Plasmonic Electronic Raman Scattering as Internal Standard for Spatial and Temporal Calibration in Quantitative Surface-enhanced Raman Spectroscopy

Published

October 28, 2020

Author(s)

Wonil Nam, Yuming Zhao, Junyeob Song, Seied Ali Safiabadi Tali, Seju Kang, Wenqi Zhu, Henri Lezec, Amit Agrawal, Peter J. Vikesland, Wei Zhou

Abstract

Ultrasensitive surface-enhanced Raman spectroscopy (SERS) still faces difficulties in quantitative analysis because of its susceptibility to local optical field variations at plasmonic hotspots in metallo-dielectric nanostructures. Current SERS calibration approaches using Raman tags have inherent limitations due to spatial occupation competition with analyte molecules, spectral interference with analyte Raman peaks, and photodegradation. Here, we report that plasmon-enhanced electronic Raman scattering (ERS) signals can serve as an internal standard for spatial and temporal calibration of molecular Raman scattering (MRS) signals at the same hotspots, enabling rigorous quantitative SERS analysis. We observe a linear dependence between ERS and MRS signal intensities upon spatial and temporal variations of excitation optical fields, manifesting the |E|^4 enhancements for both ERS and MRS processes at the same hotspots. Furthermore, we find that the performance limit of ERS calibration is caused by the effects from orientation variations of analyte molecules at hotspots.

Citation

The Journal of Physical Chemistry Letters

Volume

11

Issue

22

Pub Type

Journals

Download Paper

https://doi.org/10.1021/acs.jpclett.0c03056

Local Download

Citation

Nam, W. , Zhao, Y. , Song, J. , Safiabadi Tali, S. , Kang, S. , Zhu, W. , Lezec, H. , Agrawal, A. , Vikesland, P. and Zhou, W. (2020), Plasmonic Electronic Raman Scattering as Internal Standard for Spatial and Temporal Calibration in Quantitative Surface-enhanced Raman Spectroscopy, The Journal of Physical Chemistry Letters, [online], https://doi.org/10.1021/acs.jpclett.0c03056, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=931130 (Accessed July 6, 2025)