Two‐Dimensional Palladium Diselenide with Strong In‐Plane Optical Anisotropy and High Mobility Grown by Chemical Vapor Deposition

Two-dimensional (2D) palladium diselenide (PdSe₂ ) has strong interlayer coupling and a puckered pentagonal structure, leading to remarkable layer-dependent electronic structures and highly anisotropic in-plane optical and electronic properties. However, the lack of high-quality, 2D PdSe₂ crystals grown by bottom-up approaches limits the study of their exotic properties and practical applications. In this work, chemical vapor deposition growth of highly crystalline few-layer (≥2 layers) PdSe₂ crystals on various substrates is reported. The high quality of the PdSe₂ crystals is confirmed by low-frequency Raman spectroscopy, scanning transmission electron microscopy, and electrical characterization. In addition, strong in-plane optical anisotropy is demonstrated via polarized Raman spectroscopy and second-harmonic generation maps of the PdSe₂ flakes. A theoretical model based on kinetic Wulff construction theory and density functional theory calculations is developed and described the observed evolution of "square-like" shaped PdSe₂ crystals into rhombus due to the higher nucleation barriers for stable attachment on the (1,1) and (1,-1) edges, which results in their slower growth rates. Few-layer PdSe₂ field-effect transistors reveal tunable ambipolar charge carrier conduction with an electron mobility up to ≈294 cm² V^-1 s^-1 , which is comparable to that of exfoliated PdSe₂ , indicating the promise of this anisotropic 2D material for electronics.