Crystalline poly(3-alkylthiophene) (P3AT) nanofibers are promising materials for a myriad of device applications, but nanofiber length control and colloidal stability are difficult to achieve. We report an in-depth study of the solution self-assembly of regioregular poly(3-octylthiophene)-b-poly(dimethylsiloxane) (P3OT-b-PDMS) diblock copolymers with a crystallizable π-conjugated core-forming block. Use of the “living” crystallization-driven self-assembly (CDSA) seeded-growth method in solvents selective for PDMS allowed access to relatively low length dispersity, colloidally stable P3OT-b-PDMS fiber-like micelles with a crystalline, tape-like P3OT core, a PDMS corona, and lengths up to ca. 600 nm under optimized conditions. Significantly, the presence of a small percentage of common solvent and the use of slightly elevated temperature (35 °C) were found to enhance the length control. Analogous studies for P3OT-b-PS (PS = polystyrene) suggest that solvent composition and temperature represent key parameters for the general optimization of fiber formation by living CDSA for P3AT block copolymers.

中文翻译：

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迈向具有π共轭核的均匀纳米纤维：优化具有聚（3-辛基噻吩）核形成嵌段的二嵌段共聚物的“活性”结晶驱动自组装

结晶的聚（3-烷基噻吩）（P3AT）纳米纤维是用于多种设备应用的有前途的材料，但是很难实现纳米纤维长度的控制和胶体稳定性。我们报告了具有可结晶的π-共轭核心形成嵌段的区域规则的聚（3-辛基噻吩）-b-聚（二甲基硅氧烷）（P3OT- b- PDMS）二嵌段共聚物的溶液自组装的深入研究。在选择PDMS的溶剂中使用“活性”结晶驱动的自组装（CDSA）晶种生长方法，可获得相对较低的长度分散性，胶体稳定的P3OT- b-PDMS纤维状胶束，具有结晶的，带状的P3OT核，PDMS电晕，长度可达到约20毫米。在优化条件下为600 nm。值得注意的是，发现少量的普通溶剂和使用稍微升高的温度（35°C）可以增强长度控制。对P3OT- b -PS（PS =聚苯乙烯）的类似研究表明，溶剂组成和温度代表了通过活性CDSA对P3AT嵌段共聚物进行纤维形成的一般优化的关键参数。