Tip-Selective Growth of Silver on Gold Nanostars for Surface-Enhanced Raman Scattering

Nanogaps as "hot spots" with highly localized surface plasmon can generate ultrastrong electromagnetic fields. Superior to the exterior nanogaps obtained via aggregation and self-assembly, interior nanogaps within Au and Ag nanostructures give stable and reproducible surface-enhanced Raman scattering (SERS) signals. However, the synthesis of nanostructures with interior hot spots is still challenging because of the lack of high-yield strategies and clear design principles. Herein, gold-silver nanoclusters (Au-Ag NCs) with multiple interior hot spots were fabricated as SERS platforms via selective growth of Ag nanoparticles on the tips of Au nanostars (Au NSs). Furthermore, the interior gap sizes of Au-Ag NCs can be facilely tuned by changing the amount of AgNO₃ used. Upon 785 nm excitation, single Au-Ag NC₃₅₀ exhibits 43-fold larger SERS enhancement factor and the optimal signal reproducibility relative to single Au NS. The SERS enhancement factors and signal reproducibility of Au-Ag NCs increase with the decrease of gap sizes. Collectively, the Au-Ag NCs could serve as a flexible, reproducible, and active platform for SERS investigation.