Intramolecular Noncovalent Interaction‐Enabled Dopant‐Free Hole‐Transporting Materials for High‐Performance Inverted Perovskite Solar Cells

Abstract Intramolecular noncovalent interactions (INIs) have served as a powerful strategy for accessing organic semiconductors with enhanced charge transport properties. Herein, we apply the INI strategy for developing dopant‐free hole‐transporting materials (HTMs) by constructing two small‐molecular HTMs featuring an INI‐integrated backbone for high‐performance perovskite solar cells (PVSCs). Upon incorporating noncovalent S⋅⋅⋅O interaction into their simple‐structured backbones, the resulting HTMs, BTORA and BTORCNA, showed self‐planarized backbones, tuned energy levels, enhanced thermal properties, appropriate film morphology, and effective defect passivation. More importantly, the high film crystallinity enables the materials with substantial hole mobilities, thus rendering them as promising dopant‐free HTMs. Consequently, the BTORCNA‐based inverted PVSCs delivered a power conversion efficiency of 21.10 % with encouraging long‐term device stability, outperforming the devices based on BTRA without S⋅⋅⋅O interaction (18.40 %). This work offers a practical approach to designing charge transporting layers with high intrinsic mobilities for high‐performance PVSCs.