Quantitative Surface-Enhanced Raman Spectroscopy for Field Detections Based on Structurally Homogeneous Silver-Coated Silicon Nanocone Arrays

Practical application of surface-enhanced Raman spectroscopy (SERS) is greatly limited by the inaccurate quantitative analyses due to the measuring parameter's fluctuations induced by different operators, different Raman spectrometers, and different test sites and moments, especially during the field tests. Herein, we develop a strategy of quantitative SERS for field detection via designing structurally homogeneous and ordered Ag-coated Si nanocone arrays. Such an array is fabricated as SERS chips by depositing Ag on the template etching-induced Si nanocone array. Taking 4-aminothiophenol as the typical analyte, the influences of fluctuations in measuring parameters (such as defocusing depth and laser powers) on Raman signals are systematically studied, which significantly change SERS measurements. It has been shown that the silicon underneath the Ag coating in the chip can respond to the measuring parameters' fluctuations synchronously with and similar to the analyte adsorbed on the chip surface, and the normalization with Si Raman signals can well eliminate the big fluctuations (up to 1 or 2 orders of magnitude) in measurements, achieving highly reproducible measurements (mostly, <5% in signal fluctuations) and accurate quantitative SERS analyses. Finally, the simulated field tests demonstrate that the developed strategy enables quantitatively analyzing the highly scattered SERS measurements well with 1 order of magnitude in signal fluctuation, exhibiting good practicability. This study provides a new practical chip and reliable quantitative SERS for the field detection of real samples.