CN103965445A - Polymer containing dithiophen benzothiadiazole unit and preparation method thereof, and solar cell device - Google Patents

Polymer containing dithiophen benzothiadiazole unit and preparation method thereof, and solar cell device Download PDF

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CN103965445A
CN103965445A CN201310038496.7A CN201310038496A CN103965445A CN 103965445 A CN103965445 A CN 103965445A CN 201310038496 A CN201310038496 A CN 201310038496A CN 103965445 A CN103965445 A CN 103965445A
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unit
polymer
preparation
polymkeric substance
bithiophene benzthiadiazole
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CN103965445B (en
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周明杰
王平
张振华
黄辉
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Pizhou Shunbang Biotechnology Co ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201610114355.2A priority patent/CN105601889B/en
Priority to CN201610115300.3A priority patent/CN105585693B/en
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Abstract

The invention provides a polymer containing a dithiophen benzothiadiazole unit, wherein the polymer has the following structure general, R is C1-C20 alkyl, and n is an integer of 10-100. The dithiophen benzothiadiazole base polymer is a donor-acceptor type conjugated polymer, has characteristics of high hole mobility, high open circuit voltage, good solubility and good film-forming property, and has a wide absorption range in a 300-800 nm range so as to solve the problem of low efficiency of the solar cell device. The present invention further provides a preparation method for the polymer containing the dithiophen benzothiadiazole unit, and a solar cell device using the polymer containing the dithiophen benzothiadiazole unit.

Description

Containing polymkeric substance of bithiophene benzthiadiazole unit and preparation method thereof and solar cell device
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of polymkeric substance containing bithiophene benzthiadiazole unit and preparation method thereof and the solar cell device that uses this containing the polymkeric substance of bithiophene benzthiadiazole 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 with its outstanding photoelectric properties, attracted numerous scientists to study.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 the conjugation material that this class has 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 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 polymkeric substance containing bithiophene benzthiadiazole unit.
In addition, be also necessary to provide the solar cell device using containing the polymkeric substance of bithiophene benzthiadiazole unit.
A polymkeric substance containing bithiophene benzthiadiazole unit, has following structural formula:
Wherein, R is C 1~ C 20alkyl, the integer that n is 10 ~ 100.
A preparation method who contains the polymkeric substance 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 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, at 70 ℃～130 ℃, carry out Stille coupling reaction 6 hours～60 hours, described catalyzer is organic palladium or is the mixture of 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 tetrahydrofuran (THF).
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.
Organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1: 100.
The temperature of reaction of described Stille coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 12 hours ~ 48 hours.
Also comprise the step that the polymer P containing bithiophene benzthiadiazole unit is carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction, 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 bithiophene benzthiadiazole unit after purifying.
Described extracting adopts apparatus,Soxhlet's to carry out.
A 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 bithiophene benzthiadiazole unit of following structural formula:
Wherein, R is C 1~ C 20alkyl, 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 polymkeric substance containing bithiophene benzthiadiazole unit is donor-receiver type conjugated polymers, it has higher hole mobility, high open circuit voltage, good solubility property and film forming properties, 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 polymkeric substance containing bithiophene benzthiadiazole 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 containing the polymkeric substance of bithiophene benzthiadiazole 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 of the polymkeric substance containing bithiophene benzthiadiazole unit of embodiment 1 preparation;
Fig. 4 is the thermogravimetic analysis (TGA) figure of the polymkeric substance containing bithiophene benzthiadiazole unit of embodiment 1 preparation.
[embodiment]
In order to understand better the content of patent of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein monomer A is bought and is obtained from the market, and monomers B is bought and obtained from the market.
The polymkeric substance containing bithiophene benzthiadiazole unit of one embodiment, has following structural formula:
Wherein, R is C 1~ C 20alkyl, the integer that n is 10 ~ 100.
Above-mentioned should be donor-receiver type conjugated polymers containing the polymkeric substance of bithiophene benzthiadiazole unit, it has higher hole mobility, high open circuit voltage, good solubility property and film forming properties, 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 polymkeric substance 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, R is C 1~ C 20alkyl.
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 that is 1:1 ~ 1:1.2 by mol ratio and compd B are added in the organic solvent that contains catalyzer, at 70 ℃～130 ℃, carry out Stille coupling reaction 6 hours～60 hours, described catalyzer 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 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 ℃ ~ 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 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.
To described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction, 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 bithiophene benzthiadiazole unit after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collecting evaporating solvent after chloroformic solution, obtain the polymer P containing bithiophene benzthiadiazole unit after purifying under vacuum 50 ℃～70 ℃, dry 24 hours～48 hours.
The preparation method of the above-mentioned polymkeric substance containing bithiophene benzthiadiazole 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 bithiophene benzthiadiazole unit of following structural formula:
Wherein, R is C 1~ C 20alkyl, 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 discloses following poly-{ 2,6-, bis-base-4,8-bis-(5-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) of structural formula:
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-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 ℃ and carries out Stille coupling reaction 36h.Subsequently, after cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, and under vacuum pump, taking out spends the night obtains product poly-{ 2,6-bis-base-4,8-bis-(5-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 formula of the polymer P 1 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=36.8kDa, M w/ M n=2.2.
Referring to accompanying drawing 3, 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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is 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 semiconductor material P1 of the present embodiment 1 preparation, 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 464 ℃.
ITO/PEDOT:PSS/ the present embodiment 1 polymer P 1/Au of take is 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 adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 5.7 * 10 -5cm 2/ Vs.
Embodiment 2
The present embodiment discloses 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) of structural formula:
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 gas mixture; by 2; 6-bis-tin trimethyl-4; 8-bis-(5-thiotolene) 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 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 is 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-(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 formula of the polymer P 2 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=27.1kDa, M w/ M n=2.3.
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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 572nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material P2 of the present embodiment 2 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT 2960 instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T d) be 478 ℃.
ITO/PEDOT:PSS/ the present embodiment 2 polymer P 2/Au of take are 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 adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 6.2 * 10 -5cm 2/ Vs.
Embodiment 3
The present embodiment discloses following poly-{ 2,6-, bis-base-4,8-bis-(5-NSC 62789 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) of structural formula:
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-NSC 62789 base thiophene) benzene 1,4-Dithiapentalene (372mg, 0.3mmol), 4,7-bis-(the bromo-4-thiotolene-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 ℃ 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 is 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-(5-NSC 62789 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 formula of the polymer P 3 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=31.5kDa, M w/ M n=2.2.
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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 575nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material P3 of the present embodiment 3 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT 2960 instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T d) be 449 ℃.
ITO/PEDOT:PSS/ the present embodiment 3 polymer P 3/Au of take are 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 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 -5cm 2/ Vs.
Embodiment 4
The present embodiment discloses 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) of structural formula:
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 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 90 ℃ and carries out Stille coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, 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 formula of the polymer P 4 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=74.6kDa, M w/ M n=2.0.
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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 570nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material P4 of the present embodiment 4 preparations, 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 473 ℃.
ITO/PEDOT:PSS/ the present embodiment 4 polymer P 4/Au of take are 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 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 -5cm 2/ Vs.
Embodiment 5
The present embodiment discloses 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) of structural formula:
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 gas 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-normal 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 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 joined to 90 ℃ and carry out Stille coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ 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 formula of the polymer P 5 of bithiophene benzthiadiazole unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=52.0kDa, M w/ M n=2.1.
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 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 556nm.
The thermogravimetic analysis (TGA) of the organic semiconductor material P5 of the present embodiment 5 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature (T d) be 454 ℃.
ITO/PEDOT:PSS/ the present embodiment 5 polymer P 5/Au of take are 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 adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility that obtains polymkeric substance is 7.1 * 10 -5cm 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.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 is for being ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/.
Buffer layer 63 is formed at anode 62 away from a side surface of substrate 61.The material of buffer layer 63 is poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (PEDOT:PSS).
Active coating 64 is formed at buffer layer 63 away from a side surface of anode 62.Active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2, and wherein electron acceptor material is (6,6) phenyl-C 61-methyl-butyrate (PCBM), electron donor material 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 active coating 64 away from a side surface of buffer layer 63.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 100nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
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, on anode 62 surfaces, be coated with the PEDOT:PSS that last layers play modification and form buffer layer 63.
On buffer layer 64, apply one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, the P1 of preparation in the embodiment mono-that electron donor material is.
On active coating 64 surfaces, form negative electrode 65.In present embodiment, the aluminium lamination of negative electrode 65 for being formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this 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 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 3.6% 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 is used, under illumination, light transmission substrate 61 and anode 62, the conduction hole type electroluminescent material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to negative electrode 65, transmit and be collected by negative electrode, transmit and collected by anode 62 along electron donor material anode 62 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, be convenient to large batch of preparation.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (9)

1. containing a polymkeric substance for bithiophene benzthiadiazole unit, it is characterized in that thering is following structural formula:
Wherein, R is C 1~ C 20alkyl, the integer that n is 10 ~ 100.
2. contain a preparation method for the polymkeric substance of bithiophene benzthiadiazole unit, it is characterized in that, comprise the steps:
The compd A and the compd B that provide following structural formula to represent,
A is: b is:
Wherein, R is 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, at 70 ℃～130 ℃, carry out Stille coupling reaction 6 hours～60 hours, described catalyzer is organic palladium or is the mixture of 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.
3. the preparation method of the polymkeric substance containing bithiophene benzthiadiazole 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 bithiophene benzthiadiazole 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 bithiophene benzthiadiazole 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 bithiophene benzthiadiazole 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.
7. the preparation method of the polymkeric substance containing bithiophene benzthiadiazole unit according to claim 2, it is characterized in that, also comprise the step that the polymer P containing bithiophene benzthiadiazole unit is carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Stille coupling reaction, 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 bithiophene benzthiadiazole 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 bithiophene benzthiadiazole unit of following structural formula:
Wherein, R is C 1~ C 20alkyl, the integer that n is 10 ~ 100.
9. solar cell device according to claim 8, is characterized in that, the mol ratio of described electron donor material and described electron acceptor material is 1:2～1:5.
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