Bias induced transition from an ohmic to a non-ohmic interface in supramolecular tunneling junctions with Ga2O3/EGaIn top electrodes.

This study describes that the current rectification ratio, R ≡ |J|(-2.0 V)/|J|(+2.0 V) for supramolecular tunneling junctions with a top-electrode of eutectic gallium indium (EGaIn) that contains a conductive thin (0.7 nm) supporting outer oxide layer (Ga2O3), increases by up to four orders of magnitude under an applied bias of >+1.0 V up to +2.5 V; these junctions did not change their electrical characteristics when biased in the voltage range of ±1.0 V. The increase in R is caused by the presence of water and ions in the supramolecular assemblies which react with the Ga2O3/EGaIn layer and increase the thickness of the Ga2O3 layer. This increase in the oxide thickness from 0.7 nm to ∼2.0 nm changed the nature of the monolayer-top-electrode contact from an ohmic to a non-ohmic contact. These results unambiguously expose the experimental conditions that allow for a safe bias window of ±1.0 V (the range of biases studies of charge transport using this technique are normally conducted) to investigate molecular effects in molecular electronic junctions with Ga2O3/EGaIn top-electrodes where electrochemical reactions are not significant. Our findings also show that the interpretation of data in studies involving applied biases of >1.0 V may be complicated by electrochemical side reactions which can be recognized by changes of the electrical characteristics as a function voltage cycling or in current retention experiments.

Electron-induced dynamics of heptathioether ß-cyclodextrin molecules.

Variable-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) measurements are performed on heptathioether ß-cyclodextrin (ß-CD) self-assembled monolayers (SAMs) on Au. The ß-CD molecules exhibit very rich dynamical behavior, which is not apparent in ensemble-averaged studies. The dynamics are reflected in the tunneling current-time traces, which are recorded with the STM feedback loop disabled. The dynamics are temperature independent, but increase with increasing tunneling current and sample bias, thus indicating that the conformational changes of the ß-CD molecules are induced by electrons that tunnel inelastically. Even for sample biases as low as 10 mV, well-defined levels are observed in the tunneling current-time traces. These jumps are attributed to the excitations of the molecular vibration of the macrocyclic ß-CD molecule. The results are of great importance for a proper understanding of transport measurements in SAMs.