Insight into the Heterogeneity of Longitudinal Plasmonic Field in a Nanocavity Using an Intercalated Two-Dimensional Atomic Crystal Probe with a ∼7 Å Resolution.

Quantitative measurement of the plasmonic field distribution is of great significance for optimizing highly efficient optical nanodevices. However, the quantitative and precise measurement of the plasmonic field distribution is still an enormous challenge. In this work, we design a unique nanoruler with a ∼7 Å spatial resolution, which is based on a two-dimensional atomic crystal where the intercalated monolayer WS 2 is a surface-enhanced Raman scattering (SERS) probe and four layers of MoS 2 are a reference layer in a nanoparticle-on-mirror (NPoM) structure to quantitatively and directionally probe the longitudinal plasmonic field distribution at high permittivity by the quantitative SERS intensity of WS 2 located in different layers. A subnanometer two-dimensional atomic crystal was used as a spacer layer to overcome the randomness of the molecular adsorption and Raman vibration direction. Combined with comprehensive theoretical derivation, numerical calculations, and spectroscopic measurements, it is shown that the longitudinal plasmonic field in an individual nanocavity is heterogeneously distributed with an unexpectedly large intensity gradient. We analyze the SERS enhancement factor on the horizontal component, which shows a great attenuation trend in the nanocavity and further provides precise insight into the horizontal component distribution of the longitudinal plasmonic field. We also provide a direct experimental verification that the longitudinal plasmonic field decays more slowly in high dielectric constant materials. These precise experimental insights into the plasmonic field using a two-dimensional atomic crystal itself as a Raman probe may propel understanding of the nanostructure optical response and applications based on the plasmonic field distribution.