Humidity‐Insensitive, Large‐Area‐Applicable, Hot‐Air‐Assisted Ambient Fabrication of 2D Perovskite Solar Cells

2D layered perovskites (LPs) have shown great potential to deliver high-performance photovoltaic devices with long-term stability. Despite many signs of progress being made in film quality and device performance, LP films are mainly processed in strict conditions and through non-scalable techniques. Here, the hot-air-assisted ambient fabrication technique is introduced to prepare LP films for efficient and stable solar cells. The high-quality LP films with good crystallinity, preferable orientation and desirable morphology are obtained by balancing the crystal nucleation and growth processes. Employing the synchrotron-based in situ grazing-incidence X-ray diffraction technique, hot air induces the solidification of solutes and forms an intermediate at the air-liquid interface, which transforms into 3D-like perovskite, followed by the growth of the 2D species toward the substrate. The optimal LP film delivers a device power conversion efficiency of 16.36%, the best value for the LP-based solar cells prepared by the non-spin-coating techniques. The solar cell performance is insensitive to the film processing humidity and the device size is upscalable, which promises real-world deployment of LP-based optoelectronic devices.