Inorganic Chemistry, Vol.58, No.21, 14389-14402, 2019
Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides
Cation ordering/disordering in spinel oxides plays an essential role in the rich physical and chemical properties which are hallmarks of the structural archetype. A variety of cation -ordering motifs have been reported for spinel oxides with multiple cations residing on the octahedral site (or B-site). This has attracted tremendous attention from both experimental and theoretical communities in the last few decades. However, no unified view has been reached, presumably due to the richness of cation species and corresponding complex arrangements emergent in this large family of compounds. In this report, local cation-ordered ground states of (inverse) spinel oxides with two different cations on the octahedral site have been thoroughly investigated using neutron and X-ray total scattering, and a comprehensive theory has been proposed to explain the commonly observed cation-ordered polymorphs. It is found that a cationzigzag-ordered structure (space group P4,22) is the ground state for inverse spinel oxides with a pure or strong ionic lattice, while a cation-linear-ordered arrangement (space group Imma) emerges when one of the B-site cations forms very strong directional covalent bonds with lattice oxygen. The degree and length scale of cation ordering is strongly correlated with the charge and ionic radius difference between the two octahedral site cations. More complicated cation ordering schemes can be formed when there is a concomitant charge and orbital ordering which fall on a similar energy scale. This can lead to the formation of orbital-driven cation clusters or the broad concept of "molecules" in solid-state compounds. It is expected these findings will help to better understand the observed physical properties of spinel oxides and thus facilitate design strategies for improved functional materials.