Electrostatically driven charge-ordering in Fe_2OBO_3

摘要

Charge-ordering is an important phenomenon in conducting metal oxides: it leads to metal-insulator transitions in manganite perovskites (which show 'colossal' magnetoresistances), and the Verwey transition in magnetite (in which the material becomes insulating at low temperatures when the conduction electrons freeze into a regular array). Charge-ordered 'stripes' are found in some manganites and copper oxide superconductors; in the latter case, dynamic fluctuations of the stripes have been proposed as a mechanism of high-temperature superconductivity. But an important unresolved issue is whether the charge-ordering in oxides is driven by electrostatic repulsions between the charges (Wigner crystallization), or by the strains arising from electron-lattice interactions (such as Jahn-Teller distortions) involving different localized electronic states. Here we report measurements on iron oxoborate, Fe_2OBO_3, that support the electrostatic repulsion charge-ordering mechanism: the system adopts a charge-ordered state below 317 K, in which Fe~(2+) and Fe~(3+) ions are equally distributed over structurally distinct Fe sites. In contrast, the isostructural manganese oxoborate, Mn_2OBO_3, has been previously shown to undergo charge-ordering through Jahn-Teller distortions. We therefore conclude that both mechanisms occur within the same structural arrangement.