Real time observation of ZnO nanostructure formation via the solid-vapor and solid-solid-vapor mechanisms

We report in situ transmission electron microscopy studies of the formation of ZnO nanostructures--nanoscale depressions, nanoholes, nanoribbons, and nanosheets--and the phase stability and kinetics of Au catalysts on ZnO. During annealing, the ZnO layer produces hexagonally shaped, vertical nanoscale depressions, which increase in size along the 〈 0001 〉 growth direction through preferential dissociation from the {101[combining macron]0} facet and which subsequently form hexagonal islands at their six-fold junctions. Real time observations of the annealing of Au deposited on ZnO show that the catalysts remain solid up to 900 °C, an observation that has implications regarding ZnO nanowire growth via the vapor-solid-solid mechanism (VSS). The Au also creates hexagonal nanoscale holes only at the location of solid Au catalysts, via the solid-solid-vapor (SSV) mechanism. Importantly, coarsening of the Au particles is negligible due to limited Au diffusion on the side facets of the nanoscale depressions, suggesting an approach to the growth of uniform hybrid nanowires with control over both diameter and location. Furthermore, we directly monitor the evolution of the transformation of a nanoribbon into a nanosheet with {101[combining macron]0} facets. This process takes place through a periodic, kinetic roughening transition of the surface, which is controlled by the kinetic competition between surface growth and the transfer of evaporated gases. In total, these observations give new insights into multiple growth processes occurring in this important materials system.