CN103848962A - Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device - Google Patents
Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device Download PDFInfo
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- CN103848962A CN103848962A CN201210492958.8A CN201210492958A CN103848962A CN 103848962 A CN103848962 A CN 103848962A CN 201210492958 A CN201210492958 A CN 201210492958A CN 103848962 A CN103848962 A CN 103848962A
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- NIKLLBFAZFYRTL-UHFFFAOYSA-N benzene;thiophene Chemical group C=1C=CSC=1.C=1C=CSC=1.C1=CC=CC=C1 NIKLLBFAZFYRTL-UHFFFAOYSA-N 0.000 title claims description 58
- 229920000642 polymer Polymers 0.000 title claims description 40
- 238000002360 preparation method Methods 0.000 title claims description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229910052763 palladium Inorganic materials 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 238000006619 Stille reaction Methods 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 4
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- QBBOCSNLIYAOFH-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.[P] Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.[P] QBBOCSNLIYAOFH-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 0 CC(C)(C)c1cc(C(c2cc(-c3c(C4(c5ccc(*)cc5)c5ccc(*)cc5)cc(-c5cc6c(*)c([s]c(C(C)(C)C)c7)c7c(*)c6[s]5)[s]3)c4cc2-2)(c3ccc(*)cc3)c3ccc(*)cc3)c-2[s]1 Chemical compound CC(C)(C)c1cc(C(c2cc(-c3c(C4(c5ccc(*)cc5)c5ccc(*)cc5)cc(-c5cc6c(*)c([s]c(C(C)(C)C)c7)c7c(*)c6[s]5)[s]3)c4cc2-2)(c3ccc(*)cc3)c3ccc(*)cc3)c-2[s]1 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- NSLJAYQJTGJPBW-UHFFFAOYSA-N S1C=CC2=C1C=CS2.C2=CC=CC=C2 Chemical compound S1C=CC2=C1C=CS2.C2=CC=CC=C2 NSLJAYQJTGJPBW-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- -1 decyl phenyl Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- CEPPKKLWDGWJEJ-UHFFFAOYSA-N 2-bromo-4,4-bis(4-octylphenyl)indeno[1,2-b]thiophene Chemical compound BrC1=CC2=C(S1)C1=CC=CC=C1C2(C2=CC=C(C=C2)CCCCCCCC)C2=CC=C(C=C2)CCCCCCCC CEPPKKLWDGWJEJ-UHFFFAOYSA-N 0.000 description 1
- BHOXHGABWKVVQN-UHFFFAOYSA-N Bc1cc(C(c2cc(-c([s]3)c(C4(c5ccc(C)cc5)c5ccc(CCCCCC)cc5)cc3Br)c4cc2-2)(c3ccc(C)cc3)c3ccc(CCCCCC)cc3)c-2[s]1 Chemical compound Bc1cc(C(c2cc(-c([s]3)c(C4(c5ccc(C)cc5)c5ccc(CCCCCC)cc5)cc3Br)c4cc2-2)(c3ccc(C)cc3)c3ccc(CCCCCC)cc3)c-2[s]1 BHOXHGABWKVVQN-UHFFFAOYSA-N 0.000 description 1
- YUZMZVFXBNTPGW-UHFFFAOYSA-N BrC1=CC2=C(S1)C1=CC=CC=C1C2(C2=CC=C(C=C2)CN)C2=CC=C(C=C2)CN Chemical compound BrC1=CC2=C(S1)C1=CC=CC=C1C2(C2=CC=C(C=C2)CN)C2=CC=C(C=C2)CN YUZMZVFXBNTPGW-UHFFFAOYSA-N 0.000 description 1
- DADZIMNFQANSAN-UHFFFAOYSA-N C(C1=CC=CC=C1)CC(C)=O.[Ar] Chemical compound C(C1=CC=CC=C1)CC(C)=O.[Ar] DADZIMNFQANSAN-UHFFFAOYSA-N 0.000 description 1
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 description 1
- HZAWPPRBCALFRN-UHFFFAOYSA-N Cc1ccc(Cc2ccc(C)cc2)cc1 Chemical compound Cc1ccc(Cc2ccc(C)cc2)cc1 HZAWPPRBCALFRN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
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Images
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
A polymer containing a thiophene-benzene-thiophene unit has the following structural formula shown in the description, wherein R1 is C1-C20 alkyl, R2 is C1-C20 alkyl, and n is an integer from 10 to 100. The polymer containing the thiophene-benzene-thiophene unit contains the thiophene-benzene-thiophene unit and a benzodithiophene unit; the polymer has higher hole mobility, has higher absorption coefficient on sunlight, has the energy gap in a range of 1.4 eV-1.7 eV, and has wider absorption range and easily modified photophysical properties in a wavelength range of 350 nm-700 nm. The thiophene-benzene-thiophene based polymer is applied to a solar cell and thus can solve the problem of low efficiency of the solar cell. The invention also provides a preparation method of the polymer containing the thiophene-benzene-thiophene unit and a solar cell device employing the polymer containing the thiophene-benzene-thiophene unit.
Description
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of polymkeric substance containing thiophene-benzene-thiophene unit and preparation method thereof and the solar cell device that uses this containing the polymkeric substance of thiophene-benzene-thiophene unit.
[background technology]
Since Japanese scientist's Hideki Shirakawa in 1977 is found polyacetylene conduction, this being called as the conductive polymers of " the 4th generation polymer " material attracted numerous scientists to study with its outstanding photoelectric properties.Conducting polymer is compared with the inorganic materials with identical or close purposes, has density low, and easily processing, synthesizes the advantages such as range of choice is wide.Due to the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may being applied on many electronics or opto-electronic device, for example comprise polymer LED, photovoltaic cell, field-effect etc.Potential application prospect and wide application field impel scientist competitively to study this class to have the conjugation material of photoelectric activity, comprise conjugated structure small molecules, and polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes etc.
Researchist is making great efforts to seek to improve the method for polymer LED, photovoltaic cell, field effect behavior always, and material is one of most important factor.So being devoted to exploitation always, many research groups there is high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good, and the polymkeric substance that visible-range absorption bands is wide, carrier mobility is high.Realize these targets, need to develop more novel conjugated molecular material and polymer materials, wherein, design synthesizing new conjugate unit just seems very important.
[summary of the invention]
Based on this, be necessary the polymkeric substance containing thiophene-benzene-thiophene unit that provides a kind of energy conversion efficiency higher.
In addition, be also necessary to provide a kind of preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit.
In addition, be also necessary to provide the solar cell device using containing the polymkeric substance of thiophene-benzene-thiophene unit.
Containing a polymkeric substance for thiophene-benzene-thiophene unit, there is following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
A preparation method who contains the polymkeric substance of thiophene-benzene-thiophene unit, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added into and in the organic solvent that contains catalyzer, carry out Stille coupling reaction, described catalyzer is organic palladium or the mixture for organic palladium and organophosphorus ligand, obtains the polymer P containing thiophene-benzene-thiophene unit that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
In a preferred embodiment, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
In a preferred embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
In a preferred embodiment, the mol ratio of the organic palladium in described catalyzer and described compd A is 1:20 ~ 1:100.
In a preferred embodiment, the temperature of reaction of described Stille coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 6 hours ~ 60 hours.
In a preferred embodiment, also comprise the step of carrying out separation and purification containing the polymer P of thiophene-benzene-thiophene unit, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing thiophene-benzene-thiophene unit after purifying.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
A kind of solar cell device, comprises activity layer by layer, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate, described electron donor material has the polymer P containing thiophene-benzene-thiophene unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Above-mentioned hole mobility higher containing containing thiophene-benzene-thiophene unit and benzo two thiophene units, its polymkeric substance in the polymkeric substance of thiophene-benzene-thiophene unit, sunlight is had to higher uptake factor, energy gap is at 1.4eV～1.7eV, the photophysical property that has wider absorption region and easily modify within the scope of 350nm～700nm, is applied to above-mentioned thiophene-benzene-thienyl multipolymer in solar cell and can solves solar cell low efficiency problem.
The preparation method of the above-mentioned polymkeric substance containing thiophene-benzene-thiophene unit, 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, applicable to solar cell device.
[accompanying drawing explanation]
Fig. 1 is the preparation method's of the polymkeric substance containing thiophene-benzene-thiophene unit of an embodiment schema;
Fig. 2 is the uv-visible absorption spectra figure containing the polymkeric substance of thiophene-benzene-thiophene unit prepared by embodiment 1;
Fig. 3 is the thermogravimetic analysis (TGA) figure containing the polymkeric substance of thiophene-benzene-thiophene unit prepared by embodiment 1;
Fig. 4 is the structural representation of the solar cell device of an embodiment.
[embodiment]
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 monomer A is bought and is obtained from the market, monomers B reference literature (Adv.Funct.Mater., 2009,19,3063) disclosed method is synthetic obtains.
The polymkeric substance containing thiophene-benzene-thiophene unit of one embodiment, has following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Above-mentioned hole mobility higher containing containing thiophene-benzene-thiophene unit and benzo two thiophene units, its polymkeric substance in the polymkeric substance of thiophene-benzene-thiophene unit, sunlight is had to higher uptake factor, energy gap is at 1.4eV～1.8eV, the photophysical property that has wider absorption region and easily modify within the scope of 350nm～700nm, is applied to above-mentioned thiophene-benzene-thienyl multipolymer in solar cell and can solves solar cell low efficiency problem.
The preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit of one embodiment, as shown in Figure 1, comprises the following steps:
Step S1, provide compd A and compd B.
The structural formula of compd A is:
wherein, R
1for C
1~ C
20alkyl.
The structural formula of compd B is:
wherein, R
2for C
1~ C
20alkyl.
Step S2, preparation contain the polymer P of thiophene-benzene-thiophene unit.
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added into and in the organic solvent that contains catalyzer, carry out Stille coupling reaction, described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand, obtains the polymer P containing thiophene-benzene-thiophene unit that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
In present embodiment, Stille coupling reaction carries out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).Be appreciated that organic solution also can be used other solvents, as long as can dissolved compound A and compd B.
In present embodiment, organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, and organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl.In the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand is 1:4 ~ 1:8.Preferably, adopt the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine as catalyzer.Be appreciated that organic palladium, organophosphorus ligand are all not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Stille coupling reaction
In present embodiment, in catalyzer, the mol ratio of organic palladium and compd A is 1:20 ~ 1:100.The mol ratio that is appreciated that organic palladium and compd A is not limited to 1:20 ~ 1:100, to adding the catalyzer that adds catalytic amount in the organic solvent of compd A and compd B.
In present embodiment, the temperature of reaction of Stille coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 6 hours ~ 60 hours.Preferably, the temperature of reaction of Stille coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 12 hours ~ 48 hours.The temperature of reaction that is appreciated that Stille coupling reaction is not limited to 70 ℃ ~ 130 ℃, as long as can make compd A and compd B react; Reaction times is also not limited to 6 hours ~ and 60 hours, as long as can make compd A and compd B react completely as far as possible.
Step S3, separation and purification contain the polymer P of thiophene-benzene-thiophene unit.
Carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing thiophene-benzene-thiophene unit after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collect evaporating solvent after chloroformic solution obtain the polymer P containing thiophene-benzene-thiophene unit after purifying under vacuum 50 ℃～70 ℃ dry 24 hours～48 hours.
The preparation method of the above-mentioned polymkeric substance containing thiophene-benzene-thiophene unit, synthetic route is comparatively simple, has reduced manufacturing cost.
A kind of solar cell device in one embodiment, comprises active coating, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate, described electron donor material has the polymer P containing thiophene-benzene-thiophene unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Be specific embodiment below.
Embodiment 1
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(n-octyloxy) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-octyl phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 1 of thiophene-benzene-thiophene unit):
The preparation process of the above-mentioned polymer P 1 containing thiophene-benzene-thiophene unit is as follows:
Under argon shield, by 2,6-bis-tin trimethyl-4,8-bis-(n-octyloxy) benzene 1,4-Dithiapentalene (151mg, 0.2mmol), two (2-bromo-4,4-bis-(4-n-octyl phenyl)-indeno [1,2-b] thiophene) (235mg, 0.2mmol) add in the flask that fills 10ml toluene solvant fully and dissolve, vacuumize deoxygenation and be 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, in 50ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, under vacuum pump, taking out spends the night obtains product poly-{ 2,6-bis-base-4,8-bis-(n-octyloxy) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-octyl phenyl)-indeno [1,2-b] thiophene }, productive rate 75%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 1 of thiophene-benzene-thiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=82.4kDa, M
w/ M
n=2.2.
Referring to accompanying drawing 2, be the uv-visible absorption spectra figure of the organic semiconductor material P1 of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 561nm, wide absorption spectrum shows that P1 is a kind of photovoltaic material.
Referring to accompanying drawing 3, be the thermogravimetic analysis (TGA) figure of the organic semiconductor material P1 for preparing of the present embodiment 1, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T as seen from the figure
d) be 436 ℃.
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(methoxyl group) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-NSC 62789 base phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 2 of thiophene-benzene-thiophene unit):
The preparation process of the above-mentioned polymer P 2 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 2, 6-bis-tin trimethyl-4, 8-bis-(methoxyl group) benzene 1,4-Dithiapentalene (173mg, 0.3mmol), two (2-bromo-4, 4-bis-(4-NSC 62789 base phenyl)-indeno [1, 2-b] thiophene) (555mg, 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 take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain product poly-{ 2,6-bis-base-4,8-bis-(methoxyl group) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-NSC 62789 base phenyl)-indeno [1,2-b] thiophene }.Productive rate is 71%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 2 of thiophene-benzene-thiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=201.6kDa, M
w/ M
n=2.0.
The uv-visible absorption spectra figure of the organic semiconductor material P2 of preparation in the present embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 557nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P2 prepared by the present embodiment 2, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 424 ℃.
Embodiment 3
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(NSC 62789 oxygen base) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-aminomethyl phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 3 of thiophene-benzene-thiophene unit):
The preparation process of the above-mentioned polymer P 3 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen protection, by 2,6-bis-tin trimethyl-4,8-bis-(NSC 62789 oxygen base) benzene 1,4-Dithiapentalene (332mg, 0.3mmol), two (2-bromo-4,4-bis-(4-aminomethyl phenyl)-indeno [1,2-b] thiophene) (259mg, 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 and fully dissolve, in flask, lead to after the about 30min 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 to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, be product poly-{ 2,6-, bis-base-4,8-bis-(NSC 62789 oxygen base) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-aminomethyl phenyl)-indeno [1,2-b] thiophene }, productive rate is 78%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 3 of thiophene-benzene-thiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=15.9kDa, M
w/ M
n=2.4.
The uv-visible absorption spectra figure of the organic semiconductor material P3 of preparation in the present embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 552nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P3 prepared by the present embodiment 3, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 426 ℃.
Embodiment 4
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(normal butane oxygen base) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(the positive decyl phenyl of 4-)-indeno [1,2-b] thiophene } (containing the polymer P 4 of thiophene-benzene-thiophene unit):
The preparation process of the above-mentioned polymer P 4 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen protection, by 2,6-bis-tin trimethyl-4,8-bis-(n-butoxy) benzene 1,4-Dithiapentalene (198mg, 0.3mmol), two (2-bromo-4,4-bis-(the positive decyl phenyl of 4-)-indeno [1,2-b] thiophene) (464mg, 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, fully dissolve, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Stille coupling reaction 12h.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 to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, be product poly-{ 2,6-, bis-base-4,8-bis-(normal butane oxygen base) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(the positive decyl phenyl of 4-)-indeno [1,2-b] thiophene }, productive rate is 80%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 4 of thiophene-benzene-thiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=37.9kDa, M
w/ M
n=2.3.
The uv-visible absorption spectra figure of the organic semiconductor material P4 of preparation in the present embodiment 4, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 561nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P4 prepared by the present embodiment 4, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 434 ℃.
Embodiment 5
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(n-dodecane oxygen base) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-hexyl phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 5 of thiophene-benzene-thiophene unit):
The preparation process of the above-mentioned polymer P 5 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 2, 6-bis-tin trimethyl-4, 8-bis-(n-dodecane oxygen base) benzene 1,4-Dithiapentalene (226mg, 0.3mmol), two (2-bromo-4, 4-bis-(4-normal hexane base phenyl)-indeno [1, 2-b] thiophene) (319mg, 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 to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain product poly-{ 2,6-bis-base-4,8-bis-(n-dodecane oxygen base) benzene 1,4-Dithiapentalene-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-hexyl phenyl)-indeno [1,2-b] thiophene }.Productive rate is 75%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 5 of thiophene-benzene-thiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=105.3kDa, M
w/ M
n=2.2.
The uv-visible absorption spectra figure of the organic semiconductor material P5 of preparation in the present embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 563nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P5 prepared by the present embodiment 5, thermogravimetric curve (TGA) test is carried out on TA SDT 2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 437 ℃.
Use German Zahner IM6e electrochemical workstation to measure the chemical property of polymkeric substance in the embodiment of the present invention, adopt cyclic voltammetry to study the chemical property of the polymkeric substance of preparation in the embodiment of the present invention 1～embodiment 5, adopt E
g=E
lUMO-E
hOMOthe energy gap width that can calculate polymkeric substance, test result is in table 1.
Table 1
| Embodiment | HOMO(eV) | LUMO(eV) | E g（eV） |
| Embodiment 1 polymer P 1 | -5.13 | -3.57 | 1.56 |
| |
-5.03 | -3.61 | 1.42 |
| Embodiment 3 polymer Ps 3 | -5.15 | -3.55 | 1.60 |
| Embodiment 4 polymer Ps 4 | -5.38 | -3.64 | 1.70 |
| Embodiment 5 polymer Ps 5 | -5.00 | -3.52 | 1.48 |
The energy gap width of the polymkeric substance that as can be seen from Table 1, prepared by the present invention is between 1.4eV～1.7eV.
Embodiment 6
Refer to Fig. 4, a kind of solar cell 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 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
Be appreciated that buffer layer 63 can omit, now active coating 64 is directly formed at anode 62 surfaces.
The manufacturing processed of this solar cell 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, be coated with the PEDOT:PSS that last layers play modification on anode 62 surfaces 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 mono-that electron donor material is.
Form negative electrode 65 on active coating 64 surfaces.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 solar cell device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after solar cell device is annealed, can effectively increase order and the regularity between the 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 3.8% of the body heterojunction solar cell device 60 that the copolymer p 1 based in embodiment 1 is donor material.
When this solar cell device 60 uses, 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 transmit along electron acceptor material to negative electrode 65 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, when 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 (9)
1. containing a polymkeric substance for thiophene-benzene-thiophene unit, it is characterized in that thering is following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
2. a preparation method who contains the polymkeric substance of thiophene-benzene-thiophene unit, is characterized in that, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added into and in the organic solvent that contains catalyzer, carry out Stille coupling reaction, described catalyzer is organic palladium or the mixture for organic palladium and organophosphorus ligand, obtains the polymer P containing thiophene-benzene-thiophene unit that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
3. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
4. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, it is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
5. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1: 100.
6. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, the temperature of reaction of described Stille coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 6 hours ~ 60 hours.
7. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, the temperature of reaction of described Stille coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 12 hours ~ 48 hours.
8. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, it is characterized in that, also comprise the step of carrying out separation and purification containing the polymer P of thiophene-benzene-thiophene unit, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collecting chloroformic solution, evaporating solvent obtains the polymer P containing thiophene-benzene-thiophene unit after purifying.
9. a solar cell device, comprises active coating, it is characterized in that, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate, described electron donor material has the polymer P containing thiophene-benzene-thiophene unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
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Application publication date: 20140611 |