Controlled growth and monitoring of tantalum oxidenanostructures

Abstract

Nanoporous metal oxide structures produced by the electrochemical anodization of valve metals, such as Zr, Ti, W, Nb, Al, and recently Ta, have attracted increasing interest because of their potential use as catalysts, waveguides, and three-dimensionally arranged Bragg-stack reflectors. Here we demonstrate the formation of either supported nanotubular Ta oxide films or free-standing Ta oxide membranes, produced by controlling the conditions of Ta anodization in organic-free aqueous HF/H₂SO₄ solutions. The supported oxide nanotubes, which are at least 15 μm in length, are characterized by very good adhesion to the Ta substrate, and extremely smooth and homogeneous walls. It is also reported here, for the first time, that these nanotubular films can be removed as free-standing Ta oxide membranes that are easily transferable to other substrates, making them potentially useful in sensors, optics, and catalysis. We also show that, when the Ta oxide nanotubes detach to form the membranes, they leave behind an ordered array of dimples in the Ta surface, with the dimples having the identical distribution and size as the pores in the previously attached nanotubes. Finally, we demonstrate how the in situ electrochemical response during anodization can be used to determine which of these highly useful Ta surface morphologies (nanotubes vs. dimples) are formed, without the need for post factum microscopic analysis. Knowledge of the meaning of these in situ signals can now serve to accelerate the controlled formation of oxide nanotubes or dimpled surfaces using other combinations of metals and anodization conditions.