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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.

Fluoride-Induced Negative Differential Resistance in Nanopores: Experimental and Theoretical Characterization