Optofluidic Accumulation of Silica Beads on Gel-Based Three-Dimensional SERS Substrate To Enhance Sensitivity Using Multiple Photonic Nanojets.

This paper presents a gel-based three-dimensional (3D) substrate for surface-enhanced Raman spectroscopy (SERS) mediated by photonic nanojets (PNJs) to enhance the sensitivity of SERS detection. The porous structure of the gel-based substrate allowed small molecules to diffuse into the substrate, while the placement of silica beads on the substrate surface resulted in the generation of photonic nanojets during SERS measurements. Because the gel-based SERS substrate had electromagnetic (EM) hot spots along the Z -direction for several tens of microns, the focuses of the PNJs, which were located a few microns away from the substrate surface, could excite the EM hot spots located within the substrate. Our objective was to maximize SERS signal intensity by coating the substrate with a close-packed array of silica beads to enable the generation of multiple PNJs. The bead array was formed using an optical fiber decorated with gold nanorods (AuNRs) to create a temperature gradient in a mixture containing silica beads, thereby enabling their arrangement and deposition in arbitrary locations across the substrate. In experiments, the Raman enhancement provided by multiple PNJs significantly exceeded that provided by single PNJs. The proposed PNJ-mediated SERS method reduced the limit of detection for malachite green by 100 times, compared to SERS results obtained using the same substrate without beads. The proposed enhancement scheme using a gel-based 3D SERS substrate with a close-packed array of silica beads could be utilized to achieve high-sensitivity SERS detection for a variety of molecules in a diverse range of applications.