Growth Mechanisms and Mechanical Response of 3D Superstructured Cubic and Hexagonal Hf$_{1-x}$Al$_x$N Thin Films

Transition metal aluminum nitrides are a technologically important class of multifunctional ceramics, however, the HfAlN system remains largely unexplored. We investigate phase stability, nanostructure design, and mechanical behavior of Hf$_{1-x}$Al$_x$N$_y$ thin films deposited on MgO(001) substrates using ion-assisted reactive magnetron sputtering. Compared to growth temperature and ion assistance, backscattered Ar neutrals are shown to have a dominant influence on the film structure. The Al-rich (x > 0.41) films form a nanocrystalline morphology consisting of Hf- and Al-rich nanodomains in a wurtzite-hexagonal(h) 0001 fiber-texture exhibiting about 22 GPa hardness, considerably higher than that of a binary AlN. For low Al contents, x < 0.30, surface-driven spinodal decomposition by energetic Ar neutrals during deposition in combination with quenching of sub-surface diffusion results in an unusual - and unique for nitrides - three-dimensional checkerboard superstructure of AlN- and HfN-rich nanodomains in the single-crystal rocksalt-cubic (c) phase. Lattice-resolved scanning transmission electron microscopy complemented with x-ray and electron diffraction reveals that the superstructure periodicity extends along <100> directions and the size increases linearly from 9 to 13 A with rising Al content. Consequently, the nanoindentation hardness increases sharply from 26 GPa for HfN$_y$, to \~38 GPa for c-Hf$_{1-x}$Al$_x$N$_y$, due to dislocation pinning at the superstructure strain fields. Micropillar compression of c-Hf$_{0.93}$Al$_{0.07}$N$_{1.15}$ shows a considerably higher yield stress compared to HfN$_y$ and controlled brittle fracture occurs via {110}<011> slip systems, attributed to superstructure inhibited dislocation motion. In contrast, nanocrystalline h-Hf$_{0.59}$Al$_{0.41}$N$_{1.23}$ exhibits a high yield stress and limited plasticity before strain burst failure.