CN103848964A - Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device - Google Patents

Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device Download PDF

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CN103848964A
CN103848964A CN201210492982.1A CN201210492982A CN103848964A CN 103848964 A CN103848964 A CN 103848964A CN 201210492982 A CN201210492982 A CN 201210492982A CN 103848964 A CN103848964 A CN 103848964A
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thiophene
benzene
preparation
polymkeric substance
compd
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周明杰
王平
张振华
钟铁涛
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering 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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Abstract

A polymer containing a thiophene-benzene-thiophene unit has the following structural formula shown in the description, wherein R1 is C1-C20 alkyl, R2 is C1-C20 alkyl, and n is an integer from 10 to 100. The polymer containing the thiophene-benzene-thiophene unit contains the thiophene-benzene-thiophene unit and a triphenylamine unit; the polymer has higher hole mobility, has higher absorption coefficient on sunlight, has the energy gap in a range of 1.6 eV-1.8 eV, and has wider absorption range and easily modified photophysical properties in a wavelength range of 350 nm-700 nm. The polymer is used in a solar cell and thus solves the problem of low efficiency of a solar cell device. The invention also provides a preparation method of the polymer containing the thiophene-benzene-thiophene unit and the solar cell device employing the polymer containing the thiophene-benzene-thiophene unit.

Description

Contain polymkeric substance of thiophene-benzene-thiophene 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 thiophene-benzene-thiophene unit and preparation method thereof and the solar cell device that uses this containing the polymkeric substance of thiophene-benzene-thiophene unit.
[background technology]
Since Japanese scientist's Hideki Shirakawa in 1977 is found polyacetylene conduction, this being called as the conductive polymers of " the 4th generation polymer " material attracted numerous scientists to study with its outstanding photoelectric properties.Conducting polymer is compared with the inorganic materials with identical or close purposes, has density low, and easily processing, synthesizes the advantages such as range of choice is wide.Due to the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may being applied on many electronics or opto-electronic device, for example comprise polymer LED, photovoltaic cell, field-effect etc.Potential application prospect and wide application field impel scientist competitively to study this class to have the conjugation material of photoelectric activity, comprise conjugated structure small molecules, and polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes etc.
Researchist is making great efforts to seek to improve the method for polymer LED, photovoltaic cell, field effect behavior always, and material is one of most important factor.So being devoted to exploitation always, many research groups there is high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good, and the polymkeric substance that visible-range absorption bands is wide, carrier mobility is high.Realize these targets, need to develop more novel conjugated molecular material and polymer materials, wherein, design synthesizing new conjugate unit just seems very important.
[summary of the invention]
Based on this, be necessary the polymkeric substance containing thiophene-benzene-thiophene unit that provides a kind of energy conversion efficiency higher.
In addition, be also necessary to provide a kind of preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit.
In addition, be also necessary to provide the solar cell device using containing the polymkeric substance of thiophene-benzene-thiophene unit.
Containing a polymkeric substance for thiophene-benzene-thiophene unit, there is following structural formula:
Wherein, R 1for C 1~ C 20alkyl, R 2for C 1~ C 20alkyl, the integer that n is 10 ~ 100.
A preparation method who contains the polymkeric substance of thiophene-benzene-thiophene unit, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
Figure BDA00002479380600022
b is:
Figure BDA00002479380600023
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 and alkaline solution, carry out Suzuki coupling reaction 12 hours～96 hours at 70 ℃～130 ℃, described catalyzer is organic palladium or the mixture for organic palladium and organophosphorus ligand, obtains the polymer P containing thiophene-benzene-thiophene unit that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
In a preferred embodiment, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
In a preferred embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-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 Suzuki coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 24 hours ~ 72 hours.
In a preferred embodiment, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
In a preferred embodiment, the mol ratio of the solute in described alkaline solution and compd A is 20:1 ~ 50:1.
In a preferred embodiment, also comprise the step of carrying out separation and purification containing the polymer P of thiophene-benzene-thiophene unit, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing thiophene-benzene-thiophene unit after purifying.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
A kind of solar cell device, comprises activity layer by layer, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate or [6,6]-phenyl-C 71-methyl-butyrate, described electron donor material has the polymer P containing thiophene-benzene-thiophene unit of following structural formula:
Figure BDA00002479380600031
Wherein, R 1for C 1~ C 20alkyl, R 2for C 1~ C 20alkyl, the integer that n is 10 ~ 100.
The above-mentioned polymkeric substance containing thiophene-benzene-thiophene unit contains thiophene-benzene-thiophene unit and carbazole unit, the hole mobility of polymkeric substance higher, sunlight is had to higher uptake factor, energy gap is at 1.6eV～1.8eV, the advantages such as the photophysical property that there is wider absorption region and easily modify within the scope of 350nm～700nm, be a kind of well behaved polymer luminescent material, this polymkeric substance uses aspect solar cell and then solves solar cell device low efficiency problem.
The preparation method of the above-mentioned polymkeric substance containing thiophene-benzene-thiophene unit, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, applicable to solar cell device.
[accompanying drawing explanation]
Fig. 1 is the preparation method's of the polymkeric substance containing thiophene-benzene-thiophene unit of an embodiment schema;
Fig. 2 is the uv-visible absorption spectra figure containing the polymkeric substance of thiophene-benzene-thiophene unit prepared by embodiment 1;
Fig. 3 is the thermogravimetic analysis (TGA) figure containing the polymkeric substance of thiophene-benzene-thiophene unit prepared by embodiment 1;
Fig. 4 is the structural representation of the solar cell device of an embodiment.
[embodiment]
In order to understand better the content of patent of the present invention, further illustrate technology case of the present invention below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein monomer A is bought and is obtained from the market, monomers B reference literature (Adv.Funct.Mater., 2009,19,3063) disclosed method is synthetic obtains.
The polymkeric substance containing thiophene-benzene-thiophene unit of one embodiment, has following structural formula:
Wherein, R 1for C 1~ C 20alkyl, R 2for C 1~ C 20alkyl, the integer that n is 10 ~ 100.
The above-mentioned polymkeric substance that should contain thiophene-benzene-thiophene unit contain thiophene-benzene-thiophene unit and carbazole unit, the hole mobility of polymkeric substance higher, sunlight is had to higher uptake factor, energy gap is at 1.6eV～1.8eV, the advantages such as the photophysical property that there is wider absorption region and easily modify within the scope of 350nm～700nm, be a kind of well behaved polymer luminescent material, this polymkeric substance uses aspect solar cell and then solves solar cell device low efficiency problem.
The preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit of one embodiment, as shown in Figure 1, comprises the following steps:
Step S1, provide compd A and compd B.
The structural formula of compd A is:
Figure BDA00002479380600051
wherein, R 1for C 1~ C 20alkyl.
The structural formula of compd B is:
Figure BDA00002479380600052
wherein, R 2for C 1~ C 20alkyl.
Step S2, preparation contain the polymer P of thiophene-benzene-thiophene unit.
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, carry out Suzuki coupling reaction 12 hours～96 hours at 70 ℃～130 ℃, described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand, obtains the polymer P containing thiophene-benzene-thiophene unit that following structural formula represents:
Figure BDA00002479380600053
Wherein, the integer that n is 10 ~ 100.
In present embodiment, Suzuki 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 phosphine-2 ', 6 '-dimethoxy-biphenyl.In the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand is 1:4 ~ 1:8.Preferably, adopt the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine as catalyzer.Be appreciated that organic palladium, organophosphorus ligand are all not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Suzuki 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 Suzuki coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 12 hours ~ 96 hours.Preferably, the temperature of reaction of Suzuki coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 24 hours ~ 72 hours.The temperature of reaction that is appreciated that Suzuki 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 96 hours, as long as can make compd A and compd B react completely as far as possible.
In present embodiment, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, wherein the solute of sodium carbonate solution is sodium carbonate, and the solute of solution of potassium carbonate is that the solute of salt of wormwood and sodium hydrogen carbonate solution is sodium bicarbonate;
In present embodiment, the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
Step S3, separation and purification contain the polymer P of thiophene-benzene-thiophene unit.
Carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the polymer P containing thiophene-benzene-thiophene unit after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collect evaporating solvent after chloroformic solution obtain the polymer P containing thiophene-benzene-thiophene unit after purifying under vacuum 50 ℃～70 ℃ dry 24 hours～48 hours.
The preparation method of the above-mentioned polymkeric substance containing thiophene-benzene-thiophene unit, synthetic route is comparatively simple, has reduced manufacturing cost.
A kind of solar cell device in one embodiment, comprises active coating, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate or [6,6]-phenyl-C 71-methyl-butyrate, described electron donor material has the polymer P containing thiophene-benzene-thiophene unit of following structural formula:
Figure BDA00002479380600071
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 discloses following poly-{ 4-(the n-octyloxy)-N of structural formula, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-octyl phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 1 of thiophene-benzene-thiophene unit):
Figure BDA00002479380600072
The preparation process of the above-mentioned polymer P 1 containing thiophene-benzene-thiophene unit is as follows:
Under argon shield, by 4-(n-octyloxy)-N, N-bis-(4-pinacol borate phenyl) aniline (125mg, 0.2mmol), two (2-bromo-4,4-bis-(4-n-octyl phenyl)-indeno [1,2-b] thiophene) (235mg, 0.2mmol) add in the flask that fills 10ml toluene solvant, after fully dissolving by salt of wormwood (2mL, 2mol/L) solution joins in flask, 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 Suzuki coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in 50ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, under vacuum pump, taking out spends the night obtains poly-{ 4-(the n-octyloxy)-N of product, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-octyl phenyl)-indeno [1,2-b] thiophene }, productive rate 75%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 1 of thiophene-benzene-thiophene unit:
Figure BDA00002479380600081
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=102.7kDa, M w/ M n=2.2.
Referring to accompanying drawing 2, be the uv-visible absorption spectra figure of the organic semiconductor material P1 of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 545nm, wide absorption spectrum shows that P1 is a kind of photovoltaic material.
Referring to accompanying drawing 3, be the thermogravimetic analysis (TGA) figure of the organic semiconductor material P1 for preparing of the present embodiment 1, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, 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 416 ℃.
Embodiment 2
The present embodiment discloses following poly-{ 4-(the methoxyl group)-N of structural formula, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-NSC 62789 base phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 2 of thiophene-benzene-thiophene unit):
Figure BDA00002479380600091
The preparation process of the above-mentioned polymer P 2 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4-(methoxyl group)-N, N-bis-(4-pinacol borate phenyl) aniline (158mg, 0.3mmol), two (2-bromo-4, 4-bis-(4-NSC 62789 base phenyl)-indeno [1, 2-b] thiophene) (555mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, after fully dissolving, add again sodium bicarbonate (3mL, 2mol/L) solution, 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 Suzuki coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain poly-{ 4-(the methoxyl group)-N of product, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-NSC 62789 base phenyl)-indeno [1,2-b] thiophene }.Productive rate is 78%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 2 of thiophene-benzene-thiophene unit:
Figure BDA00002479380600092
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=164.2kDa, M d/ M n=2.1.
The uv-visible absorption spectra figure of the organic semiconductor material P2 of preparation in the present embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 541nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P2 prepared by the present embodiment 2, 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 410 ℃.
Embodiment 3
The present embodiment discloses following poly-{ 4-(NSC 62789 oxygen the base)-N of structural formula, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-aminomethyl phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 3 of thiophene-benzene-thiophene unit):
Figure BDA00002479380600101
The preparation process of the above-mentioned polymer P 3 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen protection, by 4-(NSC 62789 oxygen base)-N, N-bis-(4-pinacol borate phenyl) aniline (238mg, 0.3mmol), two (2-bromo-4,4-bis-(4-aminomethyl phenyl)-indeno [1,2-b] thiophene) (259mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution leads to after the about 20min of nitrogen purge gas subsequently in flask; Flask is heated to 130 ℃ and carries out Suzuki coupling reaction 12h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, be poly-{ 4-(NSC 62789 oxygen the base)-N of product, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-aminomethyl phenyl)-indeno [1,2-b] thiophene }, productive rate is 66%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 3 of thiophene-benzene-thiophene unit:
Figure BDA00002479380600111
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=37.4kDa, M w/ M n=2.4.
The uv-visible absorption spectra figure of the organic semiconductor material P3 of preparation in the present embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 539nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P3 prepared by the present embodiment 3, 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 409 ℃.
Embodiment 4
The present embodiment discloses following poly-{ 4-(normal butane oxygen the base)-N of structural formula, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-decane base phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 4 of thiophene-benzene-thiophene unit):
Figure BDA00002479380600112
The preparation process of the above-mentioned polymer P 4 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen protection, by 4-(normal butane oxygen base)-N, N-bis-(4-pinacol borate phenyl) aniline (171mg, 0.3mmol), two (2-bromo-4, 4-bis-(the positive decyl phenyl of 4-)-indeno [1, 2-b] thiophene) (464mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol) with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) join the N that fills 12mL, in the flask of dinethylformamide, after fully dissolving, add sodium bicarbonate (3mL, 2mol/L) solution, in flask, lead to after the about 20min of nitrogen purge gas subsequently, flask is heated to 120 ℃ and carries out Suzuki 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 take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuum after 50 ℃ of dry 24h, be poly-{ 4-(normal butane oxygen the base)-N of product, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-n-decane base phenyl)-indeno [1,2-b] thiophene }, productive rate is 82%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 4 of thiophene-benzene-thiophene unit:
Figure BDA00002479380600121
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=153.0kDa, 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 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 547nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P4 prepared by the present embodiment 4, 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 412 ℃.
Embodiment 5
The present embodiment discloses following poly-{ 4-(n-dodecane oxygen the base)-N of structural formula, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-normal hexane base phenyl)-indeno [1,2-b] thiophene } (containing the polymer P 5 of thiophene-benzene-thiophene unit):
Figure BDA00002479380600131
The preparation process of the above-mentioned polymer P 5 containing thiophene-benzene-thiophene unit is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4-(n-dodecane oxygen base)-N, N-bis-(4-pinacol borate phenyl) aniline (204mg, 0.3mmol), two (2-bromo-4, 4-bis-(4-normal hexane base phenyl)-indeno [1, 2-b] thiophene) (319mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, add again salt of wormwood (7.5mL, 2mol/L) solution, 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 Suzuki coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain poly-{ 4-(n-dodecane oxygen the base)-N of product, N-bis-(4-phenyl) aniline-co-2,2 '-bis-base-bis-(4,4-bis-(4-normal hexane base phenyl)-indeno [1,2-b] thiophene }.Productive rate is 75%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 5 of thiophene-benzene-thiophene unit:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=86.1kDa, M w/ M n=2.0.
The uv-visible absorption spectra figure of the organic semiconductor material P5 of preparation in the present embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 350nm ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 544nm.
The thermogravimetic analysis (TGA) of organic semiconductor material P5 prepared by the present embodiment 5, 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 421 ℃.
Use German Zahner IM6e electrochemical workstation to measure the chemical property of polymkeric substance in the embodiment of the present invention, adopt cyclic voltammetry to study the chemical property of the polymkeric substance of preparation in the embodiment of the present invention 1～embodiment 5, adopt E g=E lUMO-E hOMOthe energy gap width that can calculate polymkeric substance, test result is in table 1.
Table 1
Embodiment HOMO(eV) LUMO(eV) E g（eV）
Embodiment 1 polymer P 1 -5.26 -3.52 1.74
Embodiment 2 polymer Ps 2 -5.19 -3.59 1.60
Embodiment 3 polymer Ps 3 -5.15 -3.50 1.65
Embodiment 4 polymer Ps 4 -5.18 -3.47 1.71
Embodiment 5 polymer Ps 5 -5.23 -3.43 1.80
The energy gap width of the polymkeric substance that as shown in Table 1, prepared by the present invention is between 1.6eV～1.8eV.
Embodiment 6
Refer to Fig. 4, a kind of solar cell device 60 comprises substrate 61, anode 62, buffer layer 63, active coating 64 and negative electrode 65.Anode 62, buffer layer 63, active coating 64 and negative electrode 65 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
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/mouth.
Buffer layer 63 is formed at the side surface of anode 62 away from 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 the side surface of buffer layer 63 away from 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 thiophene-benzene-thiophene 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 coating 64 away from 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, be coated with the PEDOT:PSS that last layers play modification on anode 62 surfaces and form buffer layer 63.
On buffer layer 64, apply one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, the P1 of preparation in the embodiment mono-that electron donor material is.
Form negative electrode 65 on active coating 64 surfaces.In present embodiment, the aluminium lamination of negative electrode 65 for being formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this solar cell device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after solar cell device is annealed, can effectively increase order and the regularity between the interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
At AM1.5G100mW/cm 2under illumination, the effciency of energy transfer 3.7% 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 (10)

1. containing a polymkeric substance for thiophene-benzene-thiophene unit, it is characterized in that thering is following structural formula:
Figure FDA00002479380500011
Wherein, R 1for C 1~ C 20alkyl, R 2for C 1~ C 20alkyl, the integer that n is 10 ~ 100.
2. a preparation method who contains the polymkeric substance of thiophene-benzene-thiophene unit, is characterized in that, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
Figure FDA00002479380500012
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 and alkaline solution, carry out Suzuki coupling reaction 12 hours～96 hours at 70 ℃～130 ℃, described catalyzer is organic palladium or the mixture for organic palladium and organophosphorus ligand, obtains the polymer P containing thiophene-benzene-thiophene unit that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
3. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
4. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, it is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
5. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1: 100.
6. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, the temperature of reaction of described Suzuki coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 24 hours ~ 72 hours.
7. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, is characterized in that, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
8. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 7, is characterized in that, the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
9. the preparation method of the polymkeric substance containing thiophene-benzene-thiophene unit according to claim 2, it is characterized in that, also comprise the step of carrying out separation and purification containing the polymer P of thiophene-benzene-thiophene unit, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collecting chloroformic solution, evaporating solvent obtains the polymer P containing thiophene-benzene-thiophene unit after purifying.
10. a solar cell device, comprises active coating, it is characterized in that, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate or [6,6]-phenyl-C 71-methyl-butyrate, described electron donor material has the polymer P containing thiophene-benzene-thiophene unit of following structural formula:
Figure FDA00002479380500031
Wherein, R 1for C 1~ C 20alkyl, R 2for C 1~ C 20alkyl, the integer that n is 10 ~ 100.
CN201210492982.1A 2012-11-28 2012-11-28 Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device Pending CN103848964A (en)

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