CN103467710A - Conjugated polymer semi-conducting material and preparation method and application thereof - Google Patents
Conjugated polymer semi-conducting material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to designing, a preparation method and application of a conjugated polymer semi-conducting material, belonging to the field of organic polymer semi-conducting materials. According to the invention, a side chain containing an oxygen atom is introduced into a conjugated monomer so as to obtain a modified monomer, and then Stille coupling polymerization is employed to prepare the conjugated polymer semi-conducting material under a heating reflux condition with zero-valent palladium used as a catalyst and halogeno-benzene as a solvent; an obtained conjugated polymer and a fullerene derivative are blended and dissolved, then a polymer/fullerene derivative biphase separation film can be prepared by using a solution spin coating method without outside auxiliary conditions like thermal annealing and a solvent additive, phase separation of different scales between the polymer and PCBM can be realized through regulation and control of surface energy of the polymer, and the polymer is used as a material for a light-sensitive layer of a bulk-heterojunction polymer solar cell.
Description
Technical field
The present invention relates to a kind of design, preparation method and application of conjugated polymers semiconductor material, belong to the organic polymer field of semiconductor materials.
Background technology
Clean inexhaustible sun power is converted into to the path that electric energy is a kind of effective solution energy dilemma; developing efficient sun power becomes a kind of means of necessity; solar cell has developed into the third generation at present; with traditional inorganic solar cell, compare; third generation solar cell, based on organic materials, takes the method that the solution spin coating is printed to make, and product has frivolous; can be curling, can be made into the advantages such as big area.Through the development of short more than ten years, the efficiency that laboratory prepares battery has reached 10%, (Z. He, C. Zhong, S. Su, M. Xu, H. Wu, Y. Cao,
nat. Photonics2012,6,593; J. You, L. Dou, K. Yoshimura, T. Kato, K. Ohya, T. Moriarty, K. Emery, C.-C. Chen, J. Gao, G. Li, Y. Yang,
nat. Commun.dOI:10.1038/ncomms2411.) show good application prospect.
The Alan J. Heeger of Nobel chemistry Prize winner in 2000 etc. (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger,
science1995,270,1789) since reported first prepares to gather by the solution spin coating method high-efficiency polymer solar cell device that (3-hexyl) thiophene and fullerene derivate (PCBM) are the photoactive layer material, organic polymer solar cell arouses great concern.Professors Heeger etc. have proposed the core texture of the mutually heterogeneous joint of body first, the mutually heterogeneous joint structure of traditional face replaced, significantly promoted the efficiency of conversion of polymer solar battery, the mutually heterogeneous joint structure of this body has increased considerably polymkeric substance and has contacted with the interface of soccerballene derivative, more be conducive to the photoproduction exciton dissociation and become electronics and hole, and then the transmission of quickening current carrier, the electric current of increase battery.But, due to the difference of polymkeric substance and organic molecule soccerballene bi-material itself, make polymkeric substance and the PCBM dispersion yardstick in the heterogeneous joint of body to become a difficult problem.
Document in 2005 proposed first the device thermal annealing (W. Ma, C. Y. Yang, X. Gong, K. Lee, A. J. Heeger,
adv. Funct. Mater.2005,15,1617) method, can well control by this method the yardstick that is separated of P3HT and PCBM, further reach perfect two-phase and disperse, the efficiency of conversion of battery can bring up to 5%, due to the limitation of P3HT material to the sunlight absorption itself, the later stage scientific research personnel has designed novel narrow band gap polymkeric substance, further improves efficiency (H.-Y. Chen, the J. H. Hou of polymer solar battery, S. Q. Zhang, Y. Liang, G.W. Yang, Y. Yang, L. P. Yu, Y. Wu, G. Li
nat. Photonics2009,3,649; C. Piliego, T. W. Holcombe, J. D. Douglas, C. H. Woo, P. M. Beaujuge, J. M. J. Fr é chet,
j. Am. Chem. Soc.2010,132,7595.) still the mode of above-mentioned thermal annealing rarely has effect to novel polymer solar battery, so find in the research in early stage, adopt high boiling solvent additive (J. Peet, J. Y. Kim, N. E. Coates, W. L. Ma, D. Moses, A. J. Heeger, G. C. Bazan
nat. Mater.2007,6,497; J. K. Lee, W. L. Ma, C. J. Brabec, J. S.Moon, J. Y. Kim, K. Lee, G. C. Bazan, A. J. Heeger,
j. Am. Chem. Soc.2008,
1303619.) can reach equally and adjust the purpose be separated, but high boiling additive can remain in device, have a strong impact on the stability of device, the manufacture craft that the simultaneously this high boiling point additive containing halohydrocarbon has increased device can produce and pollute environment again, so the method that a kind of easy adjustment polymkeric substance of the need of production of later stage big area polymer solar battery and PCBM are separated.
Summary of the invention
The object of the invention is to overcome current polymer solar cell device and make the deficiency that post-processing technique exists, provide that a kind of preparation technology is simple, environmental friendliness, and have appropriate surfaces can polymkeric substance, effectively to control the surface energy of conjugated polymers semiconductor material, with making solar cell device after the PCBM blend, can reach voluntarily suitable being separated.
The technical scheme that realizes the object of the invention is to provide a kind of conjugated polymers semiconductor material, and its structural formula is:
Wherein, Ar
1and Ar
2representative does not replace or contains any one in substituent following radicals independently: vinylidene, ethynylene, monocycle arylidene, dicyclo arylidene, the many rings arylidene containing at least three rings, monocycle heteroarylidene, dicyclo heteroarylidene and containing many rings heteroarylidene of at least three rings; Described dicyclo arylidene, encircle arylidene, dicyclo heteroarylidene more, encircle in heteroarylidene more, ring with encircle between for condensing or being connected by singly-bound;
R
1, R
2represent independently any one in following radicals: hydrogen, have 1~30 carbon atom alkyl, there is the alkoxyl group of 1~30 carbon atom;
The repeating unit number of n representation polymer is 5~500 natural number.
In some embodiments of the present invention, described monocycle arylidene comprises a kind of as in lower unit:
Described dicyclo arylidene comprises a kind of as in lower unit:
Described many ring arylidene comprise a kind of as in lower unit:
A kind of preparation method of conjugated polymers semiconductor material as above, comprise the steps:
1,1:1.5~1:2.5 in molar ratio, will have the alkyl tosic acid of 1~30 carbon atom or have the alkoxyl group tosic acid of 1~30 carbon atom, with monomer A r
1or Ar
2reaction, be incorporated into the side chain that contains Sauerstoffatom in conjugative monomer, obtains the monomer A r after modification
1or Ar
2;
2,1:1 in molar ratio, by the monomer A r after modification
1or Ar
2, with monomer A or monomers B at the zeroth order palladium, be catalyzer, halogeno-benzene is solvent, under the reflux condition, by the polymerization process of Stille coupling, obtains a kind of conjugated polymers semiconductor material; Described monomer A is monomer A r
1or Ar
2, monomers B is the monomer A r after modification
1or Ar
2;
Described monomer A r
1and Ar
2independently representative does not replace or contains any one in substituent following radicals: vinylidene, ethynylene, monocycle arylidene, dicyclo arylidene, the many rings arylidene containing at least three rings, monocycle heteroarylidene, dicyclo heteroarylidene and containing many rings heteroarylidene of at least three rings; Described dicyclo arylidene, encircle arylidene, dicyclo heteroarylidene more, encircle in heteroarylidene more, ring with encircle between for condensing or being connected by singly-bound.
The described alkoxyl group tosic acid with 1~30 carbon atom is [2
-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group] tosic acid.
The application of a kind of conjugated polymers semiconductor material as above, after conjugated polymers semiconductor material and fullerene derivate are dissolved by weight 1:1~1:2 blend, adopt the solution spin coating method to obtain the film that polymkeric substance/fullerene derivate two is separated, as the photoactive layer material in the mutually heterogeneous joint polymer solar battery of body.
Compared with prior art, the invention has the beneficial effects as follows: in after polymkeric substance of the present invention and PCBM blend masking, do not needing extraneous subsidiary conditions (thermal annealing, solvent additive) can form the dispersion mutually of PCBM of the polymkeric substance of different scale, the regulation and control polymkeric substance surface can be able to realize being separated of different scale between polymkeric substance and PCBM, as the photoactive layer material in the mutually heterogeneous joint polymer solar battery of body.
The accompanying drawing explanation
Fig. 1 is the synthetic route chart that the embodiment of the present invention 1 prepares polymer P DOP;
Fig. 2 is the synthetic route chart that the embodiment of the present invention 2 prepares polymer P BOD;
Fig. 3 is the synthetic route chart that the embodiment of the present invention 3 prepares polymer P BOT;
Fig. 4 is the synthetic route chart that the embodiment of the present invention 4 prepares polymer P TO7;
Fig. 5 is the uv-visible absorption spectra figure of the polymkeric substance that provides of the embodiment of the present invention;
Fig. 6 is the cyclic voltammogram of the polymkeric substance that provides of the embodiment of the present invention;
Fig. 7 is the contact angle test result figure of the polymkeric substance that provides of the embodiment of the present invention;
Fig. 8 is the polymkeric substance that provides of the embodiment of the present invention and the shape appearance figure after the PCBM blend;
Fig. 9 is the hydrogen spectrum nuclear magnetic spectrogram of the monomer material that provides of the embodiment of the present invention;
Figure 10 is the hydrogen spectrum nuclear magnetic spectrogram of the polymkeric substance that provides of the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
The present embodiment raw material used is known compound, can on market, buy, or available methods known in the art is synthetic obtains.
2,5-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-preparation of pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, its structural formula is:
Add 2,5-bis-(ethylhexyl)-3 in the flask of 250 mL, 6-dithienyl-pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone (2.25 g, 7.5 mmol), tetra-n-butyl ammonium bromide (0.25g, 0.75 mmol), salt of wormwood (5.2 g, 32.5 mmol), [2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group] tosic acid (9.1 g, 28.5 mmol), anhydrous DMF (50 mL).120 ℃ of stirring reactions 40 hours, after reaction finishes, chloroform extraction, organic phase adds anhydrous sodium sulfate drying, and crude product is through PhastGel chromatogram (silica gel solid phasing, methylene dichloride/acetone, volume ratio 10:1, moving phase) after separating, vacuum-drying obtains product red solid (2.05 g, productive rate 41%).
1H NMR (CDCl
3) δ: 8.69 (dd, 2H), 7.56 (dd, 2H), 7.17 (dd, 2H), 4.19 (t, 4H), 3.71 (t, 2H), 3.59–3.39 (m, 16H), 3.26 (s, 6H) ppm.
2,5-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-3, the preparation of 6-bis-(5-bromothiophene)-pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, its structural formula is:
Add 2 in the flask of 100 mL, 5-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone (0.6g, 1 mmol), trichloromethane (50 mL), stirring and dissolving, N-bromo-succinimide (0.38 g, 2.1 mmol) divide five times, under the lucifuge condition, slowly add, the reaction system lucifuge is reacted 12 h.After reaction finishes, dichloromethane extraction, organic phase adds anhydrous sodium sulfate drying, crude product is through PhastGel chromatogram (silica gel solid phasing, methylene dichloride/acetone, volume ratio 10:1, moving phase), after separating, vacuum-drying obtains the purple solid (0.45 g, productive rate 59 %) of product.
1H NMR (CDCl3) δ: 8.46 (d, 2H), 7.16 (d, 2H), 4.12 (t, 4H), 3.73 (t, 4H), 3.61–3.43 (m, 16H), 3.10 (s, 6H) ppm.。
Polymer P DOP's is synthetic, and its structural formula is:
Synthetic route is referring to accompanying drawing 1.
Get 0.10 gram 2, two (the trimethyl-tin-radical)-thiophene of 5-, 0.18 gram 2,5-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-3,6-bis-(5-bromothiophene)-pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone adds in 50 milliliters of reaction tubess, adds catalyzer 0.01 gram three (dibenzalacetone) two palladiums, part 0.02 gram three o-methyl-phenyl-phosphorus, add 5 milliliters of dry toluenes, 0.5 the anhydrous DMF of milliliter, spend stirring reaction 24 hours in argon gas atmosphere 110.Polymkeric substance is cooled to room temperature, slowly pour in 70 ml methanol, after the polymer filtration of precipitation, in cable type extractor according, with methyl alcohol, normal hexane, trichloromethane, wash successively, finally with chlorobenzene, dissolve postprecipitation in methyl alcohol, filter, 100 degree vacuum-dryings obtain the solid polymer of intense violet color, productive rate 80% in 12 hours.Its weight-average molecular weight is Mw=20.8 K, dispersity PDI=1.67.
Polymer P BOD's is synthetic, and its structural formula is:
Synthetic route is referring to accompanying drawing 2.
Get 0.20 gram 4, two (trimethyl-tin-radical)-4 of 6-, two (5-(2-ethylhexyl)-thienyl)-benzo [1, the 2-b of 8-; 4,5-b '] two thiophene, 0.18 gram 2,5-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-3,6-bis-(5-bromothiophene)-pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone adds in 50 milliliters of reaction tubess, adds catalyzer 0.01 gram three (dibenzalacetone) two palladiums, part 0.02 gram three o-methyl-phenyl-phosphorus, add 5 milliliters of dry toluenes, 0.5 the anhydrous DMF of milliliter, spend stirring reaction 12 hours in argon gas atmosphere 110.Polymkeric substance is cooled to room temperature, slowly pour in 70 ml methanol, after the polymer filtration of precipitation, in cable type extractor according, with methyl alcohol, normal hexane, wash successively, finally with trichloromethane, dissolve postprecipitation in methyl alcohol, filter, 100 degree vacuum-dryings obtain the pressed powder polymkeric substance of intense violet color, productive rate 90 % in 12 hours.Its weight-average molecular weight is Mw=100.1 K, dispersity PDI=3.02.
4,8-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-benzo [1,2-b; 4,5-b '] two thiophene synthetic, its structural formula is:
Add benzo [1,2-b in the flask of 100 mL; 4,5-b '] two thiophene-4,8-diketone (2.2 g, 10 mmol), zinc powder (1.46 g, 22 mmol), 6 g sodium hydroxide, 30 mL water, return stirring 1h, add tetra-n-butyl ammonium bromide (0.25g, 0.75 mmol) subsequently, [2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group] tosic acid (9.1 g, 28.5 mmol).100
oc continues stirring reaction 6 hours, after reaction finishes, chloroform extraction, organic phase adds anhydrous sodium sulfate drying, and crude product is through PhastGel chromatogram (silica gel solid phasing, methylene dichloride/acetone, volume ratio 10:1, moving phase) after separating, vacuum-drying obtains the light yellow oily of product (3.1 g, productive rate 55 %).
1H NMR (CDCl
3) δ: 7.55 (d, 2H), 7.35 (d, 2H), 4.19 (t, 4H), 3.71 (t, 2H), 3.59–3.39 (m, 16H), 3.26 (s, 6H) ppm.
Two (trimethyl-tin-radical)-4 of 4,6-, 8-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-benzene [1,2-b; 4,5-b '] two thiophene synthetic, its structural formula is:
By 4,8-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-benzo [1,2-b; 4; 5-b '] two thiophene (0.50 g, 1.0 mmol) join in the reaction flask of 50 mL argon shield; utilize syringe to add anhydrous tetrahydro furan (20 mL);-78 ℃ of stirring and dissolving, n-Butyl Lithium (1.0 mL, 2.4 mmol) slowly is added drop-wise in reaction system by syringe; stir 60 min after dropwising under-78 ℃; trimethyltin chloride (0.44 g, 2.2 mmol) joins in reaction system, slowly is warmed up to the stirring at room reaction and spends the night.After adding 5 mL distilled water to stir 30 min, cancellation is reacted, after tetrahydrofuran (THF) is removed in decompression, and the residual substance extracted with diethyl ether, organic phase adds anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains the light yellow oily of product, productive rate 85 %
1h NMR (CDCl
3) δ: 7.55 (s, 2H), 4.19 (t, 4H), 3.71 (t, 2H), 3.59 – 3.39 (m, 16H), 3.26 (s, 6H) ppm.
Polymer P BOT, its structural formula is:
Synthetic route is referring to accompanying drawing 3.
Get 0.15 gram 4, two (trimethyl-tin-radical)-4 of 6-, 8-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-benzo [1,2-b; 4,5-b '] two thiophene, 0.10 gram 1, the bromo-5-of 3-bis-(octyl group)-5H-thiophene-[3,4-c]-pyrroles-3, the 6-diketone adds in 50 milliliters of reaction tubess, adds catalyzer 0.01 gram three (dibenzalacetone) two palladiums, part 0.02 gram three o-methyl-phenyl-phosphorus, add 5 milliliters of dry toluenes, 0.5 the anhydrous DMF of milliliter, spend stirring reaction 48 hours in argon gas atmosphere 110.Polymkeric substance is cooled to room temperature, slowly pour in 70 ml n-hexanes, after the polymer filtration of precipitation, in cable type extractor according, with acetone, normal hexane, wash successively, finally with trichloromethane, dissolve postprecipitation in methyl alcohol, filter, 100 degree vacuum-dryings obtain the pressed powder polymkeric substance of intense violet color, productive rate 83% in 12 hours.Its weight-average molecular weight is Mw=28.1 K, dispersity PDI=1.85.
Embodiment 4
Polymer P TO7, its structural formula is:
Synthetic route is referring to accompanying drawing 4.
Get 0.15 gram 4, two (trimethyl-tin-radical)-4 of 6-, 8-bis-[2-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group]-benzo [1,2-b; 4,5-b '] two thiophene, 0.85 gram 2-ethylhexyl 4, the fluoro-thiophene of the bromo-3-of 6-bis-[3,4-b] thiophene-2-carbonic ether adds in 50 milliliters of reaction tubess, add catalyzer 0.01 gram three (dibenzalacetone) two palladiums, part 0.02 gram three o-methyl-phenyl-phosphorus, add 5 milliliters of dry toluenes, 0.5 milliliter of anhydrous N, dinethylformamide, spend stirring reaction 24 hours in argon gas atmosphere 110.Polymkeric substance is cooled to room temperature, slowly pour in 70 ml n-hexanes, after the polymer filtration of precipitation, in cable type extractor according, with acetone, normal hexane, wash successively, finally with trichloromethane, dissolve postprecipitation in methyl alcohol, filter, 100 degree vacuum-dryings obtain the pressed powder polymkeric substance of intense violet color, productive rate 83% in 12 hours.Its weight-average molecular weight is Mw=18.1 K, dispersity PDI=1.56.
Referring to accompanying drawing 5, it is the ultraviolet-visible absorption spectroscopy figure of the chloroform soln of the polymkeric substance that provides of the embodiment of the present invention, as seen from Figure 5, polymer materials provided by the invention can carry out the absorption of telomerized polymer material to sunlight by the regulation and control backbone structure.
Referring to accompanying drawing 6, it is the electrical properties of the polymkeric substance that provides of the embodiment of the present invention, by common cyclic voltammetry, is recorded, and take ferrocene as interior mark.
Referring to accompanying drawing 7, it be the polymkeric substance that provides of the embodiment of the present invention show can test result figure, adopt conventional contact angle testing method, characterized electron acceptor material PCBM commonly used in gather-3-hexyl-thiophene (P3HT) of classical conjugation semi-conducting polymer and polymer solar battery simultaneously, the test result of Fig. 7 shows, by introducing the side chain of strong polarity, conjugated polymers show getable obvious adjusting, the contact angle of classical P3HT is 107 degree, and the contact angle of polymkeric substance provided by the invention does not wait from 11.4~84.6 degree, selection by side chain, can control the wetting ability of conjugated polymers, the solar cell prepared based on conjugated polymers and PCBM solution method is the outstanding representative in the novel flexible solar cell, the yardstick regulation and control that are separated of conjugated polymers and PCBM are all to hinder the obstacle that battery performance promotes for a long time, test result is excessively surperficial, the contact angle of PCBM film is 83.1 degree, and classical based on the P3HT/PCBM polymer solar battery, must could obviously improve by the processing of later stage thermal annealing efficiency (the W. Ma of solar cell, C. Y. Yang, X. Gong, K. Lee, A. J. Heeger,
adv. Funct. Mater.2005,15,1617), can reach by the surface of regulating conjugated polymers in the present invention and automatically being separated of PCBM, without the device by the later stage, process (thermal annealing, additive).
Referring to accompanying drawing 8, it is the chloroformic solution of polymkeric substance provided by the invention and PCBM blend, after the sol evenning machine spin coating, and the atomic force microscope shape appearance figure of film.The preparation method of film makes according to polymer solar cell device known in the art, as press reference (
adv. Funct. Mater.2013,23,885.) disclosed method is made.Concrete grammar is: conductive glass (ITO) cleans 20 minutes with washing composition, Virahol, each excusing from death of acetone successively, will be through the ITO that cleans ozone 15-20 minute at first, spin coating PEDOT:PSS film (4500 rpms of rotating speeds, 40 seconds time), 150 degree annealing 10 minutes, then transfer in glove box spin coating polymerization and PC
71the chloroformic solution of BM different ratios (concentration of polymkeric substance is 8 milligrams every milliliter), the atomic force microscope model is Veeco Multimode V instrument, test adopts the pattern of rapping.
Test result by Fig. 8 shows, the contact angle test of polymer P BOT is minimum, wetting ability is the strongest, after the PCBM blend, film shows the larger yardstick that is separated, increase gradually along with the polymkeric substance contact angle, the yardstick that is separated of polymkeric substance and PCBM reduces gradually, and for classical conjugation semi-conducting polymer P3HT, its contact angle is 107 degree, show certain lipophilicity, with the film of PCBM blend be also smoother, appearance significantly is not separated, need to increase by the mode of later stage thermal annealing the gathering of PCBM, thereby reach the purpose be separated, and the group of the present invention by introducing strong polarity can reach without aftertreatment the purpose that conjugated polymers and fullerene derivate are separated, and can by regulate and control surface can size control the yardstick that polymkeric substance and PCBM are separated, the method can improve the performance of big area polymer solar battery product, simplify production technique, reduce costs.
Referring to accompanying drawing 9 and 10, they are respectively the hydrogen spectrum nuclear magnetic spectrograms of the monomer material that provides of the embodiment of the present invention and polymkeric substance.
Claims (7)
1. a conjugated polymers semiconductor material is characterized in that its structural formula is:
Wherein, Ar
1and Ar
2representative does not replace or contains any one in substituent following radicals independently: vinylidene, ethynylene, monocycle arylidene, dicyclo arylidene, the many rings arylidene containing at least three rings, monocycle heteroarylidene, dicyclo heteroarylidene and containing many rings heteroarylidene of at least three rings; Described dicyclo arylidene, encircle arylidene, dicyclo heteroarylidene more, encircle in heteroarylidene more, ring with encircle between for condensing or being connected by singly-bound;
R
1, R
2represent independently any one in following radicals: hydrogen, have 1~30 carbon atom alkyl, there is the alkoxyl group of 1~30 carbon atom;
The repeating unit number of n representation polymer is 5~500 natural number.
3. a kind of conjugated polymers semiconductor material according to claim 1 is characterized in that: described dicyclo arylidene comprises a kind of as in lower unit:
。
5. the preparation method of a conjugated polymers semiconductor material as claimed in claim 1, is characterized in that comprising the steps:
(1) 1:1.5~1:2.5 in molar ratio, will have the alkyl tosic acid of 1~30 carbon atom or have the alkoxyl group tosic acid of 1~30 carbon atom, with monomer A r
1or Ar
2reaction, be incorporated into the side chain that contains Sauerstoffatom in conjugative monomer, obtains the monomer A r after modification
1or Ar
2;
(2) 1:1 in molar ratio, by the monomer A r after modification
1or Ar
2, with monomer A or monomers B at the zeroth order palladium, be catalyzer, halogeno-benzene is solvent, under the reflux condition, by the polymerization process of Stille coupling, obtains a kind of conjugated polymers semiconductor material; Described monomer A is monomer A r
1or Ar
2, monomers B is the monomer A r after modification
1or Ar
2;
Described monomer A r
1and Ar
2independently representative does not replace or contains any one in substituent following radicals: vinylidene, ethynylene, monocycle arylidene, dicyclo arylidene, the many rings arylidene containing at least three rings, monocycle heteroarylidene, dicyclo heteroarylidene and containing many rings heteroarylidene of at least three rings; Described dicyclo arylidene, encircle arylidene, dicyclo heteroarylidene more, encircle in heteroarylidene more, ring with encircle between for condensing or being connected by singly-bound.
6. the preparation method of a conjugated polymers semiconductor material as claimed in claim 1, it is characterized in that: the described alkoxyl group tosic acid with 1~30 carbon atom is [2
-[2-(2-methoxy ethoxy) oxyethyl group] oxyethyl group] tosic acid.
7. the application of a kind of conjugated polymers semiconductor material as claimed in claim 1, it is characterized in that: after conjugated polymers semiconductor material and fullerene derivate are dissolved by weight 1:1~1:2 blend, adopt the solution spin coating method to obtain the film that polymkeric substance/fullerene derivate two is separated, as the photoactive layer material in the mutually heterogeneous joint polymer solar battery of body.
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