Vapor–liquid–solid synthesis of ZnSnN2

Abstract

A series of experiments was carried out to explore the conditions under which ZnSnN2 would form by vapor–liquid–solid synthesis from a Zn–Sn melt exposed to a nitrogen plasma. ZnSnN2 precipitated at melt temperatures between 455 and 560 °C for melt compositions between 1.5 and 15 at.% Zn. Sn3N4 formed for temperatures between 440 and 560 °C for melt compositions below 1 at.% Zn. Zn3N2 apparently grew only in the vapor phase, and only at melt temperatures between 409 and 463 °C. Each of the materials was identified by its characteristic Raman spectrum and by Auger chemical analysis. The composition profiles of the melts were modeled as a function of time using the measured temperature profiles. The results were compared with post‐growth measurements of the melt compositions. These comparisons support the visual observation that exposure of the melt to the nitrogen plasma suppressed Zn evaporation substantially even prior to the formation of a solid crust of precipitate. This work helps define the range of growth conditions available for synthesis of ZnSnN2 by this vapor–liquid–solid method.Material yielded as a function of synthesis temperature and the composition of the melt, measured post‐synthesis by EDS. The two ZnSnN2 samples labeled with asterisks were grown with a plasma power of 60 W. All others were grown using a plasma power of 240 W.