The impact of anion ordering on octahedra distortion and phase transitions in SrTaO2N and BaTaO2N

In this work we synthesized BaTaO 2 N and SrTaO 2 N using a two-step high-temperature solid-state reaction method and analysed the structural distortions, relative to the ideal cubic perovskite structure, according to group theory. From a complete distortion analysis/refinement using high-resolution neutron diffraction data in the temperature range 8 to 613 K, we identified tetragonal structures for BaTaO 2 N [ P 4/ mmm (No. 123)] and SrTaO 2 N [ I 4/ mcm (No. 140)]. In contrast to an anion-disordered cubic perovskite (Pm \overline{3}m No. 221) with Ta at the cell center, both systems show a site preference for oxygen anions in the two opposite corners (along the c axis) of the Ta–O/N octahedra rather than the four square corners in the ab plane ( Γ 3 + occupancy distortion), which induces a tetragonal elongation of the unit cell with the c axis being longer than the a axis. A further Ta–O/N octahedra displacement [ R 5 − ( a ,0,0), rotation about the c axis] distortion was observed in SrTaO 2 N. This distortion mode is accompanied by an increased unit-cell distortion that decreases as the temperature increases. Ultimately a second-order phase transition caused by the loss of the R 5 − ( a ,0,0) mode was observed at 400–450 K.