Periodic antiphase boundary spinel-based structures in aluminates, gallates, aluminium oxynitrides and transition aluminas

Abstract

The crystallographic structures of several transition aluminas possessing a face-centred cubic packing of oxygen anions can be considered as deriving from that of a non-stoichiometric spinel. However, they are not yet known in detail owing to the poor crystallinity of most of the samples studied by X-ray or electron diffraction. Conversely, relatively large crystals have been produced in the case of non-stoichiometric spinels in the alumina-rich (or Ga2O3-rich) parts of the Al2O3–AlN, Al2O3–MgO, Al2O3–NiO, Al2O3–Li2O and Ga2O3–MgO systems. Detailed studies of their diffraction patterns have shown that all these phases possess periodic antiphase boundary (PAPB) structures based on the spinel structure. In the case of the so-called δ-transition aluminas, various structural models have been previously proposed and in this paper we are focusing on the striking similarities between their diffraction patterns and those of several metastable PAPB aluminate structures. This makes it possible to show that at least three distinct PAPB structures must be taken into account in the case of δ-transition aluminas. APB planes are either {100} or {110} whereas APB vectors are either 1/2 ⟨001⟩ or 1/4 ⟨110⟩ when referring to the spinel structure. Neighbouring octahedral and tetrahedral incompatible sites are observed in the vicinity of each APB and cation vacancies are shown to occupy these octahedral sites.