Optimizing Molecular Packing via Steric Hindrance for Reducing Non‐Radiative Recombination in Organic Solar Cells

Abstract Innovative molecule design strategy holds promise for the development of next‐generation acceptor materials for efficient organic solar cells with low non‐radiative energy loss ( ΔE nr ). In this study, we designed and prepared three novel acceptors, namely BTP‐Biso, BTP‐Bme and BTP‐B, with sterically structured triisopropylbenzene, trimethylbenzene and benzene as side chains inserted into the shoulder of the central core. The progressively enlarged steric hindrance from BTP‐B to BTP‐Bme and BTP‐Biso induces suppressed intramolecular rotation and altered the molecule packing mode in their aggregation states, leading to significant changes in absorption spectra and energy levels. By regulating the intermolecular π–π interactions, BTP‐Bme possesses relatively reduced non‐radiative recombination rate and extended exciton diffusion lengths. The binary device based on PB2 : BTP‐Bme exhibits an impressive power conversion efficiency (PCE) of 18.5 % with a low ΔE nr of 0.19 eV. Furthermore, the ternary device comprising PB2 : PBDB‐TF : BTP‐Bme achieves an outstanding PCE of 19.3 %. The molecule design strategy in this study proposed new perspectives for developing high‐performance acceptors with low ΔE nr in OSCs.