CN102453230B - Organic semiconductor material containing carbazole and thiophene pyrrole-dione unit as well as preparation method and application thereof - Google Patents
Organic semiconductor material containing carbazole and thiophene pyrrole-dione unit as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of photoelectron materials and discloses an organic semiconductor material containing carbazole and a thiophene pyrrole-dione unit as well as a preparation method and application thereof. The organic semiconductor material has a general formula (I), wherein in the formula, R1 and R2 are C1-C20 alkyl; and n is an integral of more than 1 and less than or equal to 100. Compared with the prior art, in the preparation method disclosed by the invention, the dissolubility and molecular weight of a product are improved through introducing alkyl, so as to achieve a spinning organic semiconductor material or a spinning oligomer; and the organic semiconductor composed of a carbazole monomer and a thiophene pyrrole-dione monomer can form a strong donor-accepter structure which on one hand is beneficial to the improvement of the stability of the material and on the other hand is beneficial to reduction of the energy band gap of the material, thereof enlarging the absorption range of sun light and improving the conversion efficiency of photoelectricity.
Description
Technical field
The present invention relates to a kind of organic semiconductor material, be related to a kind of organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit more specifically.
The invention still further relates to a kind of preparation method and application thereof that contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit.
Background technology
Current world economy mainly is to be based upon with fossil energy, as the economy on the bases such as coal, oil and natural gas.Yet these non-renewable fossil energies are all in continuous exhaustion.Entered since 21 century, problems such as global energy problem and consequent environmental pollution and climate warming show especially and aggravation gradually day by day.Because sun power has and distributes generally and wide, resource quantity is many, and is pollution-free, cleaning, and safety and obtain outstanding advantages such as convenient is considered to one of most promising renewable energy source.Solar cell directly changes into electric energy to solar energy, is to utilize the practicable effective ways of sun power.Yet present commercial solar cell also is confined to inorganic solar cell such as silica-based, but their price is too expensive, has exceeded the general acceptable degree of present people, and this has limited their use range greatly.In order to reduce the battery cost, expand range of application, for a long time, people are seeking novel solar cell material always.
Organic solar batteries is a kind of novel solar cell, limited with respect to the inorganic semiconductor material source, expensive, poisonous, complicated process of preparation, cost is too high, and it has some incomparable advantages of inorganic solar cell, and is extensive as material source, structure diversity and Modulatory character, with low cost, safety and environmental protection, manufacture craft is simple, product weight is light, but large area flexible preparation etc. can be widely used in multiple fields such as building, illumination and generating, has important development and application prospect.Therefore, the research institution of lot of domestic and foreign and enterprise etc. have all given suitable concern and input.Yet up to the present, the photoelectric transformation efficiency of organic solar batteries still is much lower than inorganic solar cell.Therefore, the organic semiconductor material of development of new is significant for the efficient that improves organic solar batteries.
Summary of the invention
Based on the problems referred to above, the object of the present invention is to provide a kind of organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit.
The present invention also aims to provide a kind of preparation method and application thereof that contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit.
A kind of organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit provided by the invention has following general formula (I):
In the formula: R
1, R
2Identical or be expressed as C unequally
1-C
20Alkyl; The span of n is greater than 1 smaller or equal to 100 integer, and the span of preferred n is smaller or equal to 80 integer more than or equal to 20.
The above-mentioned preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit, it comprises the steps:
Step S1, with 2,7-, two bromo-9-alkyl-9H-carbazole (A
1) and n-Butyl Lithium (n-BuLi) under-100 ℃～-25 ℃, be added in 1: 2～1: 4 in first solvent with mol ratio, add 2-isopropoxy-4,4,5 then, 5-tetramethyl--1,3, the assorted oxygen pentaborane (C of 2-two
1), continue reaction 24～48 hours, obtain 9-alkyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1); Wherein, described first solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Described 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the mole dosage of the assorted oxygen pentaboranes of 2-two is described 2,2～4 times of 7-two bromo-9-alkyl-9H-carbazole molar weight; Reaction formula is as follows:
In the formula: R
1Be C
1-C
20Alkyl;
Step S2, with 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (A
2) and bromizating agent, as N-bromo-succinimide (NBS), under 10 ℃～30 ℃, be added in 1: 2～1: 4 in second solvent with mol ratio, reacted 12～48 hours, obtain 1,3-, two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (B
2); Wherein, described second solvent mixed solvent that is sulfuric acid and trifluoroacetic acid; Reaction formula is as follows:
In the formula: R
2Be C
1-C
20Alkyl;
In step S3, the oxygen-free environment, with the B that makes among the step S1
1With the B that makes among the step S2
2With mol ratio 1: a, add in the 3rd solvent that contains catalyzer, alkali lye, under 65 ℃～120 ℃, carry out Suzuki reaction 24～72 hours, obtain the described organic semiconductor material (I) that contains carbazole and thiophene pyrrole diketone unit; Wherein, the span of a is smaller or equal to 1.05 more than or equal to 0.95; Described catalyzer is the mixture (mol ratio of organic palladium and organophosphor ligand is 1: 1～20) of organic palladium or organic palladium and organophosphor ligand; Described catalyst consumption is described 9-alkyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) 0.005～0.1 times of mole dosage; Described organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2Described organophosphor ligand is P (o-Tol)
3Alkali lye is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, the consumption of corresponding alkali is 9-alkyl-2 in the alkali lye, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) mole dosage 2-20 doubly, the 3rd solvent is at least a in tetrahydrofuran (THF), toluene, trichloromethane or the ethyl acetate; Reaction formula is as follows:
In the formula, the span of n is smaller or equal to 100 integer greater than 1.
The above-mentioned organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit can be widely used in organic solar batteries, organic field effect tube, and organic electroluminescence device, organic optical storage is in organic non-linear optical properties and the organic laser apparatus.
Compared with prior art, major advantage of the present invention is:
1, synthesizing carbazole monomers B
1, thiophene pyrrole two ketone monomers B
2Route fairly simple and ripe, easily by introducing solvability and the molecular weight that alkyl improves product, but but with the organic polymer of realizing spin coating or the oligomer of spin coating;
2, carbazoles monomers B
1Be a kind of very excellent donor material, have optical property and electric property preferably, also have higher thermostability and second-order transition temperature, thiophene pyrrole two ketone monomers B simultaneously
2Be a kind of very excellent acceptor material, by monomers B
1, B
2The organic polymer that constitutes can form a kind of very strong donor-receiver structure, has been conducive to improve the stability of material on the one hand, is conducive to reduce the band gap of material on the other hand, thereby enlarges the sunlight absorption region, improves electricity conversion;
3, the Suzuki reaction is a kind of very ripe polyreaction, and productive rate height, and mild condition are easy to control.
Description of drawings
Fig. 1 is to be the structural representation of the organic solar batteries device of active coating with organic semiconductor material of the present invention;
Fig. 2 is to be the structural representation of the organic electroluminescence device of luminescent layer with organic semiconductor material of the present invention;
Fig. 3 is to be the structural representation of the organic field effect tube device of organic semiconductor layer with organic semiconductor material of the present invention.
Embodiment
A kind of organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit provided by the invention has following general formula (I):
In the formula: R
1, R
2Identical or be expressed as C unequally
1-C
20Alkyl; The span of n is greater than 1 smaller or equal to 100 integer, and the span of preferred n be more than or equal to 20 smaller or equal to 80 integer, and preferably the span of n is smaller or equal to 80 integer more than or equal to 20.
The present invention also provides a kind of preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit, comprises the steps:
Step S1, with 2,7-, two bromo-9-alkyl-9H-carbazole (A
1) and n-Butyl Lithium (n-BuLi) under-100 ℃～-25 ℃, be added in 1: 2～1: 4 in first solvent with mol ratio, add 2-isopropoxy-4,4,5 then, 5-tetramethyl--1,3, the assorted oxygen pentaborane (C of 2-two
1), perhaps for structural formula be
Two tetramethyl ethylene ketones close two boron, continue reaction 24～48 hours, obtain product, i.e. 9-alkyl-2,7-two (4,4,5,5-tetramethyl-s-1,3,2-mix oxygen pentaborane base-2-yl)-9H-carbazole (B
1); Wherein, first solvent is tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc., C
1Mole dosage be A
12～4 times of molar weight; Its reaction formula is as follows:
Step S2, with 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (A
2) and bromizating agent under 10 ℃～30 ℃, be added in 1: 2～1: 4 in second solvent with mol ratio, reacted 12～48 hours, obtain product, namely 1,3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (B
2); Wherein, second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid, and described bromizating agent is N-bromo-succinimide (NBS, down together); Its reaction formula is as follows:
In step S3, the oxygen-free environment, with the B that makes among the step S1
1With the B that makes among the step S2
2With mol ratio 1.0: a (wherein, 0.95≤a≤1.05) add in the 3rd solvent that contains catalyzer, alkali lye, under 65 ℃～120 ℃, carry out Suzuki reaction 24～72 hours, obtain product, i.e. the organic semiconductor material (I) of carbazole and thiophene pyrrole diketone unit; Wherein, catalyzer is the ligand mixture (mol ratio of organic palladium and organophosphor ligand is 1: 1～20) of organic palladium or organic palladium and organophosphorus; Organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2, organophosphor ligand is P (o-Tol)
3, the mole dosage of catalyzer is 9-alkyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) mole dosage 0.005-0.10 doubly; Alkali lye is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, the consumption of corresponding alkali is 9-alkyl-2 in the alkali lye, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) mole dosage 2-20 doubly, the 3rd solvent is at least a in tetrahydrofuran (THF), toluene, trichloromethane or the ethyl acetate, its reaction formula is as follows:
In the formula, the span of n is greater than 1 smaller or equal to 100 integer, and the span of preferred n is smaller or equal to 80 integer more than or equal to 20.
In order to understand the content of patent of the present invention better, further specify technology case of the present invention below by concrete example and legend, specifically comprise the preparation of material preparation and device, but these embodiments do not limit the present invention.In the present invention, contain carbazole and thiophene pyrrole diketone unit mainly as organic semiconductor material.
In the present embodiment, formed oxygen-free atmosphere is mainly nitrogen atmosphere in the oxygen-free environment, also can be other inert gas atmosphere; At this it is not limited.
Embodiment 1
Present embodiment discloses the following organic semiconductor material of a kind of structure:
In the following formula, n=20;
The preparation process of above-mentioned organic semiconductor material is as follows:
One, 9-methyl-2, the preparation of two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-:
Under-100 ℃, condition of nitrogen gas, 40.00mL (1.00M) n-butyllithium solution is added to fills 3.39g 2, in the reaction flask of 7-two bromo-9-methyl-9H-carbazoles and 100mL tetrahydrofuran (THF), stir and slowly drip 9.60mL 2-isopropoxy-4,4 after 2 hours, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, return to room temperature, continue to stir 48 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：433.2(M
+).
Two, 5-thiotolene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.97g thiophene-3, the 4-dicarboxylic acid is added in the 150mL diacetyl oxide under the room temperature, stirs 24 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 150mL toluene, adds the 1.62g methylamine subsequently, is heated to 120 ℃ of reactions 24 hours.Reaction solution is cooled to room temperature, and removal of solvent under reduced pressure adds the 270mL thionyl chloride, is heated to 90 ℃ and refluxes 4 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains product.
MALDI-TOF-MS(m/z)：167.2(M
+).
Three, 1,3-two bromo-5-thiotolene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 1.67g 5-thiotolene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 15.3mL sulfuric acid and 50mL trifluoroacetic acid, adds 5.34g NBS after stirring 1 hour under 10 ℃ in batches, continues reaction 24 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：325.0(M
+).
Four, the preparation of organic semiconductor material:
Under nitrogen protection, toward containing 0.433g 9-methyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-, 0.325g 1,3-two bromo-5-thiotolene [3,4-c]-pyrroles-4,6-diketone, 0.126g Pd (PPh
3)
4Reaction flask in add the 10mL 20%Wt tetraethyl ammonium hydroxide aqueous solution and toluene (30mL).Behind the nitrogen replacement 1 hour, be heated to 120 ℃, reacted 24 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝6928，PDI＝1.9.
Embodiment 2
Present embodiment discloses the following organic semiconductor material of a kind of structure:
In the following formula, n=62;
The preparation process of above-mentioned organic semiconductor material is as follows:
One, 9-octyl group-2, the preparation of two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-:
Under-78 ℃, condition of nitrogen gas, with syringe 10.00mL (2.00M) n-butyllithium solution is added to and fills 4.37g 2, in two mouthfuls of flasks of 7-two bromo-9-octyl group-9H-carbazoles and 100.00mL tetrahydrofuran (THF), stir and slowly drip 4.80mL 2-isopropoxy-4,4 after 2 hours, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, return to room temperature, continue to stir 33 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：531.3(M
+).
Two, 5-octyl group thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.75g thiophene-3, the 4-dicarboxylic acid is added in the 120mL diacetyl oxide under the room temperature, stirs 22 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 130mL toluene, adds the 6.69g octyl amine subsequently, is heated to 115 ℃ of reactions 26 hours.Reaction solution is cooled to room temperature, and the evaporated under reduced pressure solvent is heated to 90 ℃ and refluxed 6 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains product.
MALDI-TOF-MS(m/z)：265.4(M
+).
Three, 1,3-two bromo-5-octyl group thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 2.65g 5-octyl group thiophene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 16.0mL sulfuric acid and 50mL trifluoroacetic acid, adds 5.88g NBS after stirring 1 hour under 20 ℃ in batches, continues reaction 16 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：423.2(M
+).
Four, the preparation of organic semiconductor material:
Under nitrogen protection, toward containing 0.531g 9-octyl group-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-, 0.423g 1,3-two bromo-5-octyl group thiophene [3,4-c]-pyrroles-4,6-diketone, 0.134g Pd (PPh
3)
4Reaction flask in add 12mL 2M aqueous sodium carbonate, 0.099g quaternary ammonium salt 336 and toluene (30mL).Behind the nitrogen replacement 2 hours, be heated to 65 ℃, reacted 72 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝33652，PDI＝2.1.
Embodiment 3
Present embodiment discloses the following organic semiconductor material of a kind of structure:
In the following formula, n=80;
The preparation process of above-mentioned organic semiconductor material is as follows:
One, 9-decyl-2, the preparation of two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-:
Under-45 ℃, condition of nitrogen gas, with syringe 28.00mL (1.00M) n-butyllithium solution is added to and fills 4.65g 2, in two mouthfuls of flasks of 7-two bromo-9-decyl-9H-carbazoles and 100.00mL tetrahydrofuran (THF), stir after 2 hours slowly Dropwise 5 .70mL 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, return to room temperature, continue to stir 44 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：544.4(M
+).
Two, 5-decylthiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.86g thiophene-3, the 4-dicarboxylic acid is added in the 140mL diacetyl oxide under the room temperature, stirs 28 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 150mL toluene, adds the 6.98g decyl amine subsequently, is heated to 120 ℃ of reactions 24 hours.Reaction solution is cooled to room temperature, and the evaporated under reduced pressure solvent is heated to 90 ℃ and refluxed 10 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains product.
MALDI-TOF-MS(m/z)：293.4(M
+).
Three, 1,3-two bromo-5-decylthiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 2.93g 5-decylthiophene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 18.0mL sulfuric acid and 58mL trifluoroacetic acid, adds 5.96g NBS after stirring 1 hour under 25 ℃ in batches, continues reaction 20 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：451.2(M
+).
Four, the preparation of organic semiconductor material:
Under nitrogen protection, toward containing 0.544g 9-decyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-, 0.451g 1,3-two bromo-5-decylthiophene [3,4-c]-pyrroles-4,6-diketone, 0.101g Pd (PPh
3)
4Reaction flask in add 9mL 2M aqueous sodium carbonate, 0.079g quaternary ammonium salt 336 and toluene (30mL).Behind the nitrogen replacement 2 hours, be heated to 85 ℃, reacted 56 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝47910，PDI＝2.0.
Embodiment 4
Present embodiment discloses the following organic semiconductor material of a kind of structure:
In the following formula, n=100;
The preparation process of above-mentioned organic semiconductor material is as follows:
One, 9-eicosyl-2, the preparation of two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazoles of 7-:
Under-25 ℃, condition of nitrogen gas, with syringe 32.00mL (1.00M) n-butyllithium solution is added to and fills 6.06g 2, in two mouthfuls of flasks of 7-two bromo-9-eicosyl-9H-carbazoles and 150.00mL tetrahydrofuran (THF), stir after 2 hours slowly Dropwise 5 .90mL 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, return to room temperature, continue to stir 24 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：699.7(M
+).
Two, 5-eicosyl thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.23g thiophene-3, the 4-dicarboxylic acid is added in the 100mL diacetyl oxide under the room temperature, stirs 20 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 100mL toluene, adds 14.92g eicosyl amine subsequently, is heated to 115 ℃ of reactions 29 hours.Reaction solution is cooled to room temperature, and the evaporated under reduced pressure solvent is heated to 90 ℃ and refluxed 5 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains product.
MALDI-TOF-MS(m/z)：433.7(M
+).
Three, 1,3-two bromo-5-eicosyl thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 4.89g 5-eicosyl thiophene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 18.0mL sulfuric acid and 55mL trifluoroacetic acid, adds 6.21g NBS after stirring 1 hour under 30 ℃ in batches, continues reaction 12 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains solid product.
MALDI-TOF-MS(m/z)：591.5(M
+)
Four, the preparation of organic semiconductor material:
Under nitrogen protection, toward containing 0.700g 9-eicosyl-2,7-two (4,4; 5,5-tetramethyl--1,3, the assorted oxygen pentaborane base of 2-two-2-yls)-9H-carbazole, 0.592g 1; 3-two bromo-5-eicosyl thiophene [3,4-c]-pyrroles-4,6-diketone, 0.141g Pd (PPh
3)
4Reaction flask in add 13mL 2M aqueous sodium carbonate, 0.104g quaternary ammonium salt 336 and toluene (30mL).Behind the nitrogen replacement 2 hours, be heated to 90 ℃, reacted 62 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝87941，PDI＝1.7.
The present invention also provides a kind of organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit, and its structural formula is
In the formula, R
1, R
2Identical or be expressed as C unequally respectively
1-C
20Alkyl; The span of n is smaller or equal to 100 integer greater than 1.This organic semiconductor material can be used to organic solar batteries, organic field effect tube, and organic electroluminescence device, organic optical storage is in the fields such as organic non-linear optical properties and organic laser apparatus.
Following examples are to contain the organic semiconductor material of carbazole and thiophene pyrrole diketone unit at organic solar batteries, organic field effect tube, the application in the organic electroluminescence device.
Embodiment 5
A kind of organic solar batteries device, its structure as shown in Figure 1.Wherein, the substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic solar batteries device is: glass 11/ITO layer 12/PEDOT:PSS layer 13/ active coating 14/Al layer 15; Wherein, the material of active coating 14 is mixture, comprises electron donor material, and PCBM is electron acceptor material; Electron donor material is the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit in the present embodiment 1, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM); ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid).
This organic solar batteries preparation of devices process is:
Tin indium oxide (ITO) layer 12 in that surface deposition one deck square resistance of glass substrate 11 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is 50-300nm;
Ito glass process ultrasonic cleaning, and with after oxygen-Plasma processing, be coated with the PEDOT:PSS layer 13 that last layer plays modification on the ITO surface, thickness is 30-300nm;
Adopt spin coating technique to apply one deck active coating 14 at described poly-(3,4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, thickness is 50-300nm; The material of this active coating is the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit and [6, the 6] phenyl-C in the present embodiment 1
61The mixture of-methyl-butyrate (being called for short PCBM);
At the surface vacuum evaporation metal aluminium of described active coating, form the metal aluminium lamination 15 as negative electrode, obtain described organic solar batteries device;
With the organic solar batteries device with epoxy encapsulation after, place under 120 ℃ of air tight conditions annealing 2 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Wherein, the thickness of ITO, PEDOT:PSS, active coating, Al layer is respectively and is 120nm, 50nm, 110nm, 90nm.
Embodiment 6
A kind of organic electroluminescence device, its structure is as shown in Figure 2; Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic electroluminescence device is: glass 21/ITO layer 22/ luminescent layer 23/LiF buffer layer 24/Al layer 25; Wherein: luminescent layer is material with the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit in the present embodiment 1.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 in that surface deposition one deck square resistance of glass substrate 21 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is 50-300nm;
Be the luminescent layer 23 of material at ITO surface preparation one deck with the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit in the present embodiment 1 by spin coating technique, thickness is 50-300nm;
Vacuum evaporation LiF on luminescent layer, as buffer layer 24, thickness is 0.3-2nm;
Vacuum evaporation metallic aluminium on described luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains described organic electroluminescence device.
Embodiment 7
A kind of organic field effect tube, its structure is as shown in Figure 3; Substrate in the present embodiment adopts doped silicon wafer (Si) as substrate.
The structure of this organic field effect tube is: the SiO that Si 31/500nm is thick
2Insulation layer 32/ is used for modifying SiO
2Octadecyl trichlorosilane (OTS) layer 33/ organic semiconductor layer 34/ be source electrode (S) 35 and the drain electrode (D) 36 of material with the gold; Wherein, organic semiconductor layer is material with the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit in the present embodiment 1; Source electrode (S) and drain electrode (D) also can adopt copper material.
The preparation process of this organic field effect tube is:
At first, apply the thick SiO of one deck 500nm on a surface cleaning doped silicon wafer 31 later
2Insulation layer 32; Secondly, at described SiO
2Apply the octadecyl trichlorosilane layer 33 that one deck plays modification on the insulation layer, thickness is 10-200nm; Then, spin coating one deck is the organic semiconductor layer 34 of material with the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit in the present embodiment 1 on described octadecyl trichlorosilane layer, and thickness is 50-300nm; At last, being arranged at intervals with the gold at described organic semiconductor layer is source electrode (S) 35 and the drain electrode (D) 36 of material, obtains described organic field effect tube.
Should be understood that above-mentioned statement at preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit of following general formula (I):
In the formula: R
1, R
2Be respectively C
1-C
20Alkyl; The span of n is smaller or equal to 100 integer greater than 1.
2. the organic semiconductor material that contains carbazole and thiophene pyrrole diketone unit according to claim 1 is characterized in that, the span of described n is smaller or equal to 80 integer more than or equal to 20.
3. a preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit is characterized in that this preparation method comprises the steps:
Step S1, with 2,7-, two bromo-9-alkyl-9H-carbazole (A
1) and n-BuLi under-100 ℃～-25 ℃, be added in first solvent with mol ratio 1:2～1:4, add 2-isopropoxy-4,4,5 then, 5-tetramethyl--1,3, the assorted oxygen pentaborane (C of 2-two
1), continue reaction 24～48 hours, obtain 9-alkyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1); Reaction formula is as follows:
In the formula: R
1Be C
1-C
20Alkyl;
Step S2, with 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (A
2) and bromizating agent under 10 ℃～30 ℃, be added in second solvent with mol ratio 1:2～1:4, reacted 12～48 hours, obtain 1,3-, two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (B
2); Reaction formula is as follows:
In the formula: R
2Be C
1-C
20Alkyl;
In step S3, the oxygen-free environment, with the described 9-alkyl-2 that makes among the step S1, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) and step S2 in make described 1,3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (B
2) with mol ratio 1:a, add in the 3rd solvent that contains catalyzer, alkali lye, under 65 ℃～120 ℃, carry out Suzuki reaction 24～72 hours, obtain the described organic semiconductor material (I) that contains carbazole and thiophene pyrrole diketone unit; Wherein, the span of a is smaller or equal to 1.05 more than or equal to 0.95; Reaction formula is as follows:
In the formula, the span of n is smaller or equal to 100 integer greater than 1.
4. the preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit according to claim 3, it is characterized in that, among the step S1, described first solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Described 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the mole dosage of the assorted oxygen pentaboranes of 2-two is described 2,2～4 times of 7-two bromo-9-alkyl-9H-carbazole molar weight.
5. the preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit according to claim 3 is characterized in that, among the described step S2, described bromizating agent is the N-bromo-succinimide; Described second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid.
6. the preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit according to claim 3 is characterized in that, among the step S3, described the 3rd solvent is at least a in tetrahydrofuran (THF), toluene, trichloromethane or the ethyl acetate.
7. the preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit according to claim 3 is characterized in that, among the step S3,
Described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; Described catalyst consumption is described 9-alkyl-2, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) 0.005～0.1 times of mole dosage;
Described organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2
Described organophosphor ligand is P (o-Tol)
3
8. the preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit according to claim 3 is characterized in that described alkali lye is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3At least a in the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; The mole dosage of alkali is described 9-alkyl-2 in the described alkali lye, two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane base-2-yls)-9H-carbazole (B of 7-
1) mole dosage 2-20 doubly.
9. the preparation method who contains the organic semiconductor material of carbazole and thiophene pyrrole diketone unit according to claim 3 is characterized in that, among the step S3, the span of described n is smaller or equal to 80 integer more than or equal to 20.
10. the organic semiconductor material of carbazole and thiophene pyrrole diketone unit that contains as claimed in claim 1 is at organic solar batteries, organic field effect tube, organic electroluminescence device, organic optical storage, organic non-linear optical properties or organic laser apparatus Application for Field.
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