Negative differential resistance (NDR) phenomena are under-explored in nanostructures operating in the liquid state. We characterize experimentally the NDR and threshold switching phenomena observed when conical nanopores are immersed in two identical KF solutions at low concentration. Sharp current drops in the nA range are obtained for applied voltages exceeding thresholds close to 1 V and a wide frequency window, which suggests that the threshold switching can be used to amplify small electrical perturbations because a small change in voltage typically results in a large change in current. While we have not given a detailed physical mechanism here, a phenomenological model is also included.

We describe experimentally and theoretically the fluoride-induced negative differential resistance (NDR) phenomena observed in conical nanopores operating in aqueous electrolyte solutions. The threshold voltage switching occurs around 1 V and leads to sharp current drops in the nA range with a peak-to-valley ratio close to 10. The experimental characterization of the NDR effect with single pore and multipore samples concern different pore radii, charge concentrations, scan rates, salt concentrations, solvents, and cations. The experimental fact that the effective radius of the pore tip zone is of the same order of magnitude as the Debye length for the low salt concentrations used here is suggestive of a mixed pore surface and bulk conduction regime. Thus, we propose a two-region conductance model where the mobile cations in the vicinity of the negative pore charges are responsible for the surface conductance, while the bulk solution conductance is assumed for the pore center region.

Ion permeation across nanoscopic structures differs considerably from microfluidics because of strong steric constraints, transformed solvent properties and charge-regulation effects revealed mostly in diluted solutions. However, little is known about nanofluidics in moderately concentrated solutions, which are critically important for industrial applications and living systems. Here we show that nanoconfinement triggers general biphasic concentration patterns in a myriad of ion transport properties using two contrasting systems: a biological ion channel and a much larger synthetic nanopore. Our findings show a low concentration regime ruled by classical Debye screening and another one where ion-ion correlations and enhanced ion-surface interactions contribute differently to each electrophysiological property. Thus, different quantities (e.g., conductance vs noise) measured under the same conditions may appear contradictory because they belong to different concentration regimes. In addition, non-linear effects that are barely visible in bulk conductivity only in extremely concentrated solutions become apparent in nanochannels around physiological conditions.

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