Real‐Time Probing and Unraveling the Morphology Formation of Blade‐Coated Ternary Nonfullerene Organic Photovoltaics with In Situ X‐Ray Scattering

Abstract Characterizing the bulk heterojunction (BHJ) morphology of the active layer is essential for optimizing blade‐coated organic solar cells (OSCs). Here, the morphology evolution of a highly efficient ternary polymer:nonfullerene blend PM6:N3:N2200 under different blade coating conditions is probed in real‐time by in situ synchrotron X‐ray scattering and in situ ultraviolet‐visible (UV‐vis) spectroscopy. Besides, the morphology of blade‐coated blend films at different conditions is detailed by ex situ X‐ray scattering and microscopic imaging. The ternary blend film exhibited optimized morphology, such as superior molecular stacking structure and appropriate phase separation structure, and boosted photovoltaic performance of the binary blend, as adding a second polymer component to the host polymer:nonfullerene system can balance nucleation and crystallization of polymers and small molecules, facilitating molecular rearrangement to perfect crystallization. Both binary and ternary blends obtained optimized morphology and photovoltaic properties at medium coating speed, mainly attributed to the movement of the polymer and small molecules at the long crystallization and aggregation stage. These findings help understand morphology formation under film drying and provide guidance for optimizing the morphology in blade‐coated OSCs.