Oxide electronics

Abstract:

MnAs is a commercially available material, intensively studied, both theoretically and experimentally, since the beginning of the last century. Interest in this compound could come up again as a consequence of new ideas and conjectures formulated during the last decade in connection with the study of the colossal magnetoresistance (CMR) response in Mn perovskites. Among these ideas is the invocation of a phase separation scenario for CMR manganese oxides and related materials that might be of particular relevance in systems, like MnAs, where first-order phase transitions occur.

Abstract:

MnAs exhibits a first-order phase transition from a ferromagnetic, high-spin metal hexagonal phase to a paramagnetic, lower-spin insulator orthorhombic phase at T(C)=313 K. Here, we report the results of neutron diffraction experiments showing that an external magnetic field, B, stabilizes the hexagonal phase above T(C). The phase transformation is reversible and constitutes the first demonstration of a bond-breaking transition induced by a magnetic field. The field-induced phase transition is accompanied by an enhanced magnetoresistance of about 17% at 310 K. The phenomenon appears to be similar to that of the colossal magnetoresistance response observed in the Mn [corrected] perovskite family.

Abstract:

The crystal structure of highly stoichiometric magnetite (Fe3O4) below the Verwey transition has been refined from high-resolution neutron and synchrotron x-ray powder-diffraction data. The refined model has a monoclinic P2/c symmetry cell with orthorhombic Pmca pseudosymmetry constraints on the atomic positions, and contains four independent octahedral B site iron atoms. Charge ordering is evidenced by the presence of expanded and contracted BO6 octahedra, and by the distribution of B-B distances resulting from unequal Coulombic repulsions between the different B site charges. The B-B distances are inconsistent with dimer formation. Competition between the B-O and B-B interactions results in polar displacements of two of the B site cations. The charge ordering has a predominant [001] density modulation, which relieves a nesting instability in the electronic density of states, but a second [00 1/2] phase modulation also occurs. The monoclinic distortion at the Verwey transition is consistent with a macroscopic rhombohedral magnetostriction, driven by the localization of orbitally degenerate Fe²⁺, coincident with the microscopic charge ordering distortions that have an orthorhombic lattice symmetry.