Navigating Molecular Structures of Self‐Assembled Monolayers for High Efficiency Perovskite Photovoltaics
Limiao Li, Xiaobo Zhang, Xiaoqing Chen, Zhiyong Wang, Hui Yan, Zilong ZhengABSTRACT
Self‐assembled monolayers (SAMs) have become the cornerstone of modern inverted perovskite solar cells, driving power conversion efficiency up to 27.3% and perovskite/silicon tandem devices up to 34.85%. This revolution stems from molecular engineering governing interfacial charge extraction and defect passivation. This review decodes the structure–function relationships of SAMs, moving beyond conventional applications to explore anchoring groups, conjugated linkers, and Lewis basic terminal groups. We highlight how the molecular engineering of SAMs mitigates energy‐level offsets and suppresses nonradiative recombination via hard‐soft acid‐base interactions. Special emphasis is placed on emerging co‐SAM strategies and in situ cross‐linking techniques that overcome single‐component limitations by creating synergistic interlayers. In the end, we outline a roadmap for rational SAM design bridging molecular insights with industrial scalability.