Stretchable and Flexible Micro-Nano Substrates for SERS Detection of Organic Dyes

Surface-enhanced Raman spectroscopy (SERS) is a precise and noninvasive analytical technique to identify vibrational fingerprints of trace analytes with sensitivity down to the single-molecule level. However, substrates can influence this capability, and current SERS techniques lack uniform, reproducible, and stable substrates to control plasma hot spots over a wide spectral range. Herein, we demonstrate a flexible SERS substrate via longitudinal stretching of a polydimethylsiloxane (PDMS) film. This substrate, after stretching and shrinking, exhibits an irregular wrinkled structure with abundant gaps and grooves that function as hot spots, thereby improving the hydrophobic properties of the material. To investigate the enhancement effect of Raman signals, silver nanoparticles (AgNPs) were mixed with Rhodamine 6G (R6G) solution, and the obtained blend was dropped onto the PDMS film to form a coffee ring pattern. According to the results, the hydrophobicity of the substrate increases with the degree of PDMS stretching, achieving the optimal level at 150% stretching. Moreover, the increase in hydrophobicity makes the measured molecules more aggregated, which enhances the Raman signal. The stretching and shrinkage of the PDMS film lead to a much higher density of nanogaps among nanoparticles and nanogrooves, which serve as multiple hot spots. Being highly localized regions of intense local fields, these hot spots make a significant contribution to SERS performance, improving the sensitivity and reproducibility of the method. In particular, the relative standard deviation (RSD) was found to be 2.5544%, and the detection limit was 1 × 10^-7 M. Therefore, SERS using stretchable and flexible micro-nano substrates is a promising way for detecting dyes in wastewater.