Molecular Symmetry of Small‐Molecule Passivating Agents Improves Crystal Quality of Perovskite Solar Cells

Abstract Direct interaction with the defect sites of perovskite, functional groups have become the focal point of attention as passivating agents. However, the molecular parent nucleus determines the overall physical properties of the molecule, including the push‐pull electronic characteristics of the functional groups, which poses significant challenges in terms of selectivity. Here, we discovered that the binary acid structure based on thiophene as the parent nucleus, due to changes in molecular symmetry, caused significant changes in the molecular dipole moment, resulting in significant changes in the passivation effects on under‐coordinated Pb 2+ in perovskite solar cells. For the axially symmetric thiophen‐2,5‐dicarboxylic acid (TPDC), the high dipole moment formed a concentrated surface negative potential on the carboxyl group, showing significant superiority over the centrally symmetric thieno[3,2‐b] thiophene‐2,5‐dicarboxylic acid (TTDC) in forming high‐quality perovskite crystals, suppressing charge recombination, enhancing effective charge transport, and raising internal electric fields. The power conversion efficiencies of the fully printable mesoscopic perovskite solar cells based on TPDC and TTDC were 17.15 % and 14.79 %, respectively, exhibiting important research value in the field of small molecule passivation mechanism research.