Structures of Uncharacterised Polymorphs of Gallium Oxide from Total Neutron Diffraction

A structural investigation is reported of polymorphs of Ga₂O₃ that, despite much interest in their properties, have hitherto remained uncharacterised due to structural disorder. The most crystalline sample yet reported of γ‐Ga₂O₃ was prepared by solvothermal oxidation of gallium metal in ethanolamine. Structure refinement using the Rietveld method reveals γ‐Ga₂O₃ has a defect Fd$bar 3$ m spinel structure, while pair distribution function analysis shows that the short‐range structure is better modelled with local F$bar 4$ 3m symmetry. In further solvothermal oxidation reactions a novel gallium oxyhydroxide, Ga₅O₇(OH), is formed, the thermal decomposition of which reveals a new, transient gallium oxide polymorph, κ‐Ga₂O₃, before transformation into β‐Ga₂O_3. In contrast, the thermal decomposition of Ga(NO₃)₃?9 H₂O first forms ε‐Ga₂O₃ and then β‐Ga₂O₃. Examination of in situ thermodiffraction data shows that ε‐Ga₂O₃ is always contaminated with β‐Ga₂O₃ and with this knowledge a model for its structure was deduced and refined—space group P6₃mc with a ratio of tetrahedral/octahedral gallium of 2.2:1 in close‐packed oxide layers. Importantly, thermodiffraction provides no evidence for the existence of the speculated bixbyite structured δ‐Ga₂O₃; at the early stages of thermal decomposition of Ga(NO₃)₃?9 H₂O the first distinct phase formed is merely small particles of ε‐Ga₂O₃.