Unidirectional Current in Layered Metal Hexacyanometallate Thin Films: Implication for Alternative Wet-Processed Electronic Materials.

Rectifying behavior of alternative electronic materials is demonstrated with layered structures of a crystalline coordination network whose mixed ionic and electronic conductivity can be manipulated by switching the redox state of coordinated transition-metal ions. The coordinated transition-metal ions can convey additional functionality such as (redox)catalysis or electrochromism. In order to obtain rectifying behavior and charge trapping, layered films of such materials are explored. Specifically, layered films of iron hexacyanoruthenate (Fe-HCR) and nickel hexacyanoferrate (Ni-HCF) were formed by the combination of different deposition procedures. They comprise electrodeposition during voltammetric cycles for Fe-HCR and Ni-HCF, layer-by-layer deposition of Ni-HCF without redox chemistry, and drop casting of presynthesized Ni-HCF nanoparticles. The obtained materials were structurally characterized by X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy for nanoparticles, and scanning force microscopy (SFM). Voltammetry in 1 mol L -1 KCl and current-voltage curves ( I - V curves) recorded between a conductive SFM tip and the back electrode outside of an electrolyte solution demonstrated charge trapping and rectifying behavior based on the different formal potentials of the redox centers in the films.