Polythiophene (PT) and its derivatives have attracted long-standing attention in the organic photovoltaic community for their low cost and high scalability of synthesis. However, due to the lack of rational guidelines in controlling morphology and matching materials, the power conversion efficiencies (PCEs) based on PTs reported so far are generally below 10%. Here, we establish the first-ever relationship between miscibility, morphology, and device performance of binary blends, based on various nonfullerene acceptors (ITIC-Th1, ITIC, IT4F, IDIC, and Y6) and a PT derivative named PDCBT-Cl by scattering and calorimetric characterizations. Benefiting from a properly quenched mixed phase, PDCBT-Cl:ITIC-Th1 system shows the best efficiency of over 12%. Conversely, the blend of PDCBT-Cl and the star acceptor Y6 remained in a homogeneous state due to their high miscibility, resulting in abysmal performance with PCE of 0.5%. Specific guidelines are also proposed to remediate the performance of PDCBT-Cl:Y6, which are crucial for advancing their practical applications.

聚噻吩（PT）及其衍生物因其低成本和高合成规模而备受有机光伏界的长期关注。但是，由于缺乏控制形态和匹配材料的合理指导，到目前为止，基于PT的功率转换效率（PCE）通常低于10％。在这里，我们基于各种非富勒烯受体（ITIC-Th1，ITIC，IT4F，IDIC和Y6）和名为PDCBT-Cl的PT衍生物，建立了二元共混物的混溶性，形态和器件性能之间的首次关系。和量热表征。得益于适当淬火的混合相，PDCBT-Cl：ITIC-Th1系统显示出超过12％的最佳效率。反过来，PDCBT-Cl和星形受体Y6的混合物由于它们的高度可混溶性而保持均一状态，因此PCE为0.5％时表现很差。还提出了一些具体准则来补救PDCBT-Cl：Y6的性能，这对于提高其实际应用至关重要。