Effects of electrolyte pH and temperature on dielectric properties of anodic oxide films formed on niobium

The effects of electrolyte pH and temperature on the structure and properties of anodic oxide films formed on niobium in phosphoric acid solution with the addition of NH₄OH for pH adjustment have been investigated. The film thickness formed at the same voltage slightly increased with increasing pH and significantly increased with increasing electrolyte temperature. The capacitance of the film was independent of electrolyte pH in an acid region, while it notably increased with increasing pH in an alkaline region. The relative permittivity of the film changed 43.7-80.5 when the electrolyte pH was increased from 1.6 to 10. The incorporation depth and content of phosphorus in the film were markedly suppressed at pH 10, and nitrogen was found to penetrate into a depth of 70%. Furthermore, the apparent transport number of Nb⁵⁺ ion decreased from 0.26 to 0.02 by a pH increase from 1.6 to 10. The notable changes in structure and dielectric properties of the anodic niobia film formed in the alkaline region would primarily be caused by the different incorporation behavior of electrolyte species such as phosphorous and nitrogen.