Single molecule tunnel junctions (SMTJs) can provide important physical insights into electronic and vibrational phenomena at the molecular scale. However, observations and analysis are typically confined to sufficiently low temperatures as to suppress molecular motion and the resulting stochastic fluctuations in the tunneling current. In this work, we introduce and experimentally validate a methodology whereby a slightly higher temperature (9 K) compared to a typical SMTJ study can be used to induce sparse fluctuations in the inelastic tunneling current and provide the fingerprints of dynamics between the conformational states of the molecule. Two examples of benzene dithiol and cysteine are studied in electromigratively formed W/Au nanowire SMTJs on SiO2 at 9 K. The second-order transform of the tunneling current reveals the expected vibrational spectra. However, we show that temporal fluctuations can be analyzed using a hidden Markov Model to reveal dynamics assigned to millisecond rearrangements of the molecule, with apparent energy barriers ranging from 35 to 66 meV, consistent with theoretical predictions. The observed transitions are consistent with a model of lateral migration of the thiol-anchored molecules in an asymmetric junction. The use of temperature in SMTJs in this way can provide new insights into molecule dynamics in confined volumes and at electrode interfaces.
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films