Ion Current Rectification and Long-Range Interference in Conical Silicon Micropores (2206.14594v2)

Abstract: Fluidic devices exhibiting ion current rectification (ICR), or ionic diodes, are of broad interest for applications including desalination, energy harvesting, and sensing, amongst others. For such applications a large conductance is desirable which can be achieved by simultaneously using thin membranes and wide pores. In this paper we demonstrate ICR in micron sized conical channels in a thin silicon membrane with pore diameters comparable to the membrane thickness but both much larger than the electrolyte screening length. We show that for these pores the entrance resistance is not only key to Ohmic conductance around 0 V, but also for understanding ICR, both of which we measure experimentally and capture within a single analytic theoretical framework. The only fit parameter in this theory is the membrane surface potential, for which we find that it is voltage dependent and its value is excessively large compared to literature. From this we infer that surface charge outside the pore strongly contributes to the observed Ohmic conductance and rectification by a different extent. We experimentally verify this hypothesis in a small array of pores and find that ICR vanishes due to pore-pore interactions mediated through the membrane surface, while Ohmic conductance around 0 V remains unaffected. We find that the pore-pore interaction for ICR is set by a long-ranged decay of the concentration which explains the surprising finding that the ICR vanishes for even a sparsely populated array with a pore-pore spacing as large as 7 $\mu$m.