CN103897150B - Containing polymkeric substance and preparation method thereof and the solar cell device of thienothiophene unit - Google Patents
Containing polymkeric substance and preparation method thereof and the solar cell device of thienothiophene unit Download PDFInfo
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- CN103897150B CN103897150B CN201210578574.8A CN201210578574A CN103897150B CN 103897150 B CN103897150 B CN 103897150B CN 201210578574 A CN201210578574 A CN 201210578574A CN 103897150 B CN103897150 B CN 103897150B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Containing a polymkeric substance for thienothiophene unit, there is following structural formula:
; Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.Should, containing the concrete electrophilic sulfonyl group of polymkeric substance of thienothiophene unit, be electron acceptor(EA) unit, there is band gap narrower and sunlight is had to the advantage of higher uptake factor and wider absorption region by two thiophene after being modified; Improve structure adaptability performance and film forming properties by alkyl modified, the hole mobility of this polymkeric substance is 10
-4cm
2v
-1s
-1left and right, and then solve solar cell device low efficiency problem.The present invention also provides a kind of preparation method of the polymkeric substance containing thienothiophene unit and uses this to contain the solar cell device of the polymkeric substance of thienothiophene unit.
Description
[technical field]
The present invention relates to photoelectric field, particularly relate to a kind of polymkeric substance containing thienothiophene unit and preparation method thereof and the solar cell device using this containing the polymkeric substance of thienothiophene unit.
[background technology]
Since Japanese Scientists Hideki Shirakawa in 1977 finds polyacetylene conduction, this conductive polymers being called as " forth generation polymer " material has attracted numerous scientist to study with its outstanding photoelectric properties.The advantages such as conducting polymer is compared with the inorganic materials with identical or similar use, has density low, easily processes, and synthesis range of choice is wide.Due to the conjugate property of this kind of material structure, make its can transmission charge, stimulated luminescence, thus can or potentially may to be applied on many electronics or opto-electronic device, such as, comprise polymer LED, photovoltaic cell, field-effect etc.Potential application prospect and wide application field impel scientist competitively to study this kind of conjugated material with photoelectric activity, comprise conjugated structure small molecules, and polyacetylene, polypyrrole, Polythiophene, polyaniline, polyfluorene etc.
Researchist is making great efforts the method seeking to improve polymer LED, photovoltaic cell, field effect behavior always, and material is one of most important factor.So many research groups are devoted to exploitation have high-quantum efficiency, high color purity always, 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 the more novel conjugated molecular material of development and polymer materials, wherein, the novel conjugate unit of design and synthesis just seems very important.
[summary of the invention]
Based on this, be necessary the polymkeric substance containing thienothiophene unit providing a kind of energy conversion efficiency higher.
In addition, there is a need to the preparation method that a kind of polymkeric substance containing thienothiophene unit is provided.
In addition, there is a need to the solar cell device that the polymkeric substance used containing thienothiophene unit is provided.
Containing a polymkeric substance for thienothiophene unit, there is following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.
Containing a preparation method for the polymkeric substance of thienothiophene unit, comprise the steps:
The compd A providing following structural formula to represent and compd B,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In oxygen-free environment, be that compd A and the compd B of 1:1 ~ 1:1.2 is added in the organic solvent containing catalyzer by mol ratio, Heck coupling reaction is carried out 24 hours ~ 96 hours at 70 DEG C ~ 130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphorus ligand, obtains the polymer P containing thienothiophene unit that following structural formula represents:
Wherein, n is the integer of 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 bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three (dibenzalacetone) two palladium, 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 organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1:100.
In a preferred embodiment, the temperature of reaction of described Heck coupling reaction is 90 DEG C ~ 120 DEG C, and the reaction times is 12 hours ~ 48 hours.
In a preferred embodiment, also comprise the step of the polymer P containing thienothiophene unit being carried out separation and purification, described purification procedures is as follows: add methyl alcohol precipitating in the solution after carrying out Heck coupling reaction to described compd A and compd B and filter, extracting is carried out with methyl alcohol and normal hexane successively by filtering the solid obtained, by the solid chloroform after extracting, collect evaporating solvent after chloroformic solution obtain purifying after the polymer P containing thienothiophene unit.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
A kind of solar cell device, comprise active coating, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate, described electron donor material has the polymer P containing thienothiophene unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.
The above-mentioned concrete electrophilic sulfonyl group of polymkeric substance containing thienothiophene unit is electron acceptor(EA) unit, has band gap narrower and sunlight is had to the advantage of higher uptake factor and wider absorption region by two thiophene after being modified; Improve structure adaptability performance and film forming properties by alkyl modified, the hole mobility of this polymkeric substance is 10
-4cm
2v
-1s
-1left and right, and then solve solar cell device low efficiency problem.
The preparation method of the above-mentioned polymkeric substance containing thienothiophene unit, have employed better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And obtained polymeric material constructions is novel, solubility property is good, and film forming properties is excellent, is applicable to solar cell device.
[accompanying drawing explanation]
Fig. 1 is the schema of the preparation method of the polymkeric substance containing thienothiophene unit of an embodiment;
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 thienothiophene unit prepared by embodiment 1;
Fig. 4 is the thermogravimetic analysis (TGA) figure of the polymkeric substance containing thienothiophene unit prepared by embodiment 1.
[embodiment]
In order to understand the content of patent of the present invention better, technology case of the present invention is further illustrated 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 commercially obtains, the disclosed method synthesis of monomers B reference literature (Adv.Mater.2012, DOI:10.1002/adma.201200995.) obtains.
The polymkeric substance containing thienothiophene unit of one embodiment, has following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.
The above-mentioned concrete electrophilic sulfonyl group of polymkeric substance that should contain thienothiophene unit; it is electron acceptor(EA) unit; there is band gap narrower and sunlight is had to the advantage of higher uptake factor and wider absorption region after being modified by two thiophene; improve structure adaptability performance and film forming properties by alkyl modified, the hole mobility of this polymkeric substance is 10
-4cm
2v
-1s
-1left and right, thus solve solar cell device low efficiency problem.
The preparation method of the polymkeric substance containing thienothiophene unit of one embodiment, as shown in Figure 1, comprises the following steps:
Step S1, provide compd A and compd B.
The structural formula of compd A is:
wherein, R
1for C
1~ C
20alkyl.
The structural formula of compd B is:
wherein, R
2for C
1~ C
20alkyl.
Step S2, preparation are containing the polymer P of thienothiophene unit.
In oxygen-free environment, be that compd A and the compd B of 1:1 ~ 1:1.2 is added in the organic solvent containing catalyzer by mol ratio, Heck coupling reaction is carried out 24 hours ~ 96 hours at 70 DEG C ~ 130 DEG C, described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand, obtains the polymer P containing thienothiophene unit that following structural formula represents:
Wherein, n is the integer of 10 ~ 100.
In present embodiment, Heck 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 use other solvents, as long as can dissolved compound A and compd B.
In present embodiment, organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three (dibenzalacetone) two palladium, 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, the mixture of employing three (dibenzalacetone) two palladium and tri-butyl phosphine is 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 Heck coupling reaction.
In present embodiment, in catalyzer, the mol ratio of organic palladium and compd A is 1:20 ~ 1:100.Be appreciated that the mol ratio of organic palladium and compd A is not limited to 1:20 ~ 1:100, in the organic solvent adding compd A and compd B, add the catalyzer of catalytic amount.
In present embodiment, the temperature of reaction of Heck coupling reaction is 70 DEG C ~ 130 DEG C, and the reaction times is 12 hours ~ 96 hours.Preferably, the temperature of reaction of Heck coupling reaction is 90 DEG C ~ 120 DEG C, and the reaction times is 24 hours ~ 72 hours.Compd A and compd B be appreciated that the temperature of reaction of Heck coupling reaction is not limited to 70 DEG C ~ 130 DEG C, as long as can be made to react; Reaction times is also not limited to 12 hours ~ 96 hours, as long as compd A and compd B can be made to react completely as far as possible.
Step S3, separation and purification are containing the polymer P of thienothiophene unit.
Add methyl alcohol precipitating in solution after carrying out Heck coupling reaction to described compd A and compd B and filter, extracting is carried out with methyl alcohol and normal hexane successively by filtering the solid obtained, by the solid chloroform after extracting, collect evaporating solvent after chloroformic solution obtain purifying after the polymer P containing thienothiophene unit.
In present embodiment, extracting uses apparatus,Soxhlet's to carry out.
In present embodiment, obtain polymer P 50 DEG C under vacuo ~ 70 DEG C dryings 24 hours ~ 48 hours containing thienothiophene unit after purifying by collecting evaporating solvent after chloroformic solution.
The preparation method of the above-mentioned polymkeric substance containing thienothiophene unit, synthetic route is comparatively simple, reduces manufacturing cost.
A kind of solar cell device in one embodiment, comprises active coating, and described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate, described electron donor material has the polymer P containing thienothiophene unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.
Be specific embodiment below.
Embodiment 1
Present embodiment discloses poly-{ the N-n-octyl-3 that structural formula is following; 7-divinyl thiodiphenylamine-co-2-n-octyl alkylsulfonyl-4; 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2,6-bis-base } (polymer P 1 containing thienothiophene unit):
The preparation process of the above-mentioned polymer P 1 containing thienothiophene unit is as follows:
Under argon shield, by N-n-octyl-3,7-divinyl thiodiphenylamine (73mg, 0.2mmol), 2,6-bis-bromo-2-n-octyl alkylsulfonyls-4,6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene (128mg, 0.2mmol) adds in the flask filling 10ml toluene solvant, vacuumizes deoxygenation and be filled with argon gas, then bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol) is added; Flask is heated to 100 DEG C and carries out Heck coupling reaction 60h.Subsequently, after cooling, stop polyreaction, drip in flask in 50ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is to colourless with chloroform; collect chloroformic solution and be spin-dried for and obtain red powder; be pumped through under vacuum pump and obtain product poly-{ N-n-octyl-3 night; 7-divinyl thiodiphenylamine-co-2-n-octyl alkylsulfonyl-4; 6-bis-(thiophene-2-base) thieno-[3; 4-b] thiophene-2,6-bis-base }, productive rate 70%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 1 of thienothiophene unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): M
n=24.8kDa, M
w/ M
n=2.2.
See accompanying drawing 3, be the uv-visible absorption spectra figure of the polymer P 1 of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 523nm, and wide absorption spectrum shows that polymer P 1 is a kind of photovoltaic material.
See accompanying drawing 4, be the thermogravimetic analysis (TGA) figure of polymer P 1 prepared by the present embodiment 1, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5% as seen from the figure
d) be 406 DEG C.
With ITO/PEDOT:PSS/ the present embodiment 1 polymer P 1/Au for device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 1 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility obtaining polymkeric substance is 2.4 × 10
-4cm
2/ Vs.
Embodiment 2
Present embodiment discloses poly-{ the N-methyl-3 that structural formula is following; 7-divinyl thiodiphenylamine-co-2-NSC 62789 base alkylsulfonyl-4; 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2,6-bis-base } (polymer P 2 containing thienothiophene unit):
The preparation process of the above-mentioned polymer P 2 containing thienothiophene unit is as follows:
Under nitrogen and argon gas gas mixture are protected, by N-methyl-3, 7-divinyl thiodiphenylamine (80mg, 0.3mmol), 2, 6-bis-bromo-2-NSC 62789 base alkylsulfonyl-4, 6-bis-(thiophene-2-base) thieno-[3, 4-b] thiophene (242mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, after the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is heated to 70 DEG C and carries out Heck coupling reaction 96h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be that solvent extraction is to colourless with chloroform; collect chloroformic solution and be spin-dried for and obtain red solid; poly-{ the N-methyl-3 of product is obtained under vacuo after 50 DEG C of dry 24h after collection; 7-divinyl thiodiphenylamine-co-2-NSC 62789 base alkylsulfonyl-4; 6-bis-(thiophene-2-base) thieno-[3; 4-b] thiophene-2,6-bis-base }.Productive rate is 67%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 2 of thienothiophene unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): M
n=48.5kDa, M
w/ M
n=2.0.
The uv-visible absorption spectra figure of the polymer P 2 of preparation in the present embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 513nm.
The thermogravimetic analysis (TGA) of polymer P 2 prepared by the present embodiment 2, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 396 DEG C.
With ITO/PEDOT:PSS/ the present embodiment 2 polymer P 2/Au for device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 2 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility obtaining polymkeric substance is 2.7 × 10
-4cm
2/ Vs.
Embodiment 3
Present embodiment discloses poly-{ the N-NSC 62789 base-3 that structural formula is following; 7-divinyl thiodiphenylamine-co-2-methyl sulphonyl-4; 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2,6-bis-base } (polymer P 3 containing thienothiophene unit):
The preparation process of the above-mentioned polymer P 3 containing thienothiophene unit is as follows:
Under nitrogen protection, by N-NSC 62789 base-3,7-divinyl thiodiphenylamine (159mg, 0.3mmol), 2, the bromo-2-methyl sulphonyl-4 of 6-bis-, 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene (178mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF filling 12mL, after in flask, logical nitrogen purge gas is about 20min subsequently; Flask is heated to 130 DEG C and carries out Heck coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be that solvent extraction is to colourless with chloroform; collect chloroformic solution and be spin-dried for and obtain red powder; after collection under vacuo after 50 DEG C of dry 24h; be poly-{ the N-NSC 62789 base-3 of product; 7-divinyl thiodiphenylamine-co-2-methyl sulphonyl-4,6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2; 6-bis-base }, productive rate is 65%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 3 of thienothiophene unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): M
n=10.4kDa, M
w/ M
n=2.4.
The uv-visible absorption spectra figure of the polymer P 3 of preparation in the present embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 521nm.
The thermogravimetic analysis (TGA) of polymer P 3 prepared by the present embodiment 3, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 392 DEG C.
With ITO/PEDOT:PSS/ the present embodiment 3 polymer P 3/Au for device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 3 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility obtaining polymer P 3 is 3.0 × 10
-4cm
2/ Vs.
Embodiment 4
Present embodiment discloses poly-{ the N-normal butane base-3 that structural formula is following; the positive decyl alkylsulfonyl-4 of 7-divinyl thiodiphenylamine-co-2-; 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2,6-bis-base } (polymer P 4 containing thienothiophene unit):
The preparation process of the above-mentioned polymer P 4 containing thienothiophene unit is as follows:
Under nitrogen protection, by N-normal butane base-3,7-divinyl thiodiphenylamine (92mg, 0.3mmol), 2, the positive decyl alkylsulfonyl-4 of the bromo-2-of 6-bis-, 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene (240mg, 0.36mmol), three (dibenzalacetone) two palladium (9mg, 0.009mmol) with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N filling 12mL, in the flask of dinethylformamide, after in flask, logical nitrogen purge gas is about 20min subsequently; Flask is heated to 120 DEG C and carries out Heck coupling reaction 36h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be that solvent extraction is to colourless with chloroform; collect chloroformic solution and be spin-dried for and obtain red powder; after collection under vacuo after 50 DEG C of dry 24h; be poly-{ the N-normal butane base-3 of product; 7-divinyl thiodiphenylamine-co-2-positive decyl alkylsulfonyl-4,6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2; 6-bis-base }, productive rate is 77%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 4 of thienothiophene unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): M
n=31.4kDa, M
w/ M
n=2.1.
The uv-visible absorption spectra figure of the polymer P 4 of preparation in the present embodiment 4, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 526nm.
The thermogravimetic analysis (TGA) of polymer P 4 prepared by the present embodiment 4, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 401 DEG C.
With ITO/PEDOT:PSS/ the present embodiment 4 polymer P 4/Au for device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 4 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility obtaining polymkeric substance is 3.5 × 10
-4cm
2/ Vs.
Embodiment 5
Present embodiment discloses poly-{ the N-dodecyl-3 that structural formula is following; 7-divinyl thiodiphenylamine-co-2-n-hexyl alkylsulfonyl-4; 6-bis-(thiophene-2-base) thieno-[3,4-b] thiophene-2,6-bis-base } (polymer P 5 containing thienothiophene unit):
The preparation process of the above-mentioned polymer P 5 containing thienothiophene unit is as follows:
Under nitrogen and argon gas gas mixture are protected, by N-dodecyl-3, 7-divinyl thiodiphenylamine (126mg, 0.3mmol), 2, 6-bis-bromo-2-n-hexyl alkylsulfonyl-4, 6-bis-(thiophene-2-base) thieno-[3, 4-b] thiophene (183mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, after the gas mixture air-discharging passing into nitrogen and argon gas is about 10min, two-mouth bottle is heated to 90 DEG C and carries out Heck coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be that solvent extraction is to colourless with chloroform; collect chloroformic solution and be spin-dried for and obtain red solid; poly-{ the N-dodecyl-3 of product is obtained under vacuo after 50 DEG C of dry 24h after collection; 7-divinyl thiodiphenylamine-co-2-n-hexyl alkylsulfonyl-4; 6-bis-(thiophene-2-base) thieno-[3; 4-b] thiophene-2,6-bis-base }.Productive rate is 70%.
Above-mentioned preparation is as follows containing the reaction formula of the polymer P 5 of thienothiophene unit:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): M
n=22.9kDa, M
w/ M
n=2.3.
The uv-visible absorption spectra figure of the polymer P 5 of preparation in the present embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 524nm.
The thermogravimetic analysis (TGA) of polymer P 5 prepared by the present embodiment 5, thermogravimetric curve (TGA) test is carried out on TASDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 405 DEG C.
With ITO/PEDOT:PSS/ the present embodiment 5 polymer P 5/Au for device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 5 that luminescent layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and adopts the hole mobility of space charge limited current (SCLC) model determination polymkeric substance, and the hole mobility obtaining polymkeric substance is 3.2 × 10
-4cm
2/ Vs.
Embodiment 6
Refer to Fig. 2, a kind of solar cell device 60 comprises substrate 61, anode 62, buffer layer 63, active coating 64 and negative electrode 65.Anode 62, buffer layer 63, active coating 64 and negative electrode 65 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 for being ITO (tin indium oxide), preferably, the tin indium oxide of ITO to be square resistance be 10 ~ 20 Ω/.
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 Thiophenes 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 thienothiophene unit prepared by the present invention, and in present embodiment, electron donor material is the polymer P 1 of preparation in embodiment one.
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 surface.
The manufacturing processed of this solar cell device 60 is as follows:
Anode 62 is formed at the laggard row ultrasonic cleaning of a side surface of substrate 61, and after processing with oxygen-Plasma, is coated with the PEDOT:PSS formation buffer layer 63 that last layer plays modification on anode 62 surface.
Buffer layer 64 applies one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, and electron donor material is the polymer P 1 of preparation in embodiment one.
Negative electrode 65 is formed on active coating 64 surface.In present embodiment, negative electrode 65 is the aluminium lamination 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 room temperature again, the order and regularity that arrange between each group and molecule segment in molecule effectively can be increased after solar cell device is annealed, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
At AM1.5G100mW/cm
2under illumination, be the effciency of energy transfer 3.0% of the body heterojunction solar cell device 60 of donor material based on the polymer P 1 in embodiment 1.
When this solar cell device 60 uses, under light illumination, light transmission substrate 61 and anode 62, the Conduction cavity 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, thus form current carrier freely, i.e. electronics and hole freely.These freely electronics to transmit along electron acceptor material to negative electrode 65 and collected by negative electrode, hole to be transmitted and collected by anode 62 along electron donor material anode 62 freely, thus forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In the process, Conduction cavity type electroluminescent material has very wide spectral response range due to it, 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 be made by technology such as spin coatings, be convenient to large batch of preparation.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (8)
1., containing a polymkeric substance for thienothiophene unit, it is characterized in that there is following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.
2., containing a preparation method for the polymkeric substance of thienothiophene unit, it is characterized in that, comprise the steps:
The compd A providing following structural formula to represent and compd B,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl;
In oxygen-free environment, be that compd A and the compd B of 1:1 ~ 1:1.2 is added in the organic solvent containing catalyzer by mol ratio, Heck coupling reaction is carried out 24 hours ~ 96 hours at 70 DEG C ~ 130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphorus ligand, obtains the polymer P containing thienothiophene unit that following structural formula represents:
Wherein, n is the integer of 10 ~ 100.
3. the preparation method of the polymkeric substance containing thienothiophene unit according to claim 2, it is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
4. the preparation method of the polymkeric substance containing thienothiophene unit according to claim 2, it is characterized in that, described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three (dibenzalacetone) two palladium, 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 thienothiophene unit according to claim 2, it is characterized in that, the mol ratio of the organic palladium in described catalyzer and described compd A is 1:20 ~ 1:100.
6. the preparation method of the polymkeric substance containing thienothiophene unit according to claim 2, it is characterized in that, the temperature of reaction of described Heck coupling reaction is 90 DEG C ~ 120 DEG C, and the reaction times is 12 hours ~ 48 hours.
7. the preparation method of the polymkeric substance containing thienothiophene unit according to claim 2, it is characterized in that, also comprise the step of the polymer P containing thienothiophene unit being carried out separation and purification, described purification procedures is as follows: add methyl alcohol precipitating in the solution after carrying out Heck coupling reaction to described compd A and compd B and filter, extracting is carried out with methyl alcohol and normal hexane successively by filtering the solid obtained, by the solid chloroform after extracting, collect evaporating solvent after chloroformic solution obtain purifying after the polymer P containing thienothiophene unit.
8. a solar cell device, comprises active coating, it is characterized in that, described active coating comprises electron donor material and electron acceptor material, and described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate, described electron donor material has the polymer P containing thienothiophene unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 100.
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| Title |
|---|
| Synthesis and Electroluminescent Properties of a Phenothiazine-Based Polymer for Nondoped Polymer Light-Emitting Diodes with a Stable Orange-Red Emission;YINGLIANG LIU et al.;《Journal of Polymer Science: Part A: Polymer Chemistry》;20070914;第45卷;第4867-4878页 * |
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