Surface-Enhanced Raman Scattering Activity of ZrO₂ Nanoparticles: Effect of Tetragonal and Monoclinic Phases

The effect of the ZrO₂ crystal form on surface-enhanced Raman scattering (SERS) activity was studied. The ratio of the tetragonal (T) and monoclinic (M) phases of ZrO₂ nanoparticles (ZrO₂ NPs) was controlled by regulating the ratio of two types of additives in the hydrothermal synthesis method. The SERS intensity of 4-mercaptobenzoic acid (4-MBA) was gradually enhanced by changing the M and T phase ratio in ZrO₂ NPs. The degree of charge transfer (CT) in the enhanced 4-MBA molecule was greater than 0.5, indicating that CT was the main contributor to SERS. The intensity of SERS was strongest when the ratio of the T crystal phase in ZrO₂ was 99.7%, and the enhancement factor reached 2.21 × 10⁴. More importantly, the proposed study indicated that the T and M phases of the ZrO₂ NPs affected the SERS enhancement. This study provides a new approach for developing high-quality SERS substrates and improving the transmission efficiency of molecular sensors.