Facilitated fluorination and etching of 2D materials

Precise control of functionalization and etching have been required for surface modification and device fabrication of two-dimensional (2D) materials. Specifically, fluorination of graphene has been used to control the properties of graphene. Recently, xenon difluoride (XeF2) has been used for selective fluorination of graphene and etching of other 2D materials, such as hexagonal boron nitride (hBN) and transition metal dichalcogenides (TMDs). However, there is a lack of studies on key factors that govern the XeF2 treatment, which results in inconsistent behaviors of fluorination and etching. Here, we report control over chemical reactions between XeF2 and 2D materials using a chemical mediator of Si. Even a small amount of Si can accelerate the dissociation of XeF2, leading to the formation of chemically reactive xenon fluoride (XeF) that enhances the fluorination and etching of 2D materials. Additionally, our findings show that defects in 2D materials serve as chemically unstable sites that facilitate the additional dissociation of XeF2, generating F single atoms that easily form covalent bonds on the surface of 2D materials. Our study suggests that Si can be utilized as a reaction mediator to regulate XeF2 treatment on 2D materials, which has important implications for the fabrication of 2D electronic devices.