Reducing the graphene grain density in three steps.

The production of large-scale, single crystalline graphene is a requirement for enhancing its electronic, mechanical, and chemical properties. Chemical vapor deposition (CVD) has shown the potential to grow high quality graphene but the simultaneous nucleation of many grains limits their achievable domain size. We report here that ultralow nucleation densities can be achieved through multi-step optimization of the catalyst morphology. First, annealing in a hydrogen-free environment is required to retain a surface copper oxide which decreases the nucleation density. Second, CuO was found to be the relevant copper species for this process and air oxidation of the copper foil at 200 °C maximizes its concentration. Both pre-treatment steps were found to affect the morphology of the catalyst and a direct correlation between nucleation density and surface roughness was found which indicates that the primary role of the oxidation step is the decrease in catalyst roughness. To further enhance this determining parameter, confined CVD was carried out after sample oxidation and hydrogen-free annealing. Each of these three steps reduces the grain density by approximately one order of magnitude resulting in ultralow nucleation densities of 1.23 grains/mm(2) and high quality, single-crystalline graphene grains of several millimeter sizes were grown using this method.