Synthesis of Zn₂NbN₃ternary nitride semiconductor with wurtzite-derived crystal structure

Binary III-N nitride semiconductors with wurtzite crystal structure such as GaN and AlN have been long used in many practical applications ranging from optoelectronics to telecommunication. The structurally related ZnGeN₂or ZnSnN₂derived from the parent binary compounds by cation mutation (elemental substitution) have recently attracted attention, but such ternary nitride materials are mostly limited to II-IV-N₂compositions. This paper demonstrates synthesis and characterization of zinc niobium nitride (Zn₂NbN₃)-a previously unreported II₂-V-N₃ternary nitride semiconductor. The Zn₂NbN₃thin films are synthesized using a one-step adsorption-controlled growth that locks in the targeted stoichiometry, and a two-step deposition/annealing method that suppresses the loss of Zn and N. Measurements indicate that this sputtered Zn₂NbN₃crystalizes in cation-disordered wurtzite-derived structure, in contrast to chemically related rocksalt-derived Mg₂NbN₃compound, also synthesized here for comparison using the two-step method. The estimated wurtzite lattice parameter ratio of Zn₂NbN₃is 1.55, and the optical absorption onset is at 2.1 eV. Both of these values are lower compared to published Zn₂NbN₃computational values ofc/a= 1.62 andE_g= 3.5-3.6 eV. Additional theoretical calculations indicate that this difference is due to cation disorder in experimental samples, suggesting a way to tune the structural parameters and the resulting properties of heterovalent ternary nitride materials. Overall, this work expands the wurtzite family of nitride semiconductors to include Zn₂NbN₃, and suggests that related II₂-V-N₃and other ternary nitrides should be possible to synthesize.