Dramatic Enhancement of Tip-Enhanced Raman Scattering Mediated by Atomic Point Contact Formation

Nano Lett. 2020 Aug 12;20(8):5879-5884. doi: 10.1021/acs.nanolett.0c01791. Epub 2020 Jul 29.

Abstract

Tip-enhanced Raman scattering (TERS) in ångström-scale plasmonic cavities has drawn increasing attention. However, Raman scattering at vanishing cavity distances remains unexplored. Here, we show the evolution of TERS in transition from the tunneling regime to atomic point contact (APC). A stable APC is reversibly formed in the junction between an Ag tip and ultrathin ZnO or NaCl films on the Ag(111) surface at 10 K. An abrupt increase of the TERS intensity occurs upon APC formation for ZnO, but not for NaCl. This remarkable observation is rationalized by a difference in hybridization between the Ag tip and these films, which determines the contribution of charge transfer enhancement in the fused plasmonic junction. The strong hybridization between the Ag tip and ZnO is corroborated by the appearance of a new vibrational mode upon APC formation, whereas it is not observed for the chemically inert NaCl.

Keywords: Atomic point contact; Plamonic picocavity; Scanning tunneling microscopy; Tip-enhanced Raman spectroscopy; Ultrathin films.