Understanding of perovskite crystal growth and film formation in scalable deposition processes

Hybrid organic-inorganic perovskite photovoltaics (PSCs) have attracted significant attention during the past decade. Despite the stellar rise of laboratory-scale PSC devices, which have reached a certified efficiency over 25% to date, there is still a large efficiency gap when transiting from small-area devices to large-area solar modules. Efficiency losses would inevitably arise from the great challenges of homogeneous coating of large-area high quality perovskite films. To address this problem, we provide an in-depth understanding of the perovskite nucleation and crystal growth kinetics, including the LaMer and Ostwald ripening models, which advises us that fast nucleation and slow crystallization are essential factors in forming high-quality perovskite films. Based on these cognitions, a variety of thin film engineering approaches will be introduced, including the anti-solvent, gas-assisted and solvent annealing treatments, Lewis acid-base adduct incorporation, etc., which are able to regulate the nucleation and crystallization steps. Upscaling the photovoltaic devices is the following step. We summarize the currently developed scalable deposition technologies, including spray coating, slot-die coating, doctor blading, inkjet printing and vapour-assisted deposition. These are more appealing approaches for scalable fabrication of perovskite films than the spin coating method, in terms of lower material/solution waste, more homogeneous thin film coating over a large area, and better morphological control of the film. The working principles of these techniques will be provided, which direct us that the physical properties of the precursor solutions and surface characteristics/temperature of the substrate are both dominating factors influencing the film morphology. Optimization of the perovskite crystallization and film formation process will be subsequently summarized from these aspects. Additionally, we also highlight the significance of perovskite stability, as it is the last puzzle to realize the practical applications of PSCs. Recent efforts towards improving the stability of PSC devices to environmental factors are discussed in this part. In general, this review, comprising the mechanistic analysis of perovskite film formation, thin film engineering, scalable deposition technologies and device stability, provides a comprehensive overview of the current challenges and opportunities in the field of PSCs, aiming to promote the future development of cost-effective up-scale fabrication of highly efficient and ultra-stable PSCs for practical applications