Raman Investigation of Nanosized TiO2: Effect of Crystallite Size and Quantum Confinement

The influence of the TiO2 particle size on the enhanced Raman spectroscopy properties was systematically investigated on the nanometer-size scale. We report on the enhanced Raman spectrum of 4-mercaptobenzoic acid adsorbed on TiO2 nanoparticles. The results presented in this study highlight the major findings that the intensities of both the molecular lines and the phonon modes of TiO2 are strongly size-dependent. The TiO2 crystallite size estimated using the Scherrer equation varied from 6.8 to 14.2 nm; as a function of crystal size, a large increase in intensity is observed, with a maximum near 10.9 nm and a subsequent decline at larger sizes. Moreover, we have investigated quantum confinement effects between TiO2 and the adsorbed molecules and attribute this to a charge-transfer resonance, which is responsible for the Raman enhancement.