Horizontal-to-Vertical Transition of 2D Layer Orientation in Low-Temperature Chemical Vapor Deposition-Grown PtSe₂ and Its Influences on Electrical Properties and Device Applications

Two-dimensional (2D) transition-metal dichalcogenides (2D TMDs) in the form of MX₂ (M: transition metal, X: chalcogen) exhibit intrinsically anisotropic layered crystallinity wherein their material properties are determined by constituting M and X elements. 2D platinum diselenide (2D PtSe₂) is a relatively unexplored class of 2D TMDs with noble-metal Pt as M, offering distinct advantages over conventional 2D TMDs such as higher carrier mobility and lower growth temperatures. Despite the projected promise, much of its fundamental structural and electrical properties and their interrelation have not been clarified, and so its full technological potential remains mostly unexplored. In this work, we investigate the structural evolution of large-area chemical vapor deposition (CVD)-grown 2D PtSe₂ layers of tailored morphology and clarify its influence on resulting electrical properties. Specifically, we unveil the coupled transition of structural-electrical properties in 2D PtSe₂ layers grown at a low temperature (i.e., 400 °C). The layer orientation of 2D PtSe₂ grown by the CVD selenization of seed Pt films exhibits horizontal-to-vertical transition with increasing Pt thickness. While vertically aligned 2D PtSe₂ layers present metallic transports, field-effect-transistor gate responses were observed with thin horizontally aligned 2D PtSe₂ layers prepared with Pt of small thickness. Density functional theory calculation identifies the electronic structures of 2D PtSe₂ layers undergoing the transition of horizontal-to-vertical layer orientation, further confirming the presence of this uniquely coupled structural-electrical transition. The advantage of low-temperature growth was further demonstrated by directly growing 2D PtSe₂ layers of controlled orientation on polyimide polymeric substrates and fabricating their Kirigami structures, further strengthening the application potential of this material. Discussions on the growth mechanism behind the horizontal-to-vertical 2D layer transition are also presented.