On the Measurements of the Surface-Enhanced Raman Scattering Spectrum: Effective Enhancement Factor, Optical Configuration, Spectral Distortion, and Baseline Variation

In this paper, a comprehensive theoretical framework for understanding surface-enhanced Raman scattering (SERS) measurements in both solution and thin-film setups, focusing on electromagnetic enhancement principles, was presented. Two prevalent types of SERS substrates found in the literature were investigated: plasmonic colloidal particles, including spherical and spheroid nanoparticles, nanoparticle diameters, and thin-film-based SERS substrates, like ultra-thin substrates, bundled nanorods, plasmonic thin films, and porous thin films. The investigation explored the impact of analyte adsorption, orientation, and the polarization of the excitation laser on effective SERS enhancement factors. Notably, it considered the impact of analyte size on the SERS spectrum by examining scenarios where the analyte was significantly smaller or larger than the hot spot dimensions. The analysis also incorporated optical attenuations arising from the optical properties of the analyte and the SERS substrates. The findings provide possible explanations for many observations made in SERS measurements, such as variations in relative peak intensities during SERS assessments, reductions in SERS intensity at high analyte concentrations, and the occurrence of significant baseline fluctuations. This study offers valuable guidance for optimizing SERS substrate design, enhancing SERS measurements, and improving the quantification of SERS detection.