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Averievite: A copper oxide kagome antiferromagnet

A. S. Botana, H. Zheng, S. H. Lapidus, J. F. Mitchell, and M. R. Norman
Phys. Rev. B 98, 054421 – Published 21 August 2018

Abstract

Averievite, Cu5V2O10(CsCl), is an oxide mineral composed of Cu2+ kagome layers sandwiched by Cu2+V5+ honeycomb layers. We have synthesized this oxide and investigated its properties from ab initio calculations along with susceptibility and specific heat measurements. The data indicate a Curie-Weiss temperature of 185 K as well as long-range magnetic order at 24 K due to the significant interlayer coupling from the honeycomb copper ions. This order is suppressed by substituting copper by isoelectronic zinc, suggesting that Zn-substituted averievite is a promising spin liquid candidate. A further proposed substitution that replaces V5+ by Ti4+ not only dopes the material but is predicted to give rise to a two-dimensional electronic structure featuring Dirac crossings. As such, averievite is an attractive platform for S=1/2 kagome physics with the potential for realizing novel electronic states.

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  • Received 24 August 2017
  • Revised 7 July 2018

DOI:https://doi.org/10.1103/PhysRevB.98.054421

©2018 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

A. S. Botana1,*, H. Zheng1, S. H. Lapidus2, J. F. Mitchell1, and M. R. Norman1,†

  • 1Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA
  • 2X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

  • *Corresponding author: antiasanchezbot@gmail.com
  • norman@anl.gov

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Issue

Vol. 98, Iss. 5 — 1 August 2018

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Images

  • Figure 1
    Figure 1

    (a) Structure of averievite, composed of CuVO3 honeycomb layers (b) that sandwich Cu3O2Cl kagome layers (c) with different local environments for the Cu atoms (Cu-O and V-O distances are shown in angstroms). Each of these three-layer blocks are separated by CsO2 layers. Cs atoms are in gray, Cu atoms are in blue, O atoms are in red, V atoms are in yellow, and Cl atoms are in green. (d) Cu-Cu distances in the kagome plane (in angstroms). (e) Cu lattice involving honeycomb and kagome layers, showing pyrochlore slabs reminiscent of clinoatacamite. The interlayer Cu-Cu distance is shown in angstroms, and J1 and J2 denote magnetic couplings.

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  • Figure 2
    Figure 2

    (a) The dc magnetic susceptibility (left axis) and inverse susceptibility (right axis) of averievite. The dashed line is a Curie-Weiss fit to the high-temperature data. (b) The dc magnetic susceptibility of Zn-substituted averievite. For (a) and (b), data were collected in the field-cooled mode (H=2000 Oe). (c) Specific heat of unsubstituted (open circles) and (x=1) Zn-substituted averievite (open triangles) plotted as Cp/T. The dotted line is a polynomial background. Inset: magnetic specific heat (open circles, left axis) and derived magnetic entropy (solid curve, right axis) for averievite.

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  • Figure 3
    Figure 3

    GGA band structure and atom-resolved density of states for (a) Cu5V2O10(CsCl), (b) Cu3Zn2V2O10(CsCl), and (c) Cu3Zn2Ti2O10(CsCl). (d) A blowup around the Dirac points that shows a gap opening due to spin-orbit coupling. (e) Band structure of the nearest-neighbor tight-binding model for the kagome lattice. (f) Fermi surface of Cu3Zn2Ti2O10(CsCl).

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  • Figure 4
    Figure 4

    Charge density within GGA in an energy window that comprises the three kagome Cu d bands around EF for (a) Cu5V2O10(CsCl), (b) Cu3Zn2V2O10(CsCl), and (c) Cu3Zn2Ti2O10(CsCl).

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  • Figure 5
    Figure 5

    Synchrotron x-ray powder diffraction data for Cu5-averievite measured at 15, 295, and 400 K.

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  • Figure 6
    Figure 6

    Temperature dependence of lattice parameters for Cu5-averievite normalized to 300 K as determined by high-resolution synchrotron x-ray powder diffraction. In the P3¯m1 regime above 310 K, the lattice is described in terms of an equivalent monoclinic cell with a=c, b=a, c=a3 to facilitate comparison with the low-temperature phase. The structure below 127 K was not indexed. See text for details.

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  • Figure 7
    Figure 7

    Synchrotron x-ray powder diffraction data for Cu5- and Cu4Zn-averievite measured at 295 K.

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  • Figure 8
    Figure 8

    Synchrotron x-ray powder diffraction data for Cu4Zn- and Cu5-averievite at 15 K.

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  • Figure 9
    Figure 9

    Zero-field-cooled and field-cooled magnetic susceptibility at 2000 Oe for Cu5- and Cu4Zn-averievite.

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  • Figure 10
    Figure 10

    Heat capacity of Cu4Zn-averievite below 10 K.

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  • Figure 11
    Figure 11

    Heat capacity of Cu5-averievite and Cu4Zn-averievite between 2 and 262 K.

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  • Figure 12
    Figure 12

    GGA+U AFM band structure and atom-resolved density of states for (a) Cu5-averievite (b) and Cu3Zn2-averievite.

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  • Figure 13
    Figure 13

    GGA band structure and tight-binding fits corresponding to (a) Cu3Zn2-averievite and (b) Cu3Zn2Ti2-averievite. (c) Exchange paths within the kagome plane associated with the hopping parameters shown in Table 6. Cu atoms are shown in blue, and Cl atoms are in green.

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  • Figure 14
    Figure 14

    Band structure of Cu3ZnGaTi2O10(CsCl).

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