LAUSR

A record power conversion efficiency (PCE) of over 19% is realized in planar‐mixed heterojunction (PMHJ) organic solar cells (OSCs) by adopting the asymmetric selenium substitution strategy in making a pseudosymmetric electron acceptor, BS3TSe‐4F. The combined molecular asymmetry with more polarizable selenium substitution increases the dielectric constant of the D18/BS3TSe‐4F blend, helping lower the exciton binding energy. On the other hand, dimer packing in BS3TSe‐4F is facilitated to enable free charge generation, helping more efficient exciton dissociation and lowering the radiative recombination loss (ΔE2) of OSCs. As a result, PMHJ OSCs based on D18/BS3TSe‐4F achieve a PCE of 18.48%. By incorporating another mid‐bandgap acceptor Y6‐O into D18/BS3TSe‐4F to form a ternary PMHJ, a higher open‐circuit voltage (VOC) can be achieved to realize an impressive PCE of 19.03%. The findings of using pseudosymmetric electron acceptors in enhancing device efficiency provides an effective way to develop highly efficient acceptor materials for OSCs.