Chemical Substitution-Induced and Competitive Formation of 6H and 3C Perovskite Structures in Ba3–xSrxZnSb2O9: The Coexistence of Two Perovskites in 0.3 ≤ x≤ 1.0

6H and 3C perovskites are important prototype structures in materials science. We systemically studied the structural evolution induced by the Sr2+-to-Ba2+substitution to the parent 6H perovskite Ba3ZnSb2O9. The 6H perovskite is only stable in the narrow range of x≤ 0.2, which attributes to the impressibility of [Sb2O9]. The preference of 90° Sb–O–Sb connection and the strong Sb5+-Sb5+electrostatic repulsion in [Sb2O9] are competitive factors to stabilize or destabilize the 6H structure when chemical pressure was introduced by Sr2+incorporation. Therefore, in the following, a wide two-phase region containing 1:2 ordered 6H–Ba2.8Sr0.2ZnSb2O9and rock-salt ordered 3C–Ba2SrZnSb2O9was observed (0.3 ≤ x≤ 1.0). In the final, the successive symmetry descending was established from cubic (Fm3̅m, 1.3 ≤ x≤ 1.8) to tetragonal (I4/m, 2.0 ≤ x≤ 2.4), and finally to monoclinic (I2/m, 2.6 ≤ x≤ 3.0). Here we proved that the electronic configurations of B-site cations, with either empty, partially, or fully filled d-shell, would also affect the structure stabilization, through the orientation preference of the B–O covalent bonding. Our investigation gives a deeper understanding of the factors to the competitive formation of perovskite structures, facilitating the fine manipulation on their physical properties.