Compared to regular conjugated polymers, the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene (NF)-based polymer solar cells (PSCs) due to their disordered chemical structures. In this work, we report two random terpolymer donors (PBNB80 and PBNB50) by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione (NTD) and 1,3-bis(4-chlorothiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-c']dithiophene-4,8-dione (Cl-BDD), at the same time, the parent polymers (PBNB100 and PBNB00) are also compared to study. These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels. Importantly, aggregation and self-organization properties of the random terpolymer donors are optimized, which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4Cl. Particularly, a PBNB80:BO-4Cl blend forms an optimal nanoscale phase-separation morphology, thereby producing an outstanding power conversion efficiency of 16.0%, which is much higher than those (12.8% and 10.7%) of their parent binary polymer donor-based devices. This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.

与常规共轭聚合物相比，由于其无序的化学结构，无规共轭三元共聚物通常不利于实现高效的基于非富勒烯（NF）的聚合物太阳能电池（PSC）。在这项工作中，我们通过调节1,3-二（噻吩-2-基）萘[2,3-c]噻吩-4的电子接受单元的摩尔比来报告两个无规三元共聚物供体（PBNB80和PBNB50）， 9-二酮（NTD）和1,3-双（4-氯噻吩-2-基）-4H，8H-苯并[1,2-c：4,5-c']二噻吩-4,8-​​二酮（Cl -BDD），同时将母体聚合物（PBNB100和PBNB00）也进行了比较研究。这四个聚合物供体表现出相似的光学带隙，并逐渐加深最高的占据分子轨道水平。重要的是，优化了无规三元共聚物供体的聚集和自组织性能，在与BO-4Cl的NF受体混合后，可以得到更好的形态和晶体相干长度。尤其是，PBNB80：BO- 4Cl共混物形成了最佳的纳米级相分离形态，从而产生了16.0％的出色功率转换效率，这远远高于其母体二元聚合物供体基聚合物的转换效率（12.8％和10.7％）。设备。这项工作表明合理使用三元聚合策略制备无规三元共聚物是获得高效NF-PSC的非常重要的方法。