Molecular Design for Vertical Phase Distribution Modulation in High‐Performance Organic Solar Cells

Abstract Component distribution within the photoactive layer dictates the morphology and electronic structure and substantially influences the performance of organic solar cells (OSCs). In this study, a molecular design strategy is introduced to manipulate component and energetics distribution by adjusting side‐chain polarity. Two non‐fullerene acceptors (NFAs), ITIC‐16F and ITIC‐E, are synthesized by introducing different polar functional substituents onto the side chains of ITIC. The alterations result in different distribution tendencies in the bulk heterojunction film: ITIC‐16F with intensified hydrophobicity aligns predominantly with the top surface, while ITIC‐E with strong hydrophilicity gravitates toward the bottom. This divergence directly impacts the vertical distribution of the excitation energy levels, thereby influencing the excitation kinetics over extended time periods and larger spatial ranges including enhanced diffusion‐mediated exciton dissociation and stimulated charge carrier transport. Benefitting from the favorable energy distribution, the device incorporating ITIC‐E into the PBQx‐TF:eC9‐2Cl blend showcases an impressive power conversion efficiency of 19.4%. This work highlights side‐chain polarity manipulation as a promising strategy for designing efficient NFA molecules and underscores the pivotal role of spatial energetics distribution in OSC performance.