Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is one of the most widely used hole transporting materials in organic solar cells (OSCs). Multiple strategies have been adopted to improve the conductivity of PEDOT:PSS, however, effective strategy that can optimize the conductivity, work function, and surface energy simultaneously to reach a better energy alignment and interface contact is rare. Here, we demonstrate that oxoammonium salts (TEMPO⁺X⁻) with different counterions can act as facile and novel dopants to realize secondary doping of PEDOT:PSS. The effective charge transfer process achieved between TEMPO⁺X⁻ and PEDOT:PSS results in enhanced carrier density and improved conductivity of PEDOT:PSS. Moreover, different counterions of TEMPO⁺X⁻ can tune the work function and surface energy of PEDOT:PSS, enabling improved device performances. The resulting device with PM6:Y6 as the active layer shows a high power conversion efficiency (PCE) over 16%. Moreover, this doping strategy can also be applied to other conjugated polymers such as poly(3-hexylthiophene). This work provides a promising strategy to tune the properties of conjugated polymers through doping, thus effectively boosting the performance of organic solar cells.

聚（3,4-乙撑二氧噻吩）：聚苯乙烯磺酸盐（PEDOT：PSS）是有机太阳能电池（OSC）中使用最广泛的空穴传输材料之一。已经采取了多种策略来提高PEDOT：PSS的电导率，但是，很少有能够同时优化电导率，功函数和表面能以达到更好的能量排列和界面接触的有效策略。在这里，我们证明了氧合氨盐（TEMPO ⁺ X ^- ）具有不同抗衡离子可以作为容易的和新颖的掺杂剂起作用以实现PEDOT的二次掺杂：PSS。在TEMPO ⁺ X ⁻之间实现了有效的电荷转移过程PEDOT：PSS可以提高载流子密度并改善PEDOT：PSS的电导率。此外，TEMPO的不同抗衡离子⁺ X ^-可调谐PEDOT的功函数和表面能：PSS，能够改进装置的性能。以PM6：Y6作为有源层的最终器件显示出超过16％的高功率转换效率（PCE）。而且，该掺杂策略也可以应用于其他共轭聚合物，例如聚（3-己基噻吩）。这项工作提供了一种有前途的策略，可以通过掺杂来调整共轭聚合物的性能，从而有效地提高有机太阳能电池的性能。