Scalable Bulk Synthesis of Phase-Pure γ-Sn₃N₄ 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 N₂ 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-Sn₃N₄ was selected as the model compound. The synthesis of pure γ-Sn₃N₄ 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-Sn₃N₄ by metathesis reaction of argon-diluted SnCl₄ with Li₃N, Mg₃N₂ or Ca₃N₂ 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.