In‐Situ Gas Permeation‐Driven Ionic Current Rectification of Heterogeneously Charged Nanopore Arrays

Abstract Ionic diodes provide ionic current rectification (ICR), which is useful for micro‐/nanofluidic devices for ionic current‐mediated applications. However, the modulation of ICR is not fully developed, and current challenges include limited active control and localized modulation for further multiplexing of micro‐/nanofluidic ionic diodes. Herein, a microfluidic device integrated with particle‐assembly‐based ionic diodes (PAIDs) and a gas‐flow channel above them is presented. Exploiting in‐situ gas permeation through a polymeric film, precise control over the physiochemical conditions of the nanopores within the PAIDs, leading to the modulation of ICR is demonstrated. The investigation not only characterizes the rectification properties of the PAIDs but also unveils their capacitor‐like behavior and the ability to actively modulate ICR using various gas flows. Furthermore, the reversible modulation of ICR through dynamic switching of gas‐dissolved solutions, enabling ion‐signal amplification is showcased. This pioneering approach of in situ gas‐permeation offers programmable manipulation of ion transport along PAIDs, thereby positioning ionic diodes as versatile nanofluidic components. Looking ahead, the development of multiplexed PAIDs in an addressable manner on a chip holds promise for practical applications across diverse fields, including ion signaling, ion‐based logic, chemical reactors, and (bio)chemical sensing.