CN104177592A - Dithiazole benzo triazolyl-containing polymer and preparation method thereof and organic solar energy cell device - Google Patents
Dithiazole benzo triazolyl-containing polymer and preparation method thereof and organic solar energy cell device Download PDFInfo
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- CN104177592A CN104177592A CN201310204044.1A CN201310204044A CN104177592A CN 104177592 A CN104177592 A CN 104177592A CN 201310204044 A CN201310204044 A CN 201310204044A CN 104177592 A CN104177592 A CN 104177592A
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- 0 **[n](nc12)nc1c(-c([s]1)ncc1Br)ccc2-c1ncc(*)[s]1 Chemical compound **[n](nc12)nc1c(-c([s]1)ncc1Br)ccc2-c1ncc(*)[s]1 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the field of organic semiconductor materials, discloses a dithiazole benzo triazolyl-containing polymer and a preparation method thereof and an organic solar energy cell device; the polymer has the following structural formula shown in the specification, R1 and R2 are C1-C20 alkyl, and n is an integer between 10 and 100. The dithiazole benzo triazolyl(DTBTz)-containing polymer belongs to a donor-receptor conjugated polymer, contains a dithiazole benzotriazole unit and a dithiophene silicon-miscellaneous cyclopentadiene unit, has high hole mobility, high open circuit voltage, excellent solubility and film-forming performance, has a wide absorption range in the 300nm-700nm range, and further solves the problem of low efficiency of solar cell devices.
Description
Technical field
The present invention relates to organic semiconductor material field, relate in particular to a kind of polymkeric substance containing dithiazole benzotriazole base and preparation method thereof.The invention still further relates to use and contain the polymkeric substance of dithiazole benzotriazole base as the organic solar batteries device of active coating electron donor material.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Organic semiconductor material with its raw material be easy to get, cheap, technique is simple, stability is strong, photovoltaic effect is good etc., and advantage receives 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 Photoinduced Electron transfer phenomena after, organic polymer solar cell becomes the focus of research gradually.The research of this respect has in recent years obtained development at full speed, but organic polymer solar cell is still much lower than the efficiency of conversion of inorganic solar cell.For organic polymer solar cell is on the actual application, the type material that exploitation has a higher-energy efficiency of conversion is still the top priority in this field.
Summary of the invention
The polymkeric substance containing dithiazole benzotriazole base that provides a kind of effciency of energy transfer higher is provided problem to be solved by this invention.
Technical scheme of the present invention is as follows:
Containing a polymkeric substance for dithiazole benzotriazole base, its structural formula is as follows:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-100.
The present invention also provides the preparation method of the above-mentioned polymkeric substance containing dithiazole benzotriazole base, comprises the steps:
The compd A and the B that provide respectively following structural formula to represent,
A:
b:
wherein, R
1, R
2be C
1～C
20alkyl;
Under oxygen-free environment, the compd A that is 1:1～1.2 by mol ratio and B are added in the organic solvent that contains catalyzer and dissolve, under 70～130 ° of C, carry out Stille coupling reaction 6～60 hours subsequently, stop after coupling reaction, separating-purifying reaction solution, obtain following structural formula containing the polymkeric substance of dithiazole benzotriazole base:
in formula, the integer that n is 10-100.
The preparation method of the described polymkeric substance containing dithiazole benzotriazole base, wherein, one or both in argon gas, nitrogen of oxygen-free environment form.
The preparation method of the described polymkeric substance containing dithiazole benzotriazole base, wherein, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; Or
Described catalyzer is the mixture of organic palladium and organophosphorus ligand, and in mixture, the molar weight of organophosphorus ligand is 4～8 times of organic palladium molar weight; Described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl;
The mol ratio of described catalyzer and described compd A is 1:20～1:100.
The preparation method of the described polymkeric substance containing dithiazole benzotriazole base, wherein, described organic solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
The preparation method of the described polymkeric substance containing dithiazole benzotriazole base, wherein, Stille coupling reaction temperature is 90～120 ° of C, the reaction times is 12～48 hours.
The preparation method of the described polymkeric substance containing dithiazole benzotriazole base, wherein, separating-purifying reaction solution comprises:
After coupling reaction stops, in reaction solution, add methyl alcohol precipitating, by apparatus,Soxhlet's, filter subsequently, using successively again methyl alcohol and normal hexane extracting, obtain organic phase, then take chloroform as solvent extraction organic phase is to colourless, collect chloroformic solution and be spin-dried for, after the dry 24h of the lower 50 ° of C of vacuum, obtain described containing dithiazole benzotriazole based polyalcohol.
The invention still further relates to a kind of organic solar batteries device, the electron donor material of its active coating adopts the polymkeric substance containing dithiazole benzotriazole base of following structural formula:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-100.
Of the present invention containing in dithiazole benzotriazole base (DTBTz) polymkeric substance, contain dithiazole benzotriazole unit and two thiophene Silole unit, this polymkeric substance is donor-receiver type conjugated polymers, it has higher hole mobility, high open circuit voltage, solubility property and film forming properties have wider absorption region within the scope of 300nm～700nm preferably, and then solve solar cell device low efficiency problem.
The preparation method of above-mentioned dithiazole benzotriazole based polyalcohol, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, and absorption region is wide, and effciency of energy transfer is improved.
Accompanying drawing explanation
Fig. 1 is the polymkeric substance ultraviolet-visible absorption spectroscopy figure containing dithiazole benzotriazole base of embodiment 1;
Fig. 2 is the structural representation of the organic solar batteries device of embodiment 6.
Embodiment
In order to understand better the content of patent of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein the monomer of compd A, compd B is all bought and is obtained from the market.
Embodiment 1:
The polymkeric substance containing dithiazole benzotriazole base of the present embodiment, gather { 4,4-, bis-octane base-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-octane base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, (wherein, R
1for octane base, R
2for octane base, n=58), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under argon shield, by 4,4-, bis-octane base-2,6-bis-(tin trimethyl)-bis-thieno-[3,2-b:2', 3'-d] Silole (149mg, 0.2mmol), 2,2'-(2-octane base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-bromine thiadiazoles) (111mg, 0.2mmol) add in the flask that fills 10ml toluene solvant, vacuumize deoxygenation and are filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Stille coupling reaction 36h.Subsequently, after cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after the dry 24h of the lower 50 ° of C of vacuum, obtain product, i.e. poly-{ 4,4-, bis-octane base-bis-thieno-s [3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-octane base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, productive rate 84%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=41.3kDa, M
w/ M
n=2.2.
Fig. 1 is the polymkeric substance ultraviolet-visible absorption spectroscopy figure containing dithiazole benzotriazole unit of embodiment 1.As shown in Figure 1, this polymkeric substance has large wider absorption between 300nm～700nm, and wherein maximum absorption band is positioned at 595nm left and right.
Embodiment 2:
The polymkeric substance containing dithiazole benzotriazole base of the present embodiment, gather { 4,4-dimethyl-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-NSC 62789 base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, (wherein, R
1for methyl, R
2for NSC 62789 base, n=100), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4, 4-dimethyl-2, 6-bis-(tin trimethyl)-bis-thieno-[3, 2-b:2', 3'-d] Silole (164mg, 0.3mmol), 2, 2'-(2-NSC 62789 base-2H-benzo [d] [1, 2, 3] triazole-4, 7-bis-bases) two (5-bromine thiadiazoles) (217mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Stille coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtains product., poly-{ 4,4-dimethyl-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-NSC 62789 base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) } productive rate is 81%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=76.4kDa, M
w/ M
n=2.0.
Embodiment 3:
The polymkeric substance containing dithiazole benzotriazole base of the present embodiment, gather { 4,4-, bis-NSC 62789 base-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-methyl-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, (wherein, R
1for NSC 62789 base, R
2for methyl, n=10), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 4,4-bis-NSC 62789 base-2,6-bis-(tin trimethyl)-bis-thieno-[3,2-b:2', 3'-d] Silole (324mg, 0.3mmol), 2,2'-(2-NSC 62789 base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-bromine thiadiazoles) (151mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 130 ℃ and carries out Stille coupling reaction 6h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, obtain product, i.e. poly-{ 4,4-, bis-NSC 62789 base-bis-thieno-s [3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-methyl-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, productive rate is 82%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=11.7kDa, M
w/ M
n=2.5.
Embodiment 4:
The polymkeric substance containing dithiazole benzotriazole base of the present embodiment, gather { 4,4-di-n-butyl-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2, the 2'-(positive decyl-2H-of 2-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, (wherein, R
1for normal-butyl, R
2for positive decyl, n=72), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 4,4-di-n-butyl-2,6-bis-(tin trimethyl)-bis-thieno-[3,2-b:2', 3'-d] Silole (187mg, 0.3mmol), 2,2'-(positive decyl-the 2H-of 2-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-bromine thiadiazoles) (210mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Stille coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, obtain product, i.e. poly-{ 4,4-di-n-butyl-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2, the 2'-(positive decyl-2H-of 2-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, productive rate is 86%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=53.6kDa, M
w/ M
n=2.1.
Embodiment 5:
The polymkeric substance containing dithiazole benzotriazole base of the present embodiment, gather { 4,4-, bis-dodecyl-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-n-hexyl-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }, (wherein, R
1for dodecyl, R
2for n-hexyl, n=26), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4, 4-bis-dodecyl-2, 6-bis-(tin trimethyl)-bis-thieno-[3, 2-b:2', 3'-d] Silole (257mg, 0.3mmol), 2, 2'-(2-n-hexyl-2H-benzo [d] [1, 2, 3] triazole-4, 7-bis-bases) two (5-bromine thiadiazoles) (158mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Stille coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, obtain product, gather { 4,4-, bis-dodecyl-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-n-hexyl-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) }.Productive rate is 75%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=28.7kDa, M
w/ M
n=2.3.
Embodiment 6:
Refer to Fig. 2, a kind of organic solar batteries device 60 comprises substrate 61, anode 62, buffer layer 63, active coating 64 and negative electrode 65.Anode 62, buffer layer 63, active coating 64 and negative electrode 65 stack gradually a surface that is formed at substrate 61.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 is ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.
Buffer layer 63 is formed at anode 62 away from a side surface of substrate 61.What the material of buffer layer 63 was poly-3,4-ethylenedioxy thiazole (PEDOT) and polystyrene-sulfonic acid matrix material (PSS) mixes, and is expressed as PEDOT:PSS.
Active coating 64 is formed at buffer layer 63 away from a side surface of anode 62.Active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2, and wherein electron acceptor material is (6,6) phenyl-C
61-methyl-butyrate (PCBM), electron donor material be the present invention prepare containing dithiazole benzotriazole based polyalcohol; In present embodiment, the polymkeric substance containing dithiazole benzotriazole base of preparation in the embodiment 1 that electron donor material is, gather { 4,4-, bis-octane base-bis-thieno-[3,2-b:2', 3'-d] Silole-2,6-bis-bases-co-2,2'-(2-octane base-2H-benzo [d] [1,2,3] triazole-4,7-bis-bases) two (5-base-thiadiazoles) } (with P1, representing).
Negative electrode 65 is formed at active coating 64 away from a side surface of buffer layer 63.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 100nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
In another embodiment, buffer layer 63 can omit, and now active coating 64 is directly formed at anode 62 surfaces.
In the present embodiment 6, the manufacturing processed of organic solar batteries device 60 is as follows:
After anode 62 being formed to a side surface of substrate 61, carry out ultrasonic cleaning, and after processing with oxygen-Plasma, on anode 62 surfaces, be coated with the PEDOT:PSS that last layers play modification and form buffer layer 63.
On buffer layer 64, apply one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, the P1 of preparation in the embodiment 1 that electron donor material is.
On active coating 64 surfaces, form negative electrode 65.In present embodiment, the aluminium lamination of negative electrode 65 for being formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this organic solar batteries device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after organic solar batteries device is annealed, can effectively increase order and the regularity between interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
At AM1.5G100mW/cm
2under illumination, the effciency of energy transfer 3.0% of the body heterojunction organic solar batteries device 60 that the copolymer p 1 based in embodiment 1 is donor material.
When this organic solar batteries device 60 is used, under illumination, light transmission substrate 61 and anode 62, the conduction hole type electroluminescent material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by 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 negative electrode 65, transmit and be collected by negative electrode, transmit and collected by anode 62 along electron donor material anode 62 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, 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, be convenient to large batch of preparation.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. containing a polymkeric substance for dithiazole benzotriazole base, it is characterized in that, its structural formula is as follows:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-100.
2. the polymkeric substance containing dithiazole benzotriazole base according to claim 2, is characterized in that, comprises a kind of in following polymkeric substance:
3. contain a preparation method for the polymkeric substance of dithiazole benzotriazole base, it is characterized in that, comprise the steps:
The compd A and the B that provide respectively following structural formula to represent,
A:
b:
wherein, R
1, R
2be C
1～C
20alkyl;
Under oxygen-free environment, the compd A that is 1:1～1.2 by mol ratio and B are added in the organic solvent that contains catalyzer and dissolve, under 70～130 ° of C, carry out Stille coupling reaction 6～60 hours subsequently, stop after coupling reaction, separating-purifying reaction solution, obtain following structural formula containing the polymkeric substance of dithiazole benzotriazole base:
in formula, the integer that n is 10-100.
4. the preparation method of the polymkeric substance containing dithiazole benzotriazole base according to claim 3, is characterized in that, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and described compd A is 1:20～1:100.
5. the preparation method of the polymkeric substance containing dithiazole benzotriazole base according to claim 3, it is characterized in that, described catalyzer is the mixture of organic palladium and organophosphorus ligand, and in mixture, and the molar weight of organophosphorus ligand is 4～8 times of molar weight of organic palladium; The mol ratio of described catalyzer and described compd A is 1:20～1:100.
6. the preparation method of the polymkeric substance containing dithiazole benzotriazole base according to claim 5, is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
7. the preparation method of the polymkeric substance containing dithiazole benzotriazole base according to claim 3, is characterized in that, described organic solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
8. the preparation method of the polymkeric substance containing dithiazole benzotriazole base according to claim 3, is characterized in that, Stille coupling reaction temperature is 90～120 ° of C, and the reaction times is 12～48 hours.
9. the preparation method of the polymkeric substance containing dithiazole benzotriazole base according to claim 3, is characterized in that, separating-purifying reaction solution comprises:
After coupling reaction stops, in reaction solution, add methyl alcohol precipitating, by apparatus,Soxhlet's, filter subsequently, using successively again methyl alcohol and normal hexane extracting, obtain organic phase, then take chloroform as solvent extraction organic phase is to colourless, collect chloroformic solution and be spin-dried for, after the dry 24h of the lower 50 ° of C of vacuum, obtain described containing dithiazole benzotriazole based polyalcohol.
10. an organic solar batteries device, is characterized in that, the electron donor material of its active coating adopts the polymkeric substance containing dithiazole benzotriazole base of following structural formula:
In formula, R
1, R
2be C
1～C
20alkyl, integer between n is 10-100.
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| CN102050940A (en) * | 2011-01-28 | 2011-05-11 | 华南理工大学 | Organic semiconductor material containing 6-R group- [1, 2, 5] thiazole [3, 4-g] benzotriazole and application thereof |
| WO2011156478A2 (en) * | 2010-06-08 | 2011-12-15 | The University Of North Carolina At Chapel Hill | Polymers with tunable band gaps for photonic and electronic applications |
| WO2012028246A1 (en) * | 2010-09-04 | 2012-03-08 | Merck Patent Gmbh | Conjugated polymers |
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