<i>In Situ</i> Chemical Modification of Schottky Barrier in Solution-Processed Zinc Tin Oxide Diode

Here we present a novel <i>in situ</i> chemical modification process to form vertical Schottky diodes using palladium (Pd) rectifying bottom contacts, amorphous zinc tin oxide (Zn–Sn–O) semiconductor made via acetate-based solution process, and molybdenum top ohmic contacts. Using X-ray photoelectron spectroscopy depth profiling, we show that oxygen plasma treatment of Pd creates a PdO_<i>x</i> interface layer, which is then reduced back to metallic Pd by <i>in situ</i> reactions during Zn–Sn–O film annealing. The plasma treatment ensures an oxygen-rich environment in the semiconductor near the Schottky barrier, reducing the level of oxygen-deficiency-related defects and improving the rectifying contact. Using this process, we achieve diodes with high forward current density exceeding 10³A cm^–2 at 1 V, rectification ratios of >10², and ideality factors of around 1.9. The measured diode current–voltage characteristics are compared to numerical simulations of thermionic field emission with sub-bandgap states in the semiconductor, which we attribute to spatial variations in metal stoichiometry of amorphous Zn–Sn–O. To the best of our knowledge, this is the first demonstration of vertical Schottky diodes using solution-processed amorphous metal oxide semiconductor. Furthermore, the <i>in situ</i> chemical modification method developed here can be adapted to tune interface properties in many other oxide devices