To achieve efficient polymer solar cells (PSCs) with full utilization of the whole spectrum, the multi-component devices are of great importance to be deeply explored, especially for their capability of one-step fabrication. However, the research about one same binary system simultaneously derivated various multi-component PSC is still very limited. Herein, we achieved the whole constructions from one binary host to different ternary systems and even the quaternary one. The ternary strategies with fullerene acceptor, PC₇₁BM, and non-fullerene acceptor, BT₆IC-BO-4Cl, as the third component, both boosted the device efficiencies of PBT4Cl-Bz: IT-4F binary system from about 9% to comparatively beyond 11%. Despite the comparable improvement of performance, there existed other similarities and differences in two ternary strategies. In detail, the isotropic carrier transport of PC₇₁BM which largely elevated the fill factor (FF) in the corresponding devices, while the strong absorption of BT₆IC-BO-4Cl enhanced the short current density (J_sc) most. More interestingly, quaternary devices based on PBT4Cl-Bz: IT-4F: PC₇₁BM: BT₆IC-BO-4Cl could combine both advantages of fullerene and non-fullerene ternary strategies, further pumped the J_sc from 16.44 to the highest level of 19.66 mA cm⁻² among all devices, eventually resulted in an optimized efficiency of 11.69%. It reveals that both fullerene and non-fullerene ternary strategies have their unique feature to elevate the device performance either by efficient isotropic carrier transport or better coverage of whole sunlight spectrum and easy tunable energy levels from organic materials. The key is how to integrate the two pathways in one system and provide a more competitive solution facing high-quality PSCs.

为了充分利用整个光谱范围来获得高效的聚合物太阳能电池（PSC），多组分器件尤其是其一步制造的能力非常重要，需要深入研究。然而，关于同时衍生出多种多组分PSC的同一二进制系统的研究仍然非常有限。在这里，我们实现了从一个二进制主机到不同的三元系统甚至是四元系统的整个构造。使用富勒烯受体PC ₇₁ BM和非富勒烯受体BT ₆的三元策略IC-BO-4Cl作为第三种成分，都将PBT4Cl-Bz：IT-4F二元系统的器件效率从大约9％提高到了11％以上。尽管性能有可比较的提高，但两种三元策略在其他方面也存在相同点和不同点。详细地，PC ₇₁ BM的各向同性载流子传输大大提高了相应器件中的填充因子（FF），而BT ₆ IC-BO-4Cl的强吸收性最大地提高了短路电流密度（J _sc）。更有趣的是，基于PBT4Cl-Bz：IT-4F：PC ₇₁ BM：BT ₆ IC-BO- 4Cl的四元器件可以结合富勒烯和非富勒烯三元策略的优势，进一步抽提J_sc从16.44到19.66 mA cm ^-2的最高水平，最终使优化效率达到11.69％。它揭示了富勒烯和非富勒烯三元策略都有其独特的特征，可以通过有效的各向同性载流子传输或更好地覆盖整个太阳光光谱以及容易地调节有机材料的能级来提高器件性能。关键是如何将这两种途径整合到一个系统中，并提供面向高质量PSC的更具竞争力的解决方案。