Nanoporous oxide formation by anodic oxidation of Nb in sulphate–fluoride electrolytes

• Published in: Journal of solid state electrochemistry 2009-08, Vol.13 (8), p.1215-1226
• Main Authors: Tzvetkov, Bogdan, Bojinov, Martin, Girginov, Assen
• Format: Article
• Language: English
• Subjects: Analytical Chemistry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Condensed Matter Physics; Electrochemistry; Energy Storage; Original Paper; Physical Chemistry
• ISSN: 1432-8488; 1433-0768
• DOI: 10.1007/s10008-008-0651-y

The influence of hydrofluoric acid (HF) concentration and applied potential on the processes of anodic oxidation of Nb in sulphuric acid solution was studied by chronoamperometry, electrochemical impedance spectroscopy and scanning electron microscopy. During the first stage of the process, a compact barrier film is formed. On top of this film, a porous overlayer starts to form, then the nanopores grow into an ordered nanostructure. Subsequently, secondary 3D flower-shaped structures begin to form. These structures gradually spread all over the surface as an irregular multilayer film. The rates of the process of porous overlayer formation and subsequent growth of nanopore arrays increase with applied potential as well as with the HF concentration. The films have been characterised ex situ by electrochemical impedance spectroscopy at open circuit potential and capacitance vs. potential measurements to follow the different stages of nanoporous film formation with electrochemical methods. The impedance spectra and capacitance vs. potential curves have been interpreted using previously proposed models for the amorphous semiconductor/electrolyte interface. An attempt to rationalise the mechanism of nanoporous layer growth is presented by using the conceptual views of the mixed-conduction model and recent ideas for porous film formation on valve metals.