CN103897156B - A kind of naphtho-two thiophene-based two dimension conjugated polymers, preparation method and its usage with thiophene side chain - Google Patents
A kind of naphtho-two thiophene-based two dimension conjugated polymers, preparation method and its usage with thiophene side chain Download PDFInfo
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Abstract
The invention discloses two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b ˊ] two thiophene-based two dimension conjugated polymers of a kind of 5,10-and preparation method thereof and application. This conjugated polymer has structure as shown in the formula (I), and in formula, R1 replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R2 and R3 are all the alkyl of 6 to 20 straight or branched independently selected from hydrogen or replacement or unsubstituted carbon number; Ar is selected from the heteroarylidene that contains at least two rings of replacement; M is 0 or 1; N is the natural number between 1～10000. Such conjugated polymer in the present invention can be applied to organic solar batteries field and organic field effect tube field.
Description
Technical field
The present invention relates to a kind of naphtho-two thiophene-based two dimension conjugated polymers, preparation method and its usage with thiophene side chain, be specifically related to a kind of 5, two (5-alkylthrophene-2-yl) naphthalenes [1 of 10-, 2-b:5,6-b'] two thiophene-based two dimension conjugated polymers, preparation method and the application in photoelectric field thereof.
Background technology
In recent years, organic solar batteries, particularly the research based on polymer thin-film solar cell has caused that educational circles and industrial circle pay close attention to widely, this class battery has the incomparable advantage of inorganic semiconductor solar cell, as low in cost, lightweight, preparation technology is simple, can be prepared into flexible device etc., presented considerable research and application prospect. By the regulation and control to polymer molecule energy level, absorption spectrum and accumulation mode, add the optimization to polymer solar cell device structure, the electricity conversion of polymer thin-film solar cell has been broken through 10%(J.B.You, L.T.Dou, K.Yoshimura, T.Kato, K.Ohya, T.Moriarty, K.Emery, C.C.Chen, J.Gao, G.Li, Y.Yang, Nat.Commun.2013,4,1446.), this result has further excited people's designs, synthesizing new high efficiency polymer donor material and has continued to optimize the research enthusiasm of device architecture.
Summary of the invention
The object of the present invention is to provide a kind of novel 5, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-, it has excellent photoelectric properties, is a kind of donor material very with commercial applications prospect.
In order to achieve the above object, the present invention has adopted following technical scheme:
Two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of a kind of 5,10-, it has structure as shown in the formula (I):
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R2And R3It is all the alkyl of 6 to 20 straight or branched independently selected from hydrogen or replacement or unsubstituted carbon number; Ar is selected from the heteroarylidene that contains at least two rings of replacement; The repetitive number of thiophene π bridge in m representation polymer is 0 or 1; The number of repeat unit of n representation polymer, it is the natural number between 1～10000.
5, two (5-alkylthrophene-2-yl) naphthalenes [1 of 10-, 2-b:5,6-b'] two thiophene-based two dimensions conjugated polymers are as polymer donor material, by in naphthalene nucleus both sides extending transversely go out two thiophene units form the molecular structure of a rigidity, large plane, further expanded effective conjugate area of polymer molecule, thereby the π-π having strengthened between polymer molecule interacts, and is conducive to improve the charge transport properties between polymer molecule. In addition, by longitudinally drawing the thienyl group with alkyl chain in naphthalene nucleus both sides, on the one hand, make polymer molecule there is good dissolubility in the conventional organic solvents such as oxolane, chloroform, chlorobenzene and o-dichlorohenzene, be conducive to the preparation of film in polymer solar cell device; On the other hand, make polymer molecule form a kind of two-dimentional conjugated structure, be both conducive to improve the absorption spectrum of polymer molecule, be conducive to again improve the charge mobility between polymer molecule. Therefore, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 5,10-are that a class has good photoelectric properties, and have very much the donor material of commercial applications prospect.
Preferably, described Ar is selected from any one in following group:
Wherein, R replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched.
Exemplary 5, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-have the structure shown in formula (II):
In formula, R1, Ar and n restriction cotype (I).
Exemplary 5, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-have the structure shown in formula (III):
R1、R2, Ar and n restriction cotype (I).
Exemplary 5, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-have the structure shown in formula (IV):
R1、R3, Ar and n restriction cotype (I).
Conventionally, the number-average molecular weight of described conjugated polymer is 5000～1000000, and preferred number average molecular weight is 10000～500000, and further preferred number average molecular weight is 20000～300000.
The decentralization of conjugated polymer prepared by the present invention is less, and PDI specifically can be 1.3～2.0, and for example 1.30,1.91 or 1.99 etc.
It is a kind of as above 5 that two of object of the present invention is to provide, the preparation method of two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-, and described method comprises the steps:
(1) under ice bath environment, the compound shown in formula (V) is reacted in oxolane with n-BuLi, and then add trimethyltin chloride to continue reaction in reaction system, obtain the compound shown in formula (VI);
(2) under inert gas shielding; compound shown in formula (VI) is reacted under the catalytic action of palladium catalyst with the conjugate unit shown in formula (VII); after reaction finishes, add the poor solvent precipitating of conjugated polymer, filter and be precipitated thing, sediment is carried out to soxhlet extraction; concentrated chloroform extract; and by the poor solvent precipitating of conjugated polymer, suction filtration obtains two (5-alkylthrophene-2-yl) naphthalenes [1 of 5,10-; 2-b:5,6-b'] two thiophene-based two dimension conjugated polymers.
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R2And R3It is all the alkyl of 6 to 20 straight or branched independently selected from hydrogen or replacement or unsubstituted carbon number; Ar is selected from the heteroarylidene that contains at least two rings of replacement; The repetitive number of thiophene π bridge in m representation polymer is 0 or 1.
Preferably, step (2) sediment carries out soxhlet extraction with methyl alcohol, acetone, n-hexane and chloroform equal solvent successively.
Preferably, the reaction time of the described reaction of step (2) is 8～24 hours, for example 10 hours, 12 hours, 14 hours, 16 hours, 20 hours, 22 hours, 24 hours.
Preferably, reaction described in step (2) is carried out in solvent, and described solvent is selected from the mixture of any one or at least two kinds in toluene, DMF, chlorobenzene or o-dichlorohenzene.
Preferably, the mol ratio of the conjugate unit shown in the compound shown in the described formula of step (2) (VI) and formula (VII) is 1:1.
Preferably, the poor solvent of described conjugated polymer is that methyl alcohol is or/and n-hexane.
Compound shown in formula (V) can be with reference to prior art (Shinamura, S.; Sugimoto, R.; Yanai, N.; Takemura, N.; Kashiki, T.; Osaka, I.; Miyazaki, E.; Takimiya, K.Org.Lett.2012,14,4718 – 4721.) in disclosed method preparation.
Three of object of the present invention is to provide a kind of semiconductor blend, and it comprises as above as 5 of donor material, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] two thiophene-based two dimension conjugated polymer and the acceptor materials of 10-.
Preferably, described acceptor material is fullerene derivate, preferably [6,6]-phenyl C61Methyl butyrate (PC61BM) or/and [6,6]-phenyl C71Methyl butyrate (PC71BM）。
Preferably, described conjugated polymer and acceptor material can mix according to arbitrary proportion, if the mass ratio of conjugated polymer donor material and acceptor material is 1:1,1:2 or 1:3 etc.
Four of object of the present invention is to provide a kind of purposes of semiconductor mixtures as above, and it is for the preparation of semiconductor devices or photovoltaic device.
Five of object of the present invention is to provide a kind of photovoltaic device, and it comprises the active material layer between collecting layer, hole, electron collection layer and collecting layer, hole and electron collection layer; Described active material layer is semiconductor blend as above. The polymer solar cell device of the preferred body heterojunction structure of described photovoltaic device.
Compared with the prior art, the present invention has following beneficial effect:
Evidence, with provided by the invention 5, photovoltaic device prepared by two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-and acceptor material there is high electricity conversion, can reach more than 7%. For example, with provided by the invention 5, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers and [6,6]-phenyl C of 10-71Methyl butyrate (PC71The electricity conversion of photovoltaic device prepared by the active material layer that BM) blend forms can reach 7.5%.
Brief description of the drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the polymer P 3 prepared of embodiment 2 under chloroformic solution neutralized film state.
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of the polymer P 2 prepared of embodiment 3 under chloroformic solution neutralized film state.
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of the polymer P 4 prepared of embodiment 4 under chloroformic solution neutralized film state.
Fig. 4 has shown that structure is ITO/ZnO/ polymer P 3:PC71BM/MoO3The I-V curve of the polymer solar cell device of/Ag.
Fig. 5 has shown that structure is ITO/ZnO/ polymer P 2:PC71BM/MoO3The I-V curve of the polymer solar cell device of/Ag.
Fig. 6 has shown that structure is ITO/ZnO/ polymer P 4:PC71BM/MoO3The I-V curve of the polymer solar cell device of/Ag.
Detailed description of the invention
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and by detailed description of the invention.
Embodiment 1:(5, two (5-(2-ethylhexyl) thiophene-2-yl) naphthalene [1,2-b:5,6-b'] two thiophene-2 of 10-, 7-bis-bases) two (trimethyl-tin-radicals) synthetic
Chemical reaction flow process is as follows, and concrete reactions steps and reaction condition are as follows:
By 478mg(0.76mmol) compound 9(preparation process bibliography Shinamura, S.; Sugimoto, R.; Yanai, N.; Takemura, N.; Kashiki, T.; Osaka, I.; Miyazaki, E.; Takimiya, K.Org.Lett.2012,14,4718 – 4721.) be dissolved in the super dry tetrahydrofuran of 25mL, under 0 DEG C, argon atmosphere, slowly drip the hexane solution (1.60mmol, 1.6mol/L) of 1mL n-BuLi, drip under rear room temperature and react 2 hours, slowly drip again the tetrahydrofuran solution (2.28mmol, 1mol/L) of 2.28mL trimethyltin chloride, drip under rear room temperature and react 12 hours. After reaction finishes, reactant liquor is poured into water, uses dichloromethane extraction three times, merge organic phase and use again anhydrous magnesium sulfate drying, be then spin-dried for organic phase, be finally recrystallized and obtain 552mg compound 10(yellow solid with isopropyl alcohol), productive rate 76%. MS (MALDI-TOF): m/z=954.16.1HNMR(400MHz,CDCl3,ppm):δ8.09(s,2H),7.95(s,2H),7.31(d,2H),6.88(d,2H),2.87(d,4H),1.71(m,2H),1.34(m,16H),0.96(m,12H),0.47(t,18H)。
Embodiment 2: polymer P 3 synthetic
Chemical reaction flow process is shown below, and concrete reactions steps and reaction condition are as follows:
In 50mL there-necked flask; add 172mg(0.18mmol) compound 10 and 186mg(0.18mmol) compound 13; add again the super dry chlorobenzene of 20mL; logical three (dibenzalacetone) two palladiums and three (o-methyl-phenyl-) phosphine of adding rapidly after argon gas for 20 minutes; take out again inflation three times; slowly temperature is risen to 130 DEG C afterwards, lucifuge reaction 24 hours under argon shield. Question response finishes, reaction system naturally cools to after room temperature, reactant liquor is splashed into and in 200mL methyl alcohol, carries out precipitating, leach sediment and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, n-hexane and chloroform successively, the concentrated chloroform extract finally obtaining, and be added dropwise to and in 200mL methyl alcohol, carried out precipitating again, filter out and precipitate and carry out vacuum drying, finally obtain 330mg polymer P 3, productive rate 85%. At room temperature record the number-average molecular weight Mn=293.1K of this polymer taking oxolane as mobile phase by gel exclusion chromatography, decentralization PDI=1.99.
Embodiment 3: polymer P 2 synthetic
Shown under chemical reaction flow process, concrete reactions steps and reaction condition are as follows:
In 50mL there-necked flask; add 172mg(0.18mmol) compound 10 and 186mg(0.18mmol) compound 12; add again the super dry chlorobenzene of 20mL; logical three (dibenzalacetone) two palladiums and three (o-methyl-phenyl-) phosphine of adding rapidly after argon gas for 20 minutes; take out again inflation three times; slowly temperature is risen to 130 DEG C afterwards, lucifuge reaction 24 hours under argon shield. Question response finishes, reaction system naturally cools to after room temperature, reactant liquor is splashed into and in 200mL methyl alcohol, carries out precipitating, leach sediment and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, n-hexane and chloroform successively, the concentrated chloroform extract finally obtaining, and be added dropwise to and in 200mL methyl alcohol, carried out precipitating again, filter out and precipitate and carry out vacuum drying, finally obtain 260mg polymer P 2, productive rate 73%. At room temperature record the number-average molecular weight Mn=24.6K of this polymer taking oxolane as mobile phase by gel exclusion chromatography, decentralization PDI=1.30.
Embodiment 4: polymer P 4 synthetic
Chemical reaction flow process is shown below, and concrete reactions steps and reaction condition are as follows:
In 50mL there-necked flask; add 133mg(0.14mmol) compound 10 and 139mg(0.14mmol) compound 14; add again the super dry toluene of 12mL and the super dry N of 3mL; dinethylformamide; lead to and after argon gas, add rapidly tetra-triphenylphosphine palladium in 20 minutes; take out again inflation three times, slowly temperature is risen to 110 DEG C afterwards, lucifuge reaction 24 hours under argon shield. Question response finishes, reaction system naturally cools to after room temperature, reactant liquor is splashed into and in 200mL methyl alcohol, carries out precipitating, leach sediment and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, n-hexane and chloroform successively, the concentrated chloroform extract finally obtaining, and be added dropwise to and in 200mL methyl alcohol, carried out precipitating again, filter out and precipitate and carry out vacuum drying, finally obtain 230mg polymer P 3, productive rate 85%. At room temperature record the number-average molecular weight Mn=34.1K of this polymer taking oxolane as mobile phase by gel exclusion chromatography, decentralization PDI=1.91.
Embodiment 5: polymer P 1, P5～P15's is synthetic
The synthetic method of polymer P 1 is as above-described embodiment, and except only needing that compound 10 is reacted with following compound 11, chemical reaction flow process is shown below.
The synthetic method of polymer P 5～P15 is as above-described embodiment, and except only needing that compound 10 and following compound 15～25 are carried out respectively to polymerisation, chemical reaction flow process is shown below.
Embodiment 6: measure the ultraviolet-visible absorption spectroscopy of polymer under chloroformic solution neutralized film state and utilize empirical equation to calculate the optical band gap of polymer
Appropriate polymer dissolution is made into certain density solution and gets part solution in chloroform and be spin-coated to the film of making polymer on quartz plate.
The ultraviolet-visible absorption spectroscopy that polymer P 3 prepared by embodiment 2 records under chloroformic solution neutralized film state as shown in Figure 1. The optical band gap of polymer uses formula (Eg=1240/λAbsorb limit) calculate, wherein the maximum absorption band of P3 in chloroformic solution is 536nm, and the maximum absorption band under filminess is 588nm, absorbs limit at 639nm, and optical band gap is 1.94eV.
The ultraviolet-visible absorption spectroscopy that polymer P 2 prepared by embodiment 3 records under chloroformic solution neutralized film state shows as shown in Figure 2. The optical band gap of polymer uses formula (Eg=1240/λAbsorb limit) calculate, wherein the maximum absorption band of P2 in chloroformic solution is 518nm, and the maximum absorption band under filminess is 528nm, absorbs limit at 626nm, and optical band gap is 1.98eV.
The ultraviolet-visible absorption spectroscopy that polymer P 4 prepared by embodiment 4 records under chloroformic solution neutralized film state shows as shown in Figure 3. The optical band gap of polymer uses formula (Eg=1240/λAbsorb limit) calculate, wherein the maximum absorption band of P4 in chloroformic solution is 662nm, and the maximum absorption band under filminess is 668nm, absorbs limit at 730nm, and optical band gap is 1.69eV.
Embodiment 7: preparation characterize polymers solar cell device
Transparent conducting glass with ITO is used to deionized water, acetone, the each ultrasonic cleaning of isopropyl alcohol 15 minutes successively, ZnO colloidal sol is spin-coated on ITO, the rotating speed of spin coating is 3000 revs/min, and is dried 15 minutes at 150 DEG C, and obtaining thickness is the negative pole decorative layer of 30nm. In glove box by the polymer making in embodiment 2-4 and [6,6]-phenyl C71Methyl butyrate (PC71BM) be configured to the chloroformic solution of variable concentrations according to the mass ratio of 1:1, and with the rotating speed of 3000 revs/min, this solution be evenly spin-coated on negative pole decorative layer, obtain the active material layer that thickness is 100-300nm. Finally 2 × 10-6Holder vacuum under by MoO3Evaporation to active material layer, to form thickness be 10nm anodal decorative layer; And 2 × 10-6Under the vacuum of holder by Ag evaporation on anodal decorative layer, the positive pole that to form thickness be 120nm, thus obtain polymer solar cell device. The white light source that the filter set cooperation that uses 500W xenon lamp and AM1.5 is simulated solar irradiation, regulates the light intensity of device measured place to 100mW/cm-2, use Keithley open-circuit voltage, short circuit current and three parameters of fill factor, curve factor to prepared polymer solar cell device to test.
Polymer P 3 based on embodiment 2, according to step preparation the characterize polymers solar cell device of embodiment 7. Wherein open-circuit voltage Voc=0.86V, short circuit current Jsc=12.73mA/cm2, fill factor, curve factor FF=68.42%, electricity conversion PCE=7.50%.
Polymer P 2 based on embodiment 3, according to step preparation the characterize polymers solar cell device of embodiment 7. Wherein open-circuit voltage Voc=0.88V, short circuit current Jsc=6.08mA/cm2, fill factor, curve factor FF=68.97%, electricity conversion PCE=3.68%.
Polymer P 4 based on embodiment 4, according to step preparation the characterize polymers solar cell device of embodiment 7. Wherein open-circuit voltage Voc=0.97V, short circuit current Jsc=3.91mA/cm2, fill factor, curve factor FF=58.74%, electricity conversion PCE=2.22%.
Applicant's statement, the present invention illustrates detailed structure of the present invention and composition by above-described embodiment, but the present invention is not limited to above-mentioned detailed structure and composition, does not mean that the present invention must rely on above-mentioned detailed structure and composition could be implemented. Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (20)
1. one kind 5, two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] the two thiophene-based two dimension conjugated polymers of 10-Thing, is characterized in that, it has suc as formula the structure shown in (I):
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R2And R3Be all 6 to 20 straight or branched independently selected from hydrogen or replacement or unsubstituted carbon numberAlkyl; M is 0 or 1; N is the natural number between 1～10000;
Described Ar is selected from any one in following group:
Wherein, R replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched.
2. conjugated polymer as claimed in claim 1, is characterized in that, described conjugated polymer hasStructure shown in formula (II):
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; nIt is the natural number between 1～10000; Described Ar is selected from any one in following group:
Wherein, R replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched.
3. conjugated polymer as claimed in claim 1, is characterized in that, described conjugated polymer has formulaStructure shown in (III):
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R2Be selected from hydrogen or replacement or unsubstituted carbon number and be the alkyl of 6 to 20 straight or branched; N isNatural number between 1～10000; Described Ar is selected from any one in following group:
Wherein, R replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched.
4. conjugated polymer as claimed in claim 1, is characterized in that, described conjugated polymer has formulaStructure shown in (IV):
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R3Be selected from hydrogen or replacement or unsubstituted carbon number and be the alkyl of 6 to 20 straight or branched; N isNatural number between 1～10000; Described Ar is selected from any one in following group:
Wherein, R replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched.
5. conjugated polymer as claimed in claim 1, is characterized in that, the number of described conjugated polymerAverage molecular weight is 5000～1000000.
6. conjugated polymer as claimed in claim 1, is characterized in that, the number of described conjugated polymer is equalMolecular weight is 10000～500000.
7. conjugated polymer as claimed in claim 1, is characterized in that, the number of described conjugated polymer is equalMolecular weight is 20000～300000.
8. conjugated polymer as claimed in claim 1, is characterized in that, the PDI of described conjugated polymerBe 1.3～2.0.
One kind as described in one of claim 1-8 5, two (5-alkylthrophene-2-yl) naphthalenes of 10-The preparation method of [1,2-b:5,6-b'] two thiophene-based two dimension conjugated polymers, is characterized in that described method bagDraw together following steps:
(1), under ice bath environment, compound and the n-BuLi shown in formula (V) entered in oxolaneRow reaction, and then add trimethyltin chloride to continue reaction in reaction system, obtain shown in formula (VI)Compound;
(2), under inert gas shielding, make the conjugation shown in the compound shown in formula (VI) and formula (VII)Unit reacts under the catalytic action of palladium catalyst, after reaction finishes, adds the bad molten of conjugated polymerAgent precipitating, filters and is precipitated thing, and sediment is carried out to soxhlet extraction, concentrated chloroform extract, and with being total toThe poor solvent precipitating of conjugated polymer, suction filtration obtains two (5-alkylthrophene-2-yl) naphthalenes [1,2-b:5,6-b'] two of 5,10-Thiophene-based two dimension conjugated polymer;
In formula, R1For replacing or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched; R2And R3Be all 6 to 20 straight or branched independently selected from hydrogen or replacement or unsubstituted carbon numberAlkyl; M is 0 or 1; Described Ar is selected from any one in following group:
Wherein, R replaces or unsubstituted carbon number is the alkyl of 8 to 20 straight or branched.
10. method as claimed in claim 9, is characterized in that, step (2) sediment is used first successivelyAlcohol, acetone, n-hexane and chloroform carry out soxhlet extraction.
11. methods as claimed in claim 9, is characterized in that, when the reaction of the described reaction of step (2)Between be 8～24 hours.
12. methods as claimed in claim 9, is characterized in that, described in step (2), reaction is at solventIn carry out.
13. methods as claimed in claim 12, is characterized in that, described solvent is selected from toluene, N, N-The mixture of any one in dimethyl formamide, chlorobenzene or o-dichlorohenzene or at least two kinds.
14. methods as claimed in claim 9, is characterized in that, shown in the described formula of step (2) (VI)Compound and formula (VII) shown in the mol ratio of conjugate unit be 1:1.
15. methods as claimed in claim 9, is characterized in that, the poor solvent of described conjugated polymerFor methyl alcohol or/and n-hexane.
16. 1 kinds of semiconductor blends, is characterized in that, it comprises as described in one of claim 1-8Two (5-alkylthrophene-2-yl) naphthalene [1,2-b:5,6-b'] two thiophene-based two dimension conjugated polymer and the acceptor materials of 5,10-.
17. semiconductor blends as claimed in claim 16, is characterized in that, described acceptor material isFullerene derivate.
18. semiconductor blends as claimed in claim 16, is characterized in that, described acceptor material be [6,6]-Phenyl C61Methyl butyrate (PC61BM) or/and [6,6]-phenyl C71Methyl butyrate (PC71BM)。
The purposes of 19. 1 kinds of semiconductor blends as described in claim 16 or 17, is characterized in that,It is for the preparation of semiconductor devices or photovoltaic device.
20. 1 kinds of photovoltaic devices, is characterized in that, it comprises collecting layer, hole, electron collection layer and skyActive material layer between collecting layer, cave and electron collection layer; Described active material layer is as claim 16Or semiconductor blend described in 17.
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| KR20120129889A (en) * | 2009-12-25 | 2012-11-28 | 고쿠리츠다이가쿠호진 히로시마다이가쿠 | Polymer compound, and thin film and ink composition each containing same |
| CN103703583A (en) * | 2011-07-25 | 2014-04-02 | 国立大学法人广岛大学 | Organic semiconductor material |
| JP2013181071A (en) * | 2012-02-29 | 2013-09-12 | Sumitomo Chemical Co Ltd | Polymer compound, composition including the same, ink composition, thin film and element |
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