Light Emission and Conductance Fluctuations in Electrically Driven and Plasmonically Enhanced Molecular Junctions

Sakthi Priya Amirtharaj, Zhiyuan Xie, Josephine Si Yu See, Gabriele Rolleri, Wen Chen, Alexandre Bouhelier, Emanuel Lörtscher, Christophe Galland

Published 2023-07-13Version 1

Electrically connected and plasmonically enhanced molecular junctions combine the optical functionalities of high field confinement and enhancement (cavity function), and of high radiative efficiency (antenna function) with the electrical functionalities of molecular transport and electrically driven light emission. They are supposed to play a leading role in emerging nanoscale optoelectronic devices; yet, this development is hindered by an insufficient control and understanding of atomic-scale phenomena that govern the optical and electrical behavior of plasmonic nanojunctions under ambient operating conditions. For instance, displacement of a single atom may drastically influence the junction's conductance and its optical near-field distribution. Here, we investigate tunneling-induced light emission from a self-assembled metal-molecule-metal junction embedded in a plasmonic cavity at room-temperature. We find that despite the presence of hundreds of molecules in the junction, electrical conductance and light emission are both highly sensitive to atomic-scale fluctuations - a phenomenology reminiscent of picocavities observed in Raman scattering and of luminescence blinking from photo-excited plasmonic junctions. We present a minimal electrical model that is able to capture all main experimental features. Contrasting with these microscopic fluctuations, the overall plasmonic and electronic functionalities of our devices feature an excellent long-term stability and reproducibility at room temperature and under electrical bias of several volts, allowing for measurements over several months. Our work contributes to the understanding of atomic fluctuations in molecular plasmonic junctions and to the development of more robust and scalable platforms for nanoscale optoelectronics.