Initial Oxidation Kinetics of Cu(100), (110), and (111) Thin Films Investigated by in Situ Ultra-high-vacuum Transmission Electron Microscopy

The initial oxidation stages of Cu(100), (110), and (111) surfaces have been investigated by using in situ ultra-high-vacuum transmission electron microscopy (TEM) techniques to visualize the nucleation and growth of oxide islands. The kinetic data on the nucleation and growth of oxide islands shows a highly enhanced initial oxidation rate on the Cu(110) surface as compared with Cu(100), and it is found that the dominant mechanism for the nucleation and growth is oxygen surface diffusion in the oxidation of Cu(100) and (110). The oxidation of Cu(111) shows a dramatically different behavior from that of the other two orientations, and the in situ TEM observation reveals that the initial stages of Cu(111) oxidation are dominated by the nucleation of oxide islands at temperatures lower than 550 °C, and are dominated by two-dimensional oxide growth at temperatures higher than 550 °C. This dependence of the oxidation behavior on the crystal orientation and temperature is attributed to the structures of the oxygen-chemisorbed layer, oxygen surface diffusion, surface energy, and the interfacial strain energy.