Hierarchical structures produced using unbalanced magnetron sputtering for photocatalytic degradation of Rhodamine 6G dye

Novel hierarchical nanostructures of ZnO-based semiconductors were synthesized on Si using unbalanced magnetron sputtering. This fabrication method is believed to be a significant breakthrough in the field of 1D nanostructure growth on substrates. These structures were created primarily as photocatalysts to degrade pollutants in water but other applications that include solar energy harvesting are possible. The crystal structure and the morphology of these materials were evaluated using X-ray diffraction and scanning electron microscopy, respectively. The morphology of the ZnO 1D nanostructures was modified from nanowires to nanofacets to nanodots by increasing substrate bias values from -12 to -70 V. In addition, hierarchical heterostructures were created by depositing Au and ZnO onto underlying ZnO nanowires. The length of the branches (30-70 nm) was found to be controlled by the deposition time of the metal oxide, while the morphology of the resulting structure was dependent on the amount of the sputtered Au speed. Based on ellipsometry studies on representative hierarchical structures, films having thicknesses of 0.9-1.3 × 10^-4 m were obtained, while their porosity reached values of 50-70 %. These heterostructures were further modified by the deposition of a TiO₂ shell. The above materials were assessed in terms of their optical properties (photoluminescence spectra) and their room temperature UV-Vis photocatalytic performance in terms of degradation of Rhodamine 6G dye (model compound). The hierarchical structures of ZnO showed an enhanced photocatalytic activity (higher rate constant, k, min^-1) compared to the ZnO nanorods, while the TiO₂ shell had a further increase which was attributed to the enhanced surface area and to charge transfer processes at the heterojunction.