CN103450190A - Organic semiconductor material, preparation method and electroluminescent device - Google Patents
Organic semiconductor material, preparation method and electroluminescent device Download PDFInfo
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- CN103450190A CN103450190A CN2012101681909A CN201210168190A CN103450190A CN 103450190 A CN103450190 A CN 103450190A CN 2012101681909 A CN2012101681909 A CN 2012101681909A CN 201210168190 A CN201210168190 A CN 201210168190A CN 103450190 A CN103450190 A CN 103450190A
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Abstract
The invention provides an organic semiconductor material, the chemical formula of which is shown as the following. The organic semiconductor material contains triphenylamine, carboline and benzene anthracene. Specifically, the triphenylamine has a high triplet state energy level and hole transport property, the carboline has good electronic transport performance, and the benzene anthracene has a very high fluorescence quantum yield. Thus, the organic semiconductor material provided by the invention is a bipolar blue light material. The invention also provides a preparation method of the organic semiconductor material, and an electroluminescent device including the organic semiconductor material.
Description
Technical field
The invention belongs to field of photovoltaic materials, be specifically related to a kind of organic semiconductor material, preparation method and electroluminescent device.
Background technology
Organic electroluminescence device has that driving voltage is low, fast response time, angular field of view is wide and can finely tune and change luminescent properties and make rich color by chemical structure, easily realize the advantages such as resolving power is high, lightweight, large-area flat-plate demonstration, be described as " 21 century flat panel display ", become the focus of the subjects such as material, information, physics and flat pannel display area research.Following commercialization Organic Light Emitting Diode efficiently will contain the organo-metallic phosphorescent substance possibly, because they can all catch singlet and triplet excitons, thereby realize 100% internal quantum efficiency.Yet, because the excited state exciton life-span of transition metal complex is relatively long, cause unwanted triplet state-triplet state (T
1-T
1) cancellation in the device real work.In order to overcome this problem, investigators often are doped to the triplet state shiner in the organic main body material.
In recent years, green and red phosphorescent OLED device exhibits goes out gratifying electroluminescent efficiency.And efficient blue phosphorescent device seldom, major cause is to lack to have carrier transmission performance and higher triplet (E preferably simultaneously
t) material of main part.
Summary of the invention
For addressing the above problem, the invention provides a kind of organic semiconductor material, this organic semiconductor material contains triphenylamine, carboline and benzene anthracene, wherein triphenylamine has high triplet and hole transport ability, carboline has good electronic transmission performance, and the benzene anthracene has very high fluorescence quantum yield.Organic semiconductor material of the present invention provides new selectable kind for the bipolarity blue light material.The present invention also provides the preparation method of this organic semiconductor material, and the electroluminescent device that comprises this organic semiconductor material.
On the one hand, the invention provides a kind of organic semiconductor material, the chemical formula of described organic semiconductor material is as follows:
Second aspect, the invention provides a kind of preparation method of organic semiconductor material, comprises the steps:
Compound D is provided:
and Compound C:
under inert atmosphere, the Compound D that is 1: 2.1～2.2 by mol ratio and Compound C are dissolved in organic solvent, add again mineral alkali and organic palladium catalyzer, return stirring reaction 10 hours～30 hours, crude product obtains making organic semiconductor material after separating-purifying, and the chemical formula of described organic semiconductor material is as follows:
Preferably, the organic palladium catalyzer be bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium or three dibenzalacetone two palladiums and 2-dicyclohexyl phosphorus-2 ', 6 '-mixture of dimethoxy-biphenyl.
Preferably, described separating-purifying process is specially decompression and removes the solvent in crude product, add methylene dichloride to dissolve, remove inorganic salt with the saturated aqueous common salt extraction, the organic phase anhydrous magnesium sulfate drying, filtrate after filtration except desolventizing, is made leacheate with methylene dichloride and sherwood oil with rotary evaporation, and silica gel column chromatography is purified.
Preferably, the mol ratio of described organic palladium catalyzer and Compound D is 1: 20～1: 100.
Preferably, described organic solvent comprises at least one in toluene, DMF, tetrahydrofuran (THF), glycol dimethyl ether, and described mineral alkali is a kind of in sodium carbonate, salt of wormwood, sodium bicarbonate.Preferably, described Compound D:
the preparation method as follows:
: 3,6-bis-is bromo-1 in oxygen-free environment, to provide compd B, 8-phenodiazine Fluorenone, and compd A: 4,4 '-dimethyltrianiline,
Mixed being incorporated under nitrogen atmosphere of the compd B that is 1: 3～5 by mol ratio and compd A heated, and Heating temperature is 110～120 ℃, then drips 1～2mL catalyzer trifluoromethanesulfonic acid, finishes to obtain crude product after reaction, then the crude product purifying is obtained to Compound D.
Preferably, the step that purifying makes Compound D comprises that adopting acetone to make solvent carries out recrystallization by crude product.
The third aspect, the invention provides a kind of electroluminescent device, comprises the substrate with anode, luminescent layer and the cathode layer that stack gradually, and described luminescent layer is organic semiconductor material as follows:
Preferably, described light emitting layer thickness 20nm～40nm.
Preferably, anode material is tin indium oxide, and negative electrode is metallic aluminium.
The invention provides a kind of organic semiconductor material, preparation method and electroluminescent device, there is following beneficial effect: there is the bipolarity blue light material, there is hole transport character and electronic transport property simultaneously, and there is higher fluorescence quantum yield, there is good thermostability, synthetic method is simple, can be used for the phosphorescent light body material of red bluish-green three looks.
The accompanying drawing explanation
Fig. 1 be take in embodiment 1 structural representation of the organic electroluminescence device that the organic semiconductor material that makes makes as material of main part;
Fig. 2 is the thermogravimetic analysis (TGA) figure of the organic semiconductor material that makes in embodiment 1;
Fig. 3 is the fluorescence spectrum figure of the organic semiconductor material of preparation in the embodiment of the present invention 1.
Embodiment
Embodiment 1:3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1, the preparation process of 8-carboline
1,9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-is bromo-1, and 8-carboline structural formula is
synthetic as follows:
Compd B: 3,6-bis-is bromo-1,8-phenodiazine Fluorenone (5.4g, 16mmol) and compd A: 4,4 '-dimethyltrianiline (15g, 55mmlo) mixes, and is heated to 120 ℃ under nitrogen atmosphere, after mixture dissolves fully, drip catalyzer trifluoromethanesulfonic acid 1mL, keep heated overnight.After reaction finishes, add methylene dichloride to dissolve unreacting material and other impurity, filter and obtain white solid Compound D: 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-is bromo-1, the 8-carboline, and productive rate is 91%.
Test data of experiment: mass spectrum: m/z 868.2 (M
++ 1); Ultimate analysis (%) C
51h
40br
2n
4: theoretical value C 70.51, and H 4.64, and N 6.45; Measured value: C 70.63, H 4.58, and N 6.47.
2,3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline structural formula is
synthetic as follows:
By Compound D: 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-is bromo-1,8-carboline (1.74g, 2mmol), Compound C: 10-benzene anthracene-9-pinacol borate (1.60g, 4.2mmol) be mixed in there-necked flask, add toluene (100mL), sodium carbonate solution (2.0M, 20mL), four triphenyl phosphorus palladiums (23mg, 0.02mol), under nitrogen atmosphere, 110 ℃ of reflux are 24 hours.After reaction finishes, removal of solvent under reduced pressure, make leacheate with methylene dichloride/sherwood oil (1: 9), silica gel column chromatography obtains oyster solid 3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1, the 8-carboline, productive rate 75%.
Test data of experiment: m/z 1214.5 (M
++ 1); Ultimate analysis (%) C
91h
66n
4: theoretical value C 89.92, and H 5.47, and N 4.61; Measured value: C 89.95, H 5.39, and N 4.75.
Referring to accompanying drawing 2, are thermogravimetic analysis (TGA) figure of the organic semiconductor material for preparing of the present embodiment, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under the nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T as seen from the figure
d) be 474 ℃.
Referring to accompanying drawing 3, are fluorescence spectrum figure of the organic semiconductor material of preparation in embodiment 1, fluorescence spectrum is measured on Jasco FP-6600 type fluorescence spectrophotometer.As seen from the figure: the maximum emission peak of the compounds of this invention is positioned at the 447nm left and right, shows this compound emission blue light.Fluorescence quantum yield Φ
fbe 0.82.
Embodiment 2:3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1, the preparation process of 8-carboline
1, Compound D: 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-is bromo-1, and the preparation of 8-carboline is referring to embodiment 1.
2,3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline structural formula is
synthetic as follows:
By Compound D: 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-bromo-1,8-carboline (1.74g, 2mmol), Compound C: 10-benzene anthracene-9-pinacol borate (1.67g, 4.4mmol) is mixed in there-necked flask, adds N, dinethylformamide (100mL), sodium hydrogen carbonate solution (2.0M, 20mL), bi triphenyl phosphine dichloride palladium (42mg, 0.06mol), under nitrogen atmosphere, 120 ℃ of reflux are 10 hours.After reaction finishes, removal of solvent under reduced pressure, make leacheate with methylene dichloride/sherwood oil (1: 9), silica gel column chromatography obtains oyster solid 3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline.Productive rate 80%.
Embodiment 3:3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1, the preparation process of 8-carboline
1, Compound D 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3, and 6-bis-is bromo-1, and the preparation of 8-carboline is referring to embodiment 1.
2,3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline structural formula is
synthetic as follows:
By Compound D: 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-bromo-1,8-carboline (1.74g, 2mmol), Compound C: 10-benzene anthracene-9-pinacol borate (1.67g, 4.4mmol) be mixed in there-necked flask, add tetrahydrofuran (THF) (100mL), solution of potassium carbonate (2.0M, 20mL), three dibenzalacetone two palladium (103mg, 0.1mmol) and 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl (164mg, 0.4mmol), under nitrogen atmosphere, 70 ℃ of reflux are 30 hours.After reaction finishes, removal of solvent under reduced pressure, make leacheate with methylene dichloride/sherwood oil (1: 9), silica gel column chromatography obtains oyster solid 3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline.Productive rate 78%.
Embodiment 4:3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1, the preparation process of 8-carboline
1, Compound D 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3, and 6-bis-is bromo-1, and the preparation of 8-carboline is referring to embodiment 1.
2,3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline structural formula is
synthetic as follows:
By Compound D: 9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-3,6-bis-bromo-1,8-carboline (1.74g, 2mmol), Compound C: 10-benzene anthracene-9-pinacol borate (1.67g, 4.4mmol) be mixed in there-necked flask, add tetrahydrofuran (THF) (100mL), solution of potassium carbonate (2.0M, 20mL), three dibenzalacetone two palladium (103mg, 0.1mmol) and 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl (328mg, 0.8mmol), under nitrogen atmosphere, 90 ℃ of reflux are 20 hours.After reaction finishes, removal of solvent under reduced pressure, make leacheate with methylene dichloride/sherwood oil (1: 9), silica gel column chromatography obtains oyster solid 3,6-bis-(10-benzene anthracene-9-base-)-9,9-bis-(4-(two-p-methylphenyl) aminophenyl)-1,8-carboline.Productive rate 74%.
Application Example
Organic electroluminescence device 300, as Fig. 1, it comprises substrate 301 to its structure, anode 302, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronic injection buffer layer 307, negative electrode 308.
In the present embodiment, the material of substrate 301 is glass, vacuum plating anode 302 successively in substrate 301, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronic injection buffer layer 307, negative electrode 308, anode 302 adopts the tin indium oxide that square resistance is 10～20 Ω/, thickness is 200nm, hole injection layer 303 adopts poly-(3, the 4-ethene dioxythiophene)-polystyrolsulfon acid thickness is 30nm, hole transmission layer 304 adopts N, N '-phenylbenzene-N, N '-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, thickness is 50nm, luminescent layer 305 luminescent materials adopt the compound 3 of the invention process 1 preparation, 6-bis-(10-benzene anthracene-9-base-)-9, 9-bis-(4-(two-p-methylphenyl) aminophenyl)-1, the 8-carboline, luminescent layer 305 thickness are 20nm, electron transfer layer 306 adopts three (oxine) aluminium, thickness is 30nm, electronic injection buffer layer 307 adopts lithium fluoride, thickness is 1nm, negative electrode 308 adopts metallic aluminium, thickness is 120nm.
This electroluminescent device has higher luminous efficiency, can be widely used in the luminous fields such as blueness or white.Electric current-the brightness-voltage characteristic of device is that all measurements that completed by the Keithley source measuring system with the correction silicon photoelectric diode (Keithley 2400Sourcemeter, Keithley 2000Cuirrentmeter) all complete in atmosphere at room temperature.The maximum luminous efficiency of device is 12.4cd/A, and high-high brightness is 28669cd/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 (10)
1. an organic semiconductor material, is characterized in that, the chemical formula of described organic semiconductor material is as follows:
2. the preparation method of an organic semiconductor material, is characterized in that, comprises the steps:
Compound D is provided:
and Compound C:
under inert atmosphere, the Compound D that is 1: 2.1～2.2 by mol ratio and Compound C are dissolved in organic solvent, add again mineral alkali and organic palladium catalyzer, return stirring reaction 10 hours～30 hours, crude product obtains making organic semiconductor material after separating-purifying, and the chemical formula of described organic semiconductor material is as follows:
3. preparation method as claimed in claim 2, is characterized in that, described organic palladium catalyzer be bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium or three dibenzalacetone two palladiums and 2-dicyclohexyl phosphorus-2 ', 6 '-mixture of dimethoxy-biphenyl.
4. preparation method as claimed in claim 2, it is characterized in that, described separating-purifying process is specially decompression and removes the solvent in crude product, add methylene dichloride to dissolve, remove inorganic salt with the saturated aqueous common salt extraction, the organic phase anhydrous magnesium sulfate drying, the filtrate after filtration is removed desolventizing with rotary evaporation, make leacheate with methylene dichloride and sherwood oil, silica gel column chromatography is purified.
5. preparation method as claimed in claim 2, is characterized in that, the mol ratio of described organic palladium catalyzer and Compound D is 1: 20～1: 100.
6. preparation method as claimed in claim 2, it is characterized in that, described organic solvent comprises at least one in toluene, DMF, tetrahydrofuran (THF), glycol dimethyl ether, and described mineral alkali is a kind of in sodium carbonate, salt of wormwood, sodium bicarbonate.
7. preparation method as claimed in claim 2, is characterized in that, described Compound D:
the preparation method as follows:
: 3,6-bis-is bromo-1 in oxygen-free environment, to provide compd B, 8-phenodiazine Fluorenone, and compd A: 4,4 '-dimethyltrianiline,
Mixed being incorporated under nitrogen atmosphere of the compd B that is 1: 3～5 by mol ratio and compd A heated, and Heating temperature is 110～120 ℃, then drips 1～2mL catalyzer trifluoromethanesulfonic acid, finishes to obtain crude product after reaction, then the crude product purifying is obtained to Compound D.
8. preparation method as claimed in claim 6, is characterized in that, the step that described purifying makes Compound D comprises that adopting acetone to make solvent carries out recrystallization by crude product.
9. an electroluminescent device, is characterized in that, comprises the substrate with anode, luminescent layer and the cathode layer that stack gradually, and described luminescent layer is organic semiconductor material as follows:
10. electroluminescent device as claimed in claim 8, is characterized in that, described light emitting layer thickness 20nm～40nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004091444A (en) * | 2002-09-04 | 2004-03-25 | Canon Inc | Diazafluorene compound and organic light emitting element using the same |
| WO2011060877A2 (en) * | 2009-11-17 | 2011-05-26 | Merck Patent Gmbh | Materials for organic light emitting devices |
-
2012
- 2012-05-28 CN CN2012101681909A patent/CN103450190A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004091444A (en) * | 2002-09-04 | 2004-03-25 | Canon Inc | Diazafluorene compound and organic light emitting element using the same |
| WO2011060877A2 (en) * | 2009-11-17 | 2011-05-26 | Merck Patent Gmbh | Materials for organic light emitting devices |
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Application publication date: 20131218 |
