Order–Disorder Transition Involving the A-Site Cations in Ln3+Mn3V4O12 Perovskites

Abstract

A crossover from the A-site-ordered double-perovskite structure with Im3̅ cubic symmetry to the simple-perovskite structure with Pnma orthorhombic symmetry is found in LnMn3V4O12 (Ln = La, Nd, Gd, Y, Lu) synthesized under high-pressure conditions. Relatively large Ln(3+) ions (La(3+), Nd(3+), and Gd(3+)) induce the a(+)a(+)a(+) in-phase cooperative tilting of the VO6 octahedra, resulting in the A-site-ordered double-perovskite structure with chemical composition Ln(3+)Mn(2+)3V(3.75+)4O12. Compounds with small Ln(3+) ions like Y(3+) and Lu(3+), on the other hand, crystallize with the Pnma simple-perovskite structure with chemical composition (Ln(3+)1/4Mn(2+)3/4)V(3.75+)O3, where the Ln(3+) and Mn(2+) ions are disordered at the A site. The random distribution of the small A-site cation induces the a(-)b(+)a(-) tilting distortion of the VO6 octahedra. The observed phase crossover is well explained by the structural stability calculation based on the bond-valence-sum model, and the most stable crystal structure gives the smallest unit-cell volume. This A-site-cation size-dependent phase transition between the A-site-ordered double-perovskite and A-site-disordered simple-perovskite structures in LnMn3V4O12 is thus a result of the structural stability due to the cooperative tilting of the VO6 octahedra. The Mn(2+) ions at the A'(A) site contribute local magnetic moments, whereas the V(3.75+) ions at the B site play a role in metallic conduction. The observed magnetic behaviors are consistent with the order-disorder distribution of the Mn(2+) ions at the A site, antiferromagnetism in the A-site-ordered double perovskites, and magnetic spin glass in the A-site-disordered simple perovskites.