New types of diodes, such as molecular and ionic diodes, have drawn considerable attention because of their advantages from the viewpoint of potential applications such as the downscaling of electronic devices, ionic circuits, and biological systems. Researchers are motivated to develop a simple, scalable, and promising system that can overcome the existing limitations because this can enable their application in various devices. This study proposes a system that not only integrates the advantages of ionic and single-molecule diodes but also avoids their disadvantages, denoting the rectification behavior due to ionic charge-selective electron transfer between two redox species, i.e., Fe(CN)63- and Ru(NH3)63+, on the polyelectrolyte multilayer (PEM)-modified flexible indium tin oxide (ITO) electrodes. Flexible current rectification devices were easily prepared by sandwiching an electrolytic solution of ionic redox species using bare and PEM-modified plastic ITO electrodes. An ionic bilayer was initially formed via Coulombic interactions on a PEM-modified charge-selective ITO surface. The ionic bilayer was analogous to a conventional single-molecule diode's monolayer with consecutive molecular orbitals of two ionic redox species. Furthermore, the rectification ratio (RR) was increased from ∼6 to ∼10 using a conducting polymer to construct PEMs.
Keywords: charge-selective electrode; current rectification; direct electron transfer; flexible; ionic redox species.