CN103159936B - Contain and polymkeric substance of thiazole unit and preparation method thereof and solar cell device - Google Patents
Contain and polymkeric substance of thiazole unit and preparation method thereof and solar cell device Download PDFInfo
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- CN103159936B CN103159936B CN201110415417.0A CN201110415417A CN103159936B CN 103159936 B CN103159936 B CN 103159936B CN 201110415417 A CN201110415417 A CN 201110415417A CN 103159936 B CN103159936 B CN 103159936B
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- 0 *c(cc1)ccc1N(c1ccc(C=C)cc1)c1ccc(C=C)cc1 Chemical compound *c(cc1)ccc1N(c1ccc(C=C)cc1)c1ccc(C=C)cc1 0.000 description 2
- HRESODPOEYLDHQ-UHFFFAOYSA-N Cc1c(-c2nc([s]c(-c([s]3)c(C)cc3Br)n3)c3[s]2)[s]c(Br)c1 Chemical compound Cc1c(-c2nc([s]c(-c([s]3)c(C)cc3Br)n3)c3[s]2)[s]c(Br)c1 HRESODPOEYLDHQ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/549—Organic PV cells
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Abstract
Contain and a polymkeric substance for thiazole 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 ~ 50.The energy gap that should contain the polymkeric substance of also thiazole unit is narrower, and effciency of energy transfer obtains and significantly improves.The present invention also provide a kind of above-mentioned containing and the preparation method of the polymkeric substance of thiazole unit and use this to contain and the solar cell device of polymkeric substance of thiazole unit.
Description
[technical field]
The present invention relates to photoelectric field, particularly relate to a kind of containing and polymkeric substance and preparation method thereof of thiazole unit and use this containing and the solar cell device of the polymkeric substance of thiazole unit.
[background technology]
Energy problem is the significant problem that countries in the world are extremely paid close attention to.Sun power is the optimal substitute energys of the following mankind, is that the solar cell of electric energy is also the focus studied by solar energy converting.The conjugated polymer thin films solar cell of rising in recent years has that cost is low, lightweight, manufacture craft simple, can be prepared into the outstanding advantages such as flexible device.In addition, organic materials is of a great variety, designability is strong, is hopeful by the design of material and optimizes the performance improving solar cell.
Contain and in the polymkeric substance of thiazole unit, because thiazole is typical electron deficiency unit, comprise an electrophilic imine group, the polymkeric substance therefore containing also thiazole unit has higher hole mobility, shows excellent photovoltaic performance.But, existing containing and the band gap (energy level difference between HOMO energy level and lumo energy) of polymkeric substance of thiazole unit is wider, reduce the specific absorption to photon in solar spectral, thus make to use the effciency of energy transfer of the organic solar batteries of the polymkeric substance containing also thiazole unit lower.
[summary of the invention]
Based on this, be necessary the polymkeric substance containing also thiazole unit providing a kind of energy conversion efficiency higher.
In addition, there is a need to provide a kind of contain and the preparation method of the polymkeric substance of thiazole unit.
In addition, there is a need to provide the solar cell device using the polymkeric substance containing also thiazole unit.
Contain and a polymkeric substance for thiazole 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 ~ 50.
Contain and a preparation method for the polymkeric substance of thiazole 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, by mol ratio be 1: 1 ~ 1: 1.2 compd A and compd B be added into containing catalyzer organic solvent in carry out Heck coupling reaction, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, the polymer P containing also thiazole unit obtaining that following structural formula represents:
Wherein, n is the integer of 10 ~ 50.
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 or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-butyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1: 4 ~ 1: 8.
In a preferred embodiment, the 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 70 DEG C ~ 130 DEG C, and the reaction times is 24 hours ~ 96 hours.
In a preferred embodiment, the temperature of reaction of described Heck coupling reaction is 90 DEG C ~ 120 DEG C.
In a preferred embodiment, also comprise the step that the polymer P that will contain also thiazole unit carries 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, containing and the polymer P of thiazole unit after evaporating solvent obtains purifying after collecting chloroformic solution.
In a preferred embodiment, described extracting adopts apparatus,Soxhlet's to carry out.
A kind of solar cell device, comprises active coating, and the material of described active coating is have containing and the polymer P of thiazole unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 50.
The above-mentioned polymkeric substance containing also thiazole unit, owing to introducing triphenylamine nitrogen-containing hetero aromatic ring and thienyl in the structure, thienyl can reduce the band gap of multipolymer, can improve effciency of energy transfer; Triphenylamine nitrogen-containing hetero aromatic ring is electron deficiency unit, forms the structure of push-and-pull electronics between triphenylamine nitrogen-containing hetero aromatic ring unit and other unit of polymkeric substance, strengthens the delocalization of π-electron, reaches absorption spectrum Einstein shift, reduces the object of polymkeric substance band gap; Thiazole comprises an electrophilic imine group, is an electron deficiency unit, makes polymers exhibit go out higher hole mobility, and the above-mentioned polymer application containing also thiazole unit can be increased substantially effciency of energy transfer in solar cell device.
[accompanying drawing explanation]
Fig. 1 is containing of an embodiment and the schema of the preparation method of the polymkeric substance of thiazole unit;
Fig. 2 is the ultraviolet-visible absorption spectroscopy spectrogram containing the polymkeric substance of also thiazole unit prepared by embodiment one;
Fig. 3 is the structural representation of the solar cell device of an embodiment.
[embodiment]
Contain polymkeric substance of also thiazole unit and its preparation method and application to illustrate further below in conjunction with the drawings and specific embodiments.
Containing and the polymkeric substance of thiazole unit of one embodiment, there is following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 50.
The above-mentioned polymkeric substance containing also thiazole unit, owing to introducing triphenylamine nitrogen-containing hetero aromatic ring and thienyl in the structure, thienyl can reduce the band gap of multipolymer, can improve effciency of energy transfer; Triphenylamine nitrogen-containing hetero aromatic ring is electron deficiency unit, forms the structure of push-and-pull electronics between triphenylamine nitrogen-containing hetero aromatic ring unit and other unit of polymkeric substance, strengthens the delocalization of π-electron, reaches absorption spectrum Einstein shift, reduces the object of polymkeric substance band gap; Thiazole comprises an electrophilic imine group, is an electron deficiency unit, makes polymers exhibit go out higher hole mobility, and the above-mentioned polymer application containing also thiazole unit can be increased substantially effciency of energy transfer in solar cell device.
Containing and the preparation method of the polymkeric substance of thiazole unit of one embodiment, as shown in Figure 1, comprise 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.
In present embodiment, compd A can refer to the disclosed method synthesis of document (Advancedmaterials, 2007,19,4257) or commercially obtains, and compd B can commercially obtain.
Step S2, preparation contain and the polymer P of thiazole unit.
In oxygen-free environment, by mol ratio be 1: 1 ~ 1: 1.2 compd A and compd B be added into containing catalyzer organic solvent in carry out Heck coupling reaction, described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains the polymer P containing also thiazole unit that following structural formula represents:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 50.
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 or three dibenzalacetone two palladiums, and organophosphorus ligand is tri-butyl phosphine, tri-butyl 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 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 24 hours ~ 96 hours.Preferably, the temperature of reaction of Heck coupling reaction is 90 DEG C ~ 120 DEG C, and the reaction times is 48 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 24 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 contain and the polymer P of thiazole 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, containing and the polymer P of thiazole unit after evaporating solvent obtains purifying after collecting chloroformic solution.
In present embodiment, extracting uses apparatus,Soxhlet's to carry out.
In present embodiment, by collect evaporating solvent after chloroformic solution obtain after purifying containing and the 50 DEG C of dryings 24 hours under vacuo of the polymer P of thiazole unit.
The above-mentioned preparation method containing the polymkeric substance of also thiazole unit, synthetic route is comparatively simple, reduces manufacturing cost; The polymkeric substance containing also thiazole unit of preparation has higher hollow mobility and lower band gap.
Be specific embodiment below.
Embodiment 1
Present embodiment discloses structural formula following poly-{ 2,5-bis-(3-octyl group-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl is to octyloxyphenyl pentanoic } (containing and the polymer P 1 of thiazole unit):
Above-mentioned containing and the preparation process of polymer P 1 of thiazole unit is as follows:
Under nitrogen protection; 4; 4 '-divinyl is to octyloxyphenyl pentanoic (213mg; 0.5mmol) He 2; 5-bis-(the bromo-3-octyl group of 5--2-thiophene) thiazole also [5; 4-d] thiazole (345mg, 0.5mmol) and tri-o-tolyl phosphine (37mg, 0.12mmol) put into two mouthfuls of flasks of 50mL.By DMF (6mL), after fully logical nitrogen purge gas is about 10min, then add three dibenzalacetones two palladium (18.3mg, 0.02mmol).After fully logical nitrogen purge gas is about 20min again, stirring reaction 24h 90 DEG C time, and then at 110 DEG C, continue reaction 24h.Stop polyreaction after cooling, in flask, drip 30mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, after collection, be polymkeric substance after 40 DEG C of dry 24h under vacuo.Productive rate is 43%.
Above-mentioned preparation contains and the reaction formula of the polymer P 1 of thiazole unit is as follows:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): m
n=35.1kDa, m
w/ M
n=2.3.
Refer to Fig. 2, by carrying out ultraviolet-visible absorption spectroscopy test to poly-{ 2,5-bis-(3-octyl group-2-thiophene) thiazole also [5, the 4-d] thiazole-co-4,4 '-divinyl is to octyloxyphenyl pentanoic } in embodiment 1.Result shows that this conjugated polymers has comparatively large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at about 612nm.
Embodiment 2
Present embodiment discloses structural formula following poly-{ 2,5-bis-(3-methyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl is to eicosane oxygen base phenyl pentanoic } (containing and the polymer P 2 of thiazole unit):
Above-mentioned containing and the preparation process of polymer P 2 of thiazole unit is as follows:
Under nitrogen protection; 4; 4 '-divinyl is to eicosane oxygen base phenyl pentanoic (178mg; 0.3mmol); 2; 5-bis-(the bromo-3-methyl of 5--2-thiophene) thiazole also [5; 4-d] thiazole (148mg; 0.3mmol) and 10mL toluene join respectively in the two-mouth bottle of 50mL; after fully logical nitrogen purge gas is about 20min, then bi triphenyl phosphorus palladium chloride (4.2mg, 0.006mmol) is added wherein; after fully logical nitrogen purge gas is about 10min again, at 120 DEG C of stirring reaction 24h.Stop polyreaction after cooling, 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 solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, be polymkeric substance after 50 DEG C of dry 24h under vacuo.Productive rate is 53%.
Above-mentioned preparation contains and the reaction formula of the polymer P 2 of thiazole unit is as follows:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): m
n=35.8kDa, m
w/ M
n=2.3.
By carrying out ultraviolet-visible absorption spectroscopy test to poly-{ 2,5-bis-(3-methyl-2-thiophene) thiazole also [5, the 4-d] thiazole-co-4,4 '-divinyl is to eicosane oxygen base phenyl pentanoic } in embodiment 2.Result shows that this conjugated polymers has comparatively large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at about 607nm.
Embodiment 3
Present embodiment discloses structural formula following poly-{ 2,5-bis-(3-eicosyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl p-methoxyphenyl pentanoic } (containing and the polymer P 3 of thiazole unit):
Above-mentioned containing and the preparation process of polymer P 3 of thiazole unit is as follows:
Under nitrogen protection; 4; 4 '-divinyl p-methoxyphenyl pentanoic (98mg; 0.3mmol); 2; 5-bis-(the bromo-3-eicosyl of 5--2-thiophene) thiazole also [5; 4-d] thiazole (308mg; 0.3mmol) and 15mL tetrahydrofuran (THF) join respectively in the two-mouth bottle of 50mL; after fully logical nitrogen purge gas is about 20min, then tetra-triphenylphosphine palladium (17mg, 0.015mmol) is added wherein; after fully logical nitrogen purge gas is about 10min again, at 90 DEG C of stirring reaction 72h.Stop polyreaction after cooling, 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 solvent extraction with chloroform to colourless, collect chloroformic solution and be also spin-dried for, obtain red solid, after collection, obtain product after 50 DEG C of dry 24h under vacuo.Productive rate is 61%.
Above-mentioned preparation contains and the reaction formula of the polymer P 3 of thiazole unit is as follows:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): m
n=43.6kDa, m
w/ M
n=2.1.
By carrying out ultraviolet-visible absorption spectroscopy test to poly-{ 2,5-bis-(3-eicosyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4, the 4 '-divinyl p-methoxyphenyl pentanoic } in embodiment 3.Result shows that this conjugated polymers has comparatively large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at about 605nm.
Embodiment 4
Present embodiment discloses structural formula following poly-{ 2,5-bis-(3-normal-butyl-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl aligns dodecyloxy phenyl pentanoic } (containing and the polymer P 4 of thiazole unit):
Above-mentioned containing and the preparation process of polymer P 4 of thiazole unit is as follows:
Under nitrogen protection; 4; 4 '-divinyl aligns dodecyloxy phenyl pentanoic (145mg; 0.3mmol); 2; 5-bis-(the bromo-3-normal-butyl of 5--2-thiophene) thiazole also [5; 4-d] thiazole (173mg; 0.33mmol) and 10mL toluene join respectively in the two-mouth bottle of 50mL; after fully logical nitrogen purge gas is about 20min, then bi triphenyl phosphorus palladium chloride (10.5mg, 0.015mmol) is added wherein; after fully logical nitrogen purge gas is about 10min again, at 130 DEG C of stirring reaction 24h.Stop polyreaction after cooling, 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 solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, be polymkeric substance after 50 DEG C of dry 24h under vacuo.Productive rate is 66%.
Above-mentioned preparation contains and the reaction formula of the polymer P 4 of thiazole unit is as follows:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): m
n=36.9kDa, M
w/ M
n=2.4.
By carrying out ultraviolet-visible absorption spectroscopy test to poly-{ 2,5-bis-(3-normal-butyl-2-thiophene) thiazole also [5, the 4-d] thiazole-co-4,4 '-divinyl aligns dodecyloxy phenyl pentanoic } in embodiment 4.Result shows that this conjugated polymers has comparatively large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at about 614nm.
Embodiment 5
Present embodiment discloses structural formula following poly-{ 2,5-bis-(3-normal hexane base-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl is to n-decane oxygen base phenyl pentanoic } (containing and the polymer P 5 of thiazole unit):
Above-mentioned containing and the preparation process of polymer P 5 of thiazole unit is as follows:
Under nitrogen protection; 4; 4 '-divinyl is to n-decyloxy phenyl pentanoic (227mg; 0.5mmol) He 2; 5-bis-(5-bromo-3-normal hexane base-2-thiophene) thiazole also [5; 4-d] thiazole (380mg, 0.6mmol) and tri-o-tolyl phosphine (12mg, 0.04mmol) put into two mouthfuls of flasks of 50mL.By DMF (6mL), after fully logical nitrogen purge gas is about 10min, then add three dibenzalacetones two palladium (4.6mg, 0.005mmol).After fully logical nitrogen purge gas is about 20min again, stirring reaction 24h 90 DEG C time, and then at 110 DEG C, continue reaction 24h.Stop polyreaction after cooling, in flask, drip 30mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, after collection, be polymkeric substance after 40 DEG C of dry 24h under vacuo.Productive rate is 48%.
Above-mentioned preparation contains and the reaction formula of the polymer P 5 of thiazole unit is as follows:
Molecule measuring test result is: Molecularweight (GPC, THF, R.I): m
n=37.3kDa, m
w/ M
n=2.3.
By carrying out ultraviolet-visible absorption spectroscopy test to poly-{ 2,5-bis-(3-normal hexane base-2-thiophene) thiazole also [5, the 4-d] thiazole-co-4,4 '-divinyl is to n-decane oxygen base phenyl pentanoic } in embodiment 5.Result shows that this conjugated polymers has comparatively large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at about 616nm.
Embodiment 6
Refer to Fig. 3, 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 ITO (tin indium oxide), preferably, and the tin indium oxide of ITO to be square resistance be 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 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 that the present invention prepares the polymer P containing also thiazole unit, in present embodiment, in the embodiment one that electron donor material is, preparation gathers { 2,5-bis-(3-octyl group-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl is to octyloxyphenyl pentanoic }.
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 150nm, 35nm, 120nm or 70nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 150nm.
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 40 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, wherein electron acceptor material is PCBM, in the embodiment one that electron donor material is, preparation gathers { 2,5-bis-(3-octyl group-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl is to octyloxyphenyl pentanoic }.
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 150nm.
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.
The solar cell device of comparative example is roughly the same with embodiment 6, and its difference is: the solar cell device of comparative example is with poly-two thiophene-thiazoles and thiazole is donor material.
At AM1.5G100mW/cm
2under illumination, be the effciency of energy transfer 3.5% of the body heterojunction solar cell device 40 of donor material based on the multipolymer in embodiment 1, the effciency of energy transfer of the solar cell device of comparative example is 2.2%.The energy transformation ratio of the solar cell device that solar cell device 40 prepared by embodiment 6 is prepared than comparative example is enhanced.
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 (10)
1. contain and a polymkeric substance for thiazole 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 ~ 50.
2. contain and a preparation method for the polymkeric substance of thiazole 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 carry out Heck coupling reaction during the compd A of 1:1 ~ 1:1.2 and compd B are added into containing catalyzer organic solvent by mol ratio, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, the polymer P containing also thiazole unit obtaining that following structural formula represents:
Wherein, n is the integer of 10 ~ 50.
3. the preparation method containing the polymkeric substance of also thiazole 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 containing the polymkeric substance of also thiazole unit according to claim 2, it is characterized in that, described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetrakis triphenylphosphine palladium or three (dibenzalacetone) two palladium, described organophosphorus ligand is tri-butyl 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 containing the polymkeric substance of also thiazole 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 containing the polymkeric substance of also thiazole unit according to claim 2, it is characterized in that the temperature of reaction of described Heck coupling reaction is 70 DEG C ~ 130 DEG C, the reaction times is 24 hours ~ 96 hours.
7. the preparation method containing the polymkeric substance of also thiazole 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.
8. the preparation method containing the polymkeric substance of also thiazole unit according to claim 2, it is characterized in that, also comprise the step that the polymer P that will contain also thiazole unit carries 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, containing and the polymer P of thiazole unit after evaporating solvent obtains purifying after collecting chloroformic solution.
9. the preparation method containing the polymkeric substance of also thiazole unit according to claim 8, is characterized in that, described extracting adopts apparatus,Soxhlet's to carry out.
10. a solar cell device, comprises active coating, it is characterized in that, the material of described active coating is have containing and the polymer P of thiazole unit of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, R
2for C
1~ C
20alkyl, n is the integer of 10 ~ 50.
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| JP2006028263A (en) * | 2004-07-13 | 2006-02-02 | Mitsubishi Paper Mills Ltd | Polymer compound containing specific triphenylamine derivative, charge transport material and electrophotographic photoreceptor |
| WO2007145482A1 (en) * | 2006-06-15 | 2007-12-21 | Lg Chem, Ltd. | Thiazolothiazole derivatives and organic electronic device using the same |
| WO2008100085A1 (en) * | 2007-02-13 | 2008-08-21 | Lg Chem, Ltd. | Organic transistor using thiazolothiazole derivatives and method for fabricating the same |
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