Orientation-Controlled Large-Area Epitaxial PbI₂ Thin Films with Tunable Optical Properties

Lead iodide (PbI₂) as a layered material has emerged as an excellent candidate for optoelectronics in the visible and ultraviolet regime. Micrometer-sized flakes synthesized by mechanical exfoliation from bulk crystals or by physical vapor deposition have shown a plethora of applications from low-threshold lasing at room temperature to high-performance photodetectors with large responsivity and faster response. However, large-area centimeter-sized growth of epitaxial thin films of PbI₂ with well-controlled orientation has been challenging. Additionally, the nature of grain boundaries in epitaxial thin films of PbI₂ remains elusive. Here, we use mica as a model substrate to unravel the growth mechanism of large-area epitaxial PbI₂ thin films. The partial growth leading to uncoalesced domains reveals the existence of inversion domain boundaries in epitaxial PbI₂ thin films on mica. Combining the experimental results with first-principles calculations, we also develop an understanding of the thermodynamic and kinetic factors that govern the growth mechanism, which paves the way for the synthesis of high-quality large-area PbI₂ on other substrates and heterostructures of PbI₂ on single-crystalline graphene. The ability to reproducibly synthesize high-quality large-area thin films with precise control over orientation and tunable optical properties could open up unique and hitherto unavailable opportunities for the use of PbI₂ and its heterostructures in optoelectronics, twistronics, substrate engineering, and strain engineering.