Synthesis and properties of bulk Mg$_3$WN$_4$ in a wurtzite-derived structure

Abstract

Experimental synthesis of theoretically predicted materials with controlled elemental coordination environments can lead to realization of useful properties, such as facile ion transport or ferroelectric switching. Among such materials are new ternary nitrides in the Mg-W-N composition space, where several new stable and metastable compounds have been predicted and synthesized recently in bulk and film forms. Here, we report for the first time on the bulk synthesis of Mg$_3$WN$_4$ in a wurtzite-derived crystal structure via a solid state metathesis reaction. $In$ $situ$ synchrotron powder X-ray diffraction shows how the ion exchange proceeds from Li$_6$WN$_4$ + 3 MgCl$_2$ precursors to Mg$_3$WN$_4$ + 6 LiCl products, with the reaction starting slowly near 380 $^\circ$C and completing by 600 $^\circ$C, including the presence of a competing disordered rocksalt-derived phase (Mg,W)N above 440 $^\circ$C. The follow up $ex$ $situ$ powder synthesis at 400 $^\circ$C for 0.5 hour with 10% excess MgCl$_2$ reveals the cation-ordered nature of the wurtzite-derived Mg$_3$WN$_4$ structure with polar symmetry confirmed by second harmonic generation measurements. Optical absorption spectra, chemical composition analysis, and electron microscopy imaging suggests that bulk wurtzite Mg$_3$WN$_4$ is prone to defect formation. Overall, this study shows that selective $ex$ $situ$ synthesis of the phase pure ternary nitrides, informed by \textit{in situ} measurements, is possible by carefully controlling the thermal budget of the reaction, and paves a way towards property characterization of wurtzite Mg$_3$WN$_4$.