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.