Ordering effect on the electrical properties of stoichiometric Ba$_{3}$CaNb$_{2}$O$_{9}$-based perovskite ceramics

TL;DR

This study investigates how B-site cation ordering affects the electrical properties of stoichiometric Ba₃CaNb₂O₉ ceramics, revealing that 1:1 order increases conductivity but does not fully explain the high performance of related non-stoichiometric proton conductors.

Contribution

It provides the first detailed analysis of the isolated effects of long-range B-site order on the electrical properties of stoichiometric Ba₃CaNb₂O₉ ceramics using Raman spectroscopy and phenomenological modeling.

Findings

1:1 order increases dc conductivity.

B-site order influences electrical relaxation behavior.

Long-range order effects differ from non-stoichiometric systems.

Abstract

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$_{9-\delta}$-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$_{9-\delta}$-based proton conductors.