CN102443143A - Organic semiconductor material containing thiophene pyrrole dione unit and preparation method and application thereof - Google Patents
Organic semiconductor material containing thiophene pyrrole dione unit and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of an optoelectronic material, and discloses an organic semiconductor material containing a thiophene pyrrole dione unit and a preparation method and an application thereof. The organic semiconductor material is shown in Formula (I), wherein R1, R2 and R3 are C1-C20 alkyl, and n is an integer more than 1 and less than or equal to 100. Compared with the prior art, the solubility and molecular weight of the product can be improved due to introduction of alkyl to realize the spin-coating polymer or spin-coating copolymer; and the polymer formed with thiophene pyrrole diketone monomers and thienothiophene monomers can achieve a strong donor-acceptor structure, thereby helping to improve the stability of the material and reduce the energy band gap of the material, expanding the scope of sunlight absorption, and improving the optoelectronic conversion efficiency.
Description
Technical field
The present invention relates to a kind of organic semiconductor material, relate to a kind of unitary organic semiconductor material of thiophene pyrrole diketone that contains more specifically.
The invention still further relates to a kind of preparation method and application thereof that contains the unitary organic semiconductor material of thiophene pyrrole diketone.
Background technology
Current world economy mainly is to be based upon with fossil energy, like the economy on the bases such as coal, oil and natural gas.Yet these non-renewable fossil energies are all in continuous exhaustion.Got into 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 general and widely, resource quantity is many, and is pollution-free, cleaning, and safety and obtain outstanding advantages such as convenient is considered to one of renewable energy source the most likely.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, this big limitations their use range.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, and is limited with respect to the inorganic polymer source, costs an arm and a leg, poisonous; Complicated process of preparation, cost are too high, and it has some incomparable advantages of inorganic solar cell; Extensive like material source, structure diversity and Modulatory character, with low cost; Safety and environmental protection, manufacture craft is simple, and product weight is light; But large area flexible preparation or the like 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 polymer of development of new is significant for the efficient that improves organic solar batteries.
Summary of the invention
The object of the present invention is to provide a kind of unitary organic semiconductor material of thiophene pyrrole diketone that contains, in order to address the above problem.
A kind of unitary organic semiconductor material of thiophene pyrrole diketone that contains of the present invention has following general formula (I):
In the formula: R
1, R
2, R
3Be respectively C identical or inequality
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 scheme that contains the unitary organic semiconductor material of thiophene pyrrole diketone, it comprises the steps:
Step S 1, compd A is provided
1, A
2:
Wherein, compd A
1Be two thienothiophene compounds; Compd A
2Be 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone; In the formula, R
1, R
2, R
3Be respectively C identical or inequality
1-C
20Alkyl;
Step S2: in the oxygen-free environment, with compd A
1And n-Butyl Lithium (n-BuLi) was added to mol ratio under-100 ℃～-25 ℃ and reacted in first solvent 0.5～5 hour in 1: 2～1: 4, added trimethyltin chloride (Me then
3SnCl, its consumption are compd A
12～4 times of molar weight), continue reaction 24～48 hours, obtain (3, and 5-dialkyl group two thieno-s [3,2-b; 2 ', 3 '-d] thiophene-2,6-two bases) two (tin trimethyls), i.e. compd B
1Wherein, first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE; Reaction formula is following:
Step S3: with compd A
2And bromizating agent, as 1,3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4; 6-diketone (NBS, down together) was added in second solvent with mol ratio under 10 ℃～30 ℃ in 1: 2～1: 4, reacted 12～48 hours, obtained 1; 3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone, i.e. compd B
2Wherein, second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid; Reaction formula is following:
Step S4: in the oxygen-free environment, with said compd B
1And B
2With mol ratio 1: a (wherein; 0.95≤a≤1.05) be dissolved in the 3rd solvent that contains catalyzer and mix; Under 65 ℃～120 ℃, carry out Stille reaction 24～72 hours, obtain containing thienothiophene and two thienothiophenes and the unitary organic semiconductor material of thiophene pyrrole diketone (I); Reaction formula is following:
In the formula, the span of n is smaller or equal to 100 integer greater than 1;
Wherein, catalyzer is an organic palladium, as, Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2, or organic palladium and organophosphor ligand be 1: 1～10 blended mixtures in molar ratio, as, Pd
2(dba)
3/ P (o-Tol)
3, catalyst consumption is said 3,6-dialkyl group thieno-[3,2-b] thiophene-2,5-two bases) 0.005-0.1 of two (tin trimethyl) mole dosage doubly, the 3rd solvent is at least a in THF, toluene, trichloromethane or the ETHYLE ACETATE.
The above-mentioned thiophene pyrrole diketone unit organic semiconductor material that contains can be widely used in organic solar batteries, organic field effect tube, and organic electroluminescence device, organic optical storage is in the fields such as organic non-linear device and organic laser apparatus.
Compared with prior art, major advantage of the present invention is:
1, synthetic ring penta 2 thienothiophene class monomers B
1, thiophene pyrrole two ketone monomers B
2Route fairly simple and ripe, be prone to help film forming processing through introducing solvability and the molecular weight that alkyl improves product;
2, ring penta 2 thienothiophene class monomers B
1Be a kind of very excellent donor material, thiophene pyrrole two ketone monomers B
2Have simple in structurely, symmetrical, advantage such as the electron delocalization performance is good, and have two dimensional structure is a kind of very excellent acceptor material, by monomers B
1, B
2The polymkeric substance that constitutes can form a kind of very strong donor-receiver structure, has helped improving the stability of material on the one hand, helps reducing the band gap of material on the other hand, thereby enlarges the sunshine absorption region, improves electricity conversion;
3, the Stille reaction is a kind of very sophisticated polyreaction, and productive rate is high, and mild condition, is 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 thiophene pyrrole diketone unit organic semiconductor material that contains provided by the invention has following general formula (I):
In the formula: R
1, R
2, R
3Be respectively identical 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 said preparation method who contains the unitary organic semiconductor material of thiophene pyrrole diketone comprises the steps:
Step S1: in the oxygen-free environment, with two thienothiophene compounds (A
1) and n-Butyl Lithium (n-BuLi) under-100 ℃～-25 ℃, be added in 1: 2～1: 4 and reacted in first solvent 0.5～5 hour with mol ratio, add trimethyltin chloride (Me then
3SnCl, its consumption are 2～4 times of two thienothiophene compounds molar weights), continue reaction 24～48 hours, obtain product, promptly (3, and 5-dialkyl group two thieno-s [3,2-b; 2 ', 3 '-d] thiophene-2,6-two bases) two (tin trimethyl) (B
1); Wherein, first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE, R
1, R
2Identical or be C unequally
1-C
20Alkyl; Its reaction formula is following:
Step S2: with 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (A
2) and 1,3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone (NBS; Down with) under 10 ℃～30 ℃, be added in 1: 2～1: 4 in second solvent with mol ratio, reacted 12～48 hours, obtain product, promptly 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, R
3Be C
1-C
20Alkyl; Its reaction formula is following:
Step S3: in the oxygen-free environment, with said B
1And B
2With mol ratio 1: a (wherein; 0.95≤a≤1.05), in the presence of 65 ℃～120 ℃, catalyzer and the 3rd solvent, carry out Stille reaction 24～72 hours; Obtain product, promptly contain thienothiophene and two thienothiophenes and the unitary organic semiconductor material of thiophene pyrrole diketone (I); Wherein, catalyzer is an organic palladium, as, Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2, or organic palladium and organophosphor ligand be 1: 1～10 blended mixtures in molar ratio, as, Pd
2(dba)
3/ P (o-Tol)
3Catalyst consumption is said 3; 6-dialkyl group thieno-[3,2-b] thiophene-2,5-two bases) 0.005-0.20 of two (tin trimethyl) mole dosage doubly; The 3rd solvent is at least a in THF, toluene, trichloromethane or the ETHYLE ACETATE, and the span of n is smaller or equal to 100 integer greater than 1; Its reaction formula is following:
Oxygen-free environment of the present invention, promptly the anaerobic protective atmosphere is made up of nitrogen and/or rare gas element.
In order to understand the content of patent of the present invention better, further specify technological case of the present invention through concrete instance and legend below, specifically comprise the preparation of material prepn and device, but these embodiments do not limit the present invention.In the present invention, contain the unitary organic semiconductor material of thiophene pyrrole diketone mainly as organic semiconductor material.
Embodiment 1, present embodiment disclose the following multipolymer as organic semiconductor material of a kind of structure:
In the following formula, n=20;
The preparation process of above-mentioned multipolymer is following:
One, 4,4-dimethyl--2, the preparation of two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene:
Under-100 ℃, condition of nitrogen gas; 20.00mL (2.00M) n-butyllithium solution is added to fills 2.06g 4, and 4-dimethyl--4H-ring penta [2,1-b:3; 4-b '] in the reaction flask of two thiophene and 60mL THF; Stir and slowly drip the 7.74g trimethyltin chloride after 1 hour, 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 recrystallization obtains product.
MALDI-TOF-MS(m/z)：531.9(M
+).
Two, 5-thiotolene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.97g thiophene-3, the 4-dicarboxylicacid 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, after stirring 1 hour under 10 ℃, adds 5.34g NBS 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 multipolymer:
Under nitrogen protection, toward containing 0.532g 4,4-dimethyl--2; Two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene, 0.325g 1; 3-two bromo-5-thiotolene [3,4-c]-pyrroles-4 add 0.0118g Pd in 6-diketone, the 25mL reaction of toluene bottle
2(dba)
3With 0.0094g P (o-Tol)
3Behind 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＝7430，PDI＝1.9.
Embodiment 2, present embodiment disclose the following multipolymer as organic semiconductor material of a kind of structure:
In the following formula, n=59;
The preparation process of above-mentioned multipolymer is following:
One, 4,4-dioctyl-2, the preparation of two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene:
Under-78 ℃, condition of nitrogen gas; 20.00mL (1.00M) n-butyllithium solution is added to fills 4.03g 4, and 4-dioctyl-4H-ring penta [2,1-b:3; 4-b '] in the reaction flask of two thiophene and 70mL THF; Stir and slowly drip the 3.96g trimethyltin chloride after 1 hour, return to room temperature, continue to stir 32 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and recrystallization obtains product.
MALDI-TOF-MS(m/z)：728.3(M
+).
Two, 5-octyl group thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.75g thiophene-3, the 4-dicarboxylicacid 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, after stirring 1 hour under 20 ℃, adds 5.88g NBS 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 multipolymer:
Under nitrogen protection, toward containing 0.728g 4,4-dioctyl-2; Two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene, 0.426g 1; 3-two bromo-5-octyl group thiophene [3,4-c]-pyrroles-4 add 0.0119g Pd in 6-diketone, the 30mL reaction of toluene bottle
2(dba)
3With 0.0096g P (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 100 ℃, reacted 58 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝39297，PDI＝1.8.
Embodiment 3, present embodiment disclose the following multipolymer as organic semiconductor material of a kind of structure:
In the following formula, n=80;
The preparation process of above-mentioned multipolymer is following:
One, 4,4-didecyl-2, the preparation of two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene:
Under-56 ℃, condition of nitrogen gas; 15.00mL (2.00M) n-butyllithium solution is added to fills 4.59g 4; 4-didecyl-4H-ring penta
in the reaction flask of two thiophene and 100mL THF; Stir after 1 hour slowly Dropwise 5 .39g trimethyltin chloride; Return to room temperature, continue to stir 27 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and recrystallization obtains product.
MALDI-TOF-MS(m/z)：784.4(M
+).
Two, 5-decylthiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.86g thiophene-3, the 4-dicarboxylicacid 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, after stirring 1 hour under 25 ℃, adds 5.96g NBS 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 multipolymer:
Under nitrogen protection, toward containing 0.784g 4,4-didecyl-2; Two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene, 0.451g 1; 3-two bromo-5-decylthiophene [3,4-c]-pyrroles-4 add 0.0101g Pd in 6-diketone, the 30mL reaction of toluene bottle
2(dba)
3With 0.0890g P (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 85 ℃, reacted 69 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝60017，PDI＝1.9.
Embodiment 4, present embodiment disclose the following multipolymer as organic semiconductor material of a kind of structure:
In the following formula, n=100;
The preparation process of above-mentioned multipolymer is following:
One, 4, the two eicosyls-2 of 4-, the preparation of two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene:
Under-25 ℃, argon gas condition; 10.00mL (2.00M) n-butyllithium solution is added to fills 7.39g 4, and the two eicosyls of 4--4H-ring penta [2,1-b:3; 4-b '] in the reaction flask of two thiophene and 100mL THF; Stir and slowly drip the 4.13g trimethyltin chloride after 1 hour, 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 recrystallization obtains product.
MALDI-TOF-MS(m/z)：1065.0(M
+).
Two, 5-eicosyl thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.23g thiophene-3, the 4-dicarboxylicacid 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, after stirring 1 hour under 30 ℃, adds 6.21g NBS 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 multipolymer:
Under argon shield, toward containing 1.065g 4, the two eicosyls-2 of 4-; Two (the trimethyl-tin-radical)-4H-ring of 6-penta [2,1-b:3,4-b '] two thiophene, 0.592g 1; 3-two bromo-5-eicosyl thiophene [3,4-c]-pyrroles-4 add 0.0151g Pd in 6-diketone, the 50mL reaction of toluene bottle
2(dba)
3And 0.0121gP (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 65 ℃, reacted 72 hours.Reaction finishes, methyl alcohol sedimentation three times, and suction filtration, vacuum-drying obtains solid product.
GPC：Mn＝117101，PDI＝18.
The present invention also provides a kind of structural formula to do
(wherein, R
1, R
2, R
3Be C
1-C
20Alkyl; The span of n for greater than 1 smaller or equal to 100 integer) contain the unitary organic semiconductor material of thiophene pyrrole diketone at polymer solar battery; Organic field effect tube; Organic electroluminescence device; Organic optical storage, Application for Field such as organic non-linear device and organic laser apparatus.
Following examples are to contain the unitary organic semiconductor material of thiophene pyrrole diketone at polymer solar battery, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus.
Embodiment 5
A kind of polymer solar cell device, its structure is 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 polymer solar cell 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 a mixture, comprises electron donor material, and PCBM is an electron acceptor material; Electron donor material is the unitary organic semiconductor material of thiophene pyrrole diketone that contains of the present invention, 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 for gathering (3, the 4-Ethylenedioxy Thiophene), and PSS is for gathering (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 as the anodic conductive layer, and thickness is 50-300nm;
Ito glass is through ultrasonic cleaning, and with after oxygen-Plasma processing, plays the PEDOT:PSS layer 13 of modification at ITO surfaces coated last layer, and thickness is 50-300nm;
Adopt spin coating technique to apply layer of active layer 14 at said gathering (3, the 4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, thickness is 50-300nm; The material of this active coating is for containing the unitary organic semiconductor material of thiophene pyrrole diketone and [6,6] phenyl-C
61The mixture of-methyl-butyrate (being called for short PCBM);
At the surface vacuum evaporation metal aluminium of said active coating, form metal aluminium lamination 15 as negative electrode, obtain said 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 the 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, 40nm, 110nm, 100nm.
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 impact plies 24/Al layer 25; Wherein: luminescent layer is a material with the unitary organic semiconductor material of thiophene pyrrole diketone that contains of the present invention.
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 as the anodic conductive layer, and thickness is 50-300nm;
Contain luminescent layer 23 that thiophene pyrrole diketone unitary organic semiconductor material be material at ITO surface preparation one deck with of the present invention through spin coating technique, thickness is 50-300nm;
Vacuum evaporation LiF on luminescent layer, as impact plies 24, thickness is 0.3-2nm;
Vacuum evaporation metallic aluminium on said luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains said 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 31/550nm is thick
2Insulation layer 32/ is used to modify 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 a material with the unitary organic semiconductor material of thiophene pyrrole diketone that contains of the present invention; Source electrode (S) and drain electrode (D) also can adopt copper material.
The preparation process of this organic field effect tube is:
At first, on a surface cleaning doped silicon wafer 31, apply one deck SiO later
2 Insulation layer 32; Secondly, at said 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 contains the organic semiconductor layer 34 that the unitary organic semiconductor material of thiophene pyrrole diketone is a material with of the present invention on said octadecyl trichlorosilane layer, and thickness is 50-300nm; At last, on said organic semiconductor layer, being arranged at intervals with the gold is source electrode (S) 35 and the drain electrode (D) 36 of material, obtains said organic field effect tube.
Should be understood that above-mentioned statement to 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 accompanying claims.
Claims (10)
1. one kind contains the unitary organic semiconductor material of thiophene pyrrole diketone, has formula (I):
In the formula: R
1, R
2, R
3Be respectively C identical or inequality
1-C
20Alkyl; The span of n is smaller or equal to 100 integer greater than 1.
2. organic semiconductor material according to claim 1 is characterized in that, the span of said n is smaller or equal to 80 integer more than or equal to 20.
3. a preparation method who contains the thiophene pyrrole diketone with unitary organic semiconductor material is characterized in that this preparation method comprises the steps:
S1, compd A is provided
1, A
2:
In the formula, R
1, R
2, R
3Be respectively C identical or inequality
1-C
20Alkyl;
In S2, the oxygen-free environment, with compd A
1With n-Butyl Lithium under-100 ℃～-25 ℃, be added in 1: 2～1: 4 in first solvent with mol ratio, add trimethyltin chloride then, continue reaction 24～48 hours, obtain structural formula and do
Compd B
1
S3, with compd A
2Be added in 1: 2～1: 4 in second solvent with mol ratio with the N-bromo-succinimide, reaction is 12～48 hours under 10 ℃～30 ℃, obtains structural formula and does
Compd B
2
In S4, the oxygen-free environment, with said compd B
1And B
2Be dissolved in the 3rd solvent that contains catalyzer with mol ratio 1: a and mix, under 65 ℃～120 ℃ temperature, carry out Stille reaction 24～72 hours, obtain structural formula and do
The said unitary organic semiconductor material of thiophene pyrrole diketone (I) that contains; Wherein, the span of a is more than or equal to 0.95 smaller or equal to 1.05, and the span of n is smaller or equal to 100 integer greater than 1.
4. preparation method according to claim 3 is characterized in that, among the step S2, said first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE; The mole dosage of said trimethyltin chloride is said compd A
12～4 times of molar weight.
5. according to the said preparation method of claim 3, it is characterized in that among the said step S3, said second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid.
6. the preparation method of organic semiconductor material according to claim 3 is characterized in that, among the step S3, said the 3rd solvent is at least a in THF, toluene, trichloromethane or the ETHYLE ACETATE.
7. preparation method according to claim 3 is characterized in that, among the step S3,
Said catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; Said catalyst consumption is said compd B
10.005～0.1 times of mole dosage;
Said organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2
Said organophosphor ligand is P (o-Tol)
3
8. preparation method according to claim 8 is characterized in that, in the mixture of said organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1: 1～10.
9. preparation method according to claim 3 is characterized in that, among the step S4, the span of said n is smaller or equal to 80 integer more than or equal to 20.
10. the unitary organic semiconductor material of thiophene pyrrole diketone that contains as claimed in claim 1 is at organic solar batteries; Organic field effect tube; Organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear device or organic laser apparatus.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103159917A (en) * | 2011-12-09 | 2013-06-19 | 海洋王照明科技股份有限公司 | Thiophene pyrroledione based co-polymer organic semiconductor material, and preparation method and application thereof |
| JP2014027177A (en) * | 2012-07-27 | 2014-02-06 | Mitsubishi Chemicals Corp | Photoelectric conversion element, solar cell, and solar cell module |
| WO2015092909A1 (en) * | 2013-12-19 | 2015-06-25 | リンテック株式会社 | Polymeric compound, organic photoelectric conversion element, and method for producing said element |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492529A (en) * | 2008-01-25 | 2009-07-29 | 财团法人工业技术研究院 | Soluble polythiofuran derivative and uses for photoelectric assembly |
| WO2010037069A2 (en) * | 2008-09-29 | 2010-04-01 | Mallinckrodt Inc. | Dithienopyrrole dyes for imaging and therapy |
| US20100099840A1 (en) * | 2007-04-13 | 2010-04-22 | Jae-Min Moon | Dioxypyrrolo-heteroaromatic compounds and organic electronic devices using the same |
-
2010
- 2010-10-15 CN CN 201010509522 patent/CN102443143B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100099840A1 (en) * | 2007-04-13 | 2010-04-22 | Jae-Min Moon | Dioxypyrrolo-heteroaromatic compounds and organic electronic devices using the same |
| CN101492529A (en) * | 2008-01-25 | 2009-07-29 | 财团法人工业技术研究院 | Soluble polythiofuran derivative and uses for photoelectric assembly |
| WO2010037069A2 (en) * | 2008-09-29 | 2010-04-01 | Mallinckrodt Inc. | Dithienopyrrole dyes for imaging and therapy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159917A (en) * | 2011-12-09 | 2013-06-19 | 海洋王照明科技股份有限公司 | Thiophene pyrroledione based co-polymer organic semiconductor material, and preparation method and application thereof |
| JP2014027177A (en) * | 2012-07-27 | 2014-02-06 | Mitsubishi Chemicals Corp | Photoelectric conversion element, solar cell, and solar cell module |
| WO2015092909A1 (en) * | 2013-12-19 | 2015-06-25 | リンテック株式会社 | Polymeric compound, organic photoelectric conversion element, and method for producing said element |
| JPWO2015092909A1 (en) * | 2013-12-19 | 2017-03-16 | リンテック株式会社 | Polymer compound, organic photoelectric conversion element, and method for producing the element |
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