Effects of precursor pre-treatment on the vapor deposition of WS₂ monolayers

Transition metal oxide powders have been widely used as the growth precursors for monolayer transition metal dichalcogenides (TMDCs) in chemical vapor deposition (CVD). It has been proposed that metal oxide precursors in the gas phase undergo a two-step reaction during CVD growth, where transition metal sub-oxides are likely formed first and then the sulfurization of these sub-oxides leads to the formation of TMDCs. However, the effects of stoichiometry of transition metal oxide precursors on the growth of TMDC monolayers have not been studied yet. In this contribution, we report the critical role of the WO₃ precursor pre-annealing process on the growth of WS₂ monolayers. Besides, several WO₃ precursors with different types of oxygen vacancies have also been prepared and investigated by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and density functional theory calculation. Among all the non-stoichiometric WO₃ precursors, thermally annealed WO₃ powder exhibits the highest oxygen vacancy concentration and produces WS₂ monolayers with significantly improved quality in terms of lateral size, density, and crystallinity. Our comprehensive study suggests that the chemical composition of transition metal oxide precursors would be fundamentally critical for the growth of large-area and high-quality WS₂ monolayers, which further pave the way for revealing their intrinsic properties and unique applications.