Reaction mechanism of core–shell MoO₂/MoS₂nanoflakes via plasma-assisted sulfurization of MoO₃

Abstract

The sulfurization of MoO3 in an H2S/Ar plasma atmosphere has been experimentally studied and a reaction mechanism has been proposed based on the results obtained. Nanostructured thin films (NTFs) of MoO3 were sulfurized at different temperatures varying from 150 °C to 550 °C. High-resolution transmission electron microscopy (TEM) images depict core–shell nanoflakes with varying shell thicknesses as the sulfurization temperature (Tsn) is varied. The shells consist of MoS2 and the core is MoO2/MoO3. X-ray diffraction (XRD) and Raman analysis have been used to study the structural changes as MoO3 is sulfurized. The analyses showed two phases, MoO2 and MoS2, at low temperatures (≤350 °C), whereas the films sulfurized at higher temperatures show predominantly MoS2. The scanning electron microscopy (SEM) results show no noticeable changes in the surface morphology of the NTFs after sulfurization. X-ray photoelectron spectroscopy (XPS) was carried out to calculate the relative percentages of MoO3, MoO2 and MoS2. It is revealed that sulfurization of MoO3 in the plasma is affected by Tsn. The sulfurization process occurs in two steps, involving the reduction of MoO3 to form MoO2 in the first step, followed by MoO2 being converted into MoS2. It is also evident that the reduction of MoO3 is more a result of the reactive species of hydrogen (H*) than the replacement of oxygen by sulfur in the second step.