The inhibitor-dependent poly(3,4-ethylenedioxythiophene) (PEDOT) fabrication suffers major problems in the areas of controllability and film thickness. In this work, we found that anions play a key role in both the polymerization and the structure of PEDOT. As a precursor, anions greatly influence the reaction rate and oxidant solubility. In its role as a counter-ion, the anions also affect chain conductance and crystal growth. With these behaviors in mind, a self-inhibited polymerization approach using novel oxidants with appropriate anions was successfully developed to facilitate the fabrication of high quality in situ polymerized PEDOT films and solve the thickness limitation problem. Inhibitor-free heavy oxidative solutions with weakly basic anions enable the spin-coating of thick and homogeneous oxidant layers and also effectively inhibit both the crystallization of the oxidant and H⁺ formation throughout the polymerization process. PEDOT: dodecylbenzenesulfonate (PEDOT:DBSA) exhibits the highest performance among all candidates due to its appropriate anion basicity and low steric effect. An extremely high doping level of 42.9% is achieved, and an electrical conductivity of ~1100 S cm⁻¹ is successfully maintained for film thicknesses between 310 nm and 1.79 μm. In addition, the thermoelectric power factor (RT) for pristine films was improved to 77.2 μW mK⁻² from 69.6 μW mK⁻² by the dedoping treatment. This study provides a new approach for fabricating high performance PEDOT thick films using anion-based design.

依赖于抑制剂的聚（3,4-乙撑二氧噻吩）（PEDOT）的制造在可控性和膜厚度方面遭受重大问题。在这项工作中，我们发现阴离子在PEDOT的聚合和结构中都起着关键作用。作为前体，阴离子极大地影响反应速率和氧化剂溶解度。阴离子作为抗衡离子，还影响链电导和晶体生长。考虑到这些行为，成功开发了一种使用新型氧化剂和适当阴离子的自抑制聚合方法，以促进原位高质量的制备。聚合了PEDOT薄膜并解决了厚度限制问题。具有弱碱性阴离子的无抑制剂重氧化剂溶液可以旋涂厚而均匀的氧化剂层，并且还可以在整个聚合过程中有效抑制氧化剂的结晶和H ^+的形成。PEDOT：十二烷基苯磺酸盐（PEDOT：DBSA）由于其适当的阴离子碱性和低空间效应而在所有候选物中表现出最高的性能。对于310nm至1.79μm的膜厚度，实现了42.9％的极高掺杂水平，并且成功地保持〜1100 S cm ^-1的电导率。此外，原始薄膜的热电功率因数（RT）提高到77.2μWmK ^-2从69.6μWmK的^-2通过脱杂处理。这项研究提供了一种使用基于阴离子的设计制造高性能PEDOT厚膜的新方法。