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This work provides critical insights into the relationship between work function and tunneling transport in mixed molecular junctions, demonstrating that conductance and metal–orbital coupling vary exponentially with work function differences. 

We demonstrate that the transfer characteristics of electrolyte-gated transistors (EGTs) with polythiophene semiconductor channels are a strong function of gate/electrolyte interfacial contact area, i.e., gate size. Polythiophene EGTs with gate/electrolyte areas much larger than the channel/electrolyte areas show a clear peak in the drain current vs gate voltage (ID–VG) behavior, as well as peak voltage hysteresis between the forward and reverse VG sweeps. Polythiophene EGTs with small gate/electrolyte areas, on the other hand, exhibit current plateaus in the ID–VG behavior and a gate-size-dependent hysteresis loop between turn on and off. The qualitatively different transport behaviors are attributed to the relative sizes of the gate/electrolyte and channel/electrolyte interface capacitances, which are proportional to interfacial area. These interfacial capacitances are in series with each other such that the total capacitance of the full gate/electrolyte/channel stack is dominated by the interface with the smallest capacitance or area. For EGTs with large gates, most of the applied VG is dropped at the channel/electrolyte interface, leading to very high charge accumulations, up to ∼0.3 holes per ring (hpr) in the case of polythiophene semiconductors. The large charge density results in sub-band-filling and a marked decrease in hole mobility, giving rise to the peak in ID–VG. For EGTs with small gates, hole accumulation saturates near 0.15 hpr, band-filling does not occur, and hole mobility is maintained at a fixed value, which leads to the ID plateau. Potential drops at the interfaces are confirmed by in situ potential measurements inside a gate/electrolyte/polymer semiconductor stack. Hole accumulations are measured with gate current-gate voltage (IG–VG) measurements acquired simultaneously with the ID–VG characteristics. Overall, our measurements demonstrate that remarkably different ID behavior can be obtained for polythiophene EGTs by controlling the magnitude of the gate-electrolyte interfacial capacitance. 

The current–voltage behavior of molecular tunnel junctions can be analyzed with a simple model to reveal key electronic structure characteristics.