Structures, phase transitions and microwave dielectric properties of the 6H perovskites Ba3BSb2O9, B=Mg, Ca, Sr, Ba

We present a complete temperature-composition phase diagram for Ba3BSb2O9, B=Mg, Ca, Sr, Ba, along with their electrical behavior as a function of B. These compounds have long been recognized as 6H-type perovskites, but (with the exception of B=Mg) their exact structures and properties were unknown due to their low symmetries, temperature-dependent phase transitions, and difficulties in synthesizing pure samples. The full range of possible space group symmetries is observed, from ideal hexagonal P63/mmc to monoclinic C2/c   to triclinic P1¯. Direct second-order transitions between these phases are plausible according to group theory, and no evidence was seen for any further intermediate phases. The phase diagram with respect to temperature and the effective ionic radius of B is remarkably symmetrical for B=Mg, Ca, and Sr. For B=Ba, a first-order phase transition to a locally distorted phase allows a metastable hexagonal phase to persist to lower temperatures than expected before decomposing around 600 K. Electrical measurements revealed that dielectric permittivity corrected for porosity does not change significantly as a function of B and is in a good agreement with the values predicted by the Clausius–Mossotti equation.

Graphical abstractThermodynamic phase diagram for Ba3BSb2O9, B=Mg, Ca, and Sr, as a function of temperature T and effective ionic radius (IR) of the B2+ cation.Figure optionsDownload full-size imageDownload as PowerPoint slide