Ternary nitrides are of growing technological importance, with applications as semiconductors, catalysts, and magnetic materials; however, new synthetic tools are needed to advance materials discovery efforts. Here, we show that Zn3WN4 can be synthesized via metathesis reactions between Li6WN4 and ZnX2 (X = Br, Cl, F). In situ synchrotron powder X-ray diffraction and differential scanning calorimetry show that the reaction onset is correlated with the ZnX2 melting point and that product purity is inversely correlated with the reaction's exothermicity. High resolution synchrotron powder X-ray diffraction measurements show that this bulk synthesis produces a structure with substantial cation ordering, as opposed to the disordered structure initially discovered via thin film sputtering. Diffuse reflectance spectroscopy reveals that Zn3WN4 powders exhibit two optical absorption onsets at 2.5 eV and 4.0 eV, indicating wide-bandgap semiconducting behavior and suggesting a small amount of structural disorder. We hypothesize that this synthesis strategy is generalizable because many potential Li-M-N precursors (where M is a metal) are available for synthesizing new ternary nitride materials. This work introduces a promising synthesis strategy that will accelerate the discovery of novel functional ternary nitrides and other currently inaccessible materials.
@article{arxiv.2401.01964,
title = {Bulk synthesis of Zn$_3$WN$_4$ via solid-state metathesis},
author = {Christopher L. Rom and Shaun O'Donnell and Kayla Huang and Ryan A. Klein and Morgan J. Kramer and Rebecca W. Smaha and Andriy Zakutayev},
journal= {arXiv preprint arXiv:2401.01964},
year = {2024}
}