CN102924522B - Containing triphenylamine organic semiconductor material, its preparation method and application - Google Patents
Containing triphenylamine organic semiconductor material, its preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000004065 semiconductor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005401 electroluminescence Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 5
- 230000005669 field effect Effects 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 9
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 abstract description 8
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 abstract description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 6
- XCQQWDCKLLORFE-UHFFFAOYSA-N [O].C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)PC1=CC=CC=C1 XCQQWDCKLLORFE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 29
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 13
- 150000002220 fluorenes Chemical class 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- -1 fluorenes 2,7-dibromo fluorenes Chemical class 0.000 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 0 *c1ccc(-c(cc2)ccc2N(C2C=CC(C(C(C3C=C4)C=C4P(c4ccccc4)(c4ccccc4)=O)(c4c3ccc(P(c3ccccc3)(C3=CCCC=C3)=O)c4)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(C2C=CC(C(C(C3C=C4)C=C4P(c4ccccc4)(c4ccccc4)=O)(c4c3ccc(P(c3ccccc3)(C3=CCCC=C3)=O)c4)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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000002641 lithium Chemical class 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- 150000005360 2-phenylpyridines Chemical class 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical group CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
The present invention is applicable to organic materials technical field, provides a kind of containing triphenylamine organic semiconductor material, its preparation method and application.Following structural formula I should be had containing triphenylamine organic semiconductor material.The present invention is containing triphenylamine organic semiconductor material, and its structural formula comprises triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit.By triphenylamine base, diphenyl phosphine oxygen base, current carrier transfer rate is improved greatly, improve luminescent properties; It is fluorene structured that above-mentioned triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit form 9,9-bis-(triphenylamine base) spiral shell, makes this contain triphenylamine organic semiconductor material and have excellent thermal stability; Triphenylamine organic semiconductor material preparation method of the present invention, simple to operate, with low cost, be very suitable for suitability for industrialized production.
Description
Technical field
The invention belongs to organic materials technical field, particularly relate to a kind of containing triphenylamine organic semiconductor material, its preparation method and application.
Background technology
Along with the development of information age, there is the concern that the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating are more and more subject to people.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 carrying out this technology.As a kind of novel LED technology, there is active illuminating, light, thin, good contrast, energy consumption are low, organic electroluminescence device that is that can be made into the features such as flexible device proposes higher requirement to material.
At present, when OLED making and real work, the effect of heat can be subject to, the effect making luminescent material in device be vulnerable to these heat lures that other form of rete generation crystalline form or film changes (as glass transition) into, so will change organic materials physical properties originally, and then cause the phenomenon such as OLED brightness, efficiency decline, change by heat effect so repeatedly, material is easily aging, and its device lifetime of making is not high; Meanwhile, 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 present invention provides a kind of containing triphenylamine organic semiconductor material, solves luminescent material poor heat stability in 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 containing triphenylamine organic semiconductor material, 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:
9,9-bis-(triphenylamine base)-2, the 7-dibromo fluorenes providing structural formula II to represent
The alkyl derivative of lithium is added to be dissolved with that structural formula II represents 9 under anhydrous and oxygen-free and temperature are-78 DEG C ~-70 DEG C conditions, 9-bis-(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 to 10 DEG C-30 DEG C, react 3 hours ~ 12 hours, collecting reaction product is also purified, reaction product after this purification is dissolved in organic solvent, add oxygenant, react 1 hour ~ 12 hours, obtain containing triphenylamine organic semiconductor material; Reaction formula is expressed as:
Wherein, R is C
1-C
12alkyl.
The present invention further provides above-mentioned containing 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.
The embodiment of the present invention is containing triphenylamine organic semiconductor material, and its structural formula comprises triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit.By triphenylamine base, diphenyl phosphine oxygen base, current carrier transfer rate is improved greatly, improves its luminescent properties; Meanwhile, by introducing thienyl group on trianilino group, significantly can improve organic semiconductor material hole-transfer speed, the alkyl that thienyl group is introduced, effectively can 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-bis-(triphenylamine base) spiral shell, makes this contain triphenylamine organic semiconductor material and have excellent thermal stability; The embodiment of the present invention is containing triphenylamine organic semiconductor material preparation method, simple to operate, with low cost, is very suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention one 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes (DMTTPOF) luminescent spectrum figure;
Fig. 2 is the application embodiment of the present invention 1,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes (DMTTPOF) is as the organic electroluminescence device structure iron of luminescent layer.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, 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, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of containing triphenylamine organic semiconductor material, 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 present invention is containing triphenylamine organic semiconductor material, and its structural formula comprises triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit;
Triphenylamine base is electron rich group, its introducing can improve the hole transport performance of material, simultaneously, by introducing thienyl group on trianilino group, significantly can improve organic semiconductor material hole-transfer speed, the alkyl that thienyl group is introduced, effectively can improve film-forming properties and the solvability of organic semiconductor material;
Diphenyl phosphine oxygen base is 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 realizing its charge balance, current carrier (hole-electron pair) transfer rate is improved greatly, hole and electronics can more effectively be injected, realize the remarkable lifting containing triphenylamine organic semiconductor material luminescent properties;
Simultaneously, above-mentioned triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit form 9,9-bis-(triphenylamine base) spiral shell is fluorene structured, due to this 9, the very big rigidity that 9-bis-(triphenylamine base) spiral shell is fluorene structured and sterically hindered, makes this contain triphenylamine organic semiconductor material and has excellent thermal stability.
The embodiment of the present invention provides above-mentioned organic semiconductor material preparation method further, comprises the steps:
Step S01,9,9-bis-(triphenylamine base)-2, the 7-dibromo fluorenes providing structural formula II to represent
Step S02, preparation is containing triphenylamine organic semiconductor material
The alkyl derivative of lithium is added to be dissolved with that structural formula II represents 9 under anhydrous and oxygen-free and temperature are-78 DEG C ~-70 DEG C conditions, 9-bis-(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 to 10 DEG C-30 DEG C, react 3 hours ~ 12 hours, collecting reaction product is also purified, reaction product after this purification is dissolved in organic solvent, add oxygenant, react 1 hour ~ 12 hours, obtain containing 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, in step S01,9,9-bis-(triphenylamine bases)-2 that this structural formula II represents, the preparation method of 7-dibromo fluorenes, see AdvancedMaterials, 2002,14, the method recorded in 809 (Chinese periodical name: advanced material, 2002,14,809).
Particularly, in step S02, this oxygen free condition does not limit, such as, operate under the protection of nitrogen, argon gas, helium or neon; This anhydrous condition refers to, in reaction process, does not add water, and the reactant used is also through drying treatment.
Particularly, in step S02, by structural formula II represents 9,9-bis-(triphenylamine base)-2,7-dibromo fluorenes is dissolved in organic solvent, formed and be dissolved with 9 of structural formula II expression, the organic solvent of 9-bis-(triphenylamine base)-2,7-dibromo fluorenes, this organic solvent does not limit, such as, benzene, toluene, tetrahydrofuran (THF), methylene dichloride, trichloromethane, hexanaphthene, ether etc., the consumption of this organic solvent does not limit, and structural formula II can be represented 9,9-bis-(triphenylamine base)-2,7-dibromo fluorenes dissolves;
The alkyl derivative of this lithium by the mode dripped be added to be dissolved with 9,9-bis-(triphenylamine base) that structural formula II represents-2,7-dibromo fluorenes organic solvent in, drip step and carry out under temperature be-78 DEG C ~-70 DEG C conditions, preferably-78 DEG C; Then stir, react 1 hour ~ 5 hours; After having reacted, add diphenyl phosphorus chloride, the temperature of reaction system is adjusted to room temperature, does not specifically limit, such as 10 DEG C ~ 30 DEG C, then react 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; 9,9-bis-(triphenylamine base) that the alkyl derivative of this lithium and structural formula II represent-2,7-dibromo fluorenes mol ratio be 2 ~ 2.5: 1, the alkyl derivative of this lithium and the mol ratio of diphenyl phosphorus chloride are 1: 1.
In step S02, add after diphenyl phosphorus chloride reacted, by reacted solution 90ml water quencher reaction, add extraction into ethyl acetate, collected organic layer, organic layer is concentrated, with anhydrous magnesium sulfate drying, obtain crude product, using crude product sherwood oil/organic solvent as leacheate through silica gel column chromatography separating-purifying, obtain white solid, i.e. intermediate reaction product;
Be added in organic solvent by this intermediate reaction product, this organic solvent is identical with aforementioned, does not repeat to set forth at this; Then add oxygenant, at ambient temperature stirring reaction 3 hours ~ 12 hours, this room temperature does not limit, such as 10 DEG C ~ 30 DEG C; After this oxygenant and above-mentioned purification, reaction product (intermediate reaction product) mol ratio is 100 ~ 160: 1.
The embodiment of the present invention is containing triphenylamine organic semiconductor material preparation method, the organic semiconductor material containing triphenylamine base unit, hexichol phosphorus oxygen base unit and fluorenyl unit is drawn by reaction preparation, the introducing of triphenylamine base, hexichol phosphorus oxygen base, make this contain triphenylamine organic semiconductor material and there is excellent carrier transport efficiency, realize the remarkable lifting of its luminescent properties; Meanwhile, excellent thermal stability, film-forming properties and resolvability should be had containing triphenylamine organic semiconductor material; The embodiment of the present invention is containing triphenylamine organic semiconductor material preparation method, simple to operate, with low cost, is very suitable for suitability for industrialized production.
The embodiment of the present invention provides above-mentioned containing 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 further.
Be described in detail containing triphenylamine organic semiconductor material preparation method above-mentioned below in conjunction with specific embodiment.
Embodiment one
The embodiment of the present invention 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes (DMTTPOF) has following structural formula:
The embodiment of the present invention 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes (DMTTPOF) preparation method, comprises the steps:
Step one, preparation 9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes 2,7-dibromo fluorenes:
Under argon shield; by 2 of 7mmol; the N of 7-dibromo fluorenone, 98mmol; the methylsulphonic acid of N-bis-(4-cyano-phenyl) anilino and 7mmol is added in reactor, stirring reaction 6 hours at 140 DEG C, and stopped reaction is also cooled to 15 DEG C; with dichloromethane extraction; again respectively with saturated sodium bicarbonate solution and distillation washing, concentration of organic layers, obtains blue solid.After crude on silica gel chromatography column separating-purifying, then obtain white solid product with acetone recrystallization, namely prepare 9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes 2,7-dibromo fluorenes, productive rate 72%.MALDI/TOF-MS：m/z：1193(M
+)。Reaction formula is expressed as:
Step 2, preparation 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes (DMTPOF):
Anhydrous, under nitrogen protection and-78 DEG C of temperature condition, by 9 of 1.5mmol, 9-bis-(N, N-bis-(4-cyano-phenyl) anilino) fluorenes 2,7-dibromo fluorenes is added in the tetrahydrofuran solution of 75mL, adds 3.75mmol n-Butyl Lithium, stir 2 hours at-78 DEG C, add rapidly diphenyl phosphine chloride 3.75mmol again, obtain transparent pale yellow solution, stirring reaction 12 hours after being naturally warming up to 15 DEG C; Then to go out reaction with 90mL shrend, be extracted with ethyl acetate, concentration of organic layers, with anhydrous magnesium sulfate drying, crude product adopts sherwood oil/methylene dichloride to obtain white solid as leacheate through silica gel column chromatography separating-purifying; White solid 60mL methylene dichloride is dissolved, adds the hydrogen peroxide that 7mL concentration is 30% (mass percent), 15 DEG C of lower stirring reactions of condition 12 hours; Be separated organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve steaming solvent, obtain white solid, adopt ethyl acetate/methanol to obtain containing triphenylamine organic semiconductor material through silica gel column chromatography separating-purifying as leacheate, productive rate is 39%.MALDI/TOF-MS：m/z：1437(M
+)。Reaction formula is expressed as:
Detected by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and when sweep velocity is 10 DEG C/min, in the present embodiment one, the heat decomposition temperature containing triphenylamine organic semiconductor material of preparation is 423 DEG C.
Refer to Fig. 1, Fig. 1 is the fluorescence emission spectra figure containing triphenylamine organic semiconductor material prepared by the embodiment of the present invention one, and as can be seen from Figure 1, prepared by embodiment one is 441 nanometers containing triphenylamine organic semiconductor material at maximum emission wavelength.
Embodiment two
The embodiment of the present invention 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-tert-butylthiophene-2-base) phenyl) anilino) fluorenes (DBTTPOF) has following structural formula:
The embodiment of the present invention 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-tert-butylthiophene-2-base) phenyl) anilino) fluorenes (DBTTPOF) preparation method, comprises the steps:
Step one, preparation 9,9-bis-(N, N-bis-(4-(5-tert-butylthiophene-2-base) phenyl) anilino) fluorenes 2,7-dibromo fluorenes:
Under argon shield; by 2 of 7mmol; the N of 7-dibromo fluorenone, 98mmol; the tertiary butyl sulfonic acid of N-bis-(4-cyano-phenyl) anilino and 7mmol is added in reactor, stirring reaction 8 hours at 140 DEG C, and stopped reaction is also cooled to 25 DEG C; with dichloromethane extraction; again respectively with saturated sodium bicarbonate solution and distillation washing, concentration of organic layers, obtains blue solid.After crude on silica gel chromatography column separating-purifying, then obtain white solid product with acetone recrystallization, namely prepare 9,9-bis-(N, N-bis-(4-(5-tert-butylthiophene-2-base) phenyl) anilino) fluorenes 2,7-dibromo fluorenes, productive rate 68%.MALDI/TOF-MS：m/z：1361(M
+)。Reaction formula is expressed as:
Step 2, preparation 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-tert-butylthiophene-2-base) phenyl) anilino) fluorenes (DBTTPOF):
Anhydrous, under nitrogen protection and-78 DEG C of temperature condition, by 9 of 1.5mmol, 9-bis-(N, N-bis-(4-cyano-phenyl) anilino) fluorenes 2,7-dibromo fluorenes is added in the tetrahydrofuran solution of 75mL, adds 3.45mmol n-Butyl Lithium, stir 2 hours at-78 DEG C, add rapidly diphenyl phosphine chloride 3.45mmol again, obtain transparent pale yellow solution, stirring reaction 7 hours after being naturally warming up to 25 DEG C; Then to go out reaction with 90mL shrend, be extracted with ethyl acetate, concentration of organic layers, with anhydrous magnesium sulfate drying, crude product adopts sherwood oil/methylene dichloride to obtain white solid as leacheate through silica gel column chromatography separating-purifying; White solid 60mL methylene dichloride is dissolved, adds the hydrogen peroxide that 7mL concentration is 30% (mass percent), 25 DEG C of lower stirring reactions of condition 7 hours; Be separated organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve steaming solvent, obtain white solid, adopt ethyl acetate/methanol to obtain containing triphenylamine organic semiconductor material through silica gel column chromatography separating-purifying as leacheate, productive rate is 30%.MALDI/TOF-MS：m/z：1605(M
+)。Reaction formula is expressed as:
Detected by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, in the present embodiment two, does is the heat decomposition temperature containing triphenylamine organic semiconductor material of preparation when sweep velocity is 10 DEG C/min? DEG C.
Embodiment three
The embodiment of the present invention 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-n-octyl thiophene-2-base) phenyl) anilino) fluorenes (DOTTPOF) has following structural formula:
The embodiment of the present invention 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-n-octyl thiophene-2-base) phenyl) anilino) fluorenes (DOTTPOF) preparation method, comprises the steps:
Step one, preparation 9,9-bis-(N, N-bis-(4-(5-n-octyl thiophene-2-base) phenyl) anilino) fluorenes 2,7-dibromo fluorenes:
Under argon shield; by 2 of 7mmol; the N of 7-dibromo fluorenone, 98mmol; the n-octyl sulfonic acid of N-bis-(4-cyano-phenyl) anilino and 7mmol is added in reactor, stirring reaction 7 hours at 140 DEG C, and stopped reaction is also cooled to 30 DEG C; with dichloromethane extraction; again respectively with saturated sodium bicarbonate solution and distillation washing, concentration of organic layers, obtains blue solid.After crude on silica gel chromatography column separating-purifying, then obtain white solid product with acetone recrystallization, namely prepare 9,9-bis-(N, N-bis-(4-(5-n-octyl thiophene-2-base) phenyl) anilino) fluorenes 2,7-dibromo fluorenes, productive rate 72%.MALDI/TOF-MS：m/z：1585(M
+)。Reaction formula is expressed as:
Step 2, preparation 2,7-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-n-octyl thiophene-2-base) phenyl) anilino) fluorenes (DOTTPOF):
Anhydrous, under nitrogen protection and-78 DEG C of temperature condition, by 9 of 1.5mmol, 9-bis-(N, N-bis-(4-cyano-phenyl) anilino) fluorenes 2,7-dibromo fluorenes is added in the tetrahydrofuran solution of 75mL, adds 3.45mmol n-Butyl Lithium, stir 1 hour at-78 DEG C, add rapidly diphenyl phosphine chloride 3.45mmol again, obtain transparent pale yellow solution, stirring reaction 3 hours after being naturally warming up to 30 DEG C; Then to go out reaction with 90mL shrend, be extracted with ethyl acetate, concentration of organic layers, with anhydrous magnesium sulfate drying, crude product adopts sherwood oil/methylene dichloride to obtain white solid as leacheate through silica gel column chromatography separating-purifying; White solid 60mL methylene dichloride is dissolved, adds the hydrogen peroxide that 7mL concentration is 30% (mass percent), 30 DEG C of lower stirring reactions of condition 3 hours; Be separated organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve steaming solvent, obtain white solid, adopt ethyl acetate/methanol to obtain containing triphenylamine organic semiconductor material through silica gel column chromatography separating-purifying as leacheate, productive rate is 26%.MALDI/TOF-MS：m/z：1830(M
+)。Reaction formula is expressed as:
Detected by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and when sweep velocity is 10 DEG C/min, in the present embodiment three, the heat decomposition temperature containing triphenylamine organic semiconductor material of preparation is 443 DEG C.
Application examples
Refer to Fig. 2, Fig. 2 display application embodiment of the present invention one containing 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 the hole blocking layer/electron transfer layer 5 be positioned 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-bis-(diphenyl phosphine oxygen base)-9,9-bis-(N, N-bis-(4-(5-thiotolene-2-base) phenyl) anilino) fluorenes } and Ir (ppy)
3{ three (2-phenylpyridines) close iridium } green phosphorescent material forms according to weight percentage 93.5%: 6.5%;
The material of this hole blocking layer/electron transfer layer 5 is TPBI (1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene);
The material of this electron injecting layer 6 is LiF;
The material of this negative electrode 8 to be weight ratio be 10: 1 Mg: Ag alloy; Each functional layer above-mentioned is prepared by vacuum evaporation mode.
The organic electroluminescence device of application examples of the present invention is tested under room temperature and atmospheric environment, has the external quantum efficiency of 20.2%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1., containing a triphenylamine organic semiconductor material, there is following structural formula I:
Wherein, R is C
1-C
6alkyl.
2., containing a triphenylamine organic semiconductor material preparation method, comprise the steps:
9,9-bis-(triphenylamine base)-2, the 7-dibromo fluorenes providing structural formula II to represent
The alkyl derivative of lithium is added to be dissolved with that structural formula II represents 9 under anhydrous and oxygen-free and temperature are-78 DEG C ~-70 DEG C conditions, 9-bis-(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 to 10 DEG C-30 DEG C, react 3 hours ~ 12 hours, collecting reaction product is also purified, reaction product after described purification is dissolved in organic solvent, adds oxygenant, react 1 hour ~ 12 hours, obtain containing triphenylamine organic semiconductor material, reaction formula is expressed as:
Wherein, R is C
1-C
6alkyl;
The alkyl derivative of described lithium is selected from n-Butyl Lithium, isobutyl-lithium, lithium methide or phenyl lithium;
Described oxygenant is selected from hydrogen peroxide, Potcrate, sodium chlorate, clorox or hypochlorous acid.
3. as claimed in claim 2 to it is characterized in that containing triphenylamine organic semiconductor material preparation method, 9,9-bis-(triphenylamine base) that the alkyl derivative of described lithium and structural formula II represent-2,7-dibromo fluorenes mol ratio be 2 ~ 2.5:1.
4. as claimed in claim 2 containing triphenylamine organic semiconductor material preparation method, it is characterized in that, the alkyl derivative of described lithium and the mol ratio of diphenyl phosphorus chloride are 1:1.
5. as claimed in claim 2 it is characterized in that containing triphenylamine organic semiconductor material preparation method, after described oxygenant and described purification, reaction product mol ratio is: 100 ~ 160:1.
6. as claimed in claim 1 containing 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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| CN1634864A (en) * | 2004-11-12 | 2005-07-06 | 中国科学院上海有机化学研究所 | 9,9-bis(triphenyl amino) fluorine derivatives and preparation and use thereof |
| JP2007153776A (en) * | 2005-12-02 | 2007-06-21 | Toyo Ink Mfg Co Ltd | Fluorene compound having carbazolyl group and application thereof |
| CN101225298A (en) * | 2007-01-18 | 2008-07-23 | 中国科学院化学研究所 | Hole-transporting type blue luminescent material as well as preparation and uses thereof |
| CN101460588A (en) * | 2006-05-31 | 2009-06-17 | 默克专利有限公司 | New materials for organic electroluminescent devices |
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2011
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| CN1634864A (en) * | 2004-11-12 | 2005-07-06 | 中国科学院上海有机化学研究所 | 9,9-bis(triphenyl amino) fluorine derivatives and preparation and use thereof |
| JP2007153776A (en) * | 2005-12-02 | 2007-06-21 | Toyo Ink Mfg Co Ltd | Fluorene compound having carbazolyl group and application thereof |
| CN101460588A (en) * | 2006-05-31 | 2009-06-17 | 默克专利有限公司 | New materials for organic electroluminescent devices |
| CN101225298A (en) * | 2007-01-18 | 2008-07-23 | 中国科学院化学研究所 | Hole-transporting type blue luminescent material as well as preparation and uses thereof |
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