Anisotropic material properties of two-dimensional (2D) crystals are not only intriguing but also of potential use for many applications. In this work, we report the anisotropy of bond-breaking reactions is governed by the structural anisotropy and significantly material-dependent for 2D semiconducting transition metal dichalcogenides (TMDs). The degree of the anisotropy that led to trigonal oxidation patterns was much higher in MoS2 and MoSe2 than WS2 and WSe2. Using optical second-harmonic generation spectroscopy, we establish crystal-facet-resolved kinetic measurements and show that the reactions proceed fastest (slowest) for chalcogen (metal)-terminated zigzag edges. Edge-specific reaction rates fed into kinetic Wulff construction also verified the material-dependent anisotropy. We also show that the reactions are initiated at substrate-mediated defects that are located on the bottom and top surfaces of 2D TMDs.
Published in: "arXiv Material Science".