Synthesis of WO3 nanoblades by the dealloying of glancing angle deposited W-Fe nanocolumnar thin films.

Glancing angle co-deposition of well-separated W-Fe nanocolumns was carried out using a W oblique angle sputter source and a Fe confocal incidence source. As-deposited nanocolumns with an overall composition of W64.6Fe35.4 (at.%) exhibited an average column width w nc of 77 ± 15 nm with predominant growth in the β-W phase. With the aim of synthesizing highly porous nanostructures, the as-deposited precursor W-Fe nanocolumnar thin films were immersed in aqueous HNO3 solution for various dealloying durations (t d ). Formation of nanoflake-, nanocactus-, and nanoblade-like structures were observed during the dealloying treatment, as a result of selective dissolution of Fe from the W-Fe precursor films and simultaneous oxidation of W adatoms. By increasing the dealloying duration, the Fe concentration within the film reduced drastically and the film thickness increased by about three times in comparison to the as-deposited film. The dealloyed film exhibited an overall composition of W95.6Fe4.4, where the effective surface area of the film increased substantially. It was found that W adatom diffusion and subsequent rearrangement are crucially important in determining the resultant thin film morphology. The morphological development, corresponding compositions and crystallographic properties of different nanostructures were found to be significantly dependent on the dealloying duration. For optimized processing parameters, the selective dissolution process led to formation of single crystal monoclinic WO3 nanoblades, with growth along [002] and [020] axes.