Ozonation of Group-IV Elemental Monolayers: A First-Principles Study

[Image: see text] Environmental effect on the physical and chemical properties of two-dimensional monolayers is a fundamental issue for their practical applications in nanoscale devices operating under ambient conditions. In this paper, we focus on the effect of ozone exposure on group-IV elemental monolayers. Using density functional theory and the climbing image nudged elastic band approach, calculations are performed to find the minimum energy path of O(3)-mediated oxidation of the group-IV monolayers, namely graphene, silicene, germanene, and stanene. Graphene and silicene are found to represent two end points of the ozonation process: the former showing resistance to oxidation with an energy barrier of 0.68 eV, while the latter exhibit a rapid, spontaneous dissociation of O(3) into atomic oxygens accompanied by the formation of epoxide like Si–O–Si bonds. Germanene and stanene also form oxides when exposed to O(3), but with a small energy barrier of about 0.3–0.4 eV. Analysis of the results via Bader’s charge and density of states shows a higher degree of ionicity of the Si–O bond followed by Ge–O and Sn–O bonds relative to the C–O bond to be the primary factor leading to the distinct ozonation response of the studied group-IV monolayers. In summary, ozonation appears to open the band gap of the monolayers with semiconducting properties forming stable oxidized monolayers, which could likely affect group-IV monolayer-based electronic and photonic devices.