Phase‐Tunable Synthesis of Ultrathin Layered Tetragonal CoSe and Nonlayered Hexagonal CoSe Nanoplates

Abstract Multiple structural phases in transition metal dichalcogenides have attracted considerable recent interest for their tunable chemical and electronic properties. Herein, a chemical vapor deposition route to ultrathin CoSe nanoplates with tunable structure phases is reported. By precisely tailoring the growth temperature, ultrathin 2D layered tetragonal CoSe nanoplates and nonlayered hexagonal CoSe nanoplates can be selectively prepared as square or hexagonal geometries, with thickness as thin as 2.3 and 3.7 nm, respectively. X‐ray diffraction, transmission electron microscopy, and selected area electron diffraction studies show that both types of nanoplates are high‐quality single crystals. Electrical transport studies reveal that both the tetragonal and hexagonal CoSe nanoplates show strong thickness‐tunable electrical properties and excellent breakdown current density. The 2D hexagonal CoSe nanoplates display metallic behavior with an excellent conductivity up to 6.6 × 10⁵ S m⁻¹ and an extraordinary breakdown current density up to 3.9 × 10⁷ A cm⁻², while the square tetragonal nanoplates show considerably lower conductivity up to 8.2 × 10⁴ S m⁻¹ with angle‐dependent magnetoresistance and weak antilocalization effect at lower field. This study offers a tunable material system for exploring multiphase 2D materials and their potential applications for electronic and magnetoelectronic devices.