COMPLEX TRANSITIONS IN CATION DEFICIENT PEROVSKITES

Crystal Structures and Phase Transitions in A-Site Deficient Perovskites Ln1/3TaO3
Q D Zhou, P J Saines, N Sharma, J Ting, B J Kennedy, Z M Zhang, R L Withers and K S Wallwork
Chem Mater 20, 6666-6676 (2008)

The synthesis and structures of the perovskites Ln1/3TaO3 are described. As the size of the Ln cation is reduced, the compounds display a sequence of structure: P4/mmm/La → Cmmm/Ce−Gd → Pmma/Tb, Dy → Pmc21/Ho, Er. Although apparently tetragonal in P4/mmm, electron diffraction patterns of Tm1/3TaO3 reveal this has a complex incommensurate structure. Likewise Gd1/3TaO3 appears metrically tetragonal, but electron diffraction and synchrotron X-ray powder diffraction demonstrate this is actually orthorhombic. The suppression of the spontaneous orthorhombic strain in Gd1/3TaO3 is thought to be due to the proximity to the first-order Cmmm−Pmma transition. Variable temperature studies show both Tb1/3TaO3 and Dy1/3TaO3 undergo a first-order Cmmm−Pmma transition upon heating.

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