CN105601889A - Preparation method of polymer containing dithiophene benzothiadiazole unit - Google Patents

Preparation method of polymer containing dithiophene benzothiadiazole unit Download PDF

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CN105601889A
CN105601889A CN201610114355.2A CN201610114355A CN105601889A CN 105601889 A CN105601889 A CN 105601889A CN 201610114355 A CN201610114355 A CN 201610114355A CN 105601889 A CN105601889 A CN 105601889A
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bithiophene benzthiadiazole
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CN105601889B (en
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不公告发明人
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Shandong Huayu Zhongchi Medical Technology Co ltd
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Abstract

The invention provides a polymer containing a dithiophene benzothiadiazole unit. The polymer has the following structural formula (please see the formula in the description), wherein R represents alkyl groups of C1-C20, and n is an integer ranging from 10 to 100. A donor-receptor type conjugated polymer is adopted as the dithiophene benzothiadiazole-based polymer, the polymer has the higher hole mobility, high open-circuit voltage, the better solubility property and film-forming property and the wider absorption range within the range of 300 nm-800 nm, and therefore the low-efficiency problem of a solar battery component is solved. The invention further provides a preparation method of the polymer containing the dithiophene benzothiadiazole unit and the solar battery component using the polymer containing the dithiophene benzothiadiazole unit.

Description

Contain the preparation method of the polymer of bithiophene benzthiadiazole unit
Contain the preparation method of the polymer of bithiophene benzthiadiazole unit
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of preparation method of the polymer containing bithiophene benzthiadiazole unit.
[background technology]
Since Japanese scientist's Hideki Shirakawa in 1977 is found polyacetylene conduction, this being called as the conducting polymer of " the 4th generation macromolecule " material attracted numerous scientists to study with its outstanding photoelectric properties. Conducting polymer is compared with the inorganic material 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 widely application impel scientist competitively to study this class to have the conjugation material of photoelectric activity, comprise the little molecule of conjugated structure, and polyacetylene, polypyrrole, polythiophene, polyaniline, poly-fluorenes etc.
Researcher 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 light emitting polymer that long-time stability are good, and the polymer that visible-range absorption bands is wide, carrier mobility is high. Realize these targets, need to develop more novel conjugated molecular material and polymeric material, wherein, design synthesizing new conjugate unit just seems very important.
[summary of the invention]
Based on this, be necessary the polymer containing bithiophene benzthiadiazole unit that provides a kind of energy conversion efficiency higher.
In addition, be also necessary to provide a kind of preparation method of the polymer containing bithiophene benzthiadiazole unit.
In addition, be also necessary to provide the solar cell device using containing the polymer of bithiophene benzthiadiazole unit.
Containing a polymer for bithiophene benzthiadiazole unit, there is following structural formula:
Wherein, R is C1～C20Alkyl, the integer that n is 10～100.
A preparation method who contains the polymer of bithiophene benzthiadiazole unit, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:B is:Wherein, R is C1～C20Alkyl;
In oxygen-free environment, the compd A and the compd B that are 1: 1～1: 1.2 by mol ratio are added in the organic solvent that contains catalyst, carry out Stille coupled reaction 6 hours～60 hours at 70 DEG C～130 DEG C, described catalyst is organic palladium or the mixture for organic palladium and organophosphor ligand, obtains the polymer P containing bithiophene benzthiadiazole unit that following structural formula represents:
Wherein, the integer that n is 10～100.
Described organic solvent is selected from least one in toluene, DMF and oxolane.
Described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand be 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.
Organic palladium in described catalyst and the mol ratio of described compd A are 1: 20～1: 100.
The reaction temperature of described Stille coupled reaction is 90 DEG C～120 DEG C, and the reaction time is 12 hours～48 hours.
Also comprise the step of carrying out separation and purification containing the polymer P of bithiophene benzthiadiazole unit, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupled reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and n-hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing bithiophene benzthiadiazole unit after purifying.
Described extracting adopts apparatus,Soxhlet's to carry out.
A kind of solar cell device, comprises active layer, and described active layer comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C61-methyl butyrate or [6,6]-phenyl-C71-methyl butyrate, described electron donor material has the polymer P containing bithiophene benzthiadiazole unit of following structural formula:
Wherein, R is C1～C20Alkyl, the integer that n is 10～100.
The mol ratio of electron donor material and described electron acceptor material is 1: 2～1: 5.
The above-mentioned polymer containing bithiophene benzthiadiazole unit is donor-receiver type conjugated polymer, it has higher hole mobility, high open-circuit voltage, solubility property and filming performance preferably, within the scope of 300nm～800nm, there is wider absorption region, be a kind of well behaved polymer luminescent material, and then solve solar cell device low efficiency problem.
The preparation method of the above-mentioned polymer containing bithiophene benzthiadiazole unit, has adopted better simply synthetic route, thereby reduces technological process, and raw material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and filming performance is good, applicable to solar cell device.
[brief description of the drawings]
Fig. 1 is the preparation method's of the polymer containing bithiophene benzthiadiazole unit of an embodiment flow chart;
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 polymer of bithiophene benzthiadiazole unit prepared by embodiment 1;
Fig. 4 is the thermogravimetic analysis (TGA) figure containing the polymer of bithiophene benzthiadiazole unit prepared by embodiment 1.
[detailed description of the invention]
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, and monomers B is bought and obtained from the market.
The polymer containing bithiophene benzthiadiazole unit of one embodiment, has following structural formula:
Wherein, R is C1～C20Alkyl, the integer that n is 10～100.
Above-mentioned should be donor-receiver type conjugated polymer containing the polymer of bithiophene benzthiadiazole unit, it has higher hole mobility, high open-circuit voltage, solubility property and filming performance preferably, within the scope of 300nm～800nm, there is wider absorption region, be a kind of well behaved polymer luminescent material, thereby solve solar cell device low efficiency problem.
The preparation method of the polymer containing bithiophene benzthiadiazole 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, the alkyl that R is C1～C20.
The structural formula of compd B is:
Step S2, preparation contain the polymer P of bithiophene benzthiadiazole unit.
In oxygen-free environment, the compd A and the compd B that are 1: 1～1: 1.2 by mol ratio are added in the organic solvent that contains catalyst, carry out Stille coupled reaction 6 hours～60 hours at 70 DEG C～130 DEG C, described catalyst is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains the polymer P containing bithiophene benzthiadiazole unit that following structural formula represents:
Wherein, the integer that n is 10～100.
In present embodiment, Stille coupled reaction carries out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least one in toluene, DMF and oxolane. 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 catalyst. 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 coupled reaction.
In present embodiment, in catalyst, 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～and 1: 100, to adding the catalyst that adds catalytic amount in the organic solvent of compd A and compd B.
In present embodiment, the reaction temperature of Stille coupled reaction is 70 DEG C～130 DEG C, and the reaction time is 6 hours～60 hours. Preferably, the reaction temperature of Stille coupled reaction is 90 DEG C～120 DEG C, and the reaction time is 12 hours～48 hours. The reaction temperature that is appreciated that Stille coupled reaction is not limited to 70 DEG C～130 DEG C, as long as can make compd A and compd B react; Reaction time is also not limited to 12 hours～and 48 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 bithiophene benzthiadiazole unit.
Carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupled reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and n-hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing bithiophene benzthiadiazole unit after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, obtain the polymer P containing bithiophene benzthiadiazole unit after purifying under vacuum 50 DEG C～70 DEG C, dry 24 hours～48 hours by collecting evaporating solvent after chloroformic solution.
The preparation method of the above-mentioned polymer containing bithiophene benzthiadiazole unit, synthetic route is comparatively simple, has reduced manufacturing cost.
A kind of solar cell device in one embodiment, comprises active layer, and described active layer comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C61-methyl butyrate or [6,6]-phenyl-C71-methyl butyrate, described electron donor material has the polymer P containing bithiophene benzthiadiazole unit of following structural formula:
Wherein, R is C1～C20Alkyl, the integer that n is 10～100.
In a preferred embodiment, the mol ratio of electron donor material and described electron acceptor material is 1: 2～1: 5.
Be specific embodiment below.
Embodiment 1
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(5-normal octane base thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (containing the polymer P 1 of bithiophene benzthiadiazole unit):
The preparation process of the above-mentioned polymer P 1 containing bithiophene benzthiadiazole unit is as follows:
Under argon shield, by 2,6-bis-tin trimethyl-4,8-bis-(5-normal octane base thiophene) benzene 1,4-Dithiapentalene (181mg, 0.2mmol), 4,7-bis-(5-bromothiophene-2-yl) diazosulfide (92mg, 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 coupled reaction 36h. Subsequently, after cooling, stop polymerisation, in 50ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and n-hexane extracting 24h. Then taking chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, under vavuum pump, taking out spends the night obtains product poly-{ 2,6-bis-base-4,8-bis-(5-normal octane base thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide }, productive rate 78%.
Above-mentioned preparation is as follows containing the reaction equation of the polymer P 1 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): Mn＝36.8kDa，Mw/Mn＝2.2。
Referring to accompanying drawing 3, be the uv-visible absorption spectra figure of the organic semiconducting materials P1 of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer. As seen from the figure: polymer of the present invention between 300nm～800nm, have large wider absorption wherein maximum absorption band be positioned at 573nm, wide absorption spectrum shows that P1 is a kind of photovoltaic material.
Referring to accompanying drawing 4, be the thermogravimetic analysis (TGA) figure of the organic semiconducting materials P1 for preparing of the present embodiment 1, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen air-flow protection, programming rate is 10K/min. 5% thermal weight loss temperature (T as seen from the figured) be 464 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 hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination polymer, the hole mobility that obtains polymer is 5.7 × 10-5cm2/Vs。
Embodiment 2
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(5-methyl thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (containing the polymer P 2 of bithiophene benzthiadiazole unit):
The preparation process of the above-mentioned polymer P 2 containing bithiophene benzthiadiazole unit is as follows:
Under nitrogen and the protection of argon gas gaseous mixture, by 2, 6-bis-tin trimethyl-4, 8-bis-(5-methylthiophene) benzene 1,4-Dithiapentalene (212mg, 0.3mmol), 4, 7-bis-(5-bromothiophene-2-yl) diazosulfide (137mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL oxolane, after fully dissolving, pass into after the about 20min of gaseous mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein again after the about 10min of gaseous mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 DEG C and carry out Stille coupled reaction 60h. subsequently, after cooling, stop polymerisation, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and n-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-(5-methyl thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide }. productive rate is 82%.
Above-mentioned preparation is as follows containing the reaction equation of the polymer P 2 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): Mn＝27.1kDa，Mw/Mn＝2.3。
The uv-visible absorption spectra figure of the organic semiconducting materials P2 of preparation in the present embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer. As seen from the figure: polymer of the present invention between 300nm～800nm, have large wider absorption, wherein maximum absorption band is positioned at 572nm.
The thermogravimetic analysis (TGA) of organic semiconducting materials P2 prepared by the present embodiment 2, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen air-flow protection, programming rate is 10K/min. 5% thermal weight loss temperature (Td) be 478 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 hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination polymer, the hole mobility that obtains polymer is 6.2 × 10-5cm2/Vs。
Embodiment 3
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(5-n-eicosane base thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (containing the polymer P 3 of bithiophene benzthiadiazole unit):
The preparation process of the above-mentioned polymer P 3 containing bithiophene benzthiadiazole unit is as follows:
Under nitrogen protection, by 2,6-bis-tin trimethyl-4,8-bis-(5-n-eicosane base thiophene) benzene 1,4-Dithiapentalene (372mg, 0.3mmol), 4,7-bis-(the bromo-4-methylthiophene-2-of 5-yl) benzo [1,2,5] thiadiazoles (153mg, 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 coupled reaction 12h. Subsequently, after cooling, stop polymerisation, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and n-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-(5-n-eicosane base thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide }, productive rate is 70%.
Above-mentioned preparation is as follows containing the reaction equation of the polymer P 3 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): Mn＝31.5kDa，Mw/Mn＝2.2。
The uv-visible absorption spectra figure of the organic semiconducting materials P3 of preparation in the present embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer. As seen from the figure: polymer of the present invention between 300nm～800nm, have large wider absorption, wherein maximum absorption band is positioned at 575nm.
The thermogravimetic analysis (TGA) of organic semiconducting materials P3 prepared by the present embodiment 3, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen air-flow protection, programming rate is 10K/min. 5% thermal weight loss temperature (Td) be 449 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 hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination polymer, the hole mobility that obtains polymer is 6.0 × 10-5cm2/Vs。
Embodiment 4
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(5-normal butane base thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (containing the polymer P 4 of bithiophene benzthiadiazole unit):
The preparation process of the above-mentioned polymer P 4 containing bithiophene benzthiadiazole unit is as follows:
Under nitrogen protection, by 2,6-bis-tin trimethyl-4,8-bis-(the positive two butane group thiophene of 5-) benzene 1,4-Dithiapentalene (238mg, 0.3mmol), 4,7-bis-(the bromo-4-n-decane of 5-base thiophene-2-yl) benzo [1,2,5] thiadiazoles (266mg, 0.36mmol), three or two argon benzylacetone two palladiums (9mg, 0.009mmol) and 2-dicyclohexyl phosphine-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 90 DEG C and carries out Stille coupled reaction 24h. Subsequently, after cooling, stop polymerisation, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and n-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-(5-normal butane base thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide }, productive rate is 81%.
Above-mentioned preparation is as follows containing the reaction equation of the polymer P 4 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): Mn＝74.6kDa，Mw/Mn＝2.0。
The uv-visible absorption spectra figure of the organic semiconducting materials P4 of preparation in the present embodiment 4, uv-visible absorption spectra is measured on Jasco-570 uv analyzer. As seen from the figure: polymer of the present invention between 300nm～800nm, have large wider absorption, wherein maximum absorption band is positioned at 570nm.
The thermogravimetic analysis (TGA) of organic semiconducting materials P4 prepared by the present embodiment 4, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen air-flow protection, programming rate is 10K/min. 5% thermal weight loss temperature (Td) be 473 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 hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination polymer, the hole mobility that obtains polymer is 6.0 × 10-5cm2/Vs。
Embodiment 5
The present embodiment disclose structural formula following poly-{ 2,6-bis-base-4,8-bis-(5-dodecyl thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide } (containing the polymer P 5 of bithiophene benzthiadiazole unit):
The preparation process of the above-mentioned polymer P 5 containing bithiophene benzthiadiazole unit is as follows:
Under nitrogen and the protection of argon gas gaseous mixture, by 2, 6-bis-tin trimethyl-4, 8-bis-(5-dodecyl thiophene) benzene 1,4-Dithiapentalene (305mg, 0.3mmol), 4, 7-bis-(the bromo-4-n-hexane of 5-base thiophene-2-yl) benzo [1, 2, 5] thiadiazoles (188mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gaseous 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 gaseous mixture air-discharging of nitrogen and argon gas, two-mouth bottle is joined to 90 DEG C and carry out Stille coupled reaction 48h. subsequently, after cooling, stop polymerisation, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and n-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-(5-dodecyl thiophene) benzene 1,4-Dithiapentalene-co-4,7-bis-(5-base-thiophene-2-yl) diazosulfide }. productive rate is 75%.
Above-mentioned preparation is as follows containing the reaction equation of the polymer P 5 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): Mn＝52.0kDa，Mw/Mn＝2.1。
The uv-visible absorption spectra figure of the organic semiconducting materials P5 of preparation in the present embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer. As seen from the figure: polymer of the present invention between 300nm～800nm, have large wider absorption, wherein maximum absorption band is positioned at 556nm.
The thermogravimetic analysis (TGA) of organic semiconducting materials P5 prepared by the present embodiment 5, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen air-flow protection, programming rate is 10K/min. 5% thermal weight loss temperature (Td) be 454 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 hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopting the hole mobility of space charge limited current (SCLC) model determination polymer, the hole mobility that obtains polymer is 7.1 × 10-5cm2/Vs。
Embodiment 6
Refer to Fig. 2, a kind of solar cell device 60 comprises substrate 61, anode 62, cushion 63, active layer 64 and negative electrode 65. Anode 62, cushion 63, active layer 64 and negative electrode 65 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61. In the present embodiment, anode 62 is for being ITO (tin indium oxide), and preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/.
Cushion 63 is formed at the side surface of anode 62 away from substrate 61. The material of cushion 63 is poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid composite (PEDOT:PSS).
Active layer 64 is formed at the side surface of cushion 63 away from anode 62. Active layer 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1: 2, and wherein electron acceptor material is (6,6) phenyl-C61-methyl butyrate (PCBM), electron donor material is the polymer P containing bithiophene benzthiadiazole unit prepared by the present invention, in present embodiment, the P1 of preparation in the embodiment mono-that electron donor material is.
Negative electrode 65 is formed at the side surface of active layer 64 away from cushion 63. Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 100nm. In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
Be appreciated that cushion 63 can omit, now active layer 64 is directly formed at anode 62 surfaces.
The manufacture process 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 cushion 63.
On cushion 64, apply one deck active layer 64. This active layer 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 layer 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 airtight 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/cm2Under illumination, the energy conversion efficiency 3.6% 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 layer 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor/acceptor material again, and electronics is transferred to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form 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 material 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 (6)

1. a preparation method who contains the polymer of bithiophene benzthiadiazole unit, is characterized in that, comprisesFollowing steps:
The compd A and the compd B that provide following structural formula to represent,
A is:B is:Wherein, R is C1～C20Alkyl;
In oxygen-free environment, be that the compd A of 1: 1～1: 1.2 and compd B are added into contain and urge by mol ratioIn the organic solvent of agent, carry out Stille coupled reaction 6 hours～60 hours at 70 DEG C～130 DEG C, described inCatalyst is organic palladium or the mixture for organic palladium and organophosphor ligand, and what obtain that following structural formula represents containsThe polymer P of bithiophene benzthiadiazole unit:
Wherein, the integer that n is 10～100.
2. the preparation method of the polymer containing bithiophene benzthiadiazole unit according to claim 1,It is characterized in that, described organic solvent is selected from toluene, DMF and oxolane at leastA kind of.
3. the preparation method of the polymer containing bithiophene benzthiadiazole unit according to claim 1,It is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or threeDibenzalacetone two palladiums, described organophosphorus ligand is that tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclo are ownBase phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1: 4～1: 8.
4. the preparation method of the polymer containing bithiophene benzthiadiazole unit according to claim 1,It is characterized in that, the organic palladium in described catalyst and the mol ratio of described compd A are 1: 20～1: 100.
5. the preparation method of the polymer containing bithiophene benzthiadiazole unit according to claim 1,It is characterized in that, the reaction temperature of described Stille coupled reaction is 90 DEG C～120 DEG C, and the reaction time is 12 littleTime～48 hour.
6. the preparation method of the polymer containing bithiophene benzthiadiazole unit according to claim 1,It is characterized in that, also comprise the step of carrying out separation and purification containing the polymer P of bithiophene benzthiadiazole unitSuddenly, described purification procedures is as follows: carry out Stille coupled reaction to described compd A and compd BAfter solution in add methyl alcohol precipitating and filter, the solid that filtration is obtained carries out with methyl alcohol and n-hexane successivelyExtracting, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains after purifyingContaining the polymer P of bithiophene benzthiadiazole unit.
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