Electron beam (EB) irradiation is a powerful technology for molecular regulation and electronic structure modification of polymer materials. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films were irradiated under 10 MeV EB by tailoring the dosage from 2.5 to 160 kGy. An intriguing phenomenon occurs in the electrical conductivity (σ) of PEDOT:PSS, where it increases first and then reduces in all the low (2.5–30 kGy), medium (30–100 kGy), and high (100–160 kGy) dosage regimes, while the Seebeck coefficient nearly remains constant. The maximum σ and power factor (PF) values of irradiated PEDOT:PSS are both about 2.5 times of those of pristine PEDOT:PSS. Dominant cross-linking promotes thermal conductivity and mechanical stability, while chain scission leads to their reduction. Structural analysis and DFT computational results have revealed that oxygen containing functional groups can be easily introduced into insulating PSS chains during irradiation, which lowers band gap energy and contributes to the enhancement of the thermoelectric performance of PEDOT:PSS. Besides, the conformation changes of PEDOT from neutral (benzoid) to oxidized (quinoid) form also benefit the carrier transport of PEDOT:PSS. The findings shed light on the modification effect of EB on conducting polymers and provide an innovative treatment and considerable reference for the universal construction of conducting polymer systems with high thermoelectric performance.

中文翻译：

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高能电子束作为 PEDOT:PSS 分子修饰和热电增强的有效方法


电子束（EB）辐照是一种用于高分子材料分子调控和电子结构修饰的强大技术。通过将剂量调整为 2.5 至 160 kGy，在 10 MeV EB 下对聚（3,4-乙撑二氧噻吩）：聚（苯乙烯磺酸）（PEDOT：PSS）薄膜进行辐照。 PEDOT:PSS 的电导率 (σ) 出现了一个有趣的现象，在低 (2.5–30 kGy)、中 (30–100 kGy) 和高 (100–160 kGy) 范围内电导率先增加然后减少。剂量方案，而塞贝克系数几乎保持不变。辐照后的 PEDOT:PSS 的最大 σ 和功率因数 (PF) 值均为原始 PEDOT:PSS 的约 2.5 倍。主要交联可提高导热性和机械稳定性，而断链会导致导热性和机械稳定性降低。结构分析和DFT计算结果表明，在辐照过程中，含氧官能团可以很容易地引入绝缘PSS链中，从而降低带隙能量，有助于提高PEDOT:PSS的热电性能。此外，PEDOT从中性（苯甲酰）到氧化（醌型）构象的变化也有利于PEDOT:PSS的载流子传输。研究结果揭示了EB对导电聚合物的改性作用，为高热电性能导电聚合物体系的通用构建提供了创新的处理方法和重要的参考。