Balanced Miscibility and Crystallinity by 2D Acceptors Enabled Halogen‐Free Solvent‐Processed Organic Solar Cells to Achieve 19.28% Efficiency

Abstract Two highly crystalline 2D acceptors, ATIC‐C11 and ATIC‐BO, with acenaphthene‐expanded quinoxaline central cores, have been demonstrated with very different characteristics in ternary organic solar cells (OSCs). The difference in side chains induces their distinctive molecular packing mode and unique crystal structure, in which ATIC‐C11 displays a 3D structure with an elliptical framework, and ATIC‐BO gives a rectangular framework. Their high crystallinity contributes to organized molecular packing in ternary devices, thus low energetic disorder and suppressed energy loss. Through the analysis of morphology and carrier kinetics, it is found that ATIC‐BO's strong self‐aggregation and immiscibility induce large aggregates and severely impede charge transfer (CT) and dissociation. Conversely, ATIC‐C11's suitable crystallinity and compatibility positively regulate the crystalline kinetics during film formation, thus forming much‐ordered molecular packing and favorable phase separation size in blend films. As a result, ATIC‐C11‐based ternary devices achieve a high efficiency of 19.28% with potential in scalability and stability, which is the top‐ranking efficiency among nonhalogenated solvent‐processed OSCs. This work not only displays highly efficient and stable halogen‐free solvent‐processed organic photovoltaics (OPVs), but also offers a new thought for material design and selection rule on the third component in highly efficient ternary OSCs.