Direct Observation of Enhanced Raman Scattering on Nano-Sized ZrO(2) Substrate: Charge-Transfer Contribution

Direct observation of the surface-enhanced Raman scattering (SERS) of molecules adsorbed on nano-sized zirconia (ZrO(2)) substrates was first reported without the need for the addition of metal particles. It was found that ZrO(2) nanoparticles can exhibit unprecedented Raman signal enhancements on the order of 10(3) for the probe molecule 4-mercaptobenzoic acid (4-MBA). The dramatic effect of the calcination temperature on the ZrO(2) nanoparticles was also investigated. The ZrO(2) nanoparticles with the particle diameter of 10.5 nm, which were prepared by calcination at a temperature of 500°C, have the highest SERS activity. A comparison between the experimental and calculation results indicates that charge transfer (CT) effects dominate the surface enhancement. The plentiful surface state of ZrO(2) active substrate that is beneficial to CT resonance occurs between molecules and ZrO(2) to produce a SERS effect. The CT process depends, to a large extent, on the intrinsic properties of the modifying molecules and the surface properties of the ZrO(2). This is a new SERS phenomenon for ZrO(2) that will expand the application of ZrO(2) to microanalysis and is beneficial for studying the basic properties of both ZrO(2) and SERS.