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

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${}_{1\mathrm{g}}$ and E${}_{2\mathrm{g}}^1$ peaks in the t-intercalated case versus a redshift for A${}_{1\mathrm{g}}$ and blueshift (sometimes accompanied by a smaller redshifted peak) for E${}_{2\mathrm{g}}^1$ 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.