Effect of Electrolyte Concentration and Pore Size on Ion Current Rectification Inversion

A thorough understanding of nanoscale transport properties is vital for the development and optimization of nanopore sensors. The thickness of the electrical double layers (EDLs) at the internal walls of a nanopore, as well as the dimensions of the nanopore itself, plays a crucial role in determining transport properties. Herein, we demonstrate the effect of the electrolyte concentration, which is inversely proportional to the EDL thickness, and the effect of pore size, which controls the extent of the electrical double layer overlap, on the ion current rectification phenomenon observed for conical nanopores. Experimental and numerical results showed that as the electrolyte concentration is decreased, the rectification ratio reaches a maximum, then decreases, and eventually inverts below unity. We also show that as the pore size is decreased, the rectification maximum and the inversion take place at higher electrolyte concentrations. Numerical investigations revealed that both phenomena occur due to the shifting of ion enrichment distributions within the nanopore as the electrolyte concentration or the pore size is varied.