Ordering effect on the electrical properties of stoichiometric Ba3CaNb2O9-based perovskite ceramics

Cation ordering is most common process detected in A$₃$B'B"$₂$O$₉$-based complex perovskites. Some important physical features of this system are due to the B-site ordering at long and short range. For microwave applications as filters and resonators, the 1:2 order is more appropriate. Otherwise, the oxygen vacancies and 1:1 order are considered the main factors behind the good performance of nonstoichiometric A$₃$B'$_1+x$B"$_2-x$O$_9-δ$-based ceramics as proton conductors. Until now, however, there are no available reports regarding the isolated effects of B-site order at long range on the electrical properties of stoichiometric systems. This work reports the preparation of 1:1 and 1:2 fully-ordered Ba$₃$CaNb$₂$O$₉$ ceramics. Here, we combine the Raman scattering and group-theory calculations to distinguish the fingerprints of the 1:1 and 1:2 orders. The electric properties of the ordered Ba$₃$CaNb$₂$O$₉$ are analyzed in terms of a phenomenological model based on a parallel combination of a resistor, constant phase element, and capacitor. In particular, the conductivity relaxation ascribed to the grain is due to the oxygen vacancies. Besides, we found that the 1:1 order increases the dc conductivity, but not enough to account the good performance reported for the non-stoichiometric Ba$₃$Ca$_1+x$Nb$_2-x$O$_9-δ$-based proton conductors.