Triplet grain growth in a-texture polycrystalline ZnO thin films

A growth of grain triplets is identified in vapor deposited, a-texture polycrystalline zinc oxide thin films, using a combination of transmission electron microscopy-based automated crystal orientation mapping and high-resolution imaging. Each triplet consists of three wurtzite phase grains, coordinated to near tetrahedral relative growth angles by the close-packed planes of a few nanometer diameter core of metastable zinc blende phase ZnO located at their triple junction. The triplets are aligned such that two of the grains have their fast growing axes (near-) parallel to the substrate normal, and so coarsen under the principle of competitive grain growth. In contrast, growth of the third grain with a texture is impeded, such that it forms a small wedge between the ends of its two larger neighbors. Remarkably, all three boundaries between the grains adhere to a coherent twin orientation relationship, which corresponds to a grain geometry that is incommensurate with a perfect crystallographic nature. This coherency is primarily achieved via the small grain having an orientation that rotates internally by 10±2° across its volume, when going between the two interfaces formed with the neighboring large grains. The energy associated with this structural distortion is compensated by the formation of the coherent twin boundaries, such that the triplets are a stable or semi-stable growth form that are abundant in the film. The small texture grains may renucleate persistently, taking either of two possible orientations from the underlying tetrahedral coordination. By developing a phenomenological model for the triplet geometry and form, we associate these two orientations to small hexagonal caps and angled wedges seen in the surface morphology of the film. These findings potentially carry relevance for a wide range of vapor deposited compact films and free-standing nanostructures of wurtzite phase octet binary semiconductor compounds. We therefore believe that these insights can stimulate new research, for instance to obtain a more fundamental understanding of the growth mechanisms at the atomistic level.