Plasmonic Imaging of Tuning Electron Tunneling Mediated by a Molecular Monolayer

[Image: see text] Probing and tuning the electron tunneling in metal electrode–insulator–metal nanoparticle systems provide a unique vision for understanding the fundamental mechanism of electrochemistry and broadening the horizon in practical applications of molecular electronics in many electrochemical systems. Here we report a plasmonic imaging technique to monitor the local double-layer charging of individual Au nanoparticles deposited on gold electrode separated by monolayer of n-alkanethiol molecules. The thickness of molecular monolayer tunes the tunneling kinetics and conductivity, which predicts the heterogeneous behavior on the modified electrode surface for different electrochemical systems. We studied the distance dependence of the electron tunneling and double layer charging processes by a plasmonic-based electrical impedance microscopy. By performing fast Fourier transform analysis of the recorded plasmonic image sequences, we can quantify the interfacial impedance of single nanoparticles and the tunneling decay constant of molecular layer. We further observed the electron neutralization dynamics during single-nanoparticle collisions on different surfaces. This optical readout of electron tunneling demonstrates an imaging approach to determine the electrical properties of metal electrode–insulator–metal nanoparticle systems, which include the electron tunneling mechanism and local impedance.