Hotspots on the Move: Active Molecular Enrichment by Hierarchically Structured Micromotors for Ultrasensitive SERS Sensing.

Surface-enhanced Raman scattering (SERS) is recognized as one of the most sensitive spectroscopic tools for chemical and biological detections. Hotspots engineering has expedited promotion of SERS performance over the past few decades. Recently, molecular enrichment has proven to be another effective approach to improve the SERS performance. In this work, we propose a concept of "motile hotspots" to realize ultrasensitive SERS sensing by combining hotspots engineering and active molecular enrichment. High-density plasmonic nanostructure-supporting hotspots are assembled on the tubular outer wall of micromotors via nanoimprint and rolling origami techniques. The dense hotspots carried on these hierarchically structured micromotors (HSMs) can be magnet-powered to actively enrich molecules in fluid. The active enrichment manner of HSMs is revealed to be effective in accelerating the process of molecular adsorption. Consequently, SERS intensity increases significantly because of more molecules being adjacent to the hotspots after active molecular enrichment. This "motile hotspots" concept provides a synergistical approach in constructing a SERS platform with high performance. Moreover, the newly developed construction method of HSMs manifests the possibility of tailoring tubular length and diameter as well as surface patterns on the outer wall of HSMs, demonstrating good flexibility in constructing customized micromotors for various applications.