Bipolar Nanochannels: A Systematic Approach to Asymmetric Problems.

Nanofluidic diodes are capable of rectifying the electrical current by several orders of magnitude. In the current state of affairs, determining the rectification factor is not possible as it depends on many system parameters. In this work, we systematically scan the effects of geometry and excess counterion concentrations (i.e., surface charge effects). We show that the current-voltage response varies between the two extreme behaviors of unipolar and bipolar responses. The exact behavior depends on the geometry and surface charge properties of the system. Here, we have gone beyond the typical setup that only considers the dynamics within the nanochannel itself and we have included the effects of the adjoining microchannels. Systems that include both nanochannels and microchannels exhibit the classical signatures of concentration polarization, such as ionic depletion and enrichment. Here, where we have scanned a wide range of parameters, we show that bipolar and semi-bipolar systems exhibit a wider range of phenomena that are intrinsically more complicated. Our system characterization is for both, the much more investigated case of steady state and the less investigated, but equally interesting, time-transient case. For example, it is common to characterize the system by its steady-state result (current-voltage response, rectification factor, and transport number). Here, we demonstrate that the time-transient behavior of the fluxes can also be used to characterize the system, and that the time-dependent rectification factors and transport numbers are meaningful. The systematic approach taken in this work, and the results presented herein, can be used to further elucidate the complicated behavior of the current-voltage response of nanofluidic diodes and to rationalize experimental results. The insights of this work can be used to enhance and improve the design of all nanofluidic diodes.