Morphology Optimization by Non‐Halogenated and Twisted Volatile Solid Additive for High‐Efficiency Organic Solar Cells

Abstract Recently, volatile solid additives have attracted tremendous interest in the field of organic solar cells (OSCs), which can effectively improve device efficiency without sacrificing the reproducibility and stability of the device. However, the structure of reported solid additives is onefold and its working mechanism needs to be further investigated. Herein, a novel non‐halogenated and twisted solid additive 1,4‐diphenoxybenzene (DPB) is employed to optimize the morphology of the active layer in OSCs. The properties of additive DPB, morphology of active layer, and carrier dynamics behaviors have been systematically investigated through theoretical calculations, in situ and ex situ spectroscopy, grazing‐incidence wide‐angle X‐ray scattering (GIWAXS), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) measurement, as well as ultrafast spectroscopy technology. The results reveal that the twisted additive DPB selectively interacts with acceptor Y6, and thus forms optimized morphology of active layer with increased molecular crystallinity, tight molecular packing, and favorable phase separation. As a result, the optimized devices deliver a remarkable power conversion efficiency (PCE) of 19.04%, which is the highest value for the D18‐Cl:N3 system to date. These results demonstrate that non‐halogenated and twisted solid additive DPB has broad prospects in the preparation of highly efficient OSCs, providing theoretical and experimental guidance for the development of high‐performance solid additives.