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Published on: July 21, 2023
Elucidating Molecule-Plasmon Interactions in Nanocavities with 2 nm Spatial Resolution and at the Single-Molecule
Fan-Li Zhang1, Jun Yi1, Wei Peng1
1MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, State Key Laboratory of Physical Chemistry of Solid, Surfaces,iChEM, College of Chemistry and Chemical Engineering, College of Materials, Xiamen University, Xiamen, 361005, China.
Abstract:
The fundamental understanding of the subtle interactions between molecules and plasmons is of great significance for the development of plasmon-enhanced spectroscopy (PES) techniques with ultrahigh sensitivity. However, this information has been elusive due to the complex mechanisms and difficulty in reliably constructing and precisely controlling interactions in well-defined plasmonic systems. Herein, the interactions in plasmonic nanocavities of film-coupled metallic nanocubes (NCs) are investigated. Through engineering the spacer layer, molecule-plasmon interactions were precisely controlled and resolved within 2 nm. Efficient energy exchange interactions between the NCs and the surface within the 1-2 nm range are demonstrated. Additionally, optical dressed molecular excited states with a huge Lamb shift of ≈7 meV at the single-molecule (SM) level were observed. This work provides a basis for understanding the underlying molecule-plasmon interaction, paving the way for fully manipulating light-matter interactions at the nanoscale.
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