Conjugated Phosphonic Acids Enable Robust Hole Transport Layers for Efficient and Intrinsically Stable Perovskite Solar Cells

Abstract High efficiency and long‐term stability are the prerequisites for the commercialization of perovskite solar cells (PSCs). However, inadequate and non‐uniform doping of hole transport layers (HTLs) still limits the efficiency improvements, while the intrinsic instability of HTLs caused by ion migration and accumulation is difficult to be addressed by external encapsulation. Here it is shown that the addition of a conjugated phosphonic acid (CPA) to the Spiro‐OMeTAD benchmark HTL can greatly enhance the device efficiency and intrinsic stability. Featuring an optimal diprotic‐acid structure, indolo(3,2‐ b )carbazole‐5,11‐diylbis(butane‐4,1‐diyl) bis(phosphonic acid) (BCZ) is developed to promote morphological uniformity and mitigate ion migration across both perovskite/HTL and HTL/Ag interfaces, leading to superior charge conductivity, reinforced ion immobilization, and remarkable film stability. The dramatically improved interfacial charge collection endows BCZ‐based n‐i‐p PSCs with a champion power conversion efficiency of 24.51%. More encouragingly, the BCZ‐based devices demonstrate remarkable stability under harsh environmental conditions by retaining 90% of initial efficiency after 3000 h in air storage. This work paves the way for further developing robust organic HTLs for optoelectronic devices.