Phase Stability and Raman/IR Signatures of Ni-Doped MoS₂ from Density-Functional Theory Studies

Ni-doped MoS$_2$ is a layered material with useful tribological, optoelectronic, and catalytic properties. Experiment and theory on doped MoS$_2$ has focused mostly on monolayers or finite particles: theoretical studies of bulk Ni-doped MoS$_2$ are lacking and the mechanisms by which Ni alters bulk properties are largely unsettled. We use density functional theory calculations to determine the structure, mechanical properties, electronic properties, and formation energies of bulk Ni-doped 2H-MoS$_2$ as a function of doping concentration. We find four meta-stable structures: Mo or S substitution, and tetrahedral (t-) or octahedral (o-) intercalation. We compute phase diagrams as a function of chemical potential to guide experimental synthesis. A convex hull analysis shows that t-intercalation (favored over o-intercalation) is quite stable against phase segregation and in comparison with other compounds containing Ni, Mo, and S; the doping formation energy is around 0.1 meV/atom. Intercalation forms strong interlayer covalent bonds and does not increase the $c$-parameter. Ni-doping creates new states in the electronic density of states in MoS$_2$ and shifts the Fermi level, which are of interest for tuning the electronic and optical properties. We calculate the infrared and Raman spectra and find new peaks and shifts in existing peaks that are unique to each dopant site, and therefore may be used to identify the site experimentally, which has been a challenge to do conclusively.