侧链含偶氮苯聚噻吩衍生物/纳米半导体复合材料的制备及其光学性能
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摘要
目前,对聚噻吩(PTh)的研究主要集中在聚合物侧链上的修饰、主链结构的调整以及与无机纳米材料的复合,这样既能改善无取代PTh分子的溶解性,又可以调节和完善PTh及其衍生物的发光颜色。
本文采用化学氧化聚合法合成了三种可溶性侧链含偶氮苯聚噻吩衍生物(AZO-PThs),通过引入不同电子结构的偶氮苯刚性基团和不同长度的柔性烷基基团,对聚噻吩的侧链进行化学修饰,提高了聚合物的溶解性,使聚噻吩类聚合物可直接旋涂成膜,简化工艺。AZO-PThs不仅保持了聚噻吩本身的故有发光特性,而且由于引入不同“推-拉”电子结构的偶氮苯刚性基团和不同长度的柔性烷基基团后,使得聚噻吩类聚合物的电子离域性增加、能隙显著降低,调节了材料的发射波长。
为了进一步改善AZO-PThs的发光性能和热性能,首次采用原位化学氧化聚合法,制备了一系列侧链含偶氮苯聚噻吩衍生物/纳米半导体复合材料。将AZO-PThs分别与纳米稀土氧化物、以及纯化的多壁碳纳米管(MWNTs)进行复合,制备了AZO-PThs/纳米稀土氧化物复合材料(如PATh4/Eu_2O_3、PBTh6/(Y_2O_3:Eu~(3+))和PATh4/(Y_2O_3:Eu~(3+))纳米复合材料)以及PATh4/MWNTs纳米复合材料。研究表明,由于无机材料的加入,对AZO-PThs的热稳定性有不同的影响;同时不同无机材料对聚合物有不同的影响,这对于材料的实际应用具有重要的指导意义;以上四种复合材料具有不同的光致发光发射波长,表现出不同的光致发光特性,这些都为其作为电致发光器件的发光层创造了有利的条件。
Presently,the study of polythiophene(PTh) mainly concentrates on the polymer side chain modification,the main chain structure adjustment as well as polymer/inorganic nanocomposites,which can not only improve solubility,but also modify and perfect luminescence color of PTh.
Three soluble Polythiophene derivatives containing azobenzene in side chain (AZO-PThs) were prepared by Chemical Oxidative-Polymerization.The solubility of three materials can be enhanced by introducing different "push-pull" electronic structure azobenzene and the flexible alkyl groups with different length to the side chain of PTh for chemical modification.Therefore,PTh films can be obtained by spin-coated method, which can simplify process technology.Not only the luminescence performance of non-substitued polythiophene can be preserved,but also the energy electron delocalization increases and band-gap decreases significantly,photoluminescence emission wavelength of PTh can be adjusted because of the introducing of different electronic structure azobenzene and the flexible alkyl groups with different length to the side chain.
In order to improve the luminescence and thermal performance of AZO-PThs,a series of Polythiophene derivatives containing azobenzene in side chain/ nano-semiconductor composites were prepared through in-situ Chemical Oxidative-Polymerization.Polythiophene derivatives containing azobenzene in side chain /rare earth oxides composites,such as PATh4/Eu_2O_3,PATh4/(Y_2O_3:Eu~(3+)),PBTh6/ (Y_2O_3:Eu~(3+)) and PATh4/MWNTs nanocomposites were prepared by the method of in-situ Chemical Oxidative-Polymerization.The results indicate that the introducing of inorganic materials influenced the thermal stability of these composites.Meanwhile,various inorganic materials have different influences on polymers,which have important guiding significance in practical application.Four composites present different photoluminescence emission wavelengths and photoluminescence characteristics. Conclusion suggests that these all provide advantageous conditions with emitting layers of electroluminescence device.
本文采用化学氧化聚合法合成了三种可溶性侧链含偶氮苯聚噻吩衍生物(AZO-PThs),通过引入不同电子结构的偶氮苯刚性基团和不同长度的柔性烷基基团,对聚噻吩的侧链进行化学修饰,提高了聚合物的溶解性,使聚噻吩类聚合物可直接旋涂成膜,简化工艺。AZO-PThs不仅保持了聚噻吩本身的故有发光特性,而且由于引入不同“推-拉”电子结构的偶氮苯刚性基团和不同长度的柔性烷基基团后,使得聚噻吩类聚合物的电子离域性增加、能隙显著降低,调节了材料的发射波长。
为了进一步改善AZO-PThs的发光性能和热性能,首次采用原位化学氧化聚合法,制备了一系列侧链含偶氮苯聚噻吩衍生物/纳米半导体复合材料。将AZO-PThs分别与纳米稀土氧化物、以及纯化的多壁碳纳米管(MWNTs)进行复合,制备了AZO-PThs/纳米稀土氧化物复合材料(如PATh4/Eu_2O_3、PBTh6/(Y_2O_3:Eu~(3+))和PATh4/(Y_2O_3:Eu~(3+))纳米复合材料)以及PATh4/MWNTs纳米复合材料。研究表明,由于无机材料的加入,对AZO-PThs的热稳定性有不同的影响;同时不同无机材料对聚合物有不同的影响,这对于材料的实际应用具有重要的指导意义;以上四种复合材料具有不同的光致发光发射波长,表现出不同的光致发光特性,这些都为其作为电致发光器件的发光层创造了有利的条件。
Presently,the study of polythiophene(PTh) mainly concentrates on the polymer side chain modification,the main chain structure adjustment as well as polymer/inorganic nanocomposites,which can not only improve solubility,but also modify and perfect luminescence color of PTh.
Three soluble Polythiophene derivatives containing azobenzene in side chain (AZO-PThs) were prepared by Chemical Oxidative-Polymerization.The solubility of three materials can be enhanced by introducing different "push-pull" electronic structure azobenzene and the flexible alkyl groups with different length to the side chain of PTh for chemical modification.Therefore,PTh films can be obtained by spin-coated method, which can simplify process technology.Not only the luminescence performance of non-substitued polythiophene can be preserved,but also the energy electron delocalization increases and band-gap decreases significantly,photoluminescence emission wavelength of PTh can be adjusted because of the introducing of different electronic structure azobenzene and the flexible alkyl groups with different length to the side chain.
In order to improve the luminescence and thermal performance of AZO-PThs,a series of Polythiophene derivatives containing azobenzene in side chain/ nano-semiconductor composites were prepared through in-situ Chemical Oxidative-Polymerization.Polythiophene derivatives containing azobenzene in side chain /rare earth oxides composites,such as PATh4/Eu_2O_3,PATh4/(Y_2O_3:Eu~(3+)),PBTh6/ (Y_2O_3:Eu~(3+)) and PATh4/MWNTs nanocomposites were prepared by the method of in-situ Chemical Oxidative-Polymerization.The results indicate that the introducing of inorganic materials influenced the thermal stability of these composites.Meanwhile,various inorganic materials have different influences on polymers,which have important guiding significance in practical application.Four composites present different photoluminescence emission wavelengths and photoluminescence characteristics. Conclusion suggests that these all provide advantageous conditions with emitting layers of electroluminescence device.
引文
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