Ultrathin and Isotropic Metal Sulfide Wrapping on Plasmonic Metal Nanoparticles for Surface Enhanced Ram Scattering-Based Detection of Trace Heavy-Metal Ions.

A facile and general strategy is presented for homogenous and ultrathin metal sulfide wrapping on plasmonic metal (PM) nanoparticles (NPs) based on a thiourea-induced isotropic shell growth. This strategy is typically implemented just via adding the thiourea into pre-formed PM colloidal solutions containing target metal ions. The validity of this strategy is demonstrated by taking the wrapped NPs with Au core and CuS shell or Au@CuS NPs as an example. They are successfully fabricated via adding the thiourea and Cu solutions into pre-formed Au NP colloidal solution. The CuS shell layer is highly homogenous (<10% in relative standard deviation of shell thickness), regardless of the NPs' shape or curvature. The shell thickness can be controlled from tens down to 0.5 nm just by the addition of different amounts of shell precursors. The formation of the shell layer on the Au NPs can be attributed to the alternative deposition of Cu and S ions on the thiourea-modified surface of Au NPs in the solution, which induces the isotropic shell growth. Further, this strategy is of good universality. Many other sulfide-wrapped PM NPs, such as Ag@CuS, Au@PtS, Au@HgS, Ag@AgS NPs, and Ag@CuS nanorods, have been successfully obtained with homogeneous and ultrathin shells. Importantly, such ultrathin sulfide-wrapped PM NPs can be used for surface enhanced Raman scattering (SERS)-based detection of trace heavy-metal ions with strong anti-interference via the ion exchange process between the metal sulfide shell and heavy-metal ions. This study provides a simple and controllable route for wrapping the homogenous and ultrathin sulfide layers on the PM NPs, and such wrapped NPs have good practical applications in the SERS-based detection of trace heavy-metal ions.