Doping is a vital method to increase the charge carrier concentration of conjugated polymers, thus improving the performance of organic electronic devices. However, the introduction of dopants may cause phase separation. The miscibility of dopants and polymers as well as the doping-induced microstructure change are always the barriers in the way to further enhance the thermoelectrical performance. Here, recent research studies about the influence of molecular doping on the microstructures of conjugated polymers are summarized, with an emphasis on the n-type doping. Highlighted topics include how to control the distribution and density of dopants within the conjugated polymers by modulating the polymer structure, dopant structure, and solution-processing method. The strong Coulombic interactions between dopants and polymers as well as the heterogeneous doping process of polymers can hinder the polymer film to achieve better miscibility of dopants/polymer and further loading of the charge carriers. Recent developments and breakthroughs provide guidance to control the film microstructures in the doping process and achieve high-performance thermoelectrical materials.

掺杂是增加共轭聚合物的电荷载流子浓度，从而改善有机电子器件性能的重要方法。但是，掺杂剂的引入可能引起相分离。掺杂剂和聚合物的混溶性以及掺杂引起的微观结构变化始终是进一步提高热电性能的障碍。在此，总结了关于分子掺杂对共轭聚合物的微观结构的影响的最新研究，重点是n型掺杂。重点讨论的主题包括如何通过调节聚合物结构，掺杂剂结构和溶液加工方法来控制共轭聚合物中掺杂剂的分布和密度。掺杂剂与聚合物之间的强库仑相互作用以及聚合物的非均质掺杂过程会阻碍聚合物薄膜获得更好的掺杂剂/聚合物混溶性，并进一步带电电荷载体。最新的发展和突破为控制掺杂过程中的薄膜微结构和实现高性能热电材料提供了指导。