Transmission electron microscopy of ultramicrotomed sections and Ruthe
rford backscattering spectroscopy have been used to quantify the signi
ficantly faster mobility of copper ions compared with Al3+ ions in ano
dic alumina films. To determine the migration rate of copper ions, an
Al-0.4 at % Cu alloy film of ca. 35 nm thickness has been sputter depo
sited onto an electropolished superpure aluminium substrate; the speci
men comprising the alloy layer superimposed on aluminium was then anod
ized at a constant current density to various voltages at high current
efficiency. The anodic oxidation of the alloy film results in the pri
or oxidation of aluminium and the accumulation of copper in a layer of
alloy, ca. 2 nm thick, just beneath the anodic film; consequently, no
copper is incorporated into the alumina film during anodizing of the
alloy. At ca. 49 V for the particular alloy thickness, the alloy film
is totally consumed by anodizing and the copper-enriched layer beneath
the anodic film is incorporated abruptly into the film, because of th
e presence of an air-modified electropolishing film sandwiched between
the alloy and aluminium regions. With further anodizing, the incorpor
ated copper ions migrate outwards at a rate ca. 3.2 times that of Al3 ions. The method employed provides a novel approach to determining th
e precise mobility of foreign ions incorporated into anodic alumina. (
C) 1997 Elsevier Science Ltd.