Orthogonal electric and ionic conductivities in the thin film of a thiophene?thiophene block copolymer
Orthogonal electric and ionic conductivities in the thin film of a thiophene?thiophene block copolymer
复制标题
噻吩?噻吩嵌段共聚物薄膜中的正交电导率和离子电导率
DOI：
10.1039/d2tc05454j
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发表时间：
2023
影响因子：
6.4
通讯作者：
Mori Atsunori
中科院分区：
文献类型：
--
作者：
Yamamoto Sonoka;Yamashita Ryutaro;Kubota Chihiro;Okano Kentaro;Kitamura Masatoshi;Funahashi Masahiro;Ye Syu-Cheng;Pan Yung-Tin;Horie Masaki;Shintani Takuji;Murata Hironori;Matsuyama Hideto;Mori Atsunori
设计并合成了一种由亲水性和疏水性侧链官能团组成的噻吩-噻吩嵌段共聚物。采用去质子金属化镍催化聚合方法成功地合成了侧链由烷基和苯磺酸酯基组成的嵌段共聚物。结果表明，在约100 ℃热处理后，嵌段共聚物的苯磺酸盐部分在膜状态下转化为亲水性磺酸。200 °C，不添加外部添加剂。因此，形成的嵌段共聚物薄膜表现出圆柱形的微相分离和亲水域被揭示为垂直于基板渗透的膜。电导率的测量表明嵌段共聚物薄膜在平行于基底放置时是导电的，而膜在垂直于基底放置时是绝缘的。电化学分析表明，锂离子通过由苯磺酸侧链组成的垂直于基底的圆柱形畴转移。这些结果代表了嵌段共聚物薄膜中电子和离子的双重和正交电导率。
A thiophene–thiophene block copolymer composed of hydrophilic and hydrophobic side chain functionalities was designed and synthesized. The deprotonative metalation nickel-catalyzed polymerization protocol successfully afforded the block copolymer, in which the side chains are derived from alkyl and benzenesulfonic acid ester groups. The benzene sulfonate moiety of the block copolymer in the film state was shown to be transformed into hydrophilic sulfonic acid upon thermal treatment at ca. 200 °C without the addition of an external additive. Thus, the formed block copolymer thin film exhibited cylindrical microphase separation and the hydrophilic domain was revealed to penetrate the film perpendicular to the substrate. The measurement of electric conductivity suggested that the block copolymer thin film was conductive when placed parallel to the substrate, while the film was insulative when placed perpendicular to the substrate. Electrochemical analyses revealed that lithium ions transfer through the cylindrical domain composed of a benzene sulfonic acid side chain, which is perpendicular to the substrate. These results represent dual and orthogonal conductivities of electrons and ions in the block copolymer thin film.