Organic semiconducting polymers are a powerful platform for the design of next-generation technologies due to their excellent optoelectronic properties and solution processability, allowing access to low-cost and scalable manufacturing techniques such as spin-coating, slot-die coating and roll-to-roll printing. However, their extended π-conjugation results in low solubility, requiring the use of toxic halogenated solvents to generate thin films and devices. Furthermore, accessible post-functionalization of semiconductors toward the development of multifunctional devices and sensors remains a challenge due to limited solid-state chemistry for alkyl side chains. In this work, an asymmetric side-chain engineering approach was used to introduce terminal hydroxyl moieties alongside traditional solubilizing branched alkyl chains into an isoindigo-based polymer. The hydroxyl moieties led to significantly improved processability in alcohol-based solvents without sacrificing electronic performance in thin film organic field-effect transistors. Solid state morphologies of the thin films processed from both alcohol-based and traditional halogenated solvents were further characterized using atomic force microscopy and grazing incidence wide angle X-ray scattering. Additionally, Cryo-EM was utilized in order to characterize the role of asymmetric side-chain functionality in solution state aggregation. The versatility of this design was further probed using fluorescein isothiocyanate to directly functionalize the asymmetric polymer in thin film. This facile solid-state post-functionalization further demonstrates asymmetric side-chain engineering to be a viable approach toward the development of sustainably manufactured multifunctional electronics.

中文翻译：

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半导体聚合物中的不对称侧链工程：有机电子产品的绿色加工和后功能化平台

有机半导体聚合物由于其出色的光电特性和溶液加工性，是下一代技术设计的强大平台，允许获得低成本和可扩展的制造技术，如旋涂、槽模涂布和卷对-卷筒印刷。然而，它们扩展的 π 共轭导致溶解度低，需要使用有毒的卤化溶剂来生成薄膜和器件。此外，由于烷基侧链的固态化学有限，实现半导体的可访问后功能化以开发多功能设备和传感器仍然是一个挑战。在这项工作中，使用不对称侧链工程方法将末端羟基部分与传统的增溶支链烷基链一起引入到基于异靛蓝的聚合物中。羟基部分显着改善了在醇基溶剂中的可加工性，而不会牺牲薄膜有机场效应晶体管的电子性能。使用原子力显微镜和掠入射广角 X 射线散射进一步表征从醇基溶剂和传统卤化溶剂加工的薄膜的固态形态。此外，还利用 Cryo-EM 来表征不对称侧链功能在溶液状态聚合中的作用。使用异硫氰酸荧光素直接功能化薄膜中的不对称聚合物进一步探讨了该设计的多功能性。这种简便的固态后功能化进一步证明了不对称侧链工程是开发可持续制造的多功能电子产品的可行方法。