Microstructural evolution and thermal stability of HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN metal/semiconductor superlattices

Nitride-based metal/semiconductor superlattices for possible applications as thermoelectric, plasmonic, and hard coating materials have been grown by magnetron sputtering. Since long-time thermal stability of the superlattices is crucial for these applications, the atomic scale microstructure and its evolution under annealing to working temperatures were investigated with high-resolution transmission electron microscopy methods. We report on epitaxial growth of three cubic superlattice systems (HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN) that show long-time thermal stability (annealing up to 120 h at 950 °C) as monitored by scanning transmission electron microscopy-based energy-dispersive X-ray spectroscopy. No interdiffusion between the metal and semiconductor layers could be observed for any of the present systems under long-time annealing, which is in contrast to earlier attempts on similar superlattice structures based on TiN as the metallic compound. Atomically resolved high-resolution transmission electron microscopy imaging revealed that even though the superlattice curves towards the substrate at regular interval column boundaries originating from threading dislocations close to the substrate interface, the cubic lattice continues coherently across the boundaries. It is found that the boundaries themselves are alloyed along the entire growth direction, while in their vicinity nanometer-size inclusions of metallic phases are observed that could be identified as the zinc blende phase of same stoichiometry as the parent rock salt transition metal nitride phase. Our results demonstrate the long-time thermal stability of metal/semiconductor superlattices based on Zr and Hf nitrides.