Investigation of selective SERS enhancement mechanism of Au nanospheres and Au nanorods based on 2T2D-SERS correlation spectroscopy

The selective enhancement mechanism in surface -enhanced Raman scattering (SERS) is demonstrated. Two different types of single nanoparticles (Au nanosphere and Au nanorod) were used to investigate the role of the localized surface plasmon resonance (LSPR) in SERS spectra by using the two -trace two-dimensional (2T2D) correlation spectroscopy. The SERS intensities of three probe molecules, 4-mercaptobenzoic acid (4 -MBA), 4aminothiophenol (4 -ATP), and 4-bromobenzenethiol (4-BBT), respectively, were enhanced but slightly different when adsorbed on Au nanospheres and Au nanorods. 2T2D correlation SERS spectra clearly showed that even with the same shape of Au nanoparticles, the main factors influencing the SERS enhancement can vary depending on the specific type of SERS tags used. Such subtle difference could not be clearly identified by the conventional spectral analysis. This result sheds light on potential applications of 2T2D correlation spectroscopy. For 4 -MBA molecules, the a1 and b2 modes are mainly affected by the Au nanospheres and Au nanorods. For 4ATP molecules, the a1 and b2 modes related to C-S stretching combined with C-C stretching band are mainly affected by Au nanorods and Au nanospheres. For 4-BBT molecules, the a1 and b2 modes of C-C (aromatic ring) stretching band are mainly affected by Au nanorods and Au nanospheres. This study offers valuable insights into the relationship between nanoparticle shape and SERS enhancement.