This paper describes how the intensive (tunneling decay coefficient β and rectification ratio R) and extensive (current density J) properties of Ag-S(CH2) n-1CH3//GaO x/EGaIn junctions ( n = 10, 14, 18) and molecular diodes of the form of Ag-S(CH2)11Fc//GaO x/EGaIn depend on Ageo, the contact area between the self-assembled monolayer and the cone-shaped EGaIn tip. Large junctions with Ageo ≥ 1000 μm2 are unreliable and defects, such as pinholes, dominate the charge transport characteristics. For S(CH2)11Fc SAMs, R decreases from 130 to unity with increasing Ageo due to an increase in the leakage current (the current flowing across the junction at reverse bias when the diodes block current flow). The value of β decreases from 1.00 ± 0.06 n-1 to 0.70 ± 0.03 n-1 with increasing Ageo which also indicates that large junctions suffer from defects. Small junctions with Ageo ≤ 300 μm2 are not stable due to the high surface tension of the bulk EGaIn resulting in unstable EGaIn tips. In addition, the contact area for such small junctions is dominated by the rough tip apex reducing the effective contact area and reproducibility significantly. The contact area of very large junctions is dominated by the relatively smooth side walls of the tips. Our findings show that there is an optimum range for the value of Ageo between 300-500 μm2 where the electrical properties of the junctions are dominated by molecular effects. In this range of Ageo, the value of J (defined by I/ Ageo where I is the measured current) increases with Ageo until it plateaus for junctions with Ageo > 1000 μm2 in agreement with recently reported findings by the Whitesides group. In this regime reproducible measurements of J can be obtained provided Ageo is kept constant.
Keywords: EGaIn; contact area; molecular diodes; molecular junctions; tunneling decay coefficient.