Combinatorial Synthesis of Magnesium Tin Nitride Semiconductors

Nitride materials feature strong chemical bonding character that leads to unique crystal structures, but many ternary nitride chemical spaces remain experimentally unexplored. The search for previously undiscovered ternary nitrides is also an opportunity to explore unique materials properties, such as transitions between cation-ordered and -disordered structures, as well as to identify candidate materials for optoelectronic applications. Here, we present a comprehensive experimental study of MgSnN₂, an emerging II–IV–N₂ compound, for the first time mapping phase composition and crystal structure, and examining its optoelectronic properties computationally and experimentally. We demonstrate combinatorial cosputtering of cation-disordered, wurtzite-type MgSnN₂ across a range of cation compositions and temperatures, as well as the unexpected formation of a secondary, rocksalt-type phase of MgSnN₂ at Mg-rich compositions and low temperatures. A computational structure search shows that the rocksalt-type phase is substantially metastable (>70 meV/atom) compared to the wurtzite-type ground state. Spectroscopic ellipsometry reveals optical absorption onsets around 2 eV, consistent with band gap tuning via cation disorder. Finally, we demonstrate epitaxial growth of a mixed wurtzite-rocksalt MgSnN₂ on GaN, highlighting an opportunity for polymorphic control via epitaxy. Collectively, these findings lay the groundwork for further exploration of MgSnN₂ as a model ternary nitride, with controlled polymorphism, and for device applications, enabled by control of optoelectronic properties via cation ordering.