CN103897152A - Polymer containing thienothiophene unit and preparation method thereof, and solar cell device - Google Patents
Polymer containing thienothiophene unit and preparation method thereof, and solar cell device Download PDFInfo
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- CN103897152A CN103897152A CN201210578612.XA CN201210578612A CN103897152A CN 103897152 A CN103897152 A CN 103897152A CN 201210578612 A CN201210578612 A CN 201210578612A CN 103897152 A CN103897152 A CN 103897152A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- 238000006619 Stille reaction Methods 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 claims description 5
- 230000035484 reaction time Effects 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
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 2
- 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
- 229920000144 PEDOT:PSS Polymers 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000001894 space-charge-limited current method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 7
- 0 C[Sn](C)(C)c1cc(c(O*)c2[s]c([Sn](C)(C)C)cc2c2O*)c2[s]1 Chemical compound C[Sn](C)(C)c1cc(c(O*)c2[s]c([Sn](C)(C)C)cc2c2O*)c2[s]1 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000006872 improvement Effects 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
- 239000002253 acid Substances 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PFZLGKHSYILJTH-UHFFFAOYSA-N thieno[2,3-c]thiophene Chemical compound S1C=C2SC=CC2=C1 PFZLGKHSYILJTH-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 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
- -1 bromo-2-n-octyl Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000005286 illumination Methods 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
- 229930192474 thiophene Natural products 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
- 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
- PEJWNVDZTYCAGJ-UHFFFAOYSA-N COc(c1c2[s]cc1)c1[s]c([Sn](C)(C)C)cc1c2OC Chemical compound COc(c1c2[s]cc1)c1[s]c([Sn](C)(C)C)cc1c2OC PEJWNVDZTYCAGJ-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
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011521 glass Substances 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
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 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
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000011160 research Methods 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
The invention provides a polymer containing a thienothiophene unit. The polymer has a structural formula as described in the specification. In the structural formula, R1 is a C1-20 alkyl group, R2 a C1-20 alkyl group, and n is an integer in a range of 10 to 100. Specifically speaking, the thienothiophene unit included in the polymer is an electron-withdrawing sulfonyl group and an electron acceptor unit and has the advantages of a narrow band gap, a high sunlight absorption coefficient and a wide absorption range after modification by bisthiophene; dissolving performance and film forming performance of the polymer are improved through modification by an alkyl group, and the polymer has hole mobility of 10<-4> cm2/Vs, so the problem of low efficiency of a solar cell device is overcome. The invention further provides a preparation method for the polymer containing the thienothiophene unit and a solar cell device using the polymer containing the thienothiophene unit.
Description
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of polymkeric substance containing thienothiophene unit and preparation method thereof and the solar cell device that uses this containing the polymkeric substance of thienothiophene 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 thienothiophene 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 thienothiophene unit.
In addition, be also necessary to provide the solar cell device using containing the polymkeric substance of thienothiophene unit.
Containing a polymkeric substance for thienothiophene 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 thienothiophene 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 in the organic solvent that contains catalyzer, carry out Stille coupling reaction 6 hours～60 hours at 70 DEG C～130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, obtains the polymer P containing thienothiophene 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 90 DEG C ~ 120 DEG C, and the reaction times is 12 hours ~ 48 hours.
In a preferred embodiment, also comprise the step of carrying out separation and purification containing the polymer P of thienothiophene 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 thienothiophene unit after purifying.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
A kind of solar cell device, 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 thienothiophene 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.
The above-mentioned concrete electrophilic sulfonyl group of polymkeric substance containing thienothiophene unit, is electron acceptor(EA) unit, after modifying, has advantages of that band gap is narrower and sunlight is had to higher uptake factor and wider absorption region by two thiophene; The solubility property and the film forming properties that improve polymkeric substance by alkyl modified, the hole mobility of this polymkeric substance is 10
-4cm
2v
-1s
-1left and right, and then solve solar cell device low efficiency problem.
The preparation method of the above-mentioned polymkeric substance containing thienothiophene 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 the polymeric material novel structure making, solubility property is good, and film forming properties is good, applicable to solar cell device.
[brief description of the drawings]
Fig. 1 is the preparation method's of the polymkeric substance containing thienothiophene unit of an embodiment schema;
Fig. 2 is the structural representation of the solar cell device of an embodiment;
Fig. 3 is the uv-visible absorption spectra figure containing the polymkeric substance of thienothiophene unit prepared by embodiment 1;
Fig. 4 is the thermogravimetic analysis (TGA) figure containing the polymkeric substance of thienothiophene unit prepared by embodiment 1.
[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, the disclosed method of monomers B reference literature (Adv.Mater.2012, DOI:10.1002/adma.201200995.) is synthetic to be obtained.
The polymkeric substance containing thienothiophene 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 should, containing the concrete electrophilic sulfonyl group of polymkeric substance of thienothiophene unit, be electron acceptor(EA) unit, after modifying, had advantages of that band gap is narrower and sunlight is had to higher uptake factor and wider absorption region by two thiophene; The solubility property and the film forming properties that improve polymkeric substance by alkyl modified, the hole mobility of this polymkeric substance is 10
-4cm
2v
-1s
-1left and right, thus solar cell device low efficiency problem solved.
The preparation method of the polymkeric substance containing thienothiophene 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 thienothiophene unit.
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added in the organic solvent that contains catalyzer, carry out Stille coupling reaction 6 hours～60 hours at 70 DEG C～130 DEG C, described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains the polymer P containing thienothiophene 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 organophosphor ligand, the mol ratio of organic palladium and organophosphor 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, organophosphor 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 DEG C ~ 130 DEG C, and the reaction times is 12 hours ~ 96 hours.Preferably, the temperature of reaction of Stille coupling reaction is 90 DEG C ~ 120 DEG C, and the reaction times is 24 hours ~ 72 hours.The temperature of reaction that is appreciated that Stille coupling reaction is not limited to 70 DEG C ~ 130 DEG C, as long as can make compd A and compd B react; Reaction times is also not limited to 12 hours ~ and 96 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 thienothiophene 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 thienothiophene 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 thienothiophene unit after purifying under vacuum 50 DEG C～70 DEG C dry 24 hours～48 hours.
The preparation method of the above-mentioned polymkeric substance containing thienothiophene 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 thienothiophene 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-n-octyl alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases } (containing the polymer P 1 of thienothiophene unit):
The preparation process of the above-mentioned polymer P 1 containing thienothiophene 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), 2, the bromo-2-n-octyl of 6-bis-alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3,4-b] thiophene (128mg, 0.2mmol) add in the flask that fills 10ml toluene solvant, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 DEG C 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 taking 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-n-octyl alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3,4-b] thiophene-2; 6-bis-bases }, productive rate 83%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 1 of thienothiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=63.4kDa, M
w/ M
n=2.2.
Referring to accompanying drawing 3, be the uv-visible absorption spectra figure of the polymer P 1 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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 572nm, wide absorption spectrum shows that polymer P 1 is a kind of photovoltaic material.
Referring to accompanying drawing 4, be the thermogravimetic analysis (TGA) figure of the polymer P 1 prepared of the present embodiment 1, thermogravimetric curve (TGA) test is carried out on TA SDT2960 instruments, 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 428 DEG C.
Taking ITO/PEDOT:PSS/ the present embodiment 1 polymer P 1/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 1 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 5.3 × 10
-4cm
2/ Vs.
Embodiment 2
The present embodiment disclose structural formula following poly-{ 2; 6-bis-base-4,8-bis-(methoxyl group) benzene 1,4-Dithiapentalene-co-2-NSC 62789 base alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases } (containing the polymer P 2 of thienothiophene unit):
The preparation process of the above-mentioned polymer P 2 containing thienothiophene 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), 2, the bromo-2-NSC 62789 base of 6-bis-alkylsulfonyl-4, 6-bis-(thiophene-2-yl) thieno-[3, 4-b] thiophene (242mg, 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 heated to 70 DEG C and carries 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 taking chloroform as solvent extraction to colourless; collect chloroformic solution and be spin-dried for and obtain red solid; after collection, under vacuum, after 50 DEG C of dry 24h, obtain product poly-{ 2; 6-bis-base-4; 8-bis-(methoxyl group) benzene 1,4-Dithiapentalene-co-2-NSC 62789 base alkylsulfonyl-4; 6-bis-(thiophene-2-yl) thieno-[3,4-b] thiophene-2,6-bis-bases }.Productive rate is 76%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 2 of thienothiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=48.1kDa, M
w/ M
n=2.3.
The uv-visible absorption spectra figure of the polymer P 2 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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 570nm.
The thermogravimetic analysis (TGA) of polymer P 2 prepared by the present embodiment 2, thermogravimetric curve (TGA) test is carried out on TASDT 2960 instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 416 DEG C.
Taking ITO/PEDOT:PSS/ the present embodiment 2 polymer P 2/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 2 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 6.0 × 10
-4cm
2/ Vs.
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-methyl sulphonyl-4,6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases } (containing the polymer P 3 of thienothiophene unit):
The preparation process of the above-mentioned polymer P 3 containing thienothiophene 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), 2, the bromo-2-of 6-bis-methyl sulphonyl-4,6-bis-(thiophene-2-yl) thieno-[3,4-b] thiophene (178mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) 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 130 DEG C 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 taking chloroform as solvent extraction to colourless; collect chloroformic solution and be spin-dried for and obtain red powder; after collection under vacuum after 50 DEG C of dry 24h; be product poly-{ 2,6-, bis-base-4,8-bis-(NSC 62789 oxygen base) benzene 1,4-Dithiapentalene-co-2-methyl sulphonyl-4; 6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases }, productive rate is 78%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 3 of thienothiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=13.6kDa, M
w/ M
n=2.4.
The uv-visible absorption spectra figure of the polymer P 3 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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 576nm.
The thermogravimetic analysis (TGA) of polymer P 3 prepared by the present embodiment 3, thermogravimetric curve (TGA) test is carried out on TASDT 2960 instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 414 DEG C.
Taking ITO/PEDOT:PSS/ the present embodiment 3 polymer P 3/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 3 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 5.1 × 10
-4cm
2/ Vs.
Embodiment 4
The present embodiment disclose structural formula following poly-{ 2; 6-bis-base-4,8-bis-(normal butane oxygen base) the positive decyl of benzene 1,4-Dithiapentalene-co-2-alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases } (containing the polymer P 4 of thienothiophene unit):
The preparation process of the above-mentioned polymer P 4 containing thienothiophene 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), 2, the positive decyl of the bromo-2-of 6-bis-alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3,4-b] thiophene (240mg, 0.36mmol), three or two argon benzyl acetone two palladiums (9mg, 0.009mmol) and 2-dicyclohexyl phosphines-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) 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 120 DEG C and carries out Stille coupling reaction 36h.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 taking chloroform as solvent extraction to colourless; collect chloroformic solution and be spin-dried for and obtain red powder; after collection under vacuum after 50 DEG C of dry 24h; be product poly-{ 2,6-, bis-base-4,8-bis-(normal butane oxygen base) the positive decyl of benzene 1,4-Dithiapentalene-co-2-alkylsulfonyl-4; 6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases }, productive rate is 87%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 4 of thienothiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=84.7kDa, M
w/ M
n=2.0.
The uv-visible absorption spectra figure of the polymer P 4 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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 577nm.
The thermogravimetic analysis (TGA) of polymer P 4 prepared by the present embodiment 4, thermogravimetric curve (TGA) test is carried out on TASDT 2960 instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 430 DEG C.
Taking ITO/PEDOT:PSS/ the present embodiment 4 polymer P 4/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 4 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 6.5 × 10
-4cm
2/ Vs.
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-n-hexyl alkylsulfonyl-4,6-bis-(thiophene-2-yl) thieno-[3; 4-b] thiophene-2,6-bis-bases } (containing the polymer P 5 of thienothiophene unit):
The preparation process of the above-mentioned polymer P 5 containing thienothiophene 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), 2, the bromo-2-n-hexyl of 6-bis-alkylsulfonyl-4, 6-bis-(thiophene-2-yl) thieno-[3, 4-b] thiophene (183mg, 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, pass into after the about 10min of gas mixture air-discharging of nitrogen and argon gas, two-mouth bottle is heated to 90 DEG C and carries 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 taking chloroform as solvent extraction to colourless; collect chloroformic solution and be spin-dried for and obtain red solid; after collection, under vacuum, after 50 DEG C of dry 24h, obtain product poly-{ 2; 6-bis-base-4; 8-bis-(n-dodecane oxygen base) benzene 1,4-Dithiapentalene-co-2-n-hexyl alkylsulfonyl-4; 6-bis-(thiophene-2-yl) thieno-[3,4-b] thiophene-2,6-bis-bases }.Productive rate is 84%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 5 of thienothiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=63.1kDa, M
w/ M
n=2.1.
The uv-visible absorption spectra figure of the polymer P 5 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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 573nm.
The thermogravimetic analysis (TGA) of polymer P 5 prepared by the present embodiment 5, thermogravimetric curve (TGA) test is carried out on TASDT 2960 instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T
d) be 425 DEG C.
Taking ITO/PEDOT:PSS/ the present embodiment 5 polymer P 5/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 5 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 6.1 × 10
-4cm
2/ Vs.
Embodiment 6
Refer to Fig. 2, 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, and electron donor material is the P1 of preparation in embodiment mono-.
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 4.2% 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 (8)
1. containing a polymkeric substance for thienothiophene 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 thienothiophene 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 in the organic solvent that contains catalyzer, carry out Stille coupling reaction 6 hours～60 hours at 70 DEG C～130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, obtains the polymer P containing thienothiophene unit that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
3. the preparation method of the polymkeric substance containing thienothiophene 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 thienothiophene 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 thienothiophene 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 thienothiophene unit according to claim 2, is characterized in that, the temperature of reaction of described Stille coupling reaction is 90 DEG C ~ 120 DEG C, and the reaction times is 12 hours ~ 48 hours.
7. the preparation method of the polymkeric substance containing thienothiophene 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 thienothiophene 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 thienothiophene unit after purifying.
8. 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 thienothiophene 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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| US20050124784A1 (en) * | 2003-10-01 | 2005-06-09 | Sotzing Gregory A. | Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof |
| US20070008603A1 (en) * | 2005-07-11 | 2007-01-11 | Sotzing Gregory A | Electrochromic devices utilizing very low band gap conjugated counter electrodes: preparation and use |
| US20090127491A1 (en) * | 2005-08-18 | 2009-05-21 | Nissan Chemical Industries, Ltd. | Thiophene compound having sulfonyl group and process for producing the same |
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2012
- 2012-12-27 CN CN201210578612.XA patent/CN103897152A/en active Pending
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| US20050124784A1 (en) * | 2003-10-01 | 2005-06-09 | Sotzing Gregory A. | Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof |
| US20070008603A1 (en) * | 2005-07-11 | 2007-01-11 | Sotzing Gregory A | Electrochromic devices utilizing very low band gap conjugated counter electrodes: preparation and use |
| US20090127491A1 (en) * | 2005-08-18 | 2009-05-21 | Nissan Chemical Industries, Ltd. | Thiophene compound having sulfonyl group and process for producing the same |
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| YE HUANG ET AL.: ""Improving the Ordering and photovoltaic properties by extending π-conjugated area of electron-donating units in polymers with D-A structure"", 《ADVENCE MATERIALS》 * |
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