Effect of Ordering‐Induced Domain Boundaries on Low‐Loss Ba(Zn 1/3 Ta 2/3 )O 3 ‐BaZrO 3 Perovskite Microwave Dielectrics

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Abstract
Small substitutions of BaZrO 3 into Ba[(Zn,Ni) 1/3 Ta 2/3 ]O 3 are utilized in the commercial preparation of low‐loss perovskite microwave dielectrics. The structures of a series of these phases with substitution levels ranging from 1% to 5% BaZrO 3 were examined using high‐resolution TEM. For ≤ 2.15% BaZrO 3 the solid solutions retain the ordered “1:2” structure of the Ba[(Zn,Ni) 1/3 Ta 2/3 ]O 3 end‐member but are comprised of small ordered domains whose size decreases as the Zr content is raised. The decrease in the size of the domains parallels a decrease in the processing time required to access a low‐loss state. Although for pure Ba[(Zn,Ni) 1/3 Ta 2/3 ]O 3 reductions in the degree of cation order produce a large increase in the dielectric loss, the Zr‐substituted ceramics retain a very low loss. We believe the low losses of the 1:2 ceramics are derived from the stabilization of the ordering‐induced domain boundaries via the partial segregation of the Zr cations. For substitutions between 3% and 5% BaZrO 3 the size of the ordered domains continues to decrease but the system undergoes an abrupt transformation to a cubic “1:1” ordered structure with a doubled perovskite repeat. The structures of these phases have been interpreted using a “random layer” model in which one site is occupied by Ta and the other by a random distribution of Zn, Zr, and the remaining Ta cations, i.e., Ba{[Zn (2‐ y )/3 Ta (1–2 y )/3 Zr y ] 1/2 [Ta 1/2 ]}O 3 . Although the ordering is confined to nano‐sized domains, these ceramics also exhibit low losses, again reflecting the relative stability of the domain boundaries. In this case we believe the low losses reflect the effectiveness of the random layer in stabilizing the anti‐phase boundaries.

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