Selective surface-enhanced Raman scattering in a bulk nanoplasmonic Bi2O3-Ag eutectic composite

A recent surge of interest in surface-enhanced Raman scattering (SERS) has stimulated the search for new systems that can be utilized to fabricate high-performance optical devices. However, the two-dimensional design of the vast majority of SERS-based assemblies has significantly hindered their real-life applicability, motivating the development of three-dimensional volumetric materials. Here, we report selective SERS observed in a volumetric Bi2O3-Ag eutectic composite obtained by the micro-pulling-down method utilizing directional solidification of eutectics. The enhancement of the Raman signal originates from the localized surface plasmon resonance, LSPR, resulting from silver nanoparticles embedded in the composite. The plasmonic origin of the enhancement is confirmed by characteristic features, such as (i) an enhancement magnitude >103, (ii) the correspondence between the Raman bands’ intensity upon excitation by different wavelengths and the localized surface plasmon resonance (LSPR) intensity, and (iii) the occurrence of overtones, which are absent in the as-grown material that does not exhibit LSPR. The examined Bi2O3-Ag eutectic-based composite is obtained by directional solidification using a simple crystal growth technique. It is the first case of a bulk SERS-active material fabricated by crystal growth techniques, which opens new perspectives towards scalable three-dimensional optical elements with tunable properties based on Raman scattering.