Abstract
Magnetoelectric multiferroics have received much attention in the past decade due to their interesting physics and promising multifunctional performance. For practical applications, simultaneous large ferroelectric polarization and strong magnetoelectric coupling are preferred. However, these two properties have not been found to be compatible in the single‐phase multiferroic materials discovered as yet. Here, it is shown that superior multiferroic properties exist in the A‐site ordered perovskite BiMn3Cr4O12 synthesized under high‐pressure and high‐temperature conditions. The compound experiences a ferroelectric phase transition ascribed to the 6s2 lone‐pair effects of Bi3+ at around 135 K, and a long‐range antiferromagnetic order related to the Cr3+ spins around 125 K, leading to the presence of a type‐I multiferroic phase with huge electric polarization. On further cooling to 48 K, a type‐II multiferroic phase induced by the special spin structure composed of both Mn‐ and Cr‐sublattices emerges, accompanied by considerable magnetoelectric coupling. BiMn3Cr4O12 thus provides a rare example of joint multiferroicity, where two different types of multiferroic phases develop subsequently so that both large polarization and significant magnetoelectric effect are achieved in a single‐phase multiferroic material.
