Rapid growth of metal–metal oxide core–shell structures through Joule resistive heating: morphological, structural, and luminescence haracterization

Abstract

The aim of this study is to prove that resistive heating enables the synthesis of metal/metal oxide composites in the form of core-shell structures. The thickness and morphology of the oxide layer depends strongly on the nature of the metal, but the influences of parameters such as the time and current profiles and the presence of an external field have also been investigated. The systems chosen for the present study are Zn/ZnO, Ti/TiO2, and Ni/NiO. The characterization of the samples was performed using techniques based on scanning electron microscopy (SEM). The thicknesses of the oxide layers varied from 10 mu m (Zn/ZnO) to 50 mu m (Ni/NiO). In the case of Zn- and Ti-based composites, the growth of nanostructures on the oxide layer was observed. Micro- and nanoneedles formed on the ZnO layer while prism-like structures appeared on the TiO2. In the case of the NiO layer, micro- and nanocrystals were observed. Applying an external electric field seemed to align the ZnO needles, whereas its effect on TiO2 and NiO was less appreciable, principally affecting the shape of their grain boundaries. The chemical compositions were analysed using X-ray spectroscopy (EDX), which confirmed the existence of an oxide layer. Structural information was obtained by means of X-ray diffraction (XRD) and was later checked using Raman spectroscopy. The oxide layers seemed to be crystalline and, although some non-stoichiometric phases appeared, the stoichiometric phases were predominant; these were wurtzite, rutile, and cubic for Zn, Ti, and Ni oxides, respectively. The photoluminescence technique was used to study the distribution of defects on the shell, and mainly visible bands (2-2.5 eV), attributed to oxygen vacancies, were present. The near-band edges of ZnO and TiO2 were also observed around 3.2-3.3 eV.