Disorder of doped conjugated polymers, which affects how effectively charge carriers are transported, is an important factor to be controlled to achieve high thermoelectric (TE) performance. However, experimentally controlling the disorder in highly doped polymers is difficult because of the limitations of dopant engineering. Here, by using a counter-ion exchange method, we systematically control the counter-ion-induced disorder in a highly doped state and analyze how the disorder changes the TE transport properties in poly(3,4-ethylenedioxythiophene) (PEDOT). Multi-cyano-functionalized counter-ions, which exhibit different Coulombic attraction with PEDOT, change the structural and energetic disorder in PEDOT. These changes in the disorder are evaluated with respect to several qualities of PEDOT: crystalline ordering, density of states (DOS), and polaron behaviors. Decreasing the counter-ion-induced localization of charge carriers in PEDOT increases the planarity of the PEDOT chains and narrows the DOS of PEDOT. In addition, an analysis of the number of unpaired polarons and the Curie susceptibility shows quantitatively how the charge carriers are localized by the counter-ion-induced disorder in PEDOT. These changes result in opposite behaviors of the electrical conductivity and the Seebeck coefficient in PEDOT in response to the extent of disorder and thereby produce a high figure of merit ZT of 0.21 with a remarkable power factor in the PEDOT film with the lowest degree of disorder.

掺杂共轭聚合物的无序会影响电荷载流子的有效传输，是实现高热电 (TE) 性能需要控制的重要因素。然而，由于掺杂工程的限制，很难通过实验控制高掺杂聚合物中的无序。在这里，通过使用抗衡离子交换方法，我们系统地控制了高掺杂状态下的抗衡离子诱导的无序，并分析了无序如何改变聚（3,4-亚乙基二氧噻吩）（PEDOT）中的 TE 传输特性。多氰基功能化的反离子与 PEDOT 表现出不同的库仑吸引力，改变了 PEDOT 的结构和能量紊乱。无序的这些变化是根据 PEDOT 的几个特性来评估的：结晶有序、状态密度 (DOS)、和极化子行为。降低 PEDOT 中电荷载流子的反离子诱导定位会增加 PEDOT 链的平面度并缩小 PEDOT 的 DOS。此外，对未配对极化子的数量和居里磁化率的分析定量地显示了电荷载流子如何被 PEDOT 中的反离子诱导的无序定位。这些变化导致 PEDOT 中电导率和塞贝克系数的相反行为响应无序程度，从而产生高品质因数 对未配对极化子的数量和居里磁化率的分析定量地显示了电荷载流子如何被 PEDOT 中的反离子诱导的无序定位。这些变化导致 PEDOT 中电导率和塞贝克系数的相反行为响应无序程度，从而产生高品质因数 对未配对极化子的数量和居里磁化率的分析定量地显示了电荷载流子如何被 PEDOT 中的反离子诱导的无序定位。这些变化导致 PEDOT 中电导率和塞贝克系数的相反行为响应无序程度，从而产生高品质因数ZT为 0.21，在无序度最低的 PEDOT 膜中具有显着的功率因数。