Fabricating chiroptical starfruit-like Au nanoparticles via interface modulation of chiral thiols.

The surface/interface matters as the size of materials enters the nanoscale. Control of surface/interface, therefore, plays an important role in creating novel nanostructures with unusual properties and in obtaining devices with high performance. Herein, we demonstrate unique interface regulation in fabricating nanostructures with strong plasmonic circular dichroism (PCD). With chiral cysteine (Cys) as surface-modulating molecules, starfruit-like Au nanoparticles (NPs) with high PCD responses are obtained via Au overgrowth on Au nanorods (AuNRs). Pre-incubation of the AuNRs with Cys is vital in achieving strong and reproducible PCD responses. Instead of contributing to PCD signals, the pre-adsorbed Cys molecules are found to play a major role in manipulating the Au growth mode and thus the formation of hotspots within the shell. Strong PCD signal mainly comes from the entrapped Cys molecules within the hotspots and is enhanced via local field effect. The distinct roles of the same ligands at different surfaces/interfaces are elucidated. Furthermore, our findings contribute to the strategy of utilizing interface modulation to fabricate complex nanostructures with novel properties.