CN103159936A - Thiazothiazole unit-containing polymer and preparation method thereof and solar battery device - Google Patents

Thiazothiazole unit-containing polymer and preparation method thereof and solar battery device Download PDF

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CN103159936A
CN103159936A CN2011104154170A CN201110415417A CN103159936A CN 103159936 A CN103159936 A CN 103159936A CN 2011104154170 A CN2011104154170 A CN 2011104154170A CN 201110415417 A CN201110415417 A CN 201110415417A CN 103159936 A CN103159936 A CN 103159936A
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thiazole
polymkeric substance
preparation
unit
thiazole unit
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CN103159936B (en
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周明杰
王平
张振华
冯小明
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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 thiazothiazole unit-containing polymer has the following structural formula: wherein R1 is an alkyl group of C1-C20, R2 is an alkyl group of C1-C20, and n is an integer of 10-50. The energy gap of the thiazothiazole unit-containing polymer is narrow, therefore the energy conversion efficiency is greatly improved. The invention also provides a preparation method of the thiazothiazole unit-containing polymer and a solar battery device using the thiazothiazole unit-containing polymer.

Description

Contain and the polymkeric substance of thiazole 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 contain and the polymkeric substance of thiazole unit and preparation method thereof with use this to contain 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, and the solar cell that is electric energy with solar energy converting is also the focus of research.The conjugated polymer thin films solar cell of rising in recent years has that cost is low, lightweight, manufacture craft is 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 the design by material and optimizes the performance that improves solar cell.
Contain and the polymkeric substance of thiazole unit in, because thiazole is typical electron deficiency unit, comprise an electrophilic imine group, therefore contain and the polymkeric substance of thiazole unit has higher hole mobility, demonstrated good photovoltaic performance.Yet, existing contain and the band gap (energy level difference between HOMO energy level and lumo energy) of the polymkeric substance of thiazole unit wider, reduced the specific absorption to photon in solar spectral, thus make use contain and the effciency of energy transfer of the organic solar batteries of the polymkeric substance of thiazole unit lower.
[summary of the invention]
Based on this, be necessary to provide a kind of energy conversion efficiency higher containing and the polymkeric substance of thiazole unit.
In addition, also be necessary to provide a kind of also preparation method of the polymkeric substance of thiazole unit that contains.
In addition, also be necessary to provide use to contain the also solar cell device of the polymkeric substance of thiazole unit.
A kind of also polymkeric substance of thiazole unit that contains has following structural formula:
Figure BDA0000119636720000021
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～50 integer.
A kind of also preparation method of the polymkeric substance of thiazole unit that contains comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is: B is:
Figure BDA0000119636720000023
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl;
In oxygen-free environment, be that the compd A of 1: 1～1: 1.2 and compd B are added into and carry out the Heck coupling reaction in the organic solvent that contains catalyzer with mol ratio, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the also polymer P of thiazole unit that contains that following structural formula represents:
Figure BDA0000119636720000024
Wherein, n is 10～50 integer.
In a preferred embodiment, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
In a preferred embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, 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 are 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 Heck coupling reaction is 70 ℃～130 ℃, and the reaction times is 24 hours～96 hours.
In a preferred embodiment, the temperature of reaction of described Heck coupling reaction is 90 ℃～120 ℃.
In a preferred embodiment, also comprise the step that contains and the polymer P of thiazole unit carries out separation and purification, described purification procedures is as follows: add the methyl alcohol precipitating and filter in described compd A and compd B carry out solution after the Heck coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, will be through the chloroform extracting of the solid after extracting, collect evaporating solvent after chloroformic solution and obtain containing and the polymer P of thiazole unit after purifying.
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 the also polymer P of thiazole unit that contains with following structural formula:
Figure BDA0000119636720000031
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～50 integer.
The above-mentioned also polymkeric substance of thiazole unit that contains, owing to having introduced triphenylamine nitrogen-containing hetero aromatic ring and thienyl in structure, thienyl can reduce the band gap of multipolymer, can improve effciency of energy transfer; Triphenylamine nitrogen-containing hetero aromatic ring is the electron deficiency unit, forms the structure of push-and-pull electronics between other unit of triphenylamine nitrogen-containing hetero aromatic ring unit and polymkeric substance, strengthens the delocalization of π-electron, reaches the purpose of absorption spectrum Einstein shift, reduction polymkeric substance band gap; Thiazole comprises an electrophilic imine group, is an electron deficiency unit, makes polymkeric substance show higher hole mobility, contains and the polymer application of thiazole unit can increase substantially effciency of energy transfer in solar cell device above-mentioned.
[description of drawings]
Fig. 1 is containing the also preparation method's of the polymkeric substance of thiazole unit the schema of an embodiment;
Fig. 2 is the ultraviolet-visible absorption spectroscopy spectrogram of the polymkeric substance of containing of embodiment one preparation and thiazole unit;
Fig. 3 is the structural representation of the solar cell device of an embodiment.
[embodiment]
Contain and the polymkeric substance of thiazole unit and its preparation method and application is further illustrated below in conjunction with the drawings and specific embodiments.
Containing and the polymkeric substance of thiazole unit of one embodiment, have following structural formula:
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～50 integer.
The above-mentioned also polymkeric substance of thiazole unit that contains, owing to having introduced triphenylamine nitrogen-containing hetero aromatic ring and thienyl in structure, thienyl can reduce the band gap of multipolymer, can improve effciency of energy transfer; Triphenylamine nitrogen-containing hetero aromatic ring is the electron deficiency unit, forms the structure of push-and-pull electronics between other unit of triphenylamine nitrogen-containing hetero aromatic ring unit and polymkeric substance, strengthens the delocalization of π-electron, reaches the purpose of absorption spectrum Einstein shift, reduction polymkeric substance band gap; Thiazole comprises an electrophilic imine group, is an electron deficiency unit, makes polymkeric substance show higher hole mobility, contains and the polymer application of thiazole unit can increase substantially effciency of energy transfer in solar cell device above-mentioned.
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 1Be C 1～C 20Alkyl.
The structural formula of compd B is:
Figure BDA0000119636720000052
Wherein, R 2Be C 1～C 20Alkyl.
In present embodiment, but the disclosed method of compd A reference literature (Advancedmaterials, 2007,19,4257) is synthetic or buy from the market and obtain, and compd B can be bought from the market and obtain.
Step S2, preparation contain the also polymer P of thiazole unit.
In oxygen-free environment, be that the compd A of 1: 1～1: 1.2 and compd B are added into and carry out the Heck coupling reaction in the organic solvent that contains catalyzer with mol ratio, described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand, and what obtain that following structural formula represents contains and the polymer P of thiazole unit:
Figure BDA0000119636720000053
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～50 integer.
In present embodiment, the Heck coupling reaction carries out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least a 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 bi triphenyl phosphine dichloride palladium, 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 all are not limited to cited kind, as long as energy catalytic cpd A and compd B carry out the Heck 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～and 1: 100, add the catalyzer of catalytic amount to get final product in the organic solvent that adds compd A and compd B.
In present embodiment, the temperature of reaction of Heck coupling reaction is 70 ℃～130 ℃, and the reaction times is 24 hours～96 hours.Preferably, the temperature of reaction of Heck coupling reaction is 90 ℃～120 ℃, and the reaction times is 48 hours～72 hours.The temperature of reaction that is appreciated that the Heck coupling reaction is not limited to 70 ℃～130 ℃, as long as compd A and compd B are reacted; Reaction times also is not limited to 24 hours～and 96 hours, as long as compd A and compd B are reacted completely as far as possible.
Step S3, separation and purification contain the also polymer P of thiazole unit.
Add the methyl alcohol precipitating and filter in described compd A and compd B carry out solution after the Heck coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, will be through the chloroform extracting of the solid after extracting, collect evaporating solvent after chloroformic solution and obtain containing and the polymer P of thiazole unit after purifying.
In present embodiment, extracting uses apparatus,Soxhlet's to carry out.
In present embodiment, obtain containing and the polymer P of thiazole unit 50 ℃ of dryings 24 hours under vacuum after purifying with collecting evaporating solvent after chloroformic solution.
The above-mentioned also preparation method of the polymkeric substance of thiazole unit that contains, synthetic route is comparatively simple, has reduced manufacturing cost; Preparation contain and the polymkeric substance of thiazole unit has higher hollow mobility and lower band gap.
The below is specific embodiment.
Embodiment 1
The present embodiment discloses following the gathering { 2,5-two (3-octyl group-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl is to the octyloxyphenyl pentanoic } (containing the also polymer P 1 of thiazole unit) of structural formula:
Figure BDA0000119636720000071
Above-mentioned contain and the preparation process of the polymer P 1 of thiazole unit as follows:
Under nitrogen protection; 4; 4 '-divinyl is to octyloxyphenyl pentanoic (213mg; 0.5mmol) and 2; 5-two (5-bromo-3-octyl group-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.With DMF (6mL), fully logical nitrogen purge gas is approximately after 10min, then adds three dibenzalacetone two palladiums (18.3mg, 0.02mmol).Fully logical nitrogen purge gas is approximately after 20min again, stirring reaction 24h in the time of 90 ℃, and then continue reaction 24h under 110 ℃.Stop polyreaction after cooling, drip 30mL methyl alcohol precipitating in flask, use successively methyl alcohol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, is polymkeric substance after 40 ℃ of dry 24h after collecting under vacuum.Productive rate is 43%.
Above-mentioned preparation contain and the reaction formula of the polymer P 1 of thiazole unit as follows:
Figure BDA0000119636720000072
The molecule measuring test result is: Molecular weight (GPC, THF, R.I): m n=35.1kDa, m w/ M n=2.3.
See also Fig. 2, by poly-{ 2,5-two (3-octyl group-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl is to the octyloxyphenyl pentanoic } in embodiment 1 carried out the ultraviolet-visible absorption spectroscopy test.Result shows that this conjugated polymers has large wider absorption between 350nm～700nm, and wherein maximum absorption band is positioned at the 612nm left and right.
Embodiment 2
The present embodiment discloses following the gathering { 2,5-two (3-methyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl is to eicosane oxygen base phenyl pentanoic } (containing the also polymer P 2 of thiazole unit) of structural formula:
Figure BDA0000119636720000081
Above-mentioned contain and the preparation process of the polymer P 2 of thiazole unit as follows:
Under nitrogen protection; 4; 4 '-divinyl is to eicosane oxygen base phenyl pentanoic (178mg; 0.3mmol); 2; 5-two (5-bromo-3-methyl-2-thiophene) thiazole also [5; 4-d] thiazole (148mg; 0.3mmol) and 10mL toluene join respectively in the two-mouth bottle of 50mL; fully logical nitrogen purge gas approximately after 20min, then adds bi triphenyl phosphorus palladium chloride (4.2mg, 0.006mmol) wherein; fully logical nitrogen purge gas is approximately after 10min, at 120 ℃ of stirring reaction 24h again.Stop polyreaction after cooling, add 40mL methyl alcohol precipitating in flask, use successively methyl alcohol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, is polymkeric substance after 50 ℃ of dry 24h after collecting under vacuum.Productive rate is 53%.
Above-mentioned preparation contain and the reaction formula of the polymer P 2 of thiazole unit as follows:
The molecule measuring test result is: Molecular weight (GPC, THF, R.I): m n=35.8kDa, m w/ M n=2.3.
By poly-{ 2,5-two (3-methyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl is to eicosane oxygen base phenyl pentanoic } in embodiment 2 carried out the ultraviolet-visible absorption spectroscopy test.Result shows that this conjugated polymers has large wider absorption between 350nm～700nm, and wherein maximum absorption band is positioned at the 607nm left and right.
Embodiment 3
The present embodiment discloses following the gathering { 2,5-two (3-eicosyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 4 '-divinyl p-methoxyphenyl pentanoic } (containing the also polymer P 3 of thiazole unit) of structural formula:
Figure BDA0000119636720000092
Above-mentioned contain and the preparation process of the polymer P 3 of thiazole unit as follows:
Under nitrogen protection, 4,4 '-divinyl p-methoxyphenyl pentanoic (98mg; 0.3mmol); 2,5-two (5-bromo-3-eicosyl-2-thiophene) thiazole is [5,4-d] thiazole (308mg also; 0.3mmol) and the 15mL tetrahydrofuran (THF) join respectively in the two-mouth bottle of 50mL; fully logical nitrogen purge gas approximately after 20min, then adds tetra-triphenylphosphine palladium (17mg, 0.015mmol) wherein; fully logical nitrogen purge gas is approximately after 10min, at 90 ℃ of stirring reaction 72h again.Stop polyreaction after cooling, add 40mL methyl alcohol precipitating in flask, use successively methyl alcohol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for, obtaining red solid, obtaining product after 50 ℃ of dry 24h after collecting under vacuum.Productive rate is 61%.
Above-mentioned preparation contain and the reaction formula of the polymer P 3 of thiazole unit as follows:
Figure BDA0000119636720000101
The molecule measuring test result is: Molecular weight (GPC, THF, R.I): m n=43.6kDa, m w/ M n=2.1.
By poly-{ 2,5-two (3-eicosyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, 4 '-divinyl p-methoxyphenyl pentanoic } in embodiment 3 carried out the ultraviolet-visible absorption spectroscopy test.Result shows that this conjugated polymers has large wider absorption between 350nm～700nm, and wherein maximum absorption band is positioned at the 605nm left and right.
Embodiment 4
The present embodiment discloses following the gathering { 2,5-two (3-normal-butyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl aligns dodecyloxy phenyl pentanoic } (containing the also polymer P 4 of thiazole unit) of structural formula:
Figure BDA0000119636720000111
Above-mentioned contain and the preparation process of the polymer P 4 of thiazole unit as follows:
Under nitrogen protection; 4; 4 '-divinyl aligns dodecyloxy phenyl pentanoic (145mg; 0.3mmol); 2; 5-two (5-bromo-3-normal-butyl-2-thiophene) thiazole also [5; 4-d] thiazole (173mg; 0.33mmol) and 10mL toluene join respectively in the two-mouth bottle of 50mL; fully logical nitrogen purge gas approximately after 20min, then adds bi triphenyl phosphorus palladium chloride (10.5mg, 0.015mmol) wherein; fully logical nitrogen purge gas is approximately after 10min, at 130 ℃ of stirring reaction 24h again.Stop polyreaction after cooling, add 40mL methyl alcohol precipitating in flask, use successively methyl alcohol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, is polymkeric substance after 50 ℃ of dry 24h after collecting under vacuum.Productive rate is 66%.
Above-mentioned preparation contain and the reaction formula of the polymer P 4 of thiazole unit as follows:
Figure BDA0000119636720000112
The molecule measuring test result is: Molecular weight (GPC, THF, R.I): m n=36.9kDa, M w/ M n=2.4.
By poly-{ 2,5-two (3-normal-butyl-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl aligns dodecyloxy phenyl pentanoic } in embodiment 4 carried out the ultraviolet-visible absorption spectroscopy test.Result shows that this conjugated polymers has large wider absorption between 350nm～700nm, and wherein maximum absorption band is positioned at the 614nm left and right.
Embodiment 5
The present embodiment discloses following the gathering { 2,5-two (3-normal hexane base-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl is to n-decane oxygen base phenyl pentanoic } (containing the also polymer P 5 of thiazole unit) of structural formula:
Above-mentioned contain and the preparation process of the polymer P 5 of thiazole unit as follows:
Under nitrogen protection; 4; 4 '-divinyl is to n-decyloxy phenyl pentanoic (227mg; 0.5mmol) and 2; 5-two (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.With DMF (6mL), fully logical nitrogen purge gas is approximately after 10min, then adds three dibenzalacetone two palladiums (4.6mg, 0.005mmol).Fully logical nitrogen purge gas is approximately after 20min again, stirring reaction 24h in the time of 90 ℃, and then continue reaction 24h under 110 ℃.Stop polyreaction after cooling, drip 30mL methyl alcohol precipitating in flask, use successively methyl alcohol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain dark red solid, is polymkeric substance after 40 ℃ of dry 24h after collecting under vacuum.Productive rate is 48%.
Above-mentioned preparation contain and the reaction formula of the polymer P 5 of thiazole unit as follows:
Figure BDA0000119636720000131
The molecule measuring test result is: Molecular weight (GPC, THF, R.I): m n=37.3kDa, m w/ M n=2.3.
By poly-{ 2,5-two (3-normal hexane base-2-thiophene) thiazole is [5,4-d] thiazole-co-4 also, and 4 '-divinyl is to n-decane oxygen base phenyl pentanoic } in embodiment 5 carried out the ultraviolet-visible absorption spectroscopy test.Result shows that this conjugated polymers has large wider absorption between 350nm～700nm, and wherein maximum absorption band is positioned at the 616nm left and right.
Embodiment 6
See also 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), and preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.
Buffer layer 63 is formed at anode 62 away from a side surface of substrate 61.The material of buffer layer 63 is poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (PEDOT:PSS).
Active coating 64 is formed at buffer layer 63 away from a side surface of anode 62.Active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1: 2, and wherein electron acceptor material is (6,6) phenyl-C 61-methyl-butyrate (PCBM), electron donor material is that the present invention prepares and contains and the polymer P of thiazole unit, in present embodiment, in the embodiment one that electron donor material is, preparation gathers { 2,5-two (3-octyl group-2-thiophene) thiazole also [5,4-d] thiazole-co-4,4 '-divinyl is to the octyloxyphenyl pentanoic }.
Negative electrode 65 is formed at active coating 64 away from a side surface of buffer layer 63.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 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, this moment, active coating 64 directly was formed at anode 62 surfaces.
The manufacturing processed of this solar cell device 40 is as follows:
Carry out ultrasonic cleaning after anode 62 being formed at a side surface of substrate 61, and after processing with oxygen-Plasma, be coated with the PEDOT:PSS that last layer plays modification on anode 62 surfaces and form buffer layer 63.
Apply one deck active coating 64 on buffer layer 64.This active coating 64 comprises electron donor material and electron acceptor material, wherein electron acceptor material is PCBM, poly-{ 2,5-two (3-octyl group-2-thiophene) thiazole also [5 of preparation in the embodiment one that electron donor material is, 4-d] thiazole-co-4,4 '-divinyl is to the octyloxyphenyl pentanoic }.
At active coating 64 surface formation negative electrodes 65.In present embodiment, negative electrode 65 is the aluminium lamination that is 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 centigrade of air tight conditions, drop to again room temperature, can effectively increase order and the regularity arranged between interior each group of molecule and molecule segment after solar cell device is annealed, improve transmission speed and the efficient of carrier mobility, improve photoelectric transformation efficiency.
The solar cell device of Comparative Examples and embodiment 6 are roughly the same, and its difference is: the solar cell device of Comparative Examples is donor material with poly-two thiophene-thiazoles and thiazole.
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 Examples is 2.2%.The solar cell device 40 of embodiment 6 preparations is enhanced than the energy transformation ratio of the solar cell device of Comparative Examples preparation.
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 electron donor(ED)/acceptor material at the interface again, and with 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 electronics 65 transmission and collected by negative electrode along electron acceptor material to negative electrode freely, transmit and collected by anode 62 along electron donor material anode 62 in the hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material can utilize luminous energy more fully because it has very wide spectral response range, 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, is 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.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. one kind contains the also polymkeric substance of thiazole unit, it is characterized in that having following structural formula:
Figure FDA0000119636710000011
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～50 integer.
2. one kind contains the also preparation method of the polymkeric substance of thiazole unit, it is characterized in that, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
Figure FDA0000119636710000012
B is:
Figure FDA0000119636710000013
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl;
In oxygen-free environment, be that the compd A of 1: 1～1: 1.2 and compd B are added into and carry out the Heck coupling reaction in the organic solvent that contains catalyzer with mol ratio, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the also polymer P of thiazole unit that contains that following structural formula represents:
Wherein, n is 10～50 integer.
3. according to claim 2 containing and the preparation method of the polymkeric substance of thiazole unit, it is characterized in that, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
4. according to claim 2 containing and the preparation method of the polymkeric substance of thiazole unit, it is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, 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 are 1: 4～1: 8.
5. the also preparation method of the polymkeric substance of thiazole unit that contains 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. according to claim 2 containing and the preparation method of the polymkeric substance of thiazole unit, the temperature of reaction that it is characterized in that described Heck coupling reaction is 70 ℃～130 ℃, and the reaction times is 24 hours～96 hours.
7. the also preparation method of the polymkeric substance of thiazole unit that contains according to claim 2, is characterized in that, the temperature of reaction of described Heck coupling reaction is 90 ℃～120 ℃.
8. according to claim 2 containing and the preparation method of the polymkeric substance of thiazole unit, it is characterized in that, also comprise the step that contains and the polymer P of thiazole unit carries out separation and purification, described purification procedures is as follows: add the methyl alcohol precipitating and filter in described compd A and compd B carry out solution after the Heck coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, will be through the chloroform extracting of the solid after extracting, collect evaporating solvent after chloroformic solution and obtain containing and the polymer P of thiazole unit after purifying.
9. the also preparation method of the polymkeric substance of thiazole unit that contains according to claim 8, is characterized in that, described extracting adopts apparatus,Soxhlet's to carry out.
10. a solar cell device, comprise active coating, it is characterized in that, the material of described active coating is the also polymer P of thiazole unit that contains with following structural formula:
Figure FDA0000119636710000021
Wherein, R 1Be C 1～C 20Alkyl, R 2Be C 1～C 20Alkyl, n is 10～50 integer.
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