A copper via structure formed when copper and a small amount of an alloying metal such as magnesium or aluminum are cosputtered onto a substrate having oxide on at least a portion of its surface. Either the wafer is held at an elevated temperature during deposition or the sputtered film is annealed without the wafer being exposed to ambient. Due to the high temperature, the alloying metal diffuses to the surface. If a surface is exposed to a low partial pressure of oxygen or contacts silicon dioxide, the magnesium or aluminum forms a thin stable oxide but also extends into the oxide a distance of about 100 nm. The alloying metal oxide having a thickness of about 6 nm on the oxide sidewalls encapsulates the copper layer to provide a barrier against copper migration, to form an adhesion layer over silicon dioxide, and to act as a seed layer for the later growth of copper, for example, by electroplating.