The novel series of hole-doped quadruple manganite perovskites Hg1−xNaxMn3Mn4O12 (HNMO) has been synthesized and its charge and orbital order behavior investigated through high-resolution synchrotron powder x-ray diffraction techniques. Through careful Rietveld refinements of structural models via symmetry-motivated approaches, we show that the ground state of HNMO compositions adopts a polar G-type charge and orbital ordered state, which is rare in manganite perovskites, and is robust as a sole phase up to a critical doping level. Upon this critical doping, coincident with that in which colossal magnetoresistance (CMR) is maximal in canonical manganite perovskites, electronic phase separation occurs between G-type and orbital order with charge disorder-type states. The latter state has recently been identified in Ca1−xNaxMn3Mn4O12 perovskites, and proposed to be the competing insulating state from which CMR phenomena emerge. We show that the mechanism for the formation of the G-type state is due to charge transfer processes which may occur through a coupling of distortions involving structural and charge and orbital degrees of freedom, ultimately driving the polar ground state through an improper-like ferroelectric polarization mechanism. These results will act as an important recipe for designing novel ferroelectric-active materials, in addition to expanding the richness of charge and orbital ordered states in manganite perovskites. Published by the American Physical Society 2024
Read full abstract