Polymorphism in metal halide perovskites

Metal halide perovskites (MHPs) are frontrunners among solution-processable materials for lightweight, large-area and flexible optoelectronics. These materials, with the general chemical formula AMX3, are structurally complex, undergoing multiple polymorph transitions as a function of temperature and pressure. In this review, we provide a detailed overview of polymorphism in three-dimensional MHPs as a function of composition, with A = Cs+, MA+, or FA+, M = Pb2+ or Sn2+, and X = Cl-, Br-, or I-. In general, perovskites adopt a highly symmetric cubic structure at elevated temperatures. With decreasing temperatures, the corner-sharing MX6 octahedra tilt with respect to one another, resulting in multiple polymorph transitions to lower-symmetry tetragonal and orthorhombic structures. The temperatures at which these phase transitions occur can be tuned via different strategies, including crystal size reduction, confinement in scaffolds and (de-)pressurization. As discussed in the final section of this review, these solid-state phase transformations can significantly affect optoelectronic properties. Understanding factors governing these transitions is thus critical to the development of high-performance, stable devices.