Multiscale Simulation of Graphene Growth on Cu(111): Insights from DFT, MD, KMC, and Thermodynamic Analyses

In chemical vapor deposition (CVD)-mediated graphene growth, copper foil serves as both a catalyst for methane decomposition and as a substrate for graphene nucleation and growth. Due to the low solubility of carbon in copper and the ease of transferring graphene from its surface, copper—particularly the Cu(111) facet—is widely favored for high-quality, monolayer graphene synthesis. In this article, the thermodynamic processes involved in methane dissociation and graphene nucleation on the Cu(111) surface were investigated using density functional theory (DFT). Molecular dynamics simulations were performed for structural optimization and to evaluate the reaction energies. Additionally, the average adsorption energies (ΔEad) of carbon clusters with varying atomic numbers on the Cu(111) surface were calculated. The graphene growth process was further modeled using the kinetic Monte Carlo (KMC) method to simulate carbon atom migration and nucleation dynamics. Thermodynamic analysis based on equilibrium component data was conducted to examine the influence of key operational parameters—temperature, pressure, and the CH4/H2 partial pressure ratio—on the graphene deposition rate.