Electronic Control of Hot Electron Transport Using Modified Schottky Barriers in Metal–Semiconductor Nanodiodes

Hot electron flux, generated by both incident light energy and the heat of the catalytic reaction, is a major element for energy conversion at the surface. Controlling hot electron flux in a reversible manner is extremely important for achieving high energy conversion efficiency. Here we demonstrate that hot electron flux can be controlled by tuning the Schottky barrier height. This phenomenon was monitored by using a Schottky nanodiode composed of a metal-semiconductor. The formation of a Schottky barrier at a nanometer scale inevitably accompanies an intrinsic image potential between the metal-semiconductor junction, which lowers the effective Schottky barrier height. When a reverse bias is applied to the nanodiode, an additional image potential participates in a secondary barrier lowering, leading to the increased hot electron flow. Besides, a decrease of tunneling width results in facile electron transport through the barrier. The increased hot electron flux by the chemical reaction (chemicurrent) and by the photon absorption (photocurrent) indicates hot electrons are captured more effectively by modifying the Schottky barrier. This study can shed light on a quantitative understanding and application of charge behavior at metal-semiconductor interfaces, in solar energy conversion, or in a catalytic reaction.