Graphene chemical vapor deposition at very low pressure: The impact of substrate surface self-diffusion in domain shape

Abstract

The initial stages of graphene chemical vapor deposition at very low pressures (<10−5 Torr) were investigated. The growth of large graphene domains (∼up to 100 μm) at very high rates (up to 3 μm2 s−1) has been achieved in a cold-wall reactor using a liquid carbon precursor. For high temperature growth (>900 °C), graphene grain shape and symmetry were found to depend on the underlying symmetry of the Cu crystal, whereas for lower temperatures (<900 °C), mostly rounded grains are observed. The temperature dependence of graphene nucleation density was determined, displaying two thermally activated regimes, with activation energy values of 6 ± 1 eV for temperatures ranging from 900 °C to 960 °C and 9 ± 1 eV for temperatures above 960 °C. The comparison of such dependence with the temperature dependence of Cu surface self-diffusion suggests that graphene growth at high temperatures and low pressures is strongly influenced by copper surface rearrangement. We propose a model that incorporates Cu surface self-diffusion as an essential process to explain the orientation correlation between graphene and Cu crystals, and which can clarify the difference generally observed between graphene domain shapes in atmospheric-pressure and low-pressure chemical vapor deposition.