Tuning Optoelectrical Properties of ZnO Nanorods with Excitonic Defects via Submerged Illumination

When applied in optoelectronic devices, a ZnO semiconductor dominantly absorbs or emits ultraviolet light because of its direct electron transition through a wide energy bandgap. On the contrary, crystal defects and nanostructure morphology are the chief key factors for indirect, interband transitions of ZnO optoelectronic devices in the visible light range. By ultraviolet illumination in ultrapure water, we demonstrate here a conceptually unique approach to tune the shape of ZnO nanorods from tapered to capped-end via apical surface morphology control. We show that oxygen vacancy point defects activated by excitonic effects near the tip-edge of a nanorod serve as an optoelectrical hotspot for the light-driven formation and tunability of the optoelectrical properties. A double increase of electron energy absorption on near band edge energy of ZnO was observed near the tip-edge of the tapered nanorod. The optoelectrical hotspot explanation rivals that of conventional electrostatics, impurity control, and alkaline pH control-associated mechanisms. Thus, it highlights a new perspective to understanding light-driven nanorod formation in pure neutral water.