Invited Paper IS+NS+TR+NC-ThM11
The Dynamics of the Initial Oxidation Stages of Cu and Cu Alloys

Thursday, October 23, 2008, 11:20 am, Room 310

Surface oxidation processes play critical roles in environmental stability, high temperature corrosion, electrochemistry, catalytic reactions, gate oxides and thin film growth as well as fuel reactions. Much is known about oxygen interaction with metal surfaces and about the macroscopic growth of thermodynamically stable oxides. At present, the transient stages of oxidation ⎯ from the nucleation of the metal oxide to the formation of the thermodynamically stable oxide ⎯ represent a scientifically challenging and technologically important terra incognito. Furthermore, since environmental stability is an essential property of most engineered materials, many theories exist to explain its mechanisms. However, nearly all classical theories assume a uniform growing film, where structural changes are not considered because of the previous lack of experimental methods to visualize this non-uniform growth under conditions that allowed for highly controlled surfaces and impurities. One can now see structural changes under controlled surface conditions, by in situ ultra-high vacuum transmission electron microscopy (UHV-TEM), and thereby challenge the commonly used assumption of a uniform oxide formation. Here, we present a systematic study of the dynamics of the initial and transient oxidation stages of a metal and alloys with in situ UHV-TEM. We have previously demonstrated that the formation of epitaxial Cu2O islands during the transient oxidation of Cu(100), (110) and (111) films bear a striking resemblance to heteroepitaxy, where the initial stages of growth are dominated by oxygen surface diffusion and strain impacts the evolution of the oxide morphologies. We are presently investigating the early stages of oxidation of Cu-Au and Cu-Ni as a function of oxygen partial pressures, temperatures and composition. For Cu-Au oxidation, the oxidation mechanisms change due to the limited Cu around the oxide island leading to a dendritic growth of the Cu2O islands. For Cu-Ni oxidation, the addition of Ni causes the formation Cu2O and/or NiO where the oxide type(s) and the relative orientation with the film depend on the Ni concentration, oxygen partial pressure and temperature. This research program is funded by the National Science Foundation (DMR 0706171) and Department of Energy (DE-FG02-07ER46446).