Publications

Electronic defects and interface potentials for Al oxide films on Al and their relationship to electrochemical properties

Sullivan, John P.; Dunn, Roberto G.; Barbour, J.C.; Wall, Frederick D.; Missert, Nancy A.

The relative electronic defect densities and oxide interface potentials were determined for naturally-occurring and synthetic Al oxides on Al. In addition, the effect of electrochemical treatment on the oxide electrical properties was assessed. The measurements revealed (1) that the open circuit potential of Al in aqueous solution is inversely correlated with the oxide electronic defect density (viz., lower oxide conductivities are correlated with higher open circuit potentials), and (2) the electronic defect density within the Al oxide is increased upon exposure to an aqueous electrolyte at open circuit or applied cathodic potentials, while the electronic defect density is reduced upon exposure to slight anodic potentials in solution. This last result, combined with recent theoretical predictions, suggests that hydrogen may be associated with electronic defects within the Al oxide, and that this H may be a mobile species, diffusing as H{sup +}. The potential drop across the oxide layer when immersed in solution at open circuit conditions was also estimated and found to be 0.3 V, with the field direction attracting positive charge towards the Al/oxide interface.