Non-Plasmonic SERS with Silicon: Is It Really Safe? New Insights into the Opto-Thermal Properties of Core/Shell Microbeads

Silicon is one of the most interesting candidates for plasmon-free surfaceenhaced
Raman scattering (SERS), because of its high-refractive index and thermal
stability. However, here we demonstrate that the alleged thermal stability of silicon
nanoshells irradiated by conventional Raman laser cannot be taken for granted. We
investigated the opto-thermal behavior of SiO2/Si core/shell microbeads (Si-rex) irradiated
with three common Raman laser sources (λ = 532, 633, 785 nm) under real working
conditions. We obtained an experimental proof of the critical role played by bead size and
aggregation in heat and light management, demonstrating that, in the case of strong optothermal
coupling, the temperature can exceed that of the melting points of both core and
shell components. In addition, we also show that weakly coupled beads can be utilized as
stable substrates for plasmon-free SERS experiments.