Fluorination of Graphene: A Spectroscopic and Microscopic Study

Since the advent of graphene, there has been intense interest in exploring the possibility of incorporating fluorinated graphene (FG), an ultrathin insulator, into graphene electronics as barriers, gate dielectrics, and optoelectronic elements. Here we report on the synthesis of FG from single-layer graphene sheets grown by chemical vapor depositition (CVD) using CF₄ plasma. We examine its properties systematically <i>via</i> microscopic and spectroscopic probes. Our studies show that, by controlling the conditions of the plasma, FG of varying fluorine coverage can be produced; however, the resulting material contains a mixture of CF_<i>x</i> (<i>x</i> = 1–3) bonds. Existing grain boundaries and lattice defects of CVD graphene play an important role in controlling its rate of fluorination and the damage of the sheet. Combining topography and current mapping, we demonstrate that the spatial distribution of fluorine on CVD graphene is highly inhomogeneous, where multilayer islands and structural features such as folds, wrinkles, and ripples are less fluorinated and consequently form a conductive network through which charge transport occurs. It is the properties of this network that manifest in the electrical transport of FG sheets. Our experiments reveal the many challenges of deriving electronics-quality FG from current CVD graphene while at the same time point to the possible solutions and potential of FG in graphene electronics and optoelectronics