High-pressure annealing of a prestructured nanocrystalline precursor to obtain tetragonal and orthorhombic polymorphs of Hf3N4

Transition metal nitrides containing metal ions in high oxidation states are a significant goal for the discovery of new families of semiconducting materials. Most metal nitride compounds prepared at high temperature and high pressure from the elements have metallic bonding. However amorphous or nanocrystalline compounds can be prepared via metal-organic chemistry routes giving rise to precursors with a high nitrogen:metal ratio. Using X-ray diffraction in parallel with high pressure laser heating in the diamond anvil cell this work highlights the possibility of retaining the composition and structure of a metastable nanocrystalline precursor under high pressure-temperature conditions. Specifically, a nanocrystalline Hf3N4 with a tetragonal defect-fluorite structure can be crystallized under high-P,T conditions. Increasing the pressure and temperature of crystallization leads to the formation of a fully recoverable orthorhombic (defect cottunite-structured) polymorph. This approach identifies a novel class of pathways to the synthesis of new crystalline nitrogen-rich transition metal nitrides