CN103626961A - Carbazole unit-containing polymer, preparation method of carbazole unit-containing polymer and organic electroluminescent device - Google Patents
Carbazole unit-containing polymer, preparation method of carbazole unit-containing polymer and organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a carbazole unit-containing polymer. The carbazole unit-containing polymer has a structural formula P shown in the patent specification, and in the structural formula, R1 represents C1-C20 alkyl, R2 represents C1-C20 alkyl and n represents an integer of 10-100. Benzodifuran of the carbazole unit-containing polymer has a large-plane conjugated structure, is conducive to charge transmission and is an excellent electron transmission unit. Through alkyl modification on the nitrogen atom, polymer solubility and film-forming performances are improved. Through introduction of a cyano group, a polymer energy grade is adjusted. Carbazole is a good hole transport unit. Through introduction of carbazolyl into the main chain of the benzodifuran-based polymer, carrier balance of an organic electroluminescent device is realized so that the problem of low efficiency of the existing organic electroluminescent device is solved. The invention also provides a preparation method of the carbazole unit-containing polymer and an organic electroluminescent device adopting the carbazole unit-containing polymer.
Description
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of polymkeric substance containing carbazole unit and preparation method thereof and the organic electroluminescence device that uses this containing the polymkeric substance of carbazole unit.
[background technology]
Since Japanese scientist's Hideki Shirakawa in 1977 is found polyacetylene conduction, this being called as the conductive polymers of " the 4th generation polymer " material with its outstanding photoelectric properties, attracted numerous scientists to study.Conducting polymer is compared with the inorganic materials with identical or close purposes, has density low, and easily processing, synthesizes the advantages such as range of choice is wide.Due to the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may being applied on many electronics or opto-electronic device, for example comprise polymer LED, photovoltaic cell, field-effect etc.Potential application prospect and wide application field impel scientist competitively to study the conjugation material that this class has photoelectric activity, comprise conjugated structure small molecules, and polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes, polycarbazole etc.
Researchist is making great efforts to seek to improve the method for polymer LED, photovoltaic cell, field effect behavior always, and material is one of most important factor.So being devoted to exploitation always, many research groups there is high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good, and the polymkeric substance that visible-range absorption bands is wide, carrier mobility is high.Realize these targets, need to develop more novel conjugated molecular material and polymer materials, wherein, design synthesizing new conjugate unit just seems very important.
[summary of the invention]
Based on this, be necessary the polymkeric substance containing carbazole unit that provides a kind of energy conversion efficiency higher.
In addition, be also necessary to provide a kind of preparation method of the polymkeric substance containing carbazole unit.
In addition, be also necessary to provide the organic electroluminescence device using containing the polymkeric substance of carbazole unit.
A polymkeric substance containing carbazole unit, has following structural formula:
P:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
A preparation method who contains the polymkeric substance of carbazole unit, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added into and in the organic solvent that contains catalyzer, carry out Stille coupling reaction, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the polymer P containing carbazole unit that following structural formula represents:
P:
Wherein, the integer that n is 10 ~ 100.
In a preferred embodiment, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
In a preferred embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
In a preferred embodiment, the mol ratio of the organic palladium in described catalyzer and described compd A is 1:20 ~ 1:100.
In a preferred embodiment, the temperature of reaction of described Stille coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 6 hours ~ 60 hours.
In a preferred embodiment, also comprise the step that the polymer P containing carbazole unit is carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing carbazole unit after purifying.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
An organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer is the polymer P containing carbazole unit with following structural formula:
P:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Above-mentioned containing in the polymer electroluminescent device of carbazole unit, benzo two furans have large plane and conjugated structure, are conducive to electric charge transmission, are good electric transmission unit; On N, pass through alkyl modified, thereby improve solubility property and the film forming properties of multipolymer, by introducing cyano group, can regulate the energy level of multipolymer, carbazole is good hole transport unit, on benzo difuryl main polymer chain, introduce carbazyl, realize the carrier balance of electroluminescent device, thereby solve organic electroluminescence device low efficiency problem.
The preparation method of the above-mentioned polymkeric substance containing carbazole unit, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, applicable to organic electroluminescence device.
[accompanying drawing explanation]
Fig. 1 is the preparation method's containing the polymkeric substance of carbazole unit of an embodiment schema;
Fig. 2 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 3 is the fluorescence spectrum figure of the polymkeric substance containing carbazole unit of embodiment 1 preparation;
Fig. 4 is the thermogravimetic analysis (TGA) figure of the polymkeric substance containing carbazole unit of embodiment 1 preparation.
[embodiment]
Polymkeric substance that contains carbazole unit below in conjunction with the drawings and specific embodiments and its preparation method and application is further illustrated.
The polymkeric substance containing carbazole unit of one embodiment, has following structural formula:
P:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Above-mentioned have large plane and conjugated structure containing benzo two furans in the polymkeric substance of carbazole unit, is conducive to electric charge transmission, is good electric transmission unit; On nitrogen-atoms by alkyl modified, thereby improve solubility property and the film forming properties of polymkeric substance, by introducing the energy level that cyano group can telomerized polymer.Carbazole is good hole transport unit, on benzo difuryl main polymer chain, introduces carbazyl, realizes the carrier balance of electroluminescent device, thereby solves organic electroluminescence device low efficiency problem.
The preparation method of the polymkeric substance containing carbazole unit of one embodiment, as shown in Figure 1, comprises the following steps:
Step S1, provide compd A and compd B.
The structural formula of compd A is:
wherein, R
1for C
1~ C
20alkyl.
The structural formula of compd B is:
wherein, R
2for C
1~ C
20alkyl.
Step S2, preparation contain the polymer P of carbazole unit.
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added into and in the organic solvent that contains catalyzer, carry out Stille coupling reaction, described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains the polymer P containing carbazole unit that following structural formula represents:
P:
Wherein, the integer that n is 10 ~ 100.
In present embodiment, Stille coupling reaction carries out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).Be appreciated that organic solution also can be used other solvents, as long as can dissolved compound A and compd B.
In present embodiment, organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, and organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl.In the mixture of organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1:4 ~ 1:8.Preferably, adopt the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine as catalyzer.Be appreciated that organic palladium, organophosphor ligand are all not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Stille coupling reaction
In present embodiment, in catalyzer, the mol ratio of organic palladium and compd A is 1:20 ~ 1:100.The mol ratio that is appreciated that organic palladium and compd A is not limited to 1:20 ~ 1:100, to adding the catalyzer that adds catalytic amount in the organic solvent of compd A and compd B.
In present embodiment, the temperature of reaction of Stille coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 6 hours ~ 60 hours.Preferably, the temperature of reaction of Stille coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 12 hours ~ 48 hours.The temperature of reaction that is appreciated that Stille coupling reaction is not limited to 70 ℃ ~ 130 ℃, as long as can make compd A and compd B react; Reaction times is also not limited to 6 hours ~ and 60 hours, as long as can make compd A and compd B react completely as far as possible.
Step S3, separation and purification contain the polymer P of carbazole unit.
To described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing carbazole unit after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collect evaporating solvent after chloroformic solution obtain the polymer P containing carbazole unit after purifying under vacuum 50 ℃ dry 24 hours.
The preparation method of the above-mentioned polymkeric substance containing carbazole unit, synthetic route is comparatively simple, has reduced manufacturing cost; The polymkeric substance containing carbazole unit of preparation is introduced carbazyl on benzo difuryl main polymer chain, realizes the carrier balance of electroluminescent device, thereby solves organic electroluminescence device low efficiency problem.
Be specific embodiment below.
Embodiment 1
The present embodiment discloses following poly-{ N-n-octyl-4,5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (containing the polymer P 1 of carbazole unit) of structural formula:
The preparation process of the above-mentioned polymer P 1 containing carbazole unit is as follows:
Under argon shield, by N-n-octyl-4,5-ethylene group-2,7-pair-(tin trimethyl) carbazole (127mg, 0.2mmol), 2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano-4,8-diiodo-benzo [1,2-b:4,5-b'] two furans (188mg, 0.2mmol) add in the flask that fills 10ml toluene solvant fully and dissolve, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Stille coupling reaction 36h.Subsequently, after cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, under vacuum pump, taking out spends the night obtains { N-n-octyl-4,5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } product, productive rate 82%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 1 of carbazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=67.2kDa, Mw/Mn=2.2.
Referring to accompanying drawing 3, be the fluorescence spectrum figure of the organic semiconductor material P1 of preparation in embodiment 1, fluorescence spectrum is measured in Jasco FP-6600 type fluorescence spectrophotometer.As seen from the figure: the maximum emission peak of polymkeric substance of the present invention is positioned at 440nm left and right, show this polymkeric substance transmitting blue light.Fluorescence quantum yield Φ
fbe 0.83.Referring to accompanying drawing 4, be the thermogravimetic analysis (TGA) figure of the organic semiconductor material P1 of the present embodiment 1 preparation, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T as seen from the figure
d) be 469 ℃.
Embodiment 2
The present embodiment discloses following poly-{ N-methyl-4,5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-bis-NSC 62789 bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (containing the polymer P 2 of carbazole unit) of structural formula:
The preparation process of the above-mentioned polymer P 2 containing carbazole unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by N-methyl-4, 5-ethylene group-2, 7-pair-(tin trimethyl) carbazole (155mg, 0.3mmol), 2, 6-bis-(N, N-bis-NSC 62789 bases are amino)-3, 7-dicyano-4, 8-diiodo-benzo [1, 2-b:4, 5-b'] two furans (484mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Stille coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain poly-{ N-methyl-4 of product, 5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-bis-NSC 62789 bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }.Productive rate is 78%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 2 of carbazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=19.5kDa, Mw/Mn=2.4.
The fluorescence spectrum of the organic semiconductor material P2 of preparation test in the present embodiment 2, fluorescence spectrum is measured in JascoFP-6600 type fluorescence spectrophotometer.Result shows: the maximum emission peak of polymkeric substance of the present invention is positioned at 437nm left and right.
The thermogravimetic analysis (TGA) of the organic semiconductor material P2 of the present embodiment 2 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 464 ℃.
Embodiment 3
The present embodiment discloses following poly-{ N-NSC 62789 base-4,5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-dimethylamino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (containing the polymer P 3 of carbazole unit) of structural formula:
The preparation process of the above-mentioned polymer P 3 containing carbazole unit is as follows:
Under nitrogen protection, by N-NSC 62789 base-4,5-ethylene group-2,7-pair-(tin trimethyl) carbazole (240mg, 0.3mmol), 2,6-bis-(N, the positive methylamino of N-bis-)-3,7-dicyano-4,8-diiodo-benzo [1,2-b:4,5-b'] two furans (180mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL and fully dissolve, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 130 ℃ and carries out Stille coupling reaction 6h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, be poly-{ N-NSC 62789 base-4 of poly-product, 5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-dimethylamino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, productive rate is 75%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 3 of carbazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=117.0kDa, Mw/Mn=2.0.
The fluorescence spectrum of the organic semiconductor material P3 of preparation test in the present embodiment 3, fluorescence spectrum is measured in JascoFP-6600 type fluorescence spectrophotometer.Result shows: the maximum emission peak of polymkeric substance of the present invention is positioned at 439nm left and right.
The thermogravimetic analysis (TGA) of the organic semiconductor material P3 of the present embodiment 3 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 467 ℃.
Embodiment 4
The present embodiment discloses following poly-{ N-normal butane base-4,5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-bis-n-decane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (containing the polymer P 4 of carbazole unit) of structural formula:
The preparation process of the above-mentioned polymer P 4 containing carbazole unit is as follows:
Under nitrogen protection, by N-normal butane base-4,5-ethylene group-2,7-pair-(tin trimethyl) carbazole (173mg, 0.3mmol), 2,6-bis-(N, N-bis-n-decane bases are amino)-3,7-dicyano-4,8-diiodo-benzo [1,2-b:4,5-b'] two furans (378mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, fully dissolve, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Stille coupling reaction 12h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, be poly-{ N-normal butane base-4 of product, 5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-bis-n-decane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }, productive rate is 85%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 4 of carbazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=37.9kDa, Mw/Mn=2.3.
The fluorescence spectrum of the organic semiconductor material P4 of preparation test in the present embodiment 4, fluorescence spectrum is measured in JascoFP-6600 type fluorescence spectrophotometer.Result shows: the maximum emission peak of polymkeric substance of the present invention is positioned at 435nm left and right.
The thermogravimetic analysis (TGA) of the organic semiconductor material P4 of the present embodiment 4 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 470 ℃.
Embodiment 5
The present embodiment discloses following poly-{ N-dodecyl-4,5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-bis-normal hexane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } (containing the polymer P 5 of carbazole unit) of structural formula:
The preparation process of the above-mentioned polymer P 5 containing carbazole unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by N-dodecyl-4, 5-ethylene group-2, 7-pair-(tin trimethyl) carbazole (206mg, 0.3mmol) (206mg, 0.3mmol), 2, 6-bis-(N, N-bis-normal hexane bases are amino)-3, 7-dicyano-4, 8-diiodo-benzo [1, 2-b:4, 5-b'] two furans (248mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Stille coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain poly-{ N-dodecyl-4 of product, 5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-bis-normal hexane bases are amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans }.Productive rate is 88%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 5 of carbazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=96.4kDa, Mw/Mn=2.1.
The fluorescence spectrum of the organic semiconductor material P5 of preparation test in the present embodiment 5, fluorescence spectrum is measured in JascoFP-6600 type fluorescence spectrophotometer.Result shows: the maximum emission peak of polymkeric substance of the present invention is positioned at 442nm left and right.
The thermogravimetic analysis (TGA) of the organic semiconductor material P5 of the present embodiment 5 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 468 ℃.
Embodiment 6
Refer to Fig. 2, a kind of organic electroluminescence device 50 comprises substrate 51, anode 52, luminescent layer 53, buffer layer 54 and negative electrode 55.Anode 52, luminescent layer 53, buffer layer 54 and negative electrode 55 are formed on substrate 51 successively, and the structure of device is: glass/ITO(150nm)/luminescent layer (30nm)/LiF (1.5nm)/Al (150nm).
In the present embodiment, substrate 51 is glass.
Be appreciated that buffer layer 54 can omit, now luminescent layer 53 is directly formed at negative electrode 55 surfaces.
The manufacturing processed of this organic electroluminescence device 50 is as follows:
The tin indium oxide (ITO) that is 10-20 Ω/mouth at surface sputtering one deck square resistance of glass substrate 51, forms the conductive layer as anode 52, base vacuum degree 2 * 10
-5pa, thickness 100～150nm.
By spin coating technique, on anode 52 surfaces, prepare one deck with poly-{ N-n-octyl-4 of the present invention, 5-ethylene group-2,7-carbazole-co-2,6-bis-(N, N-di-n-octyl is amino)-3,7-dicyano benzo [1,2-b:4,5-b'] two furans } luminescent layer 53 heats 15-60min at 100-200 ℃, rotating speed is 2000～6000rpm, and gauge control is at 20～80nm.
Vacuum evaporation LiF on luminescent layer 53, as buffer layer 54, vacuum tightness is 3 * 10
-5pa, evaporation speed is
thickness 1～2nm;
Vacuum evaporation metallic aluminium on buffer layer 54, thickness 100～200nm, forms the metal aluminium lamination as negative electrode 55, obtains described organic electroluminescence device.
In the present embodiment, the electric current-brightness-voltage characteristic of device is that all measurements that completed by the Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) with correction silicon photoelectric diode all complete in atmosphere at room temperature.The maximum luminous efficiency of device is 10.5cd/A, and high-high brightness is 16277cd/m
2.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. containing a polymkeric substance for carbazole unit, it is characterized in that thering is following structural formula:
P:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
2. containing a preparation method for the polymkeric substance of carbazole unit, it is characterized in that, the compd A and the compd B that provide following structural formula to represent be provided,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added into and in the organic solvent that contains catalyzer, carry out Stille coupling reaction, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the polymer P containing carbazole unit that following structural formula represents:
P:
Wherein, the integer that n is 10 ~ 100.
3. the preparation method of the polymkeric substance containing carbazole unit according to claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
4. the preparation method of the polymkeric substance containing carbazole unit according to claim 2, it is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
5. the preparation method of the polymkeric substance containing carbazole unit according to claim 2, is characterized in that, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1:100.
6. the preparation method of the polymkeric substance containing carbazole unit according to claim 2, is characterized in that, the temperature of reaction of described Stille coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 6 hours ~ 60 hours.
7. the preparation method of the polymkeric substance containing carbazole unit according to claim 2, is characterized in that, the temperature of reaction of described Stille coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 12 hours ~ 48 hours.
8. the preparation method of the polymkeric substance containing carbazole unit according to claim 2, it is characterized in that, also comprise the step that the polymer P containing carbazole unit is carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing carbazole unit after purifying.
9. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, the material of described luminescent layer is the polymer P containing carbazole unit with following structural formula:
P:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
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