Molecular doping plays an important role in controlling the carrier concentration of organic semiconductors. However, the introduction of dopant counterions often results in increased energetic disorder and traps due to the molecular packing disruption and Coulomb potential wells. To date, no general strategy has been proposed to reduce the counterion-induced structural and energetic disorder. Here, we demonstrate the critical role of non-covalent interactions (NCIs) between counterions and polymers. Employing a computer-aided approach, we identified the optimal counterions and discovered that NCIs determine their docking positions, which significantly affect the counterion-induced energetic disorder. With the optimal counterions, we successfully reduced the energetic disorder to levels even lower than that of the undoped polymer. As a result, we achieved a high n-doped electrical conductivity of over 200 S cm⁻¹ and an eight-fold increase in the thermoelectric power factor. We found that the NCIs have substantial effects on doping efficiency, polymer backbone planarity, and Coulomb potential landscape. Our work not only provides a general strategy for identifying the most suitable counterions but also deepens our understanding of the counterion effects on doped polymeric semiconductors.

分子掺杂在控制有机半导体的载流子浓度方面起着重要作用。然而，由于分子堆积破坏和库仑势阱，掺杂剂抗衡离子的引入通常会导致能量无序和陷阱的增加。迄今为止，尚未提出减少反离子引起的结构和能量紊乱的通用策略。在这里，我们证明了反离子和聚合物之间非共价相互作用 (NCI) 的关键作用。采用计算机辅助方法，我们确定了最佳抗衡离子，并发现 NCI 决定了它们的对接位置，这显着影响了抗衡离子引起的能量紊乱。通过最佳的抗衡离子，我们成功地将能量无序降低到甚至低于未掺杂聚合物的水平。结果，我们实现了超过 200 S cm ^-1的高 n 掺杂电导率，热电功率因数提高了八倍。我们发现 NCI 对掺杂效率、聚合物主链平面度和库仑势景观具有重大影响。我们的工作不仅提供了识别最合适的反离子的一般策略，而且加深了我们对反离子对掺杂聚合物半导体影响的理解。