Single sea urchin–MoO3 nanostructure for surface enhanced Raman spectroscopy of dyes†
Enhancing the surface-enhanced Raman scattering (SERS) activity of semiconductor metal oxide nanostructures by controlling the morphology and oxygen vacancies towards trace detection of organics is of significant interest. In this study, MoO3 with a novel sea urchin morphology is synthesized employing chemical bath deposition and consists of hundreds of ∼15 μm long spikes originating from the core forming 20–40 micron globular structures. The spikes taper to form 20 nm sharp tips. SERS of rhodamine 6G (R6G) over MoO3 sea urchins has been investigated and compared to that of 1D h-MoO3 nanorod arrays. The SERS activity is morphology dependent and the sea urchin-like morphology exhibits higher SERS activity with an enhancement factor (EF) of the order 105 and a detection limit of 100 nM, while for h-MoO3 nanorods, the corresponding values are 103 and 1 μM, respectively. X-ray photoelectron spectroscopy reveals a high concentration of Mo+5 states in sea urchins indicating lattice oxygen vacancies. The observed EF is quite high for a metal oxide substrate and is attributed to the enhanced charge transfer between analyte molecules and the substrate promoted by the oxygen vacancies along with surface defects and hydroxyl groups on MoO3 sea urchins providing more active sites for the adsorption of probe molecules. The role of oxygen vacancies is confirmed by the lower EF value exhibited by the stoichiometric 1D h-MoO3. Raman mapping of a single sea urchin is achieved with good R6G intensity and indicates that the tips of spiky features are involved in SERS enhancement. The reusability of substrates is shown for repeated cycles of R6G adsorption by UV irradiation exploiting the photocatalytic activity of MoO3 nanostructures.