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

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. Herein, we report that plasmon-enhanced electronic Raman scattering (ERS) signals from metal can serve as an internal standard for spatial and temporal calibration of molecular Raman scattering (MRS) signals from analyte molecules 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 in agreement with our theoretical prediction. Furthermore, we find that the ERS calibration's performance limit can result from orientation variations of analyte molecules at hotspots.

Sub-10 nm Nanolaminated Al2O3/HfO2 Coatings for Long-Term Stability of Cu Plasmonic Nanodisks in Physiological Environments.

By supporting localized plasmon modes, metal-based plasmonic nanostructures can confine optical fields at deep-subwavelength scale in various applications, such as biological and chemical sensing, nanoscale light emission, and solar energy harvesting. While Cu is a low-cost complementary metal oxide semiconductor (CMOS) compatible material, its poor chemical stability limits the use of Cu plasmonic nanodevices in corrosive biochemical aqueous environments. In this paper, we demonstrate that sub-10 nm Al2O3/HfO2 nanolaminated coatings can significantly extend the lifetime of Cu nanodisk arrays from ∼5 h to ∼180 days in the physiological environment of 1× phosphate-buffered saline (PBS) at 37 °C. Cu nanodisk arrays are fabricated using freestanding Au nanohole array films as the physical vapor deposition masks and sub-10 nm nanolaminated coatings composed of alternating Al2O3 and HfO2 nanolayers are grown on Cu nanodisk arrays by atomic layer deposition (ALD). Time-dependent optical extinction measurements of Cu nanodisk arrays are conducted in 1× solutions at 37 °C to investigate the anticorrosion performance for different pure and nanolaminated ALD coatings. We observe a linear relationship between the lifetime of Cu nanodisk arrays in 1× PBS at 37 °C and the nanolaminated coating thickness, and ∼1.3 nm nanolaminated coatings of ∼10 ALD cycles can extend the lifetime of Cu plasmonics up to ∼20 days. Furthermore, we find that the anticorrosion performance of Al2O3/HfO2 nanolaminated ALD coatings strongly depends on the processing and the geometric parameters, such as the annealing temperature and the nanolaminated backbone unit size.