Tuning Gate Potential Profiles and Current–Voltage Characteristics of Polymer Electrolyte-Gated Transistors by Capacitance Engineering

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 (I _D-V _G) behavior, as well as peak voltage hysteresis between the forward and reverse V _G sweeps. Polythiophene EGTs with small gate/electrolyte areas, on the other hand, exhibit current plateaus in the I _D-V _G 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 V _G 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 I _D-V _G. 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 I _D 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 (I _G-V _G) measurements acquired simultaneously with the I _D-V _G characteristics. Overall, our measurements demonstrate that remarkably different I _D behavior can be obtained for polythiophene EGTs by controlling the magnitude of the gate-electrolyte interfacial capacitance.