Vacancy-Driven Electronic Reconstruction in Monolayer PtSe$_2$: Formation Thermodynamics and Charge States

Abstract

Layered transition metal dichalcogenides are an important platform for two-dimensional materials, where the inevitable intrinsic defects provide new degrees of freedom for tuning their physical properties. Based on first-principles calculations, this work systematically investigates the formation energies, charge states, and electronic structural characteristics of V$_{\mathrm{Pt}}$, V$_{\mathrm{Se}}$, and composite vacancies in monolayer PtSe$_2$. The results indicate that while vacancy formation energies are highly sensitive to chemical potentials, the V$_{\mathrm{Se}}$ structure consistently exhibits the lowest formation energy. The charge defect calculation reveals the stable charge state intervals of V$_{\mathrm{Se}}$ and V$_{\mathrm{Pt}}$ as a function of the Fermi level, thus describing the evolution of the charge states of intrinsic vacancies at different electronic chemical potentials. Climbing Image Nudged Elastic Band calculations reveal high migration barriers for V$_{\mathrm{Se}}$ and V$_{\mathrm{Pt}}$, indicating strongly hindered vacancy diffusion at room temperature, while short Ab Initio Molecular Dynamics simulations confirm the absence of immediate structural collapse within the simulated time window. Optical property calculations indicate that point defects significantly alter the dielectric response of monolayer PtSe$_2$ and generate new low-energy absorption channels associated with in-gap defect states. These findings provide new insights into defect-mediated electronic and optical property modulation in monolayer PtSe$_2$, offering guidance for its potential device design.