Modulation of Ionic Current Rectification in Ultrashort Conical Nanopores.

Nanopores that exhibit ionic current rectification (ICR) behave like diodes such that they transport ions more efficiently in one direction than in the other. Conical nanopores have been shown to rectify ionic current, but only those with at least 500 nm in length exhibit significant ICR. Here, through the finite element method, we show how ICR of conical nanopores with lengths below 200 nm can be tuned by controlling individual charged surfaces, that is, the inner pore surface (surfaceinner) and exterior pore surfaces on the tip and base side (surfacetip and surfacebase). The charged surfaceinner and surfacetip can induce obvious ICR individually, while the effects of the charged surfacebase on ICR can be ignored. The fully charged surfaceinner alone could render the nanopore counterion-selective and induces significant ion concentration polarization in the tip region, which causes reverse ICR compared to nanopores with all surfaces charged. In addition, the direction and degree of rectification can be further tuned by the depth of the charged surfaceinner. When considering the exterior membrane surface only, the charged surfacetip causes intrapore ionic enrichment and depletion under opposite biases, which results in significant ICR. Its effective region is within ∼40 nm beyond the tip orifice. We also found that individual charged parts of the pore system contributed to ICR in an additive way because of the additive effect on the ion concentration regulation along the pore axis. With various combinations of fully/partially charged surfaceinner and surfacetip, diverse ICR ratios from ∼2 to ∼170 can be achieved. Our findings shed light on the mechanism of ICR in ultrashort conical nanopores and provide a useful guide to the design and modification of ultrashort conical nanopores in ionic circuits and nanofluidic sensors.