Surface-Enhanced Raman Scattering on Size-Classified Silver Nanoparticles Generated by Laser Ablation

This study delved into the complex interplay between the nanostructural characteristics of nanoparticles and their efficacy in surface-enhanced Raman scattering (SERS) for sensitive detection of trace chemical substances. Silver nanoparticles were prepared for the SERS substrate by combining laser ablation, postannealing processes (up to 500 °C), and electrostatic mobility classification, allowing high-purity silver nanoparticles with controlling their sizes (40-100 nm) and aggregate structures. These nanoparticles were then inertially deposited on the substrates to create SERS-active surfaces, employing Rhodamine B as a probe to assess the impact of particle size, shape, and deposition density on SERS effectiveness. Our findings revealed that spherical nanoparticles, especially those approximately 50 nm in diameter, controlled to a spherical structure through gas-phase annealing at 500 °C and subsequent classification, yielded the most significant SERS enhancement. This optimal can be explained by the particle size response of the surface plasmon resonance, where the enhancement of the Raman signal for particles up to 50 nm (1/10 of the laser wavelength used in this study, 532 nm) arises from a balance between the enhancement of dipole moment and the number of "hot spot" regions (respectively proportional to the cube and inverse square of the diameters in theory, leading to a linear relationship between signal intensity and particle diameter); meanwhile, in larger size region than 50 nm, the Raman signal was decreased owing to the attribution of the phase difference between the electric field and dipole moment. Furthermore, we found that a deposition density of 2 μg resulted in nearly a single layer of particles, which is crucial for maximizing SERS hotspots and, consequently, the enhancement effect.