Influence of Non-Stoichiometry on the Structure and Properties of Ba(Zn1/3Nb2/3)O3 Microwave Dielectrics: II. Compositional Variations in Pure BZN

The formation of non-stoichiometric cubic perovskite solid solutions based on BaZn_1/3Nb_2/3O₃ (BZN) was examined along 10 different directions in the BaO–ZnO–Nb₂O₅ ternary system. Limited ranges of non-stoichiometry were observed along several pseudo-binaries and the BZN structure can accommodate a variety of different types of defects. Although the deviations from stoichiometry are quite small, typically ～1 mole%, they induce large changes in the extent and stability of the 1:2 B-site ordering, the sintering and microstructure, and the dielectric loss properties. The highest Q × f s (～110 000 at 8 GHz) in the system, which coincide with the highest degree of order, were located in two regions along the BZN–Ba₅Nb₄O₁₅ and BZN–BaNb₂O₆ lines. The results of this study provide an explanation for the large variations in crystal structure and Q × f s previously reported for BZN and other related systems (e.g., Ba(Zn_1/3Ta_2/3)O₃), and demonstrate that non-stoichiometric starting compositions provide a route to the highest Q values.