Organic polymer thermoelectric (TE) materials have developed rapidly in recent years in terms of strategies to improve their TE performance. However, the effect of molecular mechanisms on their TE performance remains yet to be unveiled. Insights into the evolution of crystalline microstructures of conjugated polymers are critical in determining their aggregate structure and hence their TE performance. Herein, an effective approach has been developed to modify the aggregate structures of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). During annealing and subsequent solvent post-treatment, phase separation between the conductive PEDOT and the insulating PSS occurs and the excess PSS in the skin layer is effectively removed. As a result, carrier mobility and carrier concentration are synergistically boosted via the formation of well-crystallized molecular morphology and the increase of PEDOT doping level, leading to significantly enhanced TE performance with an unprecedented power factor that is 216 times of that of the pristine samples. The corresponding molecular mechanisms are discussed in detail and the aggregate structure evolution route is thoroughly proposed. It is believed that the aggregate structure evolution proposed in this work and its influential mechanisms on TE performance can be extended to other polymers and potentially direct the future design of high-performance polymer-based TE materials.

近年来，根据改善其TE性能的策略，有机聚合物热电（TE）材料发展迅速。然而，分子机理对其TE性能的影响仍有待揭示。洞察共轭聚合物晶体微观结构的演变对于确定其聚集结构并因此确定其TE性能至关重要。在本文中，已经开发了一种有效的方法来修饰聚（3,4-乙撑二氧噻吩）：聚（苯乙烯磺酸盐）（PEDOT：PSS）的聚集体结构。在退火和随后的溶剂后处理过程中，导电PEDOT和绝缘PSS之间会发生相分离，并且表皮层中多余的PSS被有效去除。因此，通过形成良好结晶的分子形态和增加PEDOT掺杂水平，可协同提高载流子迁移率和载流子浓度，从而显着提高TE性能，其空前的功率因数是原始样品的216倍。详细讨论了相应的分子机理，并提出了聚集体结构演化的途径。可以认为，这项工作中提出的聚集体结构演变及其对TE性能的影响机制可以扩展到其他聚合物，并有可能指导高性能聚合物基TE材料的未来设计。从而以无与伦比的功率因数（是原始样品的功率因数）的空前的功率因数显着提高了TE性能。详细讨论了相应的分子机理，并提出了聚集体结构演化的途径。可以认为，这项工作中提出的聚集体结构演变及其对TE性能的影响机制可以扩展到其他聚合物，并有可能指导高性能聚合物基TE材料的未来设计。从而以无与伦比的功率因数（是原始样品的功率因数）的空前的功率因数显着提高了TE性能。详细讨论了相应的分子机理，并提出了聚集体结构演化的途径。可以认为，这项工作中提出的聚集体结构演变及其对TE性能的影响机制可以扩展到其他聚合物，并有可能指导高性能聚合物基TE材料的未来设计。