Charge transport and thermoelectric conversion mechanisms in doped semicrystalline polymer films are key issues in the field of wearable electronics, whereas the complex film structure consisting of crystalline domains and non-crystalline boundaries prevents sufficient understanding of them. In this study, we fully clarify the roles of the domains and the boundaries in a typical semicrystalline polymer on macroscopic charge transport under continuous electrochemical doping. In the crystalline domains, a multi-step transformation of the transport properties from effectively metallic behavior to weak localization (WL) to variable-range hopping (VRH) is found with decreasing temperature and doping level. On the other hand, at the domain boundaries, the effectively metallic conduction changes directly to VRH. Based on these results, the extremely complicated phase diagram, including the coexistence of the WL and VRH processes, is well explained. The proposed transport mechanism further explains the thermoelectric properties of the film.

掺杂的半结晶聚合物薄膜中的电荷传输和热电转换机制是可穿戴电子领域的关键问题，而由晶畴和非晶边界构成的复杂薄膜结构使人们对其缺乏足够的了解。在这项研究中，我们充分阐明了典型的半结晶聚合物在连续电化学掺杂下宏观电荷传输中的域和边界的作用。在晶域中，发现随着温度和掺杂水平的降低，传输性能从有效的金属行为到弱局部化（WL）到可变范围跳跃（VRH）的多步转换。另一方面，在畴边界处，有效的金属传导直接变为VRH。根据这些结果，很好地解释了极其复杂的相图，包括WL和VRH过程的共存。提出的传输机制进一步解释了薄膜的热电特性。