined by the appended claims.In the accompanying drawings, for clarity, the area Ceng He can be exaggerated
The size and relative size in domain.It should be understood that when element such as layer, region or substrate are referred to as " being formed in " or " setting
" another element "upper" when, which can be arranged directly on another element, or there may also be intermediary elements.
On the contrary, intermediary element is not present when element is referred to as on " being formed directly into " or " being set up directly on " another element.
A kind of benzimidazole n-type dopant provided by the invention, the halogen containing benzimidazole with structure shown in formula (1)
The dimer class of structure shown in the neutral n-type doping material or formula (3) of structure shown in the organic ion salt of plain anion, formula (2)
N-type doping material:
Wherein: BI has structure shown in formula (4) or formula (5),
R1~R10It is identical or different, separately it is selected from hydrogen, methoxyl group, dimethylamino, substituted or unsubstituted indoles
And carbazyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base,
Substituted or unsubstituted phenoxazine base；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
Substituent group in the phenoxazine base in generation is C1-C6Alkyl, methoxyl group, dimethylamino, it is a kind of in ethyoxyl or phenyl or in which
It is several；
Ar is 2- methoxybenzene, 2,6- dimethoxy benzene or 2,4,6- trimethoxy-benzene；
X is halogen.
The organic ion salt containing benzimidazole has structure shown in formula (21)-formula (26), the neutrality n-type doping
Material has structure shown in formula (27)-formula (32), and the dimer class n-type doping material has knot shown in formula (33)-formula (38)
Structure:
R1~R6It is identical or different, it is separately selected from hydrogen, methoxyl group, dimethylamino, substituted or unsubstituted indoles is simultaneously
Carbazyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base take
Generation or unsubstituted phenoxazine base；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base take
Substituent group in the phenoxazine base in generation is C1-C6Alkyl, methoxyl group, dimethylamino, it is a kind of in ethyoxyl or phenyl or in which
It is several.
The organic ion salt containing benzimidazole has structure shown in formula (1-1)-formula (1-15), and the neutrality n-type is mixed
Miscellaneous material has structure shown in formula (2-1)-formula (2-19), and the dimer class n-type doping material has formula (3-1)-formula (3-
6) structure shown in:
Above-mentioned benzimidazole n-type dopant is used as the doping material of electron transfer layer in organic electroluminescence device
Material.
As shown in fig. 6, a kind of organic electroluminescence device, including substrate 01, and sequentially form on the substrate
Anode layer 02, organic luminescence function layer and cathode layer 03；The organic luminescence function layer includes hole injection layer 04, hole transport
Layer 05, organic luminous layer 06 and electron transfer layer 07, doped with the benzimidazole n-type in the electron transfer layer
Dopant.The benzimidazole n-type dopant accounts for the 0.5-30wt% of electron transfer layer.
The synthetic route of above compound is as follows:
1, the synthetic route of formula (1-3)
By 5.0g (23.85mmol) 2- (2- hydroxy phenyl) -1H- benzimidazole (formula 4-1) be dissolved in 40mL 5N KOH and
In 10mL alcohol mixed solution, 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.Then end of reaction, the white depositions being obtained by filtration are used ethyl alcohol recrystallization 2 times, obtain 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 preparation formula (1-1), formula (1-2) and formula (1-4) are to formula (1-15), wherein formula (1-1) and formula (1-2) are formula (4-
1) respectively with CH3Cl and CH3Br reaction；Formula (1-4), formula (1-5), formula (1-6) be formula (4-2) respectively with CH3Cl, CH3Br and
CH3I reaction；Formula (1-7), formula (1-8), formula (1-9) be formula (4-3) respectively with CH3Cl, CH3Br and CH3I reaction；Formula (1-10)
It is formula (4-4) and CH3I reaction；Formula (1-11) is formula (4-5) and CH3Cl reaction；Formula (1-12) is formula (4-6) and CH3Br reaction；
Formula (1-13) is formula (4-7) and CH3Cl reaction；Formula (1-14) is formula (4-8) and CH3I reaction；Formula (1-15) be formula (4-9) with
CH3I reaction, the same formula of reaction condition (1-3).
2, formula (2-1) synthetic route
50mL 2- oxygen tolyl aldehyde (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 twice in ethanol, 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 preparation 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 formula (5-5) and formula (5-3) 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, dry Schlenk pipe is full of mercury (ca.60g, ca.0.3mol), by the Na of fritter (ca.600mg,
Ca.26mmol it) is added into Schlenk pipe.2-Cyc-DMBI-PF6 (formula 6-1) (2.0g, 5.3mmol) and dry anaerobic is added
THF (10mL) into pipe, it is ensured that sodium amalgam can be stirred evenly in liquid condition.Solution system room temperature in the dark state
Stirring 12 hours.THF solution is removed from sodium amalgam system then, THF cleaning sodium amalgam is then used for multiple times.It will be collected into
THF solution be concentrated in the case where not heating.The solid matter being concentrated to get is suspended in the heptane of anhydrous and oxygen-free
(100mL) is then washed by DMSO (3 × 30mL) and water (30mL) respectively.The water in system finally is removed using magnesium sulfate,
Normal-temperature vacuum concentration is carried out after filtering, obtains white solid shown in formula (3-1), yield 57%.It can also be by full at -20 DEG C
It is recrystallized in normal heptane, obtains the product of higher purity.1H NMR (D8-THF, 500MHz): δ 6.43 (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；473.4 (Me+M of ESI-MS:m/z+), 229.0 (Me/2+),
When preparation 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-PF6(2.0g, 5.43mmol), by with formula (3-1)
Identical synthetic method obtains the formula (3-2) of white powder.
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), 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)
One of.
Cathode generally uses the lower metal of the 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 and metal fluoride are alternatively formed.Cathode is preferably Al layers 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。
Organic electroluminescence device of the 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 benzophenanthrene HAT- for example can be used in the material of hole injection layer
CN, 4,4', 4 "-three (3- aminomethyl phenyl aniline) triphen amino-group doping F4TCNQ, or copper phthalocyanine (CuPc) is used, or can be metal
It is oxide-based, such as molybdenum oxide, rheium oxide.
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, such as aromatic condensed ring can be used in the material of main part of electron transfer layer of the invention
Class (such as Pentacene) or o-phenanthroline class (such as Bphen, BCP) compound.
Organic electroluminescence device of the present invention, including being sequentially depositing the anode 02 being stacked on one another on substrate 01, hole passes
Defeated layer 05, luminescent layer 06, electron transfer layer 07 and cathode 03, then encapsulate.
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 encapsulation.
Embodiment 1
1 structure of device of the present embodiment is as follows:
ITO (150nm)/HATCN (40nm)/NPB (30nm)/TCTA (10nm)/CBP:5wt%Ir (ppy)3(30nm)/
Bphen (30nm)/Bphen:30wt% formula (1-3) (20nm)/Al (150nm)
Wherein, (o-MeO-DMBI-I) structural formula shown in formula (1-3) is as follows:
It is dense that 30wt% in device 1 before o-MeO-DMBI-I indicates that o-MeO-DMBI-I is adulterated in electron transport material
Degree.
The organic electroluminescence device specific the preparation method is as follows:
Firstly, being cleaned using detergent and deionized water to glass substrate, and it 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, rate of film build 0.1nm/s, vapor deposition film thickness is 40nm.
Hole transmission layer NPB and TCTA are gradually deposited on hole injection layer, total film is deposited in rate of film build 0.1nm/s
Thickness is 40nm, and wherein NPB is with a thickness of 30nm, and TCTA is with a thickness of 10nm.
Luminescent layer is deposited on the hole transport layer, is carried out using the method that double source steams altogether, CBP and Ir (ppy)3Quality hundred
Divide than by thickness monitoring instrument, adjustment rate of film build is controlled.Vapor deposition film thickness is 30nm.
On luminescent layer, continue to be deposited one layer of Bphen material as the second electron transfer layer, evaporation rate is
0.1nm/s, vapor deposition total film thickness are 30nm；
On the second electron transfer layer, using the method that double source steams altogether carry out vapor deposition the first electron transfer layer, Bphen with
The mass percent of o-MeO-DMBI-I is controlled by thickness monitoring instrument, adjustment rate of film build.Vapor deposition total film thickness is 30nm；
Finally, cathode layer of the evaporating Al layer as device on above-mentioned electron transfer layer, wherein Al layers of evaporation rate
For 1.0nm/s, with a thickness of 150nm.
Comparative example 1
Organic electroluminescence device is prepared in method identical with above-described embodiment 1,1 structure of comparative device is as follows:
ITO (150nm)/HATCN (40nm)/NPB (30nm)/TCTA (10nm)/CBP:5wt%Ir (ppy)3(30nm)/
Bphen(30nm)/Bphen(20nm)/Al(150nm)
Comparative device 1 and the structure of device 1 are only in that in the electron transfer layer of comparative device 1 and mix without o-MeO-DMBI-I
It is miscellaneous.
Comparative example 2
Organic electroluminescence device is prepared in method identical with above-described embodiment 1,2 structure of comparative device is as follows:
ITO (150nm)/HATCN (40nm)/NPB (30nm)/TCTA (10nm)/CBP:5wt%Ir (ppy)3(30nm)/
Bphen (30nm)/Bphen:30wt%Cs2CO3(20nm)/Al(150nm)
Comparative device 2 and the structure of device 1 are only in that in the electron transfer layer of comparative device 1 using Cs2CO3Doping.
Device 1 and the voltage-current density curve of comparative device 1 and comparative device 2 are shown in that Fig. 1, luminance-current efficiency are bent
Line is shown in that Fig. 2, brightness-power efficiency curve are shown in that Fig. 3, life curve are shown in that Fig. 4, voltage-brightness curve are shown in Fig. 5 from Fig. 1-Fig. 5
Know that the current efficiency of o-MeO-DMBI-I is higher than doping Cs2CO3Device, service life are also longer than the material that two comparative examples use more
Times, especially 22 times higher than the service life of pure Bphen, specific data see the table below:
The test result of table 1 device 1 and comparative device
Embodiment 2-17
To test the influence of material of main part of the invention to organic electroluminescence device performance, the present embodiment with above-mentioned reality
It applies the identical method of example 1 and prepares organic electroluminescence device, the structure of device 2-17 is as follows:
ITO (150nm)/NPB (40nm)/CBP:3% phosphorescent coloring (Ir (ppy)3)(30nm)/Bphen(20nm)/LiF
(0.5nm)/Al(150nm)。
In the present embodiment and hereinafter, the doping concentration of benzimidazole n-type dopant is wt%, i.e., and 0.5,1,
5,10,20,30 act on behalf of doping concentration respectively as 0.5wt%, 1wt%, 5wt%, 10wt%, 20wt%, 30wt%.
The performance of organic electroluminescence device indicates in the following table 4:
Table 4
Although the present invention is described in conjunction with the embodiments, the present invention is not limited to the above embodiments, should manage
Solution, under the guidance 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 (6)
1. a kind of benzimidazole n-type dopant, which is characterized in that the yin of halogen containing benzimidazole with structure shown in formula (1)
The dimer class n-type of structure shown in the neutral n-type doping material or formula (3) of structure shown in the organic ion salt of ion, formula (2)
Dopant material:
Wherein: BI has structure shown in formula (5),
R5~R10It is identical or different, separately selected from hydrogen, methoxyl group, dimethylamino, substituted or unsubstituted indoles and click
Oxazolyl, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base replace
Or unsubstituted phenoxazine base；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base are substituted
Substituent group in phenoxazine base is C1-C6Alkyl, methoxyl group, dimethylamino, it is a kind of in ethyoxyl or phenyl or in which it is several
Kind；
Ar is 2- methoxybenzene, 2,6- dimethoxy benzene or 2,4,6- trimethoxy-benzene；
X is halogen.
2. benzimidazole n-type dopant according to claim 1, which is characterized in that it is described containing benzimidazole it is organic from
Alite has structure shown in formula (24)-formula (26), and the neutrality n-type doping material has structure shown in formula (30)-formula (32),
The dimer class n-type doping material has structure shown in formula (36)-formula (38):
R1~R6It is identical or different, separately it is selected from hydrogen, methoxyl group, dimethylamino, substituted or unsubstituted indolocarbazole
Base, substituted or unsubstituted carbazyl, substituted or unsubstituted dicarbazyl, substituted or unsubstituted triphenylamine base, replace or
Unsubstituted phenoxazine base；
The substituted indolocarbazole base, substituted carbazyl, substituted dicarbazyl, substituted triphenylamine base are substituted
Substituent group in phenoxazine base is C1-C6Alkyl, methoxyl group, dimethylamino, it is a kind of in ethyoxyl or phenyl or in which it is several
Kind.
3. benzimidazole n-type dopant according to claim 2, which is characterized in that described containing the organic of benzimidazole
Ion salt has structure shown in formula (1-12)-formula (1-15), and the neutrality n-type doping material has formula (2-7)-formula (2-19)
Shown structure, the dimer class n-type doping material have structure shown in formula (3-4)-formula (3-6):
4. the described in any item benzimidazole n-type dopants of claim 1-3 are used as electricity in organic electroluminescence device
The dopant material of sub- transport layer.
5. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；The organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, spy
Sign is:
Doped with the described in any item benzimidazole n-type dopants of claim 1-3 in the electron transfer layer.
6. organic electroluminescence device according to claim 5, which is characterized in that the benzimidazole n-type dopant accounts for
The 0.5-30wt% of electron transfer layer.
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