Synthetic nanofluidic diodes with highly nonlinear current-voltage characteristics are currently of particular interest because of their potential applications in biosensing, separation, energy harvesting, and nanofluidic electronics. We report the ionic current rectification (ICR) characteristics of a porous anodic aluminum oxide membrane, whose one end of the nanochannels is closed by a barrier oxide layer. The membrane exhibits intriguing pH-dependent ion transport characteristics, which cannot be explained by the conventional surface charge governed ionic transport mechanism. We reveal experimentally and theoretically that the space charge density gradient present across the 40-nm-thick barrier oxide is mainly responsible for the evolution of ICR. Based on our findings, we demonstrate the formation of a single 5-8-nm-sized pore in each hexagonal cell of the barrier oxide. The present work would provide valuable information for the design and fabrication of future ultrathin nanofluidic devices without being limited by the engineering of the nanochannel geometry or surface charge.
Keywords: anodization; barrier oxide layer; electroporation; ionic current rectification (ICR); porous anodic aluminum oxide (AAO).