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Studies on Conduction Mechanisms for Alternating Polymers Composed of Organosilicon and π-Electron Units and Application to Functionality Materials

有机硅和π电子单元交替聚合物的导电机理研究及其在功能材料中的应用

基本信息

批准号：
12555245
负责人：
KUNAI Atsutaka
金额：
$ 6.46万
依托单位：
HIROSHIMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

The main interest of this research is placed on clarification of conduction mechanisms for polymers with alternating arrangement of an organosilicon unit and π-electron system in the main chain and also on utilization of the polymers as functionality materials. In these viewpoints, polymers with the monosilanylene (MS), disilanylene (DS), or trisilanylene (TS) unit and oligothiophene π-system (mT), and the related polymers moreover, were synthesized. The alternating Si-mT polymers exhibited a 10^<-4> - 10^<-1> S/cm level of conductivity on doping with FeCl_3 vapor, and MS-5T was found to be highly stable upon electrochemical dopirig/dedoping. These polymers exhibited excellent current-luminance characteristics as the hole-transporting materials of EL devices.The following points have been investigated by using MS-mT: (1) the role of polaron, bipolaron, and π-dimer in conduction mechanism; (2) dominating path between intrachain and interchain paths; (3) reason for the evolution of metallic conduction. It is concluded that in the lightly doped state, interchain hopping is the main path for carrier transport, and π-dimers concern in these polymers.Polyhexylthiophenes (PHT) with different regioregularity of 97%, 81%, 70%, and 54% were also prepared. In order to clarify influences of stacking of polymer chains on the transport properties of conducting polymers, the mobilities of charge carriers in the films of these PHTs were electrochemically and spectroscopically evaluated as the function of doping level. The results clearly show that (1) better ordered stacking structures enhance mobilities but affect little features of the mobility change by doping; (2) the interchain hopping transport of polarons is a dominating path of the electrical conduction in the ightly doped polymer; (3) stacking of thiophene planes is not associated with the evolution of metallic induction, although it greatly affects mobility of charge carriers.

这项研究的主要兴趣在于阐明主链上有机硅单元和π-电子体系交替排列的聚合物的导电机理，以及聚合物作为功能材料的应用。在这些观点的指导下，合成了含有单硅烯(MS)、二硅烯(DS)或三硅烯(TS)单元的聚合物和低聚硫杂环戊二烯(π)体系(MT)，以及相关的聚合物。交替的Si-MT聚合物在FeCl3蒸气掺杂时表现出10^&lt；-4&gt；-10^&lt；-1&gt；S/cm的电导率水平，而MS-5T在电化学掺杂/脱掺杂时表现出很高的稳定性。利用MS-MT研究了以下几点：(1)极化子、双极化子和π-二聚体在导电机制中的作用；(2)链内和链间路径之间的主导路径；(3)金属导电演化的原因。结果表明，在低掺杂状态下，链间跳跃是载流子传输的主要途径，π-二聚体参与其中，合成了不同区域规整度分别为97%、81%、70%和54%的聚己基噻吩型聚合物。为了阐明高分子链的堆积对导电聚合物输运性能的影响，用电化学和光谱方法研究了载流子迁移率随掺杂水平的变化。结果表明：(1)较好的有序堆积结构提高了迁移率，但对迁移率变化的影响很小；(2)极化子的链间跳跃输运是直接掺杂聚合物导电的主要途径；(3)噻吩面的堆积与金属诱导的演化无关，尽管它对载流子的迁移率有很大的影响。