Coordination Chemistry as a Universal Strategy for a Controlled Perovskite Crystallization.

The most efficient and stable perovskite solar cells (PSCs) are made from a complex mixture of precursors. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g., by vacuum, an airstream, or a so-called antisolvent. Unfortunately, most oversaturation triggers do not expel the lingering (and highly coordinating) dimethyl sulfoxide (DMSO), which is used as a precursor solvent, from the thin films; this detrimentally affects long-term stability. In this work, (the green) dimethyl sulfide (DMS) is introduced as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, MAPbI3 PSCs are processed, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6% efficiency, among the highest reported efficiencies for this system. To confirm the universality of the strategy, DMS is tested for FAPbI3 as another composition, which shows higher efficiency of 23.5% compared to 20.9% for a device fabricated with chlorobenzene. This work provides a universal strategy to control perovskite crystallization using coordination chemistry, heralding the revival of perovskite compositions with pure DMSO.

One-Step Thermal Gradient- and Antisolvent-Free Crystallization of All-Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells.

All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat-sensitive hybrid organic-inorganic counterparts. In particular, CsPbI2 Br shows the highest potential for developing thermally-stable perovskite solar cells (PSCs) among all-inorganic compositions. However, controlling the crystallinity and morphology of all-inorganic compositions is a significant challenge. Here, a simple, thermal gradient- and antisolvent-free method is reported to control the crystallization of CsPbI2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin-coating and annealing to understand and optimize the evolving film properties. This leads to high-quality perovskite films with micrometer-scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open-circuit voltage (VOC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.