Defining
the Value of Injection Current and Effective
Electrical Contact Area for EGaIn-Based Molecular Tunneling Junctions
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Abstract
Analysis of rates of tunneling across
self-assembled monolayers
(SAMs) of <i>n</i>-alkanethiolates SC<sub><i>n</i></sub> (with <i>n</i> = number of carbon atoms) incorporated
in junctions having structure Ag<sup>TS</sup>-SAM//Ga<sub>2</sub>O<sub>3</sub>/EGaIn leads to a value for the injection
tunnel current density <i>J</i><sub>0</sub> (i.e., the current
flowing through an ideal junction with <i>n</i> = 0) of
10<sup>3.6±0.3</sup> A·cm<sup>–2</sup> (<i>V</i> = +0.5 V). This estimation of <i>J</i><sub>0</sub> does
not involve an extrapolation in length, because it was possible to
measure current densities across SAMs over the range of lengths <i>n</i> = 1–18. This value of <i>J</i><sub>0</sub> is estimated under the assumption that values of the geometrical
contact area equal the values of the effective electrical contact
area. Detailed experimental analysis, however, indicates that the
roughness of the Ga<sub>2</sub>O<sub>3</sub> layer, and that of the
Ag<sup>TS</sup>-SAM, determine values of the effective electrical
contact area that are ∼10<sup>–4</sup> the corresponding
values of the geometrical contact area. Conversion of the values of
geometrical contact area into the corresponding values of effective
electrical contact area results in <i>J</i><sub>0</sub>(+0.5
V) = 10<sup>7.6±0.8</sup> A·cm<sup>–2</sup>, which
is compatible with values reported for junctions using top-electrodes
of evaporated Au, and graphene, and also comparable with values of <i>J</i><sub>0</sub> estimated from tunneling through single molecules.
For these EGaIn-based junctions, the value of the tunneling decay
factor β (β = 0.75 ± 0.02 Å<sup>–1</sup>; β = 0.92 ± 0.02 nC<sup>–1</sup>) falls within
the consensus range across different types of junctions (β =
0.73–0.89 Å<sup>–1</sup>; β = 0.9–1.1
nC<sup>–1</sup>). A comparison of the characteristics of conical
Ga<sub>2</sub>O<sub>3</sub>/EGaIn tips with the characteristics
of other top-electrodes suggests that the EGaIn-based electrodes provide
a particularly attractive technology for physical-organic studies
of charge transport across SAMs