Ultrafast Catalyst-Free Graphene Growth on Glass Assisted by Local Fluorine Supply

High-quality graphene film grown on dielectric substrates by a direct chemical vapor deposition (CVD) method promotes the application of high-performance graphene-based devices in large scale. However, due to the noncatalytic feature of insulating substrates, the production of graphene film on them always has a low growth rate and is time-consuming (typically hours to days), which restricts real potential applications. Here, by employing a local-fluorine-supply method, we have pushed the massive fabrication of a graphene film on a wafer-scale insulating substrate to a short time of just 5 min without involving any metal catalyst. The highly enhanced domain growth rate (∼37 nm min^-1) and the quick nucleation rate (∼1200 nuclei min^-1 cm^-2) both account for this high productivity of graphene film. Further first-principles calculation demonstrates that the released fluorine from the fluoride substrate at high temperature can rapidly react with CH₄ to form a more active carbon feedstock, CH₃F, and the presence of CH₃F molecules in the gas phase much lowers the barrier of carbon attachment, providing sufficient carbon feedstock for graphene CVD growth. Our approach presents a potential route to accomplish exceptionally large-scale and high-quality graphene films on insulating substrates, i.e., SiO₂, SiO₂/Si, fiber, etc., at low cost for industry-level applications.