Structure, Thermodynamics, and Raman Spectroscopy of Rhenium-Doped Bulk MoS$_2$ from First Principles

TL;DR

This study uses first-principles calculations to analyze how Re doping affects the structure, stability, and Raman spectra of bulk MoS$_2$, providing insights into dopant site identification through spectral shifts.

Contribution

It introduces a general approach to calculate Raman spectra of metallic doped materials and distinguishes dopant sites via characteristic spectral shifts in bulk Re-doped MoS$_2$.

Findings

Re doping causes characteristic Raman peak shifts depending on dopant site.

The method can distinguish between Mo-substitution and tetrahedral intercalation.

Re-doped MoS$_2$ exhibits specific spectral signatures useful for experimental identification.

Abstract

Doping MoS$_2$ with Re is known to alter the electronic, structural, and tribological properties. Re-doped MoS$_2$ has been previously mainly studied in monolayer or few-layer form, but can also be relevant for applications in many-layer or bulk form. In this work, we use density functional theory to explore the structure, phase stability, and Raman spectrum of bulk Re-doped MoS$_2$. We consider the possibility of the Re dopant existing at different locations and provide experimentally distinguishable characteristics of the most likely sites: Mo-substitution and tetrahedral (t-) intercalation. We demonstrate and benchmark a general approach to calculate Raman spectra of doped materials with metallic densities of states by using atomic Raman tensors from the pristine material. Applying this method to the metallic Re-doped structures, we find characteristic shifts in the Raman-active peaks depending on Re dopant position: redshifts in both A$_{\rm 1g}$ and E$_{\rm 2g}^1$ peaks in the t-intercalated case versus a redshift for A$_{\rm 1g}$ and blueshift (sometimes accompanied by a smaller redshifted peak) for E$_{\rm 2g}^1$ peaks in the Mo-substituted case, which can be used to identify the dopant sites in experimental samples. We analyze the interactions giving rise to these shifts.