Constructing Controlled Vertical Gradient Morphology in Pseudo‐Planar Heterojunction Organic Photovoltaics via Self‐Assembled Interface Orthogonal Strategy

Precisely regulating vertically distributed morphology by blade-coating process is crucial to realize high-performance large-scale pseudo-planar heterojunction organic photovoltaics (OPVs). However, the thermodynamic motion and random diffusion of donor/acceptor (D/A) generated from the differences in surface energy and concentration during sequentially blade-coating process will cause great challenges for obtaining ideal active layer morphology. Herein, this study have proposed a self-assembled interface orthogonal strategy by introducing low surface energy guest (N2200) to form protective layer on PM6 surface, which counteracts erosion from orthogonal solution of acceptor to enhance continuity of D/A phases, thus promoting directional carrier migration and effectively suppressing energetic disorder. Finally, N2200-modified device achieves the highest power conversion efficiency (PCE) of 19.86%, and large-area module (16.94 cm²) exhibits exceptional PCE (16.43%). This investigation presents innovative insights into morphology issue triggered by molecular motion and provides an effective method for air-printing large-scale OPVs with precisely controlled morphology based on non-halogenated solvent.