Elucidation of the reaction mechanism for the synthesis of ZnGeN(2) through Zn(2)GeO(4) ammonolysis

Ternary II–IV–N(2) materials have been considered as a promising class of materials that combine photovoltaic performance with earth-abundance and low toxicity. When switching from binary III–V materials to ternary II–IV–N(2) materials, further structural complexity is added to the system that may influence its optoelectronic properties. Herein, we present a systematic study of the reaction of Zn(2)GeO(4) with NH(3) that produces zinc germanium oxide nitrides, and ultimately approach stoichiometric ZnGeN(2), using a combination of chemical analyses, X-ray powder diffraction and DFT calculations. Elucidating the reaction mechanism as being dominated by Zn and O extrusion at the later reaction stages, we give an insight into studying structure–property relationships in this emerging class of materials.