Thermally Stable Magneto-Plasmonic Nanoparticles for SERS with Tunable Plasmon Resonance

Bifunctional magneto-plasmonic nanoparticles that exhibit synergistically magnetic and plasmonic properties are advanced substrates for surface-enhanced Raman spectroscopy (SERS) because of their excellent controllability and improved detection potentiality. In this study, composite magneto-plasmonic nanoparticles (Fe₃O₄@AgNPs) were formed by mixing colloid solutions of 50 nm-sized magnetite nanoparticles with 13 nm-sized silver nanoparticles. After drying of the layer of composite Fe₃O₄@AgNPs under a strong magnetic field, they outperformed the conventional silver nanoparticles during SERS measurements in terms of signal intensity, spot-to-spot, and sample-to-sample reproducibility. The SERS enhancement factor of Fe₃O₄@AgNP-adsorbed 4-mercaptobenzoic acid (4-MBA) was estimated to be 3.1 × 10⁷ for a 633 nm excitation. In addition, we show that simply by changing the initial volumes of the colloid solutions, it is possible to control the average density of the silver nanoparticles, which are attached to a single magnetite nanoparticle. UV-Vis and SERS data revealed a possibility to tune the plasmonic resonance frequency of Fe₃O₄@AgNPs. In this research, the plasmon resonance maximum varied from 470 to 800 nm, suggesting the possibility to choose the most suitable nanoparticle composition for the particular SERS experiment design. We emphasize the increased thermal stability of composite nanoparticles under 532 and 442 nm laser light irradiation compared to that of bare Fe₃O₄ nanoparticles. The Fe₃O₄@AgNPs were further characterized by XRD, TEM, and magnetization measurements.