Design of Magnetic Polar Double-Double Perovskite Oxides through Cation Ordering

Commencing from the centrosymmetric MnRMnSbO₆ compound, we explore the realm of magnetic polar double-double perovskite oxides characterized by significant ferroelectric polarization. Employing symmetry operations, first-principles methodologies, and Monte Carlo simulations, our investigation delves into the structural, magnetic, ferroelectric, and electronic attributes of the polar LaFeMnNiO₆ and LaTiMnNiO₆ compounds. The structural analysis uncovers that the paraelectric-ferroelectric phase transition is intricately linked to the Fe/Ti-displacement of square planar Fe/TiO₄. Notably, the magnetic LaFeMnNiO₆ and LaTiMnNiO₆ compounds demonstrate robust ferroelectric polarizations, measuring 20.0 μC/cm² and 21.8 μC/cm², respectively, accompanied by minimalist forbidden energy gaps of 1.40 eV and 1.18 eV using the GGA+U method. Furthermore, we pinpoint elevated magnetic transition temperatures for these compounds. Additionally, our study scrutinizes the energies associated with diverse spin configurations and identifies potential minimum decomposition pathways into stable oxides. This comprehensive analysis ensures the meticulous formation of the LaFeMnNiO₆ and LaTiMnNiO₆ compounds.