In Situ Determination of the Pore Opening Point during Wet-Chemical Etching of the Barrier Layer of Porous Anodic Aluminum Oxide: Nonuniform Impurity Distribution in Anodic Oxide

Wet-chemical etching of the barrier oxide layer of anodic aluminum oxide (AAO) was systematically investigated by using scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and a newly devised experimental setup that allows accurate in situ determination of the pore opening point during chemical etching of the barrier oxide layer. We found that opening of the barrier oxide layer by wet-chemical etching can be significantly influenced by anodization time (t(anodi)). According to secondary ion mass spectrometry (SIMS) analysis, porous anodic aluminum oxide (AAO) samples formed by long-term anodization contained a lower level of anionic impurity in the barrier oxide layer compared to the short-term anodized one and consequently exhibited retarded opening of the barrier oxide layer during the wet-chemical etching. The observed compositional dependence on the anodization time (t(anodi)) in the barrier oxide layer is attributed to the progressive decrease of the electrolyte concentration upon anodization. The etching rate of the outer pore wall at the bottom part is lower than that of the one at the top part due to the lower level of impurity content in that region. This indicates that a concentration gradient of anionic impurity in the outer pore wall oxide may be established along both the vertical and radial directions of cylindrical pores. Apart from the effect of electrolyte concentration on the chemical composition of the barrier oxide layer, significantly decreased current density arising from the lowered concentration of electrolyte during the long-term anodization (similar to 120 h) was found to cause disordering of pores. The results of the present work are expected to provide viable information not only for practical applications of nanoporous AAO in nanotechnology but also for thorough understanding of the self-organized formation of oxide nanopores during anodization.