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The distribution of hydroxyl ions at the surface of anodic alumina

Barrier‐type anodic films 3–15 nm thick have been formed on electropolished 99.999% aluminium. Variable‐angle XPS has been used to identify a significant proportion of hydroxyl ions at the surface of the relatively compact alumina films. The location of an oxygen‐rich region at the outer surface of the oxide has been confirmed by medium‐energy ion scattering (MEIS). Combining the information from these two techniques leads to the conclusion that a hydroxyl‐containing surface region is responsible for this oxygen‐rich surface layer, MEIS revealing an approximately linear relationship between the total oxide thickness and the thickness of the hydroxyl‐rich surface region. From consideration of the mechanisms of amorphous alumina formation by ionic transport, with incorporation of electrolyte‐derived species into the thickening film, the generation of the hydroxyl‐rich outermost region is considered to result from the formation of gel‐like material at the film/electrolyte interface. Copyright © 2003 John Wiley & Sons, Ltd.