Organic Photovoltaic Stability: Understanding the Role of Engineering Exciton and Charge Carrier Dynamics from Recent Progress

Abstract Benefiting from the synergistic development of material design, device engineering, and the mechanistic understanding of device physics, the certified power conversion efficiencies (PCEs) of single‐junction non‐fullerene organic solar cells (OSCs) have already reached a very high value of exceeding 19%. However, in addition to PCEs, the poor stability is now a challenging obstacle for commercial applications of organic photovoltaics (OPVs). Herein, recent progress made in exploring operational mechanisms, anomalous photoelectric behaviors, and improving long‐term stability in non‐fullerene OSCs are highlighted from a novel and previously largely undiscussed perspective of engineering exciton and charge carrier pathways. Considering the intrinsic connection among multiple temporal‐scale photocarrier dynamics, multi‐length scale morphologies, and photovoltaic performance in OPVs, this review delineates and establishes a comprehensive and in‐depth property‐function relationship for evaluating the actual device stability. Moreover, this review has also provided some valuable photophysical insights into employing the advanced characterization techniques such as transient absorption spectroscopy and time‐resolved fluorescence imagings. Finally, some of the remaining major challenges related to this topic are proposed toward the further advances of enhancing long‐term operational stability in non‐fullerene OSCs.