CN103626683A - Organic semiconductor material, preparation method of organic semiconductor material and electroluminescent device - Google Patents
Organic semiconductor material, preparation method of organic semiconductor material and electroluminescent device Download PDFInfo
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- CN103626683A CN103626683A CN201210295756.4A CN201210295756A CN103626683A CN 103626683 A CN103626683 A CN 103626683A CN 201210295756 A CN201210295756 A CN 201210295756A CN 103626683 A CN103626683 A CN 103626683A
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Abstract
The invention provides an organic semiconductor material. The organic semiconductor material has a chemical formula shown in the patent specification. The organic semiconductor material contains triphenylamine, fluorene and phenyl oxysulfide. Triphenylamine has hole transport performances. Fluorene and phenyl oxysulfide have electron transmission performances. Therefore, the organic semiconductor material is a bipolar red-light-emitting phosphorescent material having good hole transport performances and electron transmission performances. The invention also provides a preparation method of the organic semiconductor material and an electroluminescent device containing 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 be finely tuned and be changed 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 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 device real work.In order to overcome this problem, investigators are often doped to triplet state shiner in 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 good carrier transmission performance and higher triplet (E 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, fluorenes and phenyl sulphur oxygen, and wherein triphenylamine has hole transport performance, fluorenyl has electronic transmission performance, and phenyl sulphur oxygen has electronic transmission performance.Organic semiconductor material of the present invention has the bipolarity ruddiness phosphor material of better hole transport and electron transport ability.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: to provide Compound D:
and Compound C:
under inert atmosphere, the Compound D that is 1:2.2～1:2.5 by mol ratio and Compound C are dissolved in organic solvent, add mineral alkali, return stirring reaction is after 6～12 hours, stopped reaction is cooled to room temperature, with dichloromethane extraction, rotary evaporation is except desolventizing, collect solid, then use acetate dissolution solid, adding mass percent is 30% hydrogen peroxide again, wherein, 2, 7-bis-bromo-9, 9-bis-(2-(9-phenyl carbazole)) volume ratio of fluorenes and 30% hydrogen peroxide is 1:5～1:6, at 80～90 ℃, stirring reaction is 12～24 hours, obtain crude product, crude product obtains described organic semiconductor material after separation and purification, the chemical formula of described organic semiconductor material is as follows:
Preferably, described separating-purifying process is specially decompression and removes the solvent in crude product, respectively with saturated aqueous common salt and distillation washing crude product, collect organic phase, organic phase anhydrous magnesium sulfate drying, removes desolventizing with rotary evaporation after filtration, with chloroform and normal hexane recrystallization, purifies.
Preferred, described organic solvent comprises at least one in toluene, DMF, toluene or ethanol.
Preferred, described mineral alkali is a kind of in salt of wormwood, sodium carbonate, sodium bicarbonate or potassiumphosphate.Preferably, described Compound D:
preparation method as follows:
In oxygen-free environment, provide compd A: 2,7-dibromo fluorenone, compd B: 4,4 '-dimethyltrianiline,
Mixed being incorporated under nitrogen atmosphere of the compd A that is 1:3～5 by mol ratio and compd B heated, and Heating temperature is 110～120 ℃, then drips 1～2mL catalyzer trifluoromethanesulfonic acid, finishes to obtain crude product after reaction, then 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～50nm.
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: the phosphorescent light body material with bipolarity carrier transport ability, there is hole transport character and electronic transport property simultaneously, and there is higher triplet, effectively prevent that in luminescence process, energy returns to material of main part, make the transmission balance in hole and electronics in luminescent layer, greatly improve luminous efficiency, synthetic method is simple, can be used for ruddiness phosphorescent light body material.
Accompanying drawing explanation
Fig. 1 be take the structural representation of the organic electroluminescence device that the organic semiconductor material that makes in embodiment 1 makes as material of main part;
Fig. 2 is the thermogravimetic analysis (TGA) figure of the organic semiconductor material that makes in embodiment 1.
Embodiment
Embodiment 1:
2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation process 1, the Compound D of fluorenes: 2,7-bis-is bromo-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorene structured formula is
synthetic as follows:
Compd A: 2,7-dibromo fluorenone (5.4g, 16mmol) and compd B: 4,4 '-dimethyltrianiline (15g 55mmol) mixes, and is heated to 120 ℃, after mixture dissolves completely under nitrogen atmosphere, drip catalyzer trifluoromethanesulfonic acid 1mL, keep heated overnight.After reaction finishes, add methylene dichloride to dissolve unreacting material and other impurity, filter that to obtain white solid Compound D: 2,7-bis-bromo-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes, productive rate is 86%.
Test data of experiment: mass spectrum: m/z867.2(M
++ 1); Ultimate analysis (%) C
53h
42br
2n
2: theoretical value C73.45, H4.88, N3.23; Measured value: C73.34, H4.90, N3.26.
2,2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorene structured formula is
synthetic as follows:
By Compound D: 2, 7-bis-bromo-9, 9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes (7.8g, 9mmol) be dissolved in salt of wormwood (2.76g, N 20.0mmol), in dinethylformamide (150mL) solution, add again Compound C: thiophenol (2.2g, 19.8mmol) be mixed in there-necked flask, at 130 ℃ of stirring reactions after 6 hours, stopped reaction is cooled to room temperature, with dichloromethane extraction, rotary evaporation is except desolventizing, obtain crude product, then use acetic acid (100mL) to dissolve crude product, adding mass percent is 30% hydrogen peroxide (50mL), at 80 ℃, stirring reaction is 24 hours.Respectively with saturated aqueous common salt and distillation washing crude product, organic phase anhydrous magnesium sulfate drying, filtrate after filtration is removed desolventizing with rotary evaporation, with the mixed solvent recrystallization of chloroform and normal hexane, obtain light yellow solid product 2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes.Productive rate 90%
Test data of experiment: mass spectrum: m/z989.3(M
++ 1); Ultimate analysis (%) C
65h
52n
2o
4s
2: theoretical value C78.92, H5.30, N2.83, O6.47, P6.48; Measured value: C78.85, H5.38, N2.90, O6.43, P6.45.
Referring to accompanying drawing 2, are thermogravimetic analysis (TGA) figure of the organic semiconductor material prepared of the present embodiment, 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 is 409 ℃ as seen from the figure.
Embodiment 2:2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation process of fluorenes
1, Compound D: 2,7-bis-is bromo-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation of fluorenes is referring to embodiment 1.
2,2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorene structured formula is
synthetic as follows:
By Compound D: 2, 7-bis-bromo-9, 9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes (7.8g, 9mmol) be dissolved in salt of wormwood (2.12g, in toluene 20.0mmol) (150mL) solution, add again Compound C: thiophenol (2.3g, 20.7mmol) be mixed in there-necked flask, at 110 ℃ of stirring reactions after 10 hours, stopped reaction is cooled to room temperature, with dichloromethane extraction, rotary evaporation is except desolventizing, obtain crude product, then use acetic acid (100mL) to dissolve crude product, adding mass percent is 30% hydrogen peroxide (50mL), at 80 ℃, stirring reaction is 24 hours.Respectively with saturated aqueous common salt and distillation washing crude product, organic phase anhydrous magnesium sulfate drying, filtrate after filtration is removed desolventizing with rotary evaporation, with the mixed solvent recrystallization of chloroform and normal hexane, obtain light yellow solid product 2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes.Productive rate 85%.
Embodiment 3:2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation process of fluorenes
1, Compound D: 2,7-bis-is bromo-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation of fluorenes is referring to embodiment 1.
2,2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorene structured formula is
synthetic as follows:
By Compound D: 2, 7-bis-bromo-9, 9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes (7.8g, 9mmol) be dissolved in salt of wormwood (1.68g, in tetrahydrofuran (THF) 20.0mmol) (150mL) solution, add again Compound C: thiophenol (2.4g, 21.6mmol) be mixed in there-necked flask, at 70 ℃ of stirring reactions after 12 hours, stopped reaction is cooled to room temperature, with dichloromethane extraction, rotary evaporation is except desolventizing, obtain crude product, then use acetic acid (100mL) to dissolve crude product, adding mass percent is 30% hydrogen peroxide (50mL), at 80 ℃, stirring reaction is 24 hours.Respectively with saturated aqueous common salt and distillation washing crude product, organic phase anhydrous magnesium sulfate drying, filtrate after filtration is removed desolventizing with rotary evaporation, with the mixed solvent recrystallization of chloroform and normal hexane, obtain light yellow solid product 2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes.Productive rate 77%.
Embodiment 4:2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation process of fluorenes
1, Compound D: 2,7-bis-is bromo-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) preparation of fluorenes is referring to embodiment 1.
2,2,7-bis-is bromo-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorene structured formula is
synthetic as follows:
By Compound D: 2, 7-bis-bromo-9, 9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes (7.8g, 9mmol) be dissolved in salt of wormwood (4.24g, in dehydrated alcohol 20.0mmol) (150mL) solution, add again Compound C: thiophenol (2.5g, 22.5mmol) be mixed in there-necked flask, at 85 ℃ of stirring reactions after 8 hours, stopped reaction is cooled to room temperature, with dichloromethane extraction, rotary evaporation is except desolventizing, obtain crude product, then use acetic acid (100mL) to dissolve crude product, adding mass percent is 30% hydrogen peroxide (50mL), at 80 ℃, stirring reaction is 24 hours.Respectively with saturated aqueous common salt and distillation washing crude product, organic phase anhydrous magnesium sulfate drying, filtrate after filtration is removed desolventizing with rotary evaporation, with the mixed solvent recrystallization of chloroform and normal hexane, obtain light yellow solid product 2,7-bis-(phenyl sulphur oxygen)-9,9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes.Productive rate 83%.
Application Example
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, it is the tin indium oxide of 10 ~ 20 Ω/mouths that anode 302 adopts square resistance, thickness is 200nm, hole injection layer 303 adopts (poly-(3, 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 2 of the invention process 1 preparation, 7-bis-(phenyl sulphur oxygen)-9, 9-bis-(4-(bis--p-methylphenyl) aminophenyl) fluorenes, 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 (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) with correction silicon photoelectric diode all complete in atmosphere at room temperature.The maximum luminous efficiency of device is 16.5cd/A, and high-high brightness is 46380cd/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. an organic semiconductor material, is characterized in that, the chemical formula of described organic semiconductor material is as follows:
2. a preparation method for 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 1:2.2～1:2.5 by mol ratio and Compound C are dissolved in organic solvent, add mineral alkali, return stirring reaction is after 6～12 hours, stopped reaction is cooled to room temperature, with dichloromethane extraction, rotary evaporation is except desolventizing, collect solid, then use acetate dissolution solid, adding mass percent is 30% hydrogen peroxide again, wherein, 2, 7-bis-bromo-9, 9-bis-(2-(9-phenyl carbazole)) volume ratio of fluorenes and 30% hydrogen peroxide is 1:5～1:6, at 80～90 ℃, stirring reaction is 12～24 hours, obtain crude product, crude product obtains described organic semiconductor material after separation and purification, the chemical formula of described organic semiconductor material is as follows:
3. preparation method as claimed in claim 2, is characterized in that, described separating-purifying process is specially respectively with saturated aqueous common salt and distillation washing crude product, collect organic phase, organic phase anhydrous magnesium sulfate drying, removes desolventizing with rotary evaporation after filtration, with chloroform and normal hexane recrystallization, purifies.
4. preparation method as claimed in claim 2, is characterized in that, described organic solvent comprises at least one in toluene, DMF, toluene or ethanol.
5. preparation method as claimed in claim 2, is characterized in that, described mineral alkali is salt of wormwood, sodium carbonate, sodium bicarbonate or potassiumphosphate.
6. preparation method as claimed in claim 2, is characterized in that, described Compound D:
preparation method as follows:
In oxygen-free environment, provide compd A: 2,7-dibromo fluorenone, compd B: 4,4 '-dimethyltrianiline,
Mixed being incorporated under nitrogen atmosphere of the compd A that is 1:3～5 by mol ratio and compd B heated, and Heating temperature is 110～120 ℃, then drips 1～2mL catalyzer trifluoromethanesulfonic acid, finishes to obtain crude product after reaction, then crude product purifying is obtained to Compound D.
7. 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.
8. 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:
9. electroluminescent device as claimed in claim 9, is characterized in that, described light emitting layer thickness is 20nm～50nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922995A (en) * | 2014-04-08 | 2014-07-16 | 上海天马有机发光显示技术有限公司 | Organic electroluminescence device and display device |
| CN109748908A (en) * | 2017-11-02 | 2019-05-14 | 广东阿格蕾雅光电材料有限公司 | Bipolar host material and application based on 4,6- diphenyl sulphone (DPS) dibenzofurans |
-
2012
- 2012-08-20 CN CN201210295756.4A patent/CN103626683A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922995A (en) * | 2014-04-08 | 2014-07-16 | 上海天马有机发光显示技术有限公司 | Organic electroluminescence device and display device |
| CN103922995B (en) * | 2014-04-08 | 2018-05-18 | 上海天马有机发光显示技术有限公司 | A kind of organic electroluminescence device and display device |
| CN109748908A (en) * | 2017-11-02 | 2019-05-14 | 广东阿格蕾雅光电材料有限公司 | Bipolar host material and application based on 4,6- diphenyl sulphone (DPS) dibenzofurans |
| CN109748908B (en) * | 2017-11-02 | 2021-07-16 | 广东阿格蕾雅光电材料有限公司 | Bipolar host material based on 4, 6-diphenyl sulfone dibenzofuran and application |
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Application publication date: 20140312 |