Ion current rectification in funnel-shaped nanochannels: Hysteresis and inversion effects

Ion current rectification inversion is observed in a funnel-shaped nanochannel above a threshold voltage roughly corresponding to the under-limiting to over-limiting current transition. Previous experimental studies have examined rectification at either low-voltages (under-limiting current region) for conical nanopores/funnel-shaped nanochannels or at high-voltages (over-limiting region) for straight nanochannels with asymmetric entrances or asymmetric interfacing microchannels. The observed rectification inversion occurs because the system resistance is shifted, beyond a threshold voltage, from being controlled by intra-channel ion concentration-polarization to that controlled by external concentration-polarization. Additionally, strong hysteresis effects, due to residual concentration-polarization, manifest themselves through the dependence of the transient current rectification on voltage scan rate.