High-quality single-layered and bilayered graphene (SLG and BLG) was synthesized on copper foil surfaces by controllable chemical vapor deposition (CVD). Impurity nanoparticles formed on the copper foil surface by hightemperature annealing were found to play a crucial role in the growth of BLG. Analysis of energy-dispersive spectrometry (EDS) data indicated that these nanoparticles consisted of silicon and aluminum. According to the inverted wedding cake model, these nanoparticles served as nucleation centers for BLG growth and the free space between a nanoparticle and graphene served as the center of C injection for the continuous growth of the adlayer beneath the top layer. By combining phase-field theory simulations, we confirmed the mechanism of BLG growth and revealed more details about it in comparison with SLG growth. For the first time, this study led to a complete understanding of the BLG growth mechanism from nucleation to continuous growth in the CVD process, and it has opened a door to the thickness-controllable synthesis of graphene.

The effect of twist angle on the hydrogenation of bilayer graphene (BLG) is systematically explored by density functional theory (DFT) calculations. We found that a twist between the upper and lower layers of the graphene BLGs, either big or small, interferes with the formation of inter-layer C–C covalent bonds and this leads to strong resistance to hydrogenation. In addition, the electronic properties of stable, hydrogenated twisted BLG with different twist angles and degrees of H coverage were investigated. This study paves the way to the selective functionalization of BLG for various applications.