Salt‐Based Catalyzer to Aid Heterogeneous Nucleation Enabling >23% Efficient Electron‐Transport‐Layer‐Free Perovskite Solar Cells

Abstract Charge transport layers are critical components in perovskite solar cells (PSCs) for achieving satisfied power conversion efficiencies (PCEs) and device stability. However, these layers often bring incompatible interfaces and complex fabrication, limiting the stability and scalability of PSC technology. Here an alternative strategy of salt‐based catalyzer (SBC) is proposed to regulate the heterogeneous nucleation of perovskite, which enables uniform and well‐controlled perovskite coverage directly onto the salt‐treated substrate without electron transport layers (ETLs). By carefully adjusting the cations, anions, and the thickness of SBC, high‐quality perovskite films along with superior buried interfaces suppress the carrier recombination losses and strengthen the interfacial stability, promoting the resultant device to achieve a record PCE of 23.04%, which represents the highest reported efficiency for ETL‐free PSCs. Meanwhile, the SBC technique can be well extended to large‐area, flexible, and module‐based devices. More encouragingly, the SBC‐based unencapsulated devices exhibit remarkable operational stability by retaining over 90% of initial efficiency for 1540 h under illumination and for 6312 h in an air environment. This work provides an advisable way to fabricate efficient and stable ETL‐free PSCs toward reliable and cost‐effective production.