Intrinsic Role of Volatile Solid Additive in High‐Efficiency PM6:Y6 Series Nonfullerene Solar Cells

Organic nonfullerene solar cells (ONSCs) have made unprecedented progress; however, morphology optimization of ONSCs is proven to be particularly challenging relative to classical fullerene-based devices. Here, a novel volatile solid additive (VSA), 2-hydroxy-4-methoxybenzophenone (2-HM), is reported for achieving high-efficiency ONSCs. 2-HM functions as a universal morphology-directing agent for several well-known PM6:Y6 series nonfullerene blends, viz. PM6:Y6, PM6:BTP-eC9, PM6:L8-BO, leading to a best efficiency of 18.85% at the forefront of reported binary ONSCs. VSAs have recently emerged, while the intrinsic kinetics is still unclear. Herein, a set of in situ and ex situ characterizations is employed to first illustrate the molecule-aggregate-domain transition dynamic process assisted by the VSA. More specifically, the role of 2-HM in individual donor PM6 and acceptor Y6 systems is unlocked, and the function of 2-HM in altering the PM6:Y6 bulk heterojunction blends is further revealed for enhanced photovoltaic performance. It is believed that the achievement brings not only a deep insight into emerging volatile solid additive, but also a new hope to further improve the molecular ordering, film microstructure, and relevant performance of ONSCs.