Tailoring the Position of Ester Group on N‐Alkyl Chains of Benzotriazole‐based Small Molecule Acceptors for High‐Performance Organic Solar Cells

Abstract Side chain engineering plays a vital role in exploring high‐performance small molecule acceptors (SMAs) for organic solar cells (OSCs). In this work, we designed and synthesized a series of A‐DA'D‐A type SMAs by introducing different N ‐substituted alkyl and ester alkyl side chains on benzotriazole (BZ) central unit and aimed to investigate the effect of different ester substitution positions on photovoltaic performances. All the new SMAs with ester groups exhibit lower the lowest unoccupied molecular orbital (LUMO) energy levels and more blue‐shifted absorption, but relatively higher absorption coefficients than alkyl chain counterpart. After blending with the donor PM6, the ester side chain‐based devices demonstrate enhanced charge mobility, reduced amorphous intermixing domain size and long‐lived charge transfer state compared to the alkyl chain counterpart, which are beneficial to achieve higher short‐circuit current density ( J sc ) and fill factor (FF), simultaneously. Thereinto, the PM6 : BZ‐E31 based device achieves a higher power conversion efficiency (PCE) of 18.33 %, which is the highest PCE among the OSCs based on the SMAs with BZ‐core. Our work demonstrated the strategy of ester substituted side chain is a feasible and effective approach to develop more efficient SMAs for OSCs.