Conjugated polyelectrolytes (CPEs) have achieved vast success in organic electronics due to their appealing opt-electrical properties and convenient solution-processability. However, most of the existing n-type CPEs commonly exhibit distinct light capture in visible region. The attainment of novel n-type CPEs possessing both high electron conductivity and high visible light transparency is significant while still challenging. Herein, optimized amount of organic diradicals achieved by benzobisthiadiazo (BBT) unit are intentionally introduced into the backbone of the representative wide-band-gap polyfluorene-based conjugated polyelectrolyte via ternary copolymerization. The incorporation of diradical canonical structure could promote the quinoid resonance of conjugated skeleton, leading to increased self-doping effect. Consequently, the copolymerized CPE exhibits high visible light transmittance (AVT over 85%) and enhanced electron conductivity compared to the referenced CPE. The fabricated organic solar cell devices with the new-designed polyelectrolyte as the cathode interface layer can achieve high power conversion efficiencies of more than 16%, which is not susceptible to the thickness up to 50 nm. This work provides a feasible molecular modification strategy via organic diradicals regulation to obtain high performance n-type self-doped conjugated polyelectrolytes.

共轭聚电解质（CPE）由于具有吸引人的光电性能和便利的溶液加工性能，因此在有机电子领域取得了巨大成功。但是，大多数现有的n型CPE通常在可见光区域表现出明显的光捕获。具有高电子传导性和高可见光透明性的新型n型CPE的实现是重要的，同时仍然具有挑战性。在此，通过三元共聚有意地将通过苯并双噻二唑（BBT）单元获得的最适量的有机二价基团引入代表性的基于宽带隙的基于聚芴的共轭聚电解质的主链中。双自由基规范结构的引入可以促进共轭骨架的醌型共振，从而导致自掺杂效应的增加。所以，与参考的CPE相比，共聚的CPE表现出高的可见光透射率（AVT超过85％）和增强的电子传导性。使用新型设计的聚电解质作为阴极界面层的有机太阳能电池器件，可以实现超过16％的高功率转换效率，厚度不超过50 nm也不受影响。这项工作通过有机双自由基调节提供了可行的分子修饰策略，以获得高性能的n型自掺杂共轭聚电解质。厚度不超过50 nm不敏感。这项工作通过有机双自由基调节提供了可行的分子修饰策略，以获得高性能的n型自掺杂共轭聚电解质。厚度不超过50 nm不敏感。这项工作通过有机双自由基调节提供了可行的分子修饰策略，以获得高性能的n型自掺杂共轭聚电解质。