Multi-Layered Bipolar Ionic Diode Working in Broad Range Ion Concentration.

Ion current rectification (ICR) is the ratio of ion current by forward bias to backward bias and is a critical indicator of diode performance. In previous studies, there have been many attempts to improve the performance of this ICR, but there is the intrinsic problem for geometric changes that induce ionic rectification due to fabrication problems. Additionally, the high ICR could be achieved in the narrow salt concentration range only. Here, we propose a multi-layered bipolar ionic diode based on an asymmetric nanochannel network membrane (NCNM), which is realized by soft lithography and self-assembly of homogenous-sized nanoparticles. Owing to the freely changeable geometry based on soft lithography, the ICR performance can be explored according to the variation of microchannel shape. The presented diode with multi-layered configuration shows strong ICR performance, and in a broad range of salt concentrations (0.1 mM~100 mM), steady ICR performance. It is interesting to note that when each anion-selective (AS) and cation-selective (CS) NCNM volume was similar to each optimized volume in a single-layered device, the maximum ICR was obtained. Multi-physics simulation, which reveals greater ionic concentration at the bipolar diode junction under forward bias and less depletion under backward in comparison to the single-layer scenario, supports this tendency as well. Additionally, under different frequencies and salt concentrations, a large-area hysteresis loop emerges, which indicates fascinating potential for electroosmotic pumps, memristors, biosensors, etc.