Electric Field Manipulation of Defects and Schottky Barrier Control inside ZnO Nanowires.

We directly measure the three-dimensional movement of intrinsic point defects driven by applied electric fields inside ZnO nano- and micro-wire metal-semiconductor-metal device structures. Using depth- and spatially resolved cathodoluminescence spectroscopy (CLS) in situ to map the spatial distributions of local defect densities with increasing applied bias, we drive the reversible conversion of metal-ZnO contacts from rectifying to Ohmic and back. These results demonstrate how defect movements systematically determine Ohmic and Schottky barriers to ZnO nano- and microwires and how they can account for the widely reported instability in nanowire transport. Exceeding a characteristic threshold voltage, in situ CLS reveals a current-induced thermal runaway that drives the radial diffusion of defects toward the nanowire free surface, causing VO defects to accumulate at the metal-semiconductor interfaces. In situ post- vs pre-breakdown CLS reveal micrometer-scale wire asperities, which X-ray photoelectron spectroscopy (XPS) finds to have highly oxygen-deficient surface layers that can be attributed to the migration of preexisting VO species. These findings show the importance of in-operando intrinsic point-defect migration during nanoscale electric field measurements in general. This work also demonstrates a novel method for ZnO nanowire refinement and processing.

Native Point Defect Measurement and Manipulation in ZnO Nanostructures.

This review presents recent research advances in measuring native point defects in ZnO nanostructures, establishing how these defects affect nanoscale electronic properties, and developing new techniques to manipulate these defects to control nano- and micro- wire electronic properties. From spatially-resolved cathodoluminescence spectroscopy, we now know that electrically-active native point defects are present inside, as well as at the surfaces of, ZnO and other semiconductor nanostructures. These defects within nanowires and at their metal interfaces can dominate electrical contact properties, yet they are sensitive to manipulation by chemical interactions, energy beams, as well as applied electrical fields. Non-uniform defect distributions are common among semiconductors, and their effects are magnified in semiconductor nanostructures so that their electronic effects are significant. The ability to measure native point defects directly on a nanoscale and manipulate their spatial distributions by multiple techniques presents exciting possibilities for future ZnO nanoscale electronics.