A single hydrogen molecule as an intensity chopper in an electrically-driven plasmonic nanocavity

TL;DR

This paper demonstrates how a single hydrogen molecule can act as an intensity chopper in an electrically-driven plasmonic nanocavity, revealing adsorbate dynamics through photon statistics in a single measurement.

Contribution

It introduces a novel method combining photon correlation spectroscopy with STML to analyze individual molecule dynamics in ultrahigh vacuum.

Findings

Hydrogen molecule modulates plasmon emission in a nanocavity.

Photon bunching reveals adsorbate diffusion over microseconds to seconds.

Single measurement captures dynamics across six orders of magnitude.

Abstract

Photon statistics is a powerful tool for characterizing the emission dynamics of nanoscopic systems and their photophysics. Recent advances that combine correlation spectroscopy with scanning tunneling microscopy-induced luminescence (STML) have allowed measuring the emission dynamics from individual molecules and defects demonstrating their nature as single photon emitters. The application of correlation spectroscopy to the analysis of the dynamics of a well-characterized adsorbate system in ultrahigh vacuum remained to be shown. Here we combine single photon time correlations with STML to measure the dynamics of individual $H_2$ molecules between a gold tip and a Au(111) surface. An adsorbed $H_2$ molecule performs recurrent excursions below the tip apex. We use the fact that the presence of the $H_2$ molecule in the junction modifies plasmon emission to study the adsorbate dynamics. Using the $H_2$ molecule as a chopper for STM-induced optical emission intensity we demonstrate bunching in the plasmonic photon train in a single measurement over six orders of magnitude in the time domain (from microseconds to seconds) that takes only a few seconds. Our findings illustrate the power of using photon statistics to measure the diffusion dynamics of adsorbates with STML.