Superior Electro-Oxidation and Corrosion Resistance of Monolayer Transition Metal Disulfides

Physics of monolayer and few-layer transition metal dichalcogenides (TMDs) and chemistry of few-layer TMDs have been well studied in recent years in the context of future electronic, optoelectronic, and energy harvesting applications. However, what has escaped the attention of the scientific community is the unique chemistry of monolayer TMDs. It has been demonstrated that the basal plane of multilayer TMDs is chemically inert, whereas edge sites are chemically active. In this article, we experimentally demonstrate that the edge reactivity of the TMDs can be significantly impeded at the monolayer limit through monolayer/substrate interaction, thus making the monolayers highly resistant to electrooxidation and corrosion. In particular, we found that few-layer flakes of MoS₂ and WS₂ exfoliated on conductive TiN substrates are readily corroded beyond a certain positive electrode potential, while monolayer remnants are left behind unscathed. The electrooxidation resistance of monolayers was confirmed using a plethora of characterization techniques including atomic force microscope (AFM) imaging, Raman spectroscopy, photoluminescence (PL) mapping, scanning/transmission electron microscope (S/TEM) imaging, and selected area electron diffraction (SAED). It is believed that strong substrate monolayer interaction compared to the relatively weak interlayer van der Waals interaction is responsible for the superior monolayers chemical stability in highly corrosive oxidizing environments. Our findings could pave the way for the implementation of monolayer transition metal disulfides as superior anticorrosion coating which can have a significant socioeconomic impact.