Imaging with Raman photons: a novel use of mixed-mode spectroscopy

Surface enhanced Raman spectroscopy is today an established technique used for chemical fingerprinting. Here, we showcase an engineered hierarchical substrate, in which the plasmonically active regions, restricted to a micron scale, two dimensional hexagonal pattern are examined. Spatial variation of the enhanced Raman signal from any analyte, uniformly coating the substrate, consequently bears a high registry with the underlying pattern. This spatially contrasted enhancement allows optical imaging of the 2D pattern solely using the Raman scattered photons from the analyte. While the pattern brightness and contrast determine analyte identification and detection sensitivity, hyperspectral imaging can be exploited for increasing specificity. Proof of concept demonstration of the technique is carried out via the acquisition of Raman images with rhodamine and fluorescein dyes and then applied to detect glucose in 40 mM concentration. The large area optical imaging and the requirement of long-range uniformity in the detected patterns for positive analyte detection, is implemented using a machine learning based pattern recognition protocol which also increases the statistical confidence of detection. This simultaneous, large area signal detection sacrifices continuous spectral information at the cost of speed, reproducibility and minimising human error via automation of detection in the hyperspectral imaging technique presented here.