Layer-selective synthesis of bilayer graphene via chemical vapor deposition

A controlled synthesis of high-quality AB-stacked bilayer graphene by chemical vapor deposition demands a detailed understanding of the mechanism and kinetics. By decoupling the growth of the two layers via a growth-and-regrowth scheme, we report the kinetics and termination mechanisms of the bilayer graphene growth on copper. We observe, for the first time, that the secondary layer growth follows Gompertzian kinetics. Our observations affirm the postulate of a time-variant transition from a mass-transport-limited to a reaction-limited regimes and identify the mechanistic disparity between the monolayer growth and the secondary-layer expansion underneath the monolayer cover. It is the continuous carbon supply that drives the expansion of the graphene secondary layer, rather than the initially captured carbon amount, suggesting an essential role of the surface diffusion of reactant adsorbates in the interspace between the top graphene layer and the underneath copper surface. We anticipate that the layer selectivity of the growth relies on the entrance energetics of the adsorbed reactants to the graphene-copper interspace across the primary-layer edge, which could be engineered by tailoring the edge termination state. The temperature-reliant saturation area of the secondary-layer expansion is understood as a result of competitive attachment of carbon and hydrogen adatoms to the secondary-layer graphene edge.