Tailoring Multifunctional Self‐Assembled Hole Transporting Molecules for Highly Efficient and Stable Inverted Perovskite Solar Cells

Abstract The self‐assembled hole transporting molecules (SAHTMs) bearing anchoring groups have been established as the hole transporting layers (HTLs) for highly efficient p–i–n perovskite solar cells (PSCs), yet their stability and engineering at the molecular level remain challenging. A topological design of highly anisotropic aligned SAHTM‐based HTLs for operationally stable PSCs that exhibit exceptional solar‐to‐electric power conversion efficiencies (PCEs) is demonstrated. The judiciously designed multifunctional self‐assembled molecules comprise the donor–acceptor subunit for hole transporting and the phosphonic acid group for anchoring, realizing face‐on π‐stacking parallel to the transparent conductive oxide substrate. The high affinity of SAHTMs to the multi‐crystalline perovskite thin film benefits passivating the perovskite buried interface, strengthening interfacial contact while facilitating interfacial hole transfer. Consequently, highly efficient p–i–n PSC devices are obtained with a champion PCE of 23.24% and outstanding operational stability toward various environmental factors including long‐term full sunlight soaking at evaluated temperatures. Perovskite solar modules with a champion efficiency approaching 20% are also fabricated for an active device area above 17 cm 2 .