Application of high-performance unipolar n-type polymeric semiconductors lagged behind due to those polymers’ poor solubility in green solvents. Traditional methods, such as random copolymerization and asymmetric structuring, enhance solubility but reduce mobility. Here, a universal “lipophilicity strategy” for eco-friendly processing is reported. This strategy could effectively improve the solubility of polymers without sacrificing crystallinity thus maintaining good mobility of the devices. CF₃ group and SCF₃ group, which are famous for their high lipophilicity, are introduced to (E)-1,2-di(thiophen-2-yl)ethane (TVT). The solubility of two monomers is confirmed to be 5 and 16 times higher than the brominated counterpart, respectively. Moreover, CF₃TVT and SCF₃TVT not only improve solubility of the polymers but also reduce energy levels of donor unit due to their strong electron withdrawing property. By using Ozawa's condition, three unipolar n-type semiconducting polymers are obtained through direct (hetero)arylation polycondensation (DHAP). Among them, CF₃TVT based P2 processed by xylene solutions exhibited the best unipolar n-type mobility up to 1.37 cm² V⁻¹ s⁻¹ and reached current on/off ratio of 10⁸, for the first time realizing both green synthesis and nonchlorinated processing. In general, this lipophilicity strategy provides an effective guideline to design high-performance n-type polymer with good solubility in nonchlorinated solvents.

中文翻译：

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亲脂性增强非氯化溶解度：刚性规则 n 型聚合物半导体环境友好加工的有效策略

由于这些聚合物在绿色溶剂中的溶解性差，高性能单极性 n 型聚合物半导体的应用滞后。传统的方法，如无规共聚和不对称结构，提高了溶解度，但降低了流动性。在这里，报告了一种用于环保加工的通用“亲脂性策略”。这种策略可以有效地提高聚合物的溶解度而不牺牲结晶度，从而保持器件的良好流动性。以高亲油性着称的CF ₃基团和SCF ₃基团被引入( E )-1,2-二(噻吩-2-基)乙烷( TVT）。两种单体的溶解度被证实分别比溴化单体高 5 倍和 16 倍。此外，CF ₃ TVT和SCF ₃ TVT不仅提高了聚合物的溶解度，而且由于其强大的吸电子性而降低了给体单元的能级。利用Ozawa的条件，通过直接（杂）芳基化缩聚（DHAP）得到三种单极性n型半导体聚合物。其中，由二甲苯溶液处理的CF ₃ TVT基P2表现出最好的单极性n型迁移率高达1.37 cm ² V ^-1 s ^-1并达到电流开/关比10 ⁸，首次实现绿色合成和无氯化处理。一般来说，这种亲脂性策略为设计在非氯化溶剂中具有良好溶解性的高性能 n 型聚合物提供了有效的指导。