CN102924522A - Triphenylamine-containing organic semiconductor material, preparation method and applications thereof - Google Patents
Triphenylamine-containing organic semiconductor material, preparation method and applications thereof Download PDFInfo
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- 0 *c1ccc(-c(cc2)ccc2N(c2ccc(C3(c4cc(P(c5ccccc5)(c5ccccc5)=O)ccc4-c(cc4)c3cc4P(c3ccccc3)(c3ccccc3)=O)c(cc3)ccc3N(c(cc3)ccc3-c3ccc(*)[s]3)c(cc3)ccc3-c3ccc(*)[s]3)cc2)c(cc2)ccc2-c2ccc(*)[s]2)[s]1 Chemical compound *c1ccc(-c(cc2)ccc2N(c2ccc(C3(c4cc(P(c5ccccc5)(c5ccccc5)=O)ccc4-c(cc4)c3cc4P(c3ccccc3)(c3ccccc3)=O)c(cc3)ccc3N(c(cc3)ccc3-c3ccc(*)[s]3)c(cc3)ccc3-c3ccc(*)[s]3)cc2)c(cc2)ccc2-c2ccc(*)[s]2)[s]1 0.000 description 4
- GCCZPFFAVHCKQP-UHFFFAOYSA-N Cc(cc1)cc(C(c2c3)=O)c1-c2ccc3Br Chemical compound Cc(cc1)cc(C(c2c3)=O)c1-c2ccc3Br GCCZPFFAVHCKQP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to the technical field of organic materials, and provides a triphenylamine-containing organic semiconductor material, a preparation method and applications thereof. The triphenylamine-containing organic semiconductor material has the following structural formula I, wherein the structural formula of the triphenylamine-containing organic semiconductor material comprises a triphenylamine unit, a diphenylphosphinoxy unit and a fluorenyl unit. According to the present invention, a carrier delivery rate is substantially increased through the triphenylamine and the diphenylphosphinoxy so as to improve luminescent property; and the triphenylamine unit, the diphenylphosphinoxy unit and the fluorenyl unit form a 9,9-bis(triphenylamine)spirofluorene structure, such that the triphenylamine-containing organic semiconductor material has excellent thermal stability. The preparation method for the triphenylamine-containing organic semiconductor material has characteristics of simple operation and low cost, and is suitable for industrial production.
Description
Technical field
The invention belongs to the organic materials technical field, relate in particular to a kind of contain triphenylamine organic semiconductor material, its preparation method and application.
Background technology
Along with the development of information age, have efficient, energy-conservation, the organic EL display (OLEDs) of lightweight and the concern that the big area white-light illuminating more and more is subject to people.The OLED technology is paid close attention to by the scientist in the whole world, and relevant enterprise and laboratory are all in the research and development of carrying out this technology.As a kind of novel LED technology, have active illuminating, light, thin, good contrast, energy consumption organic electroluminescence device low, that can be made into the characteristics such as flexible device material has been proposed higher requirement.
At present, when OLED making and real work, can be subject to the effect of heat, so that other form that rete produces crystalline form or film change (such as glass transition) is lured in the effect that luminescent material is vulnerable to these heat in the device into, so will change organic materials physical properties originally, and then cause the phenomenons such as OLED brightness, efficient decline, changed by heat effect, material is easily aging, and its device lifetime of making is not high; Simultaneously, currently used luminescent material exciton transfer speed is not high, causes the luminous efficiency of device not high.
Summary of the invention
In view of this, the embodiment of the invention provides a kind of triphenylamine organic semiconductor material that contains, and solves luminescent material poor heat stability in the prior art, technical problem that exciton transfer speed is low.
The present invention is achieved in that
First aspect present invention provides a kind of triphenylamine organic semiconductor material that contains, and has following structural formula I:
Wherein, R is C
1-C
12Alkyl.
Second aspect present invention provides a kind of organic semiconductor material preparation method, comprises the steps:
Provide that the structural formula II represents 9,9-two (triphenylamine base)-2,7-dibromo fluorenes
Anhydrous and oxygen-free and temperature be under-78 ℃～-70 ℃ conditions alkyl derivative of lithium is added to be dissolved with that the structural formula II represents 9,9-two (triphenylamine base)-2, in the organic solvent of 7-dibromo fluorenes, stirring reaction 1 hour～5 hours, add diphenyl phosphorus chloride, system temperature is adjusted into 10 ℃-30 ℃, reacted 3 hours～12 hours, collecting reaction product is also purified, should be dissolved in the organic solvent by purification afterreaction product, add oxygenant, reacted 1 hour～12 hours, obtain containing the triphenylamine organic semiconductor material; Reaction formula is expressed as:
Wherein, R is C
1-C
12Alkyl.
The present invention further provides the above-mentioned application of triphenylamine organic semiconductor material in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus that contain.
The embodiment of the invention contains the triphenylamine organic semiconductor material, comprises triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit in its structural formula.By triphenylamine base, diphenyl phosphine oxygen base, the current carrier transfer rate is improved greatly, improve its luminescent properties; Simultaneously, by introducing thienyl group at trianilino group, can significantly improve organic semiconductor material hole-transfer speed, the alkyl that thienyl group is introduced can effectively improve film-forming properties and the solvability of organic semiconductor material; It is fluorene structured that above-mentioned triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit form 9,9-two (triphenylamine base) spiral shell, has excellent thermal stability so that this contains the triphenylamine organic semiconductor material; The embodiment of the invention contains triphenylamine organic semiconductor material preparation method, and is simple to operate, with low cost, is very suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the embodiment of the invention 1,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-thiotolene-2-yl) phenyl) anilino) fluorenes (DMTTPOF) luminescent spectrum figure;
Fig. 2 uses the embodiment of the invention 1,7-two (diphenyl phosphine oxygen base)-9, and 9-two (N, N-two (4-(5-thiotolene-2-yl) phenyl) anilino) fluorenes (DMTTPOF) is as the organic electroluminescence device structure iron of luminescent layer.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides a kind of triphenylamine organic semiconductor material that contains, and has following structural formula I:
Wherein, R is C
1-C
12Straight chain or branched alkyl; Be preferably C
1-C
6Straight chain or branched alkyl.
The embodiment of the invention contains the triphenylamine organic semiconductor material, comprises triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit in its structural formula;
Triphenylamine base is the electron rich group, its introducing can improve the hole transport performance of material, simultaneously, by introducing thienyl group at trianilino group, can significantly improve organic semiconductor material hole-transfer speed, the alkyl that thienyl group is introduced can effectively improve film-forming properties and the solvability of organic semiconductor material;
Diphenyl phosphine oxygen base is the electron deficiency group, and its introducing can improve the electronic transmission performance of material;
Because electron rich group and electron deficiency group exist simultaneously, be conducive to realize its charge balance, current carrier (hole-electron pair) transfer rate is improved greatly, so that hole and electronics can more effectively inject, realize containing the remarkable lifting of triphenylamine organic semiconductor material luminescent properties;
Simultaneously, above-mentioned triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit form 9,9-two (triphenylamine base) spiral shell is fluorene structured, because these are 9 years old, the very big rigidity that 9-two (triphenylamine base) spiral shell is fluorene structured and sterically hindered has excellent thermal stability so that this contains the triphenylamine organic semiconductor material.
The embodiment of the invention further provides above-mentioned organic semiconductor material preparation method, comprises the steps:
Step S01, provide that the structural formula II represents 9,9-two (triphenylamine base)-2,7-dibromo fluorenes
Step S02, preparation contains the triphenylamine organic semiconductor material
Anhydrous and oxygen-free and temperature be under-78 ℃～-70 ℃ conditions alkyl derivative of lithium is added to be dissolved with that the structural formula II represents 9,9-two (triphenylamine base)-2, in the organic solvent of 7-dibromo fluorenes, stirring reaction 1 hour～5 hours, add diphenyl phosphorus chloride, system temperature is adjusted into 10 ℃-30 ℃, reacted 3 hours～12 hours, collecting reaction product is also purified, should be dissolved in the organic solvent by purification afterreaction product, add oxygenant, reacted 1 hour～12 hours, obtain containing the triphenylamine organic semiconductor material;
The reaction formula of step S02 is expressed as:
Wherein, R is C
1-C
12Straight chain or branched alkyl; Be preferably C
1-C
6Straight chain or branched alkyl.
Particularly, among the step S01, this structural formula II represent 9,9-two (triphenylamine base)-2, the preparation method of 7-dibromo fluorenes is referring to Advanced Materials, 2002,14, the method of record in 809 (the Chinese periodical names: advanced material, 2002,14,809).
Particularly, among the step S02, this oxygen free condition for example operates under the protection of nitrogen, argon gas, helium or neon without limits; This anhydrous condition refers to, in reaction process, does not add entry, and employed reactant also passes through drying treatment.
Particularly, among the step S02, with the structural formula II represent 9,9-two (triphenylamine base)-2,7-dibromo fluorenes is dissolved in the organic solvent, formation be dissolved with that the structural formula II represents 9,9-two (triphenylamine base)-2, the organic solvent of 7-dibromo fluorenes, this organic solvent is without limits, for example, benzene, toluene, tetrahydrofuran (THF), methylene dichloride, trichloromethane, hexanaphthene, ether etc., the consumption of this organic solvent without limits, the structural formula II can be represented 9,9-two (triphenylamine base)-2, the dissolving of 7-dibromo fluorenes gets final product;
The alkyl derivative of this lithium by the mode that drips be added to be dissolved with that the structural formula II represents 9,9-two (triphenylamine base)-2, in the organic solvent of 7-dibromo fluorenes, dripping step is to carry out under-78 ℃～-70 ℃ conditions in temperature, is preferably-78 ℃; Then stir, reacted 1 hour～5 hours; After reaction is finished, add diphenyl phosphorus chloride, the temperature of reaction system is adjusted to room temperature, specifically without limits, for example 10 ℃～30 ℃, then reacted 3 hours～12 hours; The alkyl derivative of this lithium is selected from n-Butyl Lithium, isobutyl-lithium, lithium methide or phenyl lithium etc., preferred n-Butyl Lithium; The alkyl derivative of this lithium and structural formula II represent 9,9-two (triphenylamine base)-2,7-dibromo fluorenes mol ratio is 2～2.5: 1, the alkyl derivative of this lithium and the mol ratio of diphenyl phosphorus chloride are 1: 1.
Among the step S02, after the reaction of adding diphenyl phosphorus chloride is finished, reacted solution with 90ml water quencher reaction, is added ethyl acetate extraction, collected organic layer, organic layer is concentrated, use anhydrous magnesium sulfate drying, obtain crude product, use sherwood oil/organic solvent as leacheate process silica gel column chromatography separating-purifying crude product, obtain white solid, i.e. intermediate reaction product;
This intermediate reaction product is added in the organic solvent, and this organic solvent does not repeat to set forth at this with aforementioned identical; Then add oxygenant, stirring reaction is 3 hours～12 hours at ambient temperature, this room temperature without limits, for example 10 ℃～30 ℃; This oxygenant and above-mentioned purification afterreaction product (intermediate reaction product) mol ratio are 100～160: 1.
The embodiment of the invention contains triphenylamine organic semiconductor material preparation method, draw the organic semiconductor material that contains triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit by the reaction preparation, the introducing of triphenylamine base, hexichol phosphorus oxygen base, have excellent carrier transport efficient so that this contains the triphenylamine organic semiconductor material, realize the remarkable lifting of its luminescent properties; Simultaneously, this contains thermal stability, film-forming properties and resolvability that the triphenylamine organic semiconductor material has excellence; The embodiment of the invention contains triphenylamine organic semiconductor material preparation method, and is simple to operate, with low cost, is very suitable for suitability for industrialized production.
The embodiment of the invention further provides the above-mentioned application of triphenylamine organic semiconductor material in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus that contain.
Below in conjunction with specific embodiment the above-mentioned triphenylamine organic semiconductor material preparation method that contains is described in detail.
Embodiment one
The embodiment of the invention 2,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-thiotolene-2-yl) phenyl) anilino) fluorenes (DMTTPOF) has following structural formula:
The embodiment of the invention 2,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-thiotolene-2-yl) phenyl) anilino) fluorenes (DMTTPOF) preparation method comprises the steps:
Under the argon shield; with 2 of 7mmol; the N of 7-dibromo fluorenone, 98mmol; the methylsulphonic acid of N-two (4-cyano-phenyl) anilino and 7mmol is added in the reactor, and 140 ℃ of lower stirring reactions 6 hours, stopped reaction also was cooled to 15 ℃; use dichloromethane extraction; respectively with saturated sodium bicarbonate solution and distillation washing, concentrated organic layer obtains blue solid again.Crude product obtains white solid product with acetone recrystallization again behind the silica gel column chromatography separating-purifying, namely prepare 9,9-two (N, N-two (4-(5-thiotolene-2-yl) phenyl) anilino) fluorenes 2,7-dibromo fluorenes, productive rate 72%.MALDI/TOF-MS：m/z：1193(M
+)。Reaction formula is expressed as:
Anhydrous, under nitrogen protection and-78 ℃ of temperature condition, with 9 of 1.5mmol, 9-two (N, N-two (4-cyano-phenyl) anilino) fluorenes 2,7-dibromo fluorenes is added in the tetrahydrofuran solution of 75mL, adds the 3.75mmol n-Butyl Lithium,-78 ℃ of lower stirrings 2 hours, add rapidly again diphenyl phosphine chloride 3.75mmol, obtain transparent pale yellow solution, naturally be warming up to 15 ℃ after stirring reaction 12 hours; Then with the 90mL shrend reaction of going out, use ethyl acetate extraction, concentrated organic layer use anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to pass through the silica gel column chromatography separating-purifying as leacheate and obtains white solid; With the dissolving of 60mL methylene dichloride, adding 7mL concentration is the hydrogen peroxide of 30% (mass percent) with white solid, 15 ℃ of lower stirring reactions of condition 12 hours; Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid, adopt ethyl acetate/methanol to obtain containing the triphenylamine organic semiconductor material as leacheate through the silica gel column chromatography separating-purifying, productive rate is 39%.MALDI/TOF-MS：m/z：1437(M
+)。Reaction formula is expressed as:
(TGA) detects by thermogravimetric analyzer, and analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, the heat decomposition temperature that contains the triphenylamine organic semiconductor material of preparation was 423 ℃ in the present embodiment one.
See also Fig. 1, Fig. 1 is the prepared fluorescence radiation spectrogram that contains the triphenylamine organic semiconductor material of the embodiment of the invention one, and as can be seen from Figure 1, the embodiment one prepared triphenylamine organic semiconductor material that contains is 441 nanometers at the emission wavelength of maximum.
Embodiment two
The embodiment of the invention 2,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-tertiary butyl thiophene-2-yl) phenyl) anilino) fluorenes (DBTTPOF) has following structural formula:
The embodiment of the invention 2,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-tertiary butyl thiophene-2-yl) phenyl) anilino) fluorenes (DBTTPOF) preparation method comprises the steps:
Under the argon shield; with 2 of 7mmol; the N of 7-dibromo fluorenone, 98mmol; the tertiary butyl sulfonic acid of N-two (4-cyano-phenyl) anilino and 7mmol is added in the reactor, and 140 ℃ of lower stirring reactions 8 hours, stopped reaction also was cooled to 25 ℃; use dichloromethane extraction; respectively with saturated sodium bicarbonate solution and distillation washing, concentrated organic layer obtains blue solid again.Crude product obtains white solid product with acetone recrystallization again behind the silica gel column chromatography separating-purifying, namely prepare 9,9-two (N, N-two (4-(5-tertiary butyl thiophene-2-yl) phenyl) anilino) fluorenes 2,7-dibromo fluorenes, productive rate 68%.MALDI/TOF-MS：m/z：1361(M
+)。Reaction formula is expressed as:
Anhydrous, under nitrogen protection and-78 ℃ of temperature condition, with 9 of 1.5mmol, 9-two (N, N-two (4-cyano-phenyl) anilino) fluorenes 2,7-dibromo fluorenes is added in the tetrahydrofuran solution of 75mL, adds the 3.45mmol n-Butyl Lithium,-78 ℃ of lower stirrings 2 hours, add rapidly again diphenyl phosphine chloride 3.45mmol, obtain transparent pale yellow solution, naturally be warming up to 25 ℃ after stirring reaction 7 hours; Then with the 90mL shrend reaction of going out, use ethyl acetate extraction, concentrated organic layer use anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to pass through the silica gel column chromatography separating-purifying as leacheate and obtains white solid; With the dissolving of 60mL methylene dichloride, adding 7mL concentration is the hydrogen peroxide of 30% (mass percent) with white solid, 25 ℃ of lower stirring reactions of condition 7 hours; Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid, adopt ethyl acetate/methanol to obtain containing the triphenylamine organic semiconductor material as leacheate through the silica gel column chromatography separating-purifying, productive rate is 30%.MALDI/TOF-MS：m/z：1605(M
+)。Reaction formula is expressed as:
(TGA) detects by thermogravimetric analyzer, and analysis condition is nitrogen atmosphere, was the heat decomposition temperature that contains the triphenylamine organic semiconductor material of preparation in the present embodiment two when sweep velocity was 10 ℃/min? ℃.
Embodiment three
The embodiment of the invention 2,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-n-octyl thiophene-2-yl) phenyl) anilino) fluorenes (DOTTPOF) has following structural formula:
The embodiment of the invention 2,7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-n-octyl thiophene-2-yl) phenyl) anilino) fluorenes (DOTTPOF) preparation method comprises the steps:
Under the argon shield; with 2 of 7mmol; the N of 7-dibromo fluorenone, 98mmol; the n-octyl sulfonic acid of N-two (4-cyano-phenyl) anilino and 7mmol is added in the reactor, and 140 ℃ of lower stirring reactions 7 hours, stopped reaction also was cooled to 30 ℃; use dichloromethane extraction; respectively with saturated sodium bicarbonate solution and distillation washing, concentrated organic layer obtains blue solid again.Crude product obtains white solid product with acetone recrystallization again behind the silica gel column chromatography separating-purifying, namely prepare 9,9-two (N, N-two (4-(5-n-octyl thiophene-2-yl) phenyl) anilino) fluorenes 2,7-dibromo fluorenes, productive rate 72%.MALDI/TOF-MS：m/z：1585(M
+)。Reaction formula is expressed as:
Anhydrous, under nitrogen protection and-78 ℃ of temperature condition, with 9 of 1.5mmol, 9-two (N, N-two (4-cyano-phenyl) anilino) fluorenes 2,7-dibromo fluorenes is added in the tetrahydrofuran solution of 75mL, adds the 3.45mmol n-Butyl Lithium,-78 ℃ of lower stirrings 1 hour, add rapidly again diphenyl phosphine chloride 3.45mmol, obtain transparent pale yellow solution, naturally be warming up to 30 ℃ after stirring reaction 3 hours; Then with the 90mL shrend reaction of going out, use ethyl acetate extraction, concentrated organic layer use anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to pass through the silica gel column chromatography separating-purifying as leacheate and obtains white solid; With the dissolving of 60mL methylene dichloride, adding 7mL concentration is the hydrogen peroxide of 30% (mass percent) with white solid, 30 ℃ of lower stirring reactions of condition 3 hours; Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid, adopt ethyl acetate/methanol to obtain containing the triphenylamine organic semiconductor material as leacheate through the silica gel column chromatography separating-purifying, productive rate is 26%.MALDI/TOF-MS：m/z：1830(M
+)。Reaction formula is expressed as:
(TGA) detects by thermogravimetric analyzer, and analysis condition is nitrogen atmosphere, and when sweep velocity was 10 ℃/min, the heat decomposition temperature that contains the triphenylamine organic semiconductor material of preparation was 443 ℃ in the present embodiment three.
Application examples
See also Fig. 2, Fig. 2 display application embodiment of the invention one contain the triphenylamine organic semiconductor material as the organic electroluminescence device structure iron of luminescent layer, comprise substrate 1, be positioned at the ITO conducting film 2 in this substrate 1, be positioned at hole transmitting layer 3 on this conducting film 2, be positioned at the luminescent layer 4 on this hole transmission layer 3, and be positioned at hole blocking layer/electron transfer layer 5 on this luminescent layer 4, be positioned at the electron injecting layer 6 on hole blocking layer/electron transfer layer 5, be positioned at the negative electrode 7 on this electron injecting layer 6.
Wherein, the material of this hole transmission layer 3 is NPB (N, N '-two (Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines);
The material of this luminescent layer 4 is the DMTTPOF{2 of embodiment one, 7-two (diphenyl phosphine oxygen base)-9,9-two (N, N-two (4-(5-thiotolene-2-yl) phenyl) anilino) fluorenes } and Ir (ppy)
3{ three (2-phenylpyridines) close iridium } green phosphorescent material is according to 93.5%: 6.5% composition of weight percentage;
The material of this hole blocking layer/electron transfer layer 5 is TPBI (1,3,5-three (1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene);
The material of this electron injecting layer 6 is LiF;
The material of this negative electrode 8 is that weight ratio is 10: 1 Mg: the Ag alloy; Above-mentioned each functional layer prepares by the vacuum evaporation mode.
The organic electroluminescence device of application examples of the present invention is tested under room temperature and atmospheric environment, has 20.2% external quantum efficiency.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind contains the triphenylamine organic semiconductor material, has following structural formula I:
Wherein, R is C
1-C
12Alkyl.
2. the triphenylamine organic semiconductor material that contains as claimed in claim 1 is characterized in that, described R is C
1-C
6Alkyl.
3. one kind contains triphenylamine organic semiconductor material preparation method, comprises the steps:
Provide that the structural formula II represents 9,9-two (triphenylamine base)-2,7-dibromo fluorenes
Anhydrous and oxygen-free and temperature be under-78 ℃～-70 ℃ conditions alkyl derivative of lithium is added to be dissolved with that the structural formula II represents 9,9-two (triphenylamine base)-2, in the organic solvent of 7-dibromo fluorenes, stirring reaction 1 hour～5 hours, add diphenyl phosphorus chloride, system temperature is adjusted into 10 ℃-30 ℃, reacted 3 hours～12 hours, collecting reaction product is also purified, described purification afterreaction product is dissolved in the organic solvent, adds oxygenant, reacted 1 hour～12 hours, obtain containing the triphenylamine organic semiconductor material, reaction formula is expressed as:
Wherein, R is C
1-C
12Alkyl.
4. the triphenylamine organic semiconductor material preparation method that contains as claimed in claim 3 is characterized in that described R is C
1-C
6Alkyl.
5. the triphenylamine organic semiconductor material preparation method that contains as claimed in claim 3 is characterized in that the alkyl derivative of described lithium is selected from n-Butyl Lithium, isobutyl-lithium, lithium methide or phenyl lithium.
6. the triphenylamine organic semiconductor material preparation method that contains as claimed in claim 3 is characterized in that described oxygenant is selected from hydrogen peroxide, Potcrate, sodium chlorate, clorox or hypochlorous acid.
7. the triphenylamine organic semiconductor material preparation method that contains as claimed in claim 3 is characterized in that, the alkyl derivative of described lithium and structural formula II represent 9,9-two (triphenylamine base)-2,7-dibromo fluorenes mol ratio is 2～2.5: 1.
8. the triphenylamine organic semiconductor material preparation method that contains as claimed in claim 3 is characterized in that the alkyl derivative of described lithium and the mol ratio of diphenyl phosphorus chloride are 1: 1.
9. the triphenylamine organic semiconductor material preparation method that contains as claimed in claim 3 is characterized in that, described oxygenant and described purification afterreaction product mol ratio are 100～160: 1.
10. as claimed in claim 1 or 2ly contain the application of triphenylamine organic semiconductor material in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus.
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