Metal-like ductility and high hardness in nitrogen-rich HfN thin films by point defect superstructuring

The strength of refractory ceramics is much limited by their brittleness. Counterintuitively, we observe simultaneous high hardness and metallic-like ductility in highly overstoichiometric single-crystal HfN 1.22 and HfN 1.33 films grown by ion-assisted reactive magnetron sputtering. Here, we show by electron microscopy, diffraction methods, and ab-initio calculations the existence of a superstructure ordering of metal vacancies and nitrogen interstitials into sub-nanometer hyper-overstoichiometric and quasi-stoichiometric domains that self-organize into a checkerboard pattern superimposed onto the NaCl-structured lattice. A high intrinsic dislocation density and low dislocation nucleation barrier on {111} < 011> slip systems enable extraordinary ductility and strain hardening at >50% strain, in room temperature uniaxial compression of HfN 1.22 micropillars. The films simultaneously exhibit a high hardness – tunable up to 28 GPa via control of stoichiometry – and a remarkable fracture resistance due to dislocation-mediated stress dissipation. The presented findings provide a route for synthesizing nitride superstructured films with unique hardness/toughness combinations.