CN103159927A - Thiophene pyrroledione based co-polymer material, and preparation method and application thereof - Google Patents
Thiophene pyrroledione based co-polymer material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of solar cells, and discloses a thiophene pyrroledione based co-polymer material, and a preparation method and an application thereof. The co-polymer has the following structural formula (I). In the formula, both R1 and R2 represent a C1-C20 alkyl group and n is an integer ranging from 10 to 100. In the thiophene pyrroledione based co-polymer material provided by the invention, benzo-dithiophene has easily modified photophysical properties, the co-polymer of the benzo-dithiophene present excellent photovoltaic performance; thiophene pyrroledione has a simple, symmetrical and polar structure and is beneficial to electron delocalization when the thiophene pyrroledione is polymerized with other monomers; and the thiophene pyrroledione has relatively strong electron-withdrawing effect that results in reduction of an HOMO energy level and a LUMO energy level, thereby facilitating the increase of an open-circuit voltage. The performance can improve energy conversion efficiency of solar energy, so that the problem of low efficiency of polymer solar cells is solved.
Description
Technical field
The present invention relates to the solar cell material field, relate in particular to a kind of Thienopyrroles diketo copolymer material and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.The silicon wafer battery that is used for ground at present is restricted its application because complex manufacturing, cost are high.In order to reduce the battery cost, expand range of application, people are seeking novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have the good advantages such as photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, et a1.Science, 1992,258,1474) upper report conjugated polymers and C
60Between the Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.
Summary of the invention
The Thienopyrroles diketo copolymer material that provides a kind of effciency of energy transfer high is provided purpose one of the present invention.
A kind of Thienopyrroles diketo copolymer material with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer; Preferred n is 40～70.
Another object of the present invention is to provide the preparation method of above-mentioned Thienopyrroles diketo copolymer material, comprise the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
S2, under oxygen-free environment, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer, fully after the dissolving after carrying out Stille coupling reaction 6～60h under 70～130 ℃, obtain having following structural formula after the cooling stopped reaction described Thienopyrroles diketo copolymer material of (I):
In formula, n is 10～100 integer.
The preparation method of above-mentioned Thienopyrroles diketo copolymer material also comprises the steps:
S3, the Thienopyrroles diketo copolymer material that makes in step S2 is carried out purification process,
In the preparation method of above-mentioned Thienopyrroles diketo copolymer material, in described step S2:
Described catalyzer is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, and the mol ratio of described catalyzer and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer is the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine; The mol ratio of described three dibenzalacetone two palladiums and described compd A is 1: 20～1: 100, and the mol ratio of described three dibenzalacetone two palladiums and tri-butyl phosphine is 1: 4～8.
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
Preferably, in described step S2:
The preparation method of Thienopyrroles diketo copolymer material, described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 12～48h.
Another purpose of the present invention is to provide the application of above-mentioned Thienopyrroles diketo copolymer material in organic solar batteries.
Thienopyrroles diketo copolymer material provided by the invention, benzo two thiophene have the photophysical property of easy modification, and its co-polymer has demonstrated good photovoltaic performance.The Thienopyrroles diketone has simply, symmetrical, polar structure, is conducive to electron delocalization after its and other monomer polymerization, and it also has stronger sucting electronic effect and causes HOMO and lumo energy reduction, is conducive to like this raising of open circuit voltage.This performance can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem.。
Separately, in the preparation method of above-mentioned Thienopyrroles diketo multipolymer, it has adopted better simply synthetic route, thereby the minimizing technical process, starting material are cheap and easy to get, reduce manufacturing cost, the polymeric material novel structure that makes, solubility property is good, and film forming properties is good, and this copolymer material is applicable to solar cell device.
Description of drawings
Fig. 1 is preparation technology's schema of Thienopyrroles diketo copolymer material of the present invention;
Fig. 2 is the effciency of energy transfer graphic representation of the copolymer material of embodiment 1.
Fig. 3 is the structural representation of the solar cell of embodiment 7.
Embodiment
Principle of design of the present invention: thiophene [3,4-c] and pyrroles-4, the 6-diketone causes vast organic solar batteries investigators' concern in recent years because of its higher effciency of energy transfer: the advantages such as simple, compact, symmetry and plane configuration, after it and other monomer copolymerization, this advantage will be conducive to electron delocalization; In addition, it also has stronger sucting electronic effect, is conducive to reduce HOMO and lumo energy; Simultaneously, the N-H bond energy enough easily modifies to improve solvability and photoelectric properties with functional groups such as other alkyl.
The Thienopyrroles diketo copolymer material with following structural formula (I) that present embodiment provides:
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.Preferred n is 40～70.
The preparation method of above-mentioned Thienopyrroles diketo copolymer material as shown in Figure 1, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
Wherein, in compd A, R
1Be C
1～C
20Alkyl; In compd B, R
2Be C
1～C
20Alkyl;
S2, oxygen-free environment (as, the oxygen-free environment that nitrogen, argon gas or nitrogen and argon gas gas mixture etc. consist of) under, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer, fully dissolving is rear after carrying out Stille coupling reaction 6～60h under 70～130 ℃, obtain mixed solution after the cooling stopped reaction, comprise product in this mixed solution, namely have the described Thienopyrroles diketo copolymer material of following structural formula (I):
In formula, n is 10～100 integer;
S3, the product in step S2 is carried out purification process:
Add methyl alcohol in the mixed solution of step S2, carry out precipitating and process, filter with apparatus,Soxhlet's subsequently, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after 50 ℃ of dry 24h under vacuum, is obtained the Thienopyrroles diketo copolymer material of tool purifying:
In the preparation method of above-mentioned Thienopyrroles diketo copolymer material, in described step S2:
Described catalyzer is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, and the mol ratio of described catalyzer and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer is the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine; The mol ratio of described three dibenzalacetone two palladiums and described compd A is 1: 20～1: 100, and the mol ratio of described three dibenzalacetone two palladiums and tri-butyl phosphine is 1: 4～8.
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
Preferably, in described step S2:
The preparation method of Thienopyrroles diketo copolymer material, described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 12～48h.
Above-mentioned Thienopyrroles diketo copolymer material can be applied in the active coating of organic solar batteries.
In order to understand better the content of patent of the present invention, further illustrate technology case of the present invention below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, and wherein, the monomer of compd A can be bought from the market and obtain, but the monomer reference literature (J.Am.Chem.Soc. of compd B, 1997,119,5065) preparation or buy from the market obtains.
Embodiment 1
The Thienopyrroles diketo copolymer material of the present embodiment, i.e. poly-{ 4,8-two (octyloxy) benzo, two thiophene-co-N-octyl group-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be octane base, R
2Be the octane base, n is 60), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2,6-two tin trimethyls-4,8-two (n-octyloxy) benzo two thiophene (232mg, 0.3mmol), N-n-octyl-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (126mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol) and tri-butyl phosphine (24.2mg, 0.12mmol) add in the flask that fills 12mL toluene, be dissolved into solution, fully logical nitrogen purge gas is approximately after 30min in the flask, stir under 95 ℃, Stille coupling reaction 40h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (n-octyloxy) benzo two thiophene-co-N-n-octyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 78%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=43.8kDa, M
w/ M
n=2.1.
Fig. 2 is the effciency of energy transfer graphic representation of the copolymer material of embodiment 1; Result shows, at AM1.5; 100mW/cm
2Under illumination, the effciency of energy transfer that is the body heterojunction solar cell of donor material based on the polymkeric substance of embodiment 1 is 4.4%; Yang etc. have reported take benzo dithienyl multipolymer as donor material, and PCBM is that acceptor material has prepared solar cell, and effciency of energy transfer is 2.7%.(J.Phys.Chem.C.，2008，133，6461)。
Embodiment 2
The Thienopyrroles diketo copolymer material of the present embodiment, i.e. poly-{ 4,8-two (methoxyl group) benzo, two thiophene-co-N-NSC 62789 base-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be methyl, R
2Be the NSC 62789 base, n is 40), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,6-two tin trimethyls-4,8-two (methoxyl group) benzo two thiophene (115mg, 0.2mmol) and N-NSC 62789 base-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (118mg, 0.2mmol) adds the N that fills 15ml, in the dinethylformamide flask, be dissolved into solution, the evacuated flask deoxygenation also is filled with argon gas, then adds bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol), stirring, Stille coupling reaction 12h, stop polyreaction after cooling under 120 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (methoxyl group) benzo two thiophene-co-N-NSC 62789 base-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate 73%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=27.4kDa, M
w/ M
n=2.3.
Embodiment 3
The Thienopyrroles diketo copolymer material of the present embodiment, i.e. poly-{ 4,8-two (NSC 62789 oxygen base) benzo two thiophene-co-N-methyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (R
1Be positive 20 straight chained alkyls, R
2Be methyl, n is 80), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 6-two tin trimethyls-4, 8-two (eicosane oxygen base) benzo two thiophene (333mg, 0.3mmol) and N-methyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (98mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, fully lead to nitrogen and argon gas gas mixture in two-mouth bottle, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, fully logical nitrogen and argon gas gas mixture air-discharging are approximately after 10min again, stir under 80 ℃, Stille coupling reaction 48h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (NSC 62789 oxygen base) benzo two thiophene-co-N-methyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 82%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=75.7kDa, M
w/ M
n=2.1.
Embodiment 4
The Thienopyrroles diketo copolymer material of the present embodiment, i.e. poly-{ 4,8-two (n-butoxy) benzo, two thiophene-co-N-n-decane base-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be n-butoxy, R
2Be the n-decane base, n is 100, and its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,6-two tin trimethyls-4,8-two (n-butoxy) benzo two thiophene (132mg, 0.2mmol) and N-n-decane base-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (90.2mg, 0.2mmol) adds in the tetrahydrofuran (THF) flask that fills 15ml, is dissolved into solution, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (7.2mg, 0.01mmol), stirring, Stille coupling reaction 60h under 70 ℃, stop polyreaction after cooling, obtain mixed solution.
Add 50mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (n-butoxy) benzo two thiophene-co-N-n-decane base-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate 90%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=63.2kDa, M
w/ M
n=2.0.
Embodiment 5
The Thienopyrroles diketo copolymer material of the present embodiment, i.e. poly-{ 4,8-two (n-tetradecane oxygen base) benzo two thiophene-co-N-n-hexyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (R
1Be n-tetradecane oxygen base, R
2Be the normal hexane base, n is 10), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 6-two tin trimethyls-4, 8-two (n-tetradecane oxygen base) benzo two thiophene (282mg, 0.3mmol) and N-n-hexyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (118mg, 0.3mmol) add and fill 15mLN, in the two-mouth bottle of the 50mL specification of dinethylformamide, be dissolved into solution, fully lead to nitrogen and argon gas gas mixture in two-mouth bottle, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, fully logical nitrogen and argon gas gas mixture air-discharging are approximately after 10min again, stir under 130 ℃, Stille coupling reaction 6h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (n-tetradecane oxygen base) benzo two thiophene-co-N-n-hexyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 62%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=10.8kDa, M
w/ M
n=2.3.
Embodiment 6
The Thienopyrroles diketo copolymer material of the present embodiment, i.e. poly-{ 4,8-two (n-octyloxy) benzo, two thiophene-co-N-dodecyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be positive hot oxyalkyl, R
2Be positive 12 straight chained alkyls, n is 30), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2,6-two tin trimethyls-4,8-two (n-octyloxy) benzo two thiophene (232mg, 0.3mmol), N-dodecyl-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (144mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol) and tri-butyl phosphine (12.1mg, 0.06mmol) add in the flask that fills 12mL toluene, be dissolved into solution, fully logical nitrogen purge gas is approximately after 30min in the flask, stir under 110 ℃, Stille coupling reaction 72h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed solution is carried out precipitating process, then filter by apparatus,Soxhlet's, use successively afterwards methyl alcohol and normal hexane extracting filtrate 24h; Then continue take chloroform as solvent extraction filtrate to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after collecting at last is poly-{ 4 after 50 ℃ of dry 24h under vacuum, 8-two (n-octyloxy) benzo two thiophene-co-N-dodecyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 67%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=24.1kDa, M
w/ M
n=2.3.
Embodiment 7
The organic solar batteries of the present embodiment 7, its poly-{ 4,8-(octyloxy) benzo, two thiophene-co-N-octyl group-thiophene [3,4-c] and pyrroles-4,6-diketone } that adopts that embodiment 1 makes is the electron donor material of active coating.
See also Fig. 3, this organic solar batteries comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14 and the negative electrode 15 that stacks gradually.Transparent anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Middle supplementary layer 13 adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS); Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material adopts poly-{ 4,8-two (octyloxy) benzo, the two thiophene-co-N-octyl group-thiophene [3 of embodiment 1 preparation, 4-c] and pyrroles-4, the 6-diketone }, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (referred to as PCBM); Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 180nm, 30nm, 120nm or 500nm.
Glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, process supplementary layer 13 in the middle of applying with oxygen-Plasma on ito glass, in the middle of again the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend on supplementary layer 13, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.This solar cell device also needs through heating 4h under 110 degrees centigrade of air tight conditions, drop to again room temperature, can effectively increase order and the regularity arranged between interior each group of molecule and molecule segment after device is annealed, improve transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 15Al layer is respectively 180nm.
As shown in Figure 3, under illumination, light transmission glass-base 11 and ITO electrode 12, the conduction hole type electroluminescent material in active coating 14 absorbs luminous energy, and produces exciton, these excitons move to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, the hole is along electron donor material to ito anode transmission and collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load 16, can power to it.In this process, conduction hole type electroluminescent material can utilize luminous energy more fully because it has very wide spectral response range, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. Thienopyrroles diketo copolymer material with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
2. Thienopyrroles diketo copolymer material according to claim 1, is characterized in that, n is 40～70.
3. the preparation method of a Thienopyrroles diketo copolymer material, is characterized in that, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
Wherein, in described compd A, R
1Be C
1～C
20Alkyl; In described compd B, R
2Be C
1～C
20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer, fully after the dissolving after carrying out Stille coupling reaction 6～60h under 70～130 ℃, obtain having following structural formula after the cooling stopped reaction described Thienopyrroles diketo copolymer material of (I):
In formula, n is 10～100 integer.
4. the preparation method of Thienopyrroles diketo copolymer material according to claim 3, is characterized in that, in described step S2, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium.
5. the preparation method of Thienopyrroles diketo copolymer material according to claim 4, is characterized in that, in described step S2, the mol ratio of described catalyzer and described compd A is 1: 20～1: 10.
6. the preparation method of Thienopyrroles diketo copolymer material according to claim 3, is characterized in that, in described step S2, described catalyzer is the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine.
7. the preparation method of Thienopyrroles diketo copolymer material according to claim 4, is characterized in that, in described step S2, the mol ratio of described three dibenzalacetone two palladiums and described compd A is 1: 20～1: 100; The mol ratio of described three dibenzalacetone two palladiums and tri-butyl phosphine is 1: 4～8.
According to claim 3 to 7 arbitrary described Thienopyrroles diketo copolymer material the preparation method, it is characterized in that, in described step S2, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
According to claim 3 to 7 arbitrary described Thienopyrroles diketo copolymer material the preparation method, it is characterized in that, in described step S2, described Stille coupling reaction temperature is 80～110 ℃, the described Stille coupling reaction time is 12～48h.
10. the application of Thienopyrroles diketo copolymer material claimed in claim 1 in organic solar batteries.
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| CN (1) | CN103159927A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031245A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Polymer photovoltaic material, preparation method and use thereof |
| CN104448253A (en) * | 2014-03-04 | 2015-03-25 | 上海大学 | Aromatic alkyne copolymer based on benzo[1,2-b:4,5-b']dithiophene and preparation method thereof |
| CN109705314A (en) * | 2018-12-20 | 2019-05-03 | 福建师范大学 | Full polymers solar battery active layer material, the preparation method and applications of high efficiency thick film |
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2011
- 2011-12-09 CN CN2011104098109A patent/CN103159927A/en active Pending
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| DAVID GENDRON AND MARIO LECLERC: "New conjugated polymers for plastic solar cells", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
| YONG ZHANG ET AL: "Efficient Polymer Solar Cells Based on the Copolymers of Benzodithiophene and Thienopyrroledione", 《CHEMISTRY OF MATERIALS COMMUNICATION》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448253A (en) * | 2014-03-04 | 2015-03-25 | 上海大学 | Aromatic alkyne copolymer based on benzo[1,2-b:4,5-b']dithiophene and preparation method thereof |
| CN104031245A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Polymer photovoltaic material, preparation method and use thereof |
| CN104031245B (en) * | 2014-06-24 | 2016-05-18 | 国家纳米科学中心 | A kind of Polymer photovoltaic materials, preparation method and its usage |
| CN109705314A (en) * | 2018-12-20 | 2019-05-03 | 福建师范大学 | Full polymers solar battery active layer material, the preparation method and applications of high efficiency thick film |
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Application publication date: 20130619 |