Influence of Environment on the Measurement of Rates of Charge Transport across Ag^TS/SAM//Ga₂O₃/EGaIn Junctions

This paper investigates the influence of the atmosphere used in the fabrication of top electrodes from the liquid eutectic of gallium and indium (EGaIn) (the so-called “EGaIn” electrodes), and in measurements of current density, <i>J</i>(V) (A/cm²), across self-assembled monolayers (SAMs) incorporated into Ag/SR//Ga₂O₃/EGaIn junctions, on values of <i>J</i>(V) obtained using these electrodes. A gas-tight measurement chamber was used to control the atmosphere in which the electrodes were formed, and also to control the environment in which the electrodes were used to measure current densities across SAM-based junctions. Seven different atmospheresair, oxygen, nitrogen, argon, and ammonia, as well as air containing vapors of acetic acid or waterwere surveyed using both “rough” conical-tip electrodes, and “smooth” hanging-drop electrodes. (The manipulation of the oxide film during the creation of the conical-tip electrodes leads to substantial, micrometer-scale roughness on the surface of the electrode, the extrusion of the drop creates a significantly smoother surface.) Comparing junctions using both geometries for the electrodes, across a SAM of <i>n</i>-dodecanethiol, in air, gave log |<i>J</i>|_mean = −2.4 ± 0.4 for the conical tip, and log |<i>J</i>|_mean = −0.6 ± 0.3 for the drop electrode (and, thus, Δlog |<i>J</i>| ≈ 1.8); this increase in current density is attributed to a change in the effective electrical contact area of the junction. To establish the influence of the resistivity of the Ga₂O₃ film on values of <i>J</i>(V), junctions comprising a graphite electrode and a hanging-drop electrode were compared in an experiment where the electrodes did, and did not, have a surface oxide film; the presence of the oxide did not influence measurements of log |<i>J</i>(V)|, and therefore did not contribute to the electrical resistance of the electrode. However, the presence of an oxide film did improve the stability of junctions and increase the yield of working electrodes from ∼70% to ∼100%. Increasing the relative humidity (RH) in which <i>J</i>(V) was measured did not influence these values (across methyl (CH₃)- or carboxyl (CO₂H)-terminated SAMs) over the range typically encountered in the laboratory (20%–60% (RH))