Unambiguous Observation of Single-Molecule Raman Spectroscopy Enabled by Synergic Electromagnetic and Chemical Enhancement

Raman spectroscopy is a powerful tool to detect, analyze and identify molecules. It has been a long-history pursuit to push the detection limit of Raman spectroscopy down to the fundamental single-molecule (SM) level. Due to the tiny cross section of intrinsic Raman scattering of molecule, some enhancement mechanisms of light-matter interaction must be implemented to levitate the Raman scattering intensity by a huge number of ~14-15 orders of magnitude, to the level comparable with the molecule fluorescence intensity. In this work we report unambiguous observation of single-molecule Raman spectroscopy via synergic action of electromagnetic and chemical enhancement for rhodamine B (RhB) molecule absorbed within the plasmonic nanogap formed by gold nanoparticle sitting on the two-dimensional (2D) monolayer WS2 and 2 nm SiO2 coated gold thin film. Raman spectroscopy down to an extremely dilute value of 10-18 mol/L can still be clearly visible, and the statistical enhancement factor could reach 16 orders of magnitude compared with the reference detection sample of silicon plate with a detection limit of 10-2 mol/L. The electromagnetic enhancement comes from local surface plasmon resonance induced at the nanogap, which could reach ~10-11 orders of magnitude, while the chemical enhancement comes from monolayer WS2 2D material, which could reach 4-5 orders of magnitudes. The synergic implementation and action of these two prestigious Raman scattering enhancement mechanisms in this specially designed 2D material-plasmon nanogap composite nanoscale system enables unambiguous experimental observation of single-molecule Raman spectroscopy of RhB molecule. This route of Raman enhancement devices could open up a new frontier of single molecule science, allowing detection, identification, and monitor of single molecules and their spatial-temporal evolution under various internal and external stimuli.