Ligand-Free Fabrication of Ag Nanoassemblies for Highly Sensitive and Reproducible Surface-Enhanced Raman Scattering Sensing of Antibiotics

The assemblies of plasmonic nanoparticles (NPs) are the universal methods for enhancing their surface-enhanced Raman scattering (SERS) activities. However, the present methods suffer from the problems of poor reproducibility, complicated fabrication, or the adsorption of ligands on the surface, which limit their practical applications. In this work, by using a facile freeze–thaw method, we are able to fabricate the assemblies of Ag NPs with highly reproducible SERS activity without the use of ligands. Moreover, the Ag NPs can be well kept in a frozen state for a long time with few influences on the reproducibility (relative standard deviation, RSD ca. 7%), while those kept in colloid (4 °C) suffer from gradual surface oxidation and aggregation. Such a simple freeze–thaw method does not require the introduction of any ligands (or linkers) with long-term stability and reproducibility, implying its wide applications in practical SERS sensing.