Sculpting Artificial Edges in Monolayer MoS₂ for Controlled Formation of Surface-Enhanced Raman Hotspots

Hotspot engineering has the potential to transform the field of surface-enhanced Raman spectroscopy (SERS) by enabling ultrasensitive and reproducible detection of analytes. However, the ability to controllably generate SERS hotspots, with desired location and geometry, over large-area substrates, has remained elusive. In this study, we sculpt artificial edges in monolayer molybdenum disulfide (MoS₂) by low-power focused laser-cutting. We find that when gold nanoparticles (AuNPs) are deposited on MoS₂ by drop-casting, the AuNPs tend to accumulate predominantly along the artificial edges. First-principles density functional theory (DFT) calculations indicate strong binding of AuNPs with the artificial edges due to dangling bonds that are ubiquitous on the unpassivated (laser-cut) edges. The dense accumulation of AuNPs along the artificial edges intensifies plasmonic effects in these regions, creating hotspots exclusively along the artificial edges. DFT further indicates that adsorption of AuNPs along the artificial edges prompts a transition from semiconducting to metallic behavior, which can further intensify the plasmonic effect along the artificial edges. These effects are observed exclusively for the sculpted (i.e., cut) edges and not observed for the MoS₂ surface (away from the cut edges) or along the natural (passivated) edges of the MoS₂ sheet. To demonstrate the practical utility of this concept, we use our substrate to detect Rhodamine B (RhB) with a large SERS enhancement (∼10⁴) at the hotspots for RhB concentrations as low as ∼10^-10 M. The single-step laser-etching process reported here can be used to controllably generate arrays of SERS hotspots. As such, this concept offers several advantages over previously reported SERS substrates that rely on electrochemical deposition, e-beam lithography, nanoimprinting, or photolithography. Whereas we have focused our study on MoS₂, this concept could, in principle, be extended to a variety of 2D material platforms.