We discuss an experimental configuration consisting of {Au film}-molecule-{Au particle} or {Au film}-molecule-{Si particle} nanojunctions for performing wide-field surface-enhanced CARS (SE-CARS) measurements in a reproducible and controllable manner. While the allowable illumination dosage in the {Au film}-molecule-{Au particle} case is limited by the strong two-photon background from the gold, we successfully generate a detectable coherent Raman response from a molecular monolayer using the lowest reported average power densities to-date. With a vision to minimize the two-photon background and the intrinsic losses observed in all-metal plasmonic systems, we examine the possibility of using high-index dielectric particles on top of a thin metal film to generate strong nanoscopic hotspots. We demonstrate repeatable SE-CARS measurements at the {Au film}-molecule-{Si particle} heterojunction, underlining the usability of this experimental geometry. This work paves the way for the development of next-generation of chemical and biomolecular sensing assays that can minimize some of the major drawbacks encountered in fragile and lossy all-metal plasmonic systems.

Sensors using nitrogen-vacancy centers in diamond are a promising tool for small-volume nuclear magnetic resonance (NMR) spectroscopy, but the limited sensitivity remains a challenge. Here we show nearly two orders of magnitude improvement in concentration sensitivity over previous nitrogen-vacancy and picoliter NMR studies. We demonstrate NMR spectroscopy of picoliter-volume solutions using a nanostructured diamond chip with dense, high-aspect-ratio nanogratings, enhancing the surface area by 15 times. The nanograting sidewalls are doped with nitrogen-vacancies located a few nanometers from the diamond surface to detect the NMR spectrum of roughly 1 pl of fluid lying within adjacent nanograting grooves. We perform ¹H and ¹⁹F nuclear magnetic resonance spectroscopy at room temperature in magnetic fields below 50 mT. Using a solution of CsF in glycerol, we determine that 4 ± 2 × 10^{12 19}F spins in a 1 pl volume can be detected with a signal-to-noise ratio of 3 in 1 s of integration.