Electrostatically driven charge-ordering in Fe2OBO3

Abstract

Charge-ordering is an important phenomenon in conducting metal oxides: it leads to metal–insulator transitions1 in manganite perovskites (which show ‘colossal’ magnetoresistances), and the Verwey2 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 manganites3,4 and copper oxide superconductors5; in the latter case, dynamic fluctuations of the stripes have been proposed6 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 crystallization7), 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, Fe2OBO3, that support the electrostatic repulsion charge-ordering mechanism: the system adopts a charge-ordered state below 317 K, in which Fe2+ and Fe3+ ions are equally distributed over structurally distinct Fesites. In contrast, the isostructural manganese oxoborate, Mn2OBO3, has been previously shown8 to undergo charge-ordering through Jahn–Teller distortions. We therefore conclude that both mechanisms occur within the same structural arrangement.

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Figure 1: The Fe2OBO3 structure projected on the y–z plane (y vertical, z horizontal).
Figure 2: Conductivity and structural anomalies at the charge-ordering transition in Fe2OBO3.
Figure 3: Mössbauer spectra of Fe2OBO3 between 190 and 500 K, collected in transmission geometry on a conventional constant acceleration spectrometer.
Figure 4: Charge disorder and order in Fe2OBO3.

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Acknowledgements

We thank EPSRC for provision of beam time at SRS and ILL, and G. Bushnell-Wye (SRS) and A. Hewat (ILL) for assistance with data collection. Support for A.M.T.B. from EPSRC and the Daresbury Laboratory and for L.M.R.M. from the Basque Government is acknowledged.

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Correspondence to J. P. Attfield.

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Attfield, J., Bell, A., Rodriguez-Martinez, L. et al. Electrostatically driven charge-ordering in Fe2OBO3. Nature 396, 655–658 (1998). https://doi.org/10.1038/25309

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