Ion beam sputtering deposition of silver nanoparticles and TiOx/ZnO nanocomposites for use in surface enhanced vibrational spectroscopy (SERS and SEIRAS)

Angela I. López-Lorente, Rosaria A. Picca, Javier Izquierdo, Christine Kranz, Boris Mizaikoff, Cinzia Di Franco, Soledad Cárdenas, Nicola Cioffi, Gerardo Palazzo, Antonio Valentini

Hybrids consisting of silver nanoparticles (in varying fractions) and of TiOx/ZnO were prepared via top-down ion beam sputtering (IBS) deposition on silicon substrates. The deposited nanomaterials were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. It is shown that such composites represent a viable substrate for use in both surface enhanced Raman spectroscopy (SERS) and surface enhanced infrared absorption spectroscopy (SEIRAS), as exemplarily shown for crystal violet as the model analyte. The C-H bending mode at about 1181 cm-1 and the C-N vibration at 1361 cm-1 observed in the SERS and SEIRAS spectra, respectively, have been used as analytical signal. The substrate consisting of TiOx NPs with 33% fraction of silver provides the strongest enhancement in SERS (up to 10,000-fold), while TiOx/AgNPs with thickness of 2 and 1 nm in ion beam sputtering, respectively, provides the best sensitivity in SEIRAS. The substrates also display photocatalytic activity as shown by the degradation of adsorbed crystal violet under ultraviolet irradiation. Graphical abstract Schematic of the preparation of hybrid substrates consisting of Ag and TiOx/ZnO nanoparticles via ion beam sputtering deposition. They were applied in both surface enhanced Raman and surface enhanced infrared absorption spectroscopies using crystal violet as model analyte, showing enhancements up to >10,000-fold in Raman.