CN103159924A - Benzotriazole based co-polymer solar cell material, and preparation method and application thereof - Google Patents
Benzotriazole based co-polymer solar cell 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 benzotriazole based co-polymer solar cell 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 benzotriazole based co-polymer solar cell material provided by the invention, cyclopentadithiophene has a completely planar crystal structure, two thiophene rings in the structural unit of the cyclopentadithiophene are in the same plane, and the structure can effectively extend conjugated performance of a polymer and reduce a band gap of the polymer, so that energy conversion efficiency of the solar cell is increased, thereby solving the problem of low efficiency of polymer solar cells.
Description
Technical field
The present invention relates to the solar cell material field, relate in particular to a kind of benzotriazole base co-polymer solar cell 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 al.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.
Over the past two years, pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene base conjugated polymers had demonstrated good photovoltaic performance.Simultaneously, 1,2, the 3-benzotriazole is an important electron acceptor(EA) unit, and it has two strong electrophilic imido grpups, is the heterogeneous ring compound that strong electrophilic performance is arranged, simultaneously, N-H bond energy on 1,2,3-benzotriazole enough easily modifies to regulate solvability and photoelectric properties with functional groups such as other alkyl flexible chains.Relevant pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene and benzotriazole base co-polymer solar cell material do not have document and patent report so far.
Summary of the invention
The benzotriazole base co-polymer solar cell material that provides a kind of effciency of energy transfer high is provided purpose one of the present invention.
A kind of benzotriazole base co-polymer solar cell material with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
Another object of the present invention is to provide the preparation method of above-mentioned benzotriazole base co-polymer solar cell material, comprise the steps:
Under oxygen-free environment, with structural formula be
Compd A and structural formula be
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 benzotriazole base co-polymer solar cell material of (I):
Above-mentioned various in, R
1Be C
1～C
20Alkyl, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
In the preparation method of above-mentioned benzotriazole base co-polymer solar cell material:
Described catalyzer is organic palladium, and described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer also can for organic palladium (as, three dibenzalacetone two palladiums) with organophosphor ligand (as, tri-butyl phosphine) mixture, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8;
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
In the preparation method of above-mentioned benzotriazole base co-polymer solar cell material, preferably, 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 benzotriazole base co-polymer solar cell material in organic solar batteries.
Benzotriazole base co-polymer solar cell material provided by the invention, two thiphene ring pentanes have the crystalline structure on complete plane, and two thiphene ring in its structural unit are on same plane.This structure can effectively extend the conjugation performance of polymkeric substance, reduces the bandwidth of polymkeric substance.And this coplanar structure makes current carrier shift to become between two main chains and is more prone to, thereby has increased carrier mobility; 1,2,3-benzotriazole has two strong electrophilic imido grpups, is a heterogeneous ring compound that strong electrophilic performance is arranged, and the N-H bond energy on benzotriazole enough easily modifies to regulate solvability and photoelectric properties with functional groups such as other alkyl simultaneously.Above-mentioned many performances all can improve the effciency of energy transfer of sun power, thereby solve 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 benzotriazole base co-polymer solar cell material of the present invention;
Fig. 2 is the effciency of energy transfer graphic representation of the multipolymer solar cell material of embodiment 1;
Fig. 3 is the structural representation of the solar cell of embodiment 7.
Embodiment
Benzotriazole base co-polymer solar cell material with following structural formula (I) provided by the invention:
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer; Preferred n is the preparation method of 40～70 above-mentioned benzotriazole base co-polymer solar cell materials, as shown in Figure 1, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
A：
2,6-, two tin trimethyls-4,4-dialkyl cyclic pentane [2,1-b:3,4-b '] 1,4-Dithiapentalene
B：
2-alkyl-4,7-two (5-bromothiophene base)-1,2,3-benzotriazole
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 ℃, the cooling stopped reaction obtains mixed solution, comprises product in this mixed solution, namely has the described benzotriazole base co-polymer solar cell 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 benzotriazole base co-polymer solar cell material of tool purifying:
In the preparation method of above-mentioned benzotriazole base co-polymer solar cell material, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Perhaps
Described catalyzer also can for organic palladium (as, three dibenzalacetone two palladiums) with organophosphor ligand (as, tri-butyl phosphine) mixture, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8;
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
The preparation method of above-mentioned benzotriazole base co-polymer solar cell material, in described step S2, preferably:
Described Stille coupling reaction temperature is 80～110 ℃; The described Stille coupling reaction time is 12～48h.
Above-mentioned benzotriazole base co-polymer solar cell 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, wherein, but the monomer reference literature (Macromolecules of compd A, 2007,40,1981)) open method preparation or buy from the market obtains, but monomer reference literature (Polymer chemistry, 2010 of compd B, 1,1441) open method preparation or buy from the market obtains.
Embodiment 1
The benzotriazole base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,4-di-n-octyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-n-octyl-4,7-dithienyl-1,2,3-benzotriazole }, wherein, R
1Be octane base, R
2Be the octane base, n is 60, 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, 4-di-n-octyl pentamethylene [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (218mg, 0.3mmol), 2-n-octyl-4, 7-two (5-bromothiophene base)-1, 2, 3-benzotriazole (166mg, 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, 4-di-n-octyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-n-octyl-4,7-dithienyl-1,2,3-benzotriazole } product, productive rate is 78%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=47.8kDa, M
w/ M
n=2.1.
Fig. 2 is the effciency of energy transfer graphic representation of the multipolymer solar cell 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 3.7%; Zou etc. have reported that with 2,7-carbazyl multipolymer be donor material, and PCBM is that acceptor material has prepared solar cell, and effciency of energy transfer is 1.6%.(Macromolecules?2009，42，2891-2894)。
The benzotriazole base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,4-dimethylcyclopentane [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-NSC 62789 base-4,7-dithienyl-1,2,3-benzotriazole }, wherein, R
1Be methyl, R
2Be the NSC 62789 base, n is 40, 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-4,4-dimethylcyclopentane [2,1-b:3,4-b '] 1,4-Dithiapentalene (106mg, 0.2mmol) and 2-NSC 62789 base-4,7-two (5-bromothiophene base)-1,2,3-benzotriazole (144mg, 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 110 ℃, 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, 4-dimethylcyclopentane [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-NSC 62789 base-4,7-dithienyl-1,2,3-benzotriazole } product, productive rate 72%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=31.6kDa, M
w/ M
n=2.2.
Embodiment 3
The benzotriazole base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,4-two (NSC 62789 base) pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-methyl-4,7-dithienyl-1,2,3-benzotriazole }, wherein, R
1Be NSC 62789 base, R
2Be methyl, n is 80, 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, 4-two (NSC 62789 base) pentamethylene [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (320mg, 0.3mmol) and 2-methyl-4, 7-two (5-bromothiophene base)-1, 2, 3-benzotriazole (137mg, 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, 4-two (NSC 62789 base) pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-dimethyl-4,7-dithienyl-1,2,3-benzotriazole } product, productive rate is 85%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=84.2kDa, M
w/ M
n=2.1.
The benzotriazole base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,4-di-n-butyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-n-hexadecyl-4,7-dithienyl-1,2,3-benzotriazole }, wherein, R
1Be normal-butyl, R
2Be n-hexadecyl, 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-4,4-di-n-butyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene (123mg, 0.2mmol) and 2-n-hexadecyl-4,7-two (5-bromothiophene base)-1,2,3-benzotriazole (133mg, 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, 0.001mmol), 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, 4-di-n-butyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-n-hexadecyl-4,7-dithienyl-1,2,3-benzotriazole } product, productive rate 85%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=80.4kDa, M
w/ M
n=2.0.
Embodiment 5
The benzotriazole base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,4-two (dodecyl) pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-normal hexane base-4,7-dithienyl-1,2,3-benzotriazole }, wherein, R
1Be dodecyl, R
2Be the normal hexane base, n is 10, 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, 4-two (dodecyl) pentamethylene [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (252mg, 0.3mmol) and 2-normal hexane base-4, 7-two (5-bromothiophene base)-1, 2, 3-benzotriazole (158mg, 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 (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, 4-two (dodecyl) pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-normal hexane base-4,7-dithienyl-1,2,3-benzotriazole } product, productive rate is 60%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=11.2kDa, M
w/ M
n=2.3.
Embodiment 6
The benzotriazole base co-polymer solar cell material of the present embodiment, i.e. poly-{ 4,4-di-n-octyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-positive tetradecyl-4,7-dithienyl-1,2,3-benzotriazole }, wherein, R
1Be octane base, R
2Be the n-tetradecane base, n is 30, 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, 4-di-n-octyl pentamethylene [2, 1-b:3, 4-b '] 1,4-Dithiapentalene (218mg, 0.3mmol), 2-positive tetradecyl-4, 7-two (5-bromothiophene base)-1, 2, 3-benzotriazole (191mg, 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 100 ℃, Stille coupling reaction 36h, 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, 4-di-n-octyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-positive tetradecyl-4,7-dithienyl-1,2,3-benzotriazole } product, productive rate is 74%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=27.1kDa, M
w/ M
n=2.2.
Embodiment 7
The organic solar batteries of the present embodiment 7, its poly-{ 4,4 dioctyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-octyl group-4,7-dithienyl-1,2,3-benzotriazole } 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, electron donor material adopts poly-{ 4 of embodiment 1 preparation, 4-dioctyl pentamethylene [2,1-b:3,4-b '] 1,4-Dithiapentalene-co-2-octyl group-4,7-dithienyl-1,2, the 3-benzotriazole }, 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, 40nm, 130nm or 60nm.
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. benzotriazole base co-polymer solar cell material with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
2. the preparation method of a benzotriazole base co-polymer solar cell material, is characterized in that, comprises the steps:
Under oxygen-free environment, with structural formula be
Compd A and structural formula be
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 ℃, the cooling stopped reaction, obtain the having following structural formula described benzotriazole base co-polymer solar cell material of (I):
Above-mentioned various in, R
1Be C
1～C
20Alkyl, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
3. the preparation method of benzotriazole base co-polymer solar cell material according to claim 2, is characterized in that, described catalyzer is organic palladium; Described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium.
4. the preparation method of benzotriazole base co-polymer solar cell material according to claim 3, is characterized in that, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100.
5. the preparation method of benzotriazole base co-polymer solar cell material according to claim 2, is characterized in that, described catalyzer is the mixture of organic palladium and organophosphor ligand.
6. the preparation method of benzotriazole base co-polymer solar cell material according to claim 5, is characterized in that, described organic palladium is three dibenzalacetone two palladiums, and described organophosphor ligand is tri-butyl phosphine.
7. the preparation method of benzotriazole base co-polymer solar cell material according to claim 5, is characterized in that, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; The mol ratio of described organic palladium and organophosphor ligand is 1: 4～8.
According to claim 3 to 7 arbitrary described benzotriazole base co-polymer solar cell material the preparation method, it is characterized in that, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
According to claim 3 to 7 arbitrary described benzotriazole base co-polymer solar cell material the preparation method, it is characterized in that, described Stille coupling reaction temperature is 80～110 ℃, the described Stille coupling reaction time is 12～48h.
10. the application of benzotriazole base co-polymer solar cell material claimed in claim 1 in organic solar batteries.
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| CN101935389A (en) * | 2010-07-20 | 2011-01-05 | 中南大学 | 2-thiophene-benzotriazole-based polymer materials and photovoltaic application thereof |
| WO2011050048A2 (en) * | 2009-10-20 | 2011-04-28 | Cornell Research Foundation, Inc. | Methods of making patterned structures of fluorine-containing polymeric materials and fluorine-containing polymers |
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| WO2010046114A2 (en) * | 2008-10-22 | 2010-04-29 | Eni S.P.A. | π-CONJUGATED LOW-BAND-GAP COPOLYMERS CONTAINING BENZOTRIAZOLE UNITS |
| WO2011050048A2 (en) * | 2009-10-20 | 2011-04-28 | Cornell Research Foundation, Inc. | Methods of making patterned structures of fluorine-containing polymeric materials and fluorine-containing polymers |
| CN101935389A (en) * | 2010-07-20 | 2011-01-05 | 中南大学 | 2-thiophene-benzotriazole-based polymer materials and photovoltaic application thereof |
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