Side‐Chain Engineering of Non‐Fullerene Acceptors with Trialkylsilyloxy Groups for Enhanced Photovoltaic Performance^†

Comprehensive SummarySide‐chain engineering has emerged as a highly effective strategy for tailoring the aggregation behavior and charge transport properties of non‐fullerene small molecule acceptors (SMAs). In this study, we designed and synthesized two SMAs, namely BTPSi‐Bu and BTPSi‐Pr, respectively incorporating tributylsilyloxy and triisopropylsilyloxy groups in their outer positions. Notably, BTPSi‐Bu exhibited better planarity, crystallization, and favorable phase separation when paired with PM6 donor polymer compared to its counterpart, BTPSi‐Pr. The resulting organic solar cells, utilizing the PM6:BTPSi‐Bu blend, demonstrated a remarkable power conversion efficiency of 17.41% and a high open‐circuit voltage of 0.859 V. These findings underscore the significance of integrating trialkylsilyloxy side chains into SMAs as a rational design approach for enhancing the performance of photovoltaic systems.