Scalable Bulk Synthesis of Phase-Pure γ-SnN as a Model for an Argon-Flow-Mediated Metathesis Reaction.

Nitrides represent a promising class of materials for a variety of applications. However, bulk synthesis remains a challenging task due to the stability of the N molecule. In this study, we introduce a simple and scalable approach for synthesizing nitride bulk materials. Moderate reaction temperatures are achieved by using reactive starting materials, slow and continuous mixing of the starting materials, and by dissipating heat generated during the reaction. The impact on the synthesis of using different starting materials as nitrogen source and the influence of a flux were examined. γ-SnN was selected as the model compound. The synthesis of pure γ-SnN bulk material on a large scale has still been a challenge, although a few synthesis methods were already described in the literature. Here we synthesized γ-SnN by metathesis reaction of argon-diluted SnCl with LiN, MgN or CaN as nitrogen sources. Products were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, dynamic flash combustion analysis, hot gas extraction analysis, X-ray photoelectron spectroscopy, Mössbauer spectroscopy and X-ray absorption and emission spectroscopy. Additionally, single-crystal diffraction data of γ-Sn₃N₄, previously unavailable, were successfully collected.