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Tuning the flat bands of the kagome metal CoSn with Fe, In, or Ni doping

B. C. Sales, W. R. Meier, A. F. May, J. Xing, J.-Q. Yan, S. Gao, Y. H. Liu, M. B. Stone, A. D. Christianson, Q. Zhang, and M. A. McGuire
Phys. Rev. Materials 5, 044202 – Published 15 April 2021

Abstract

CoSn is a Pauli paramagnet with relatively flat d bands centered about 100 meV below the Fermi energy, EF. Single crystals of CoSn lightly doped with Fe, In, or Ni are investigated using x-ray and neutron scattering, magnetic susceptibility and magnetization, AC susceptibility, specific heat, and resistivity measurements. Within the rigid-band approximation, hole doping with a few percent of Fe or In should move the flat bands closer to EF, whereas electron doping with Ni should move the flat bands further away from EF. We provide evidence that this indeed occurs. Fe and In doping drive CoSn toward magnetism, while Ni doping suppresses CoSn's already weak magnetic response. The resulting ground state is different for Fe versus In doping. For Fe-doped crystals, Co1xFexSn, with 0.02<x<0.27, the magnetic and specific-heat data are consistent with the formation of a spin glass, with a glass temperature, Tg, ranging from 1 K for x=0.02 to 10 K for x=0.27. Powder and single-crystal neutron diffraction found no evidence of long-range magnetic order below Tg for samples with x0.17. For In-doped crystals, CoSn1yIny, both the magnetic susceptibility and the Sommerfeld coefficient, γ, increase substantially relative to pure CoSn, but with no clear indication of a magnetic transition for 0.05<y<0.2. CoSn crystals doped with Ni (Co0.93Ni0.07Sn) have a significantly smaller magnetic susceptibility and γ than pure CoSn, consistent with flat bands further from EF.

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  • Received 16 February 2021
  • Accepted 1 April 2021

DOI:https://doi.org/10.1103/PhysRevMaterials.5.044202

©2021 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

B. C. Sales1, W. R. Meier1, A. F. May1, J. Xing1, J.-Q. Yan1, S. Gao1,2, Y. H. Liu2, M. B. Stone2, A. D. Christianson1, Q. Zhang2, and M. A. McGuire1

  • 1Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37831, USA
  • 2Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37831, USA

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Vol. 5, Iss. 4 — April 2021

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  • Figure 1
    Figure 1

    (a), (b) Crystal structure of CoSn emphasizing the kagome planes of Co atoms. (c) Electronic structure of a kagome layer calculated using the tight-binding model, which assumes only nearest-neighbor interactions. (d) Electronic structure of CoSn as calculated using DFT with spin-orbit coupling, reproduced from our previous work (Ref. [13]). Bands with thicker lines have higher 3d orbital character, and the type of 3d orbital is indicated by the color. The relatively flat 3d bands with dominant xy or x2y2 character (highlighted in red) are closest to the Fermi energy. The density of states is shown on the right edge of the panel. (e) Standard notation for the high-symmetry points in the CoSn Brillouin zone.

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  • Figure 2
    Figure 2

    Combined phase diagram determined from specific heat, magnetic susceptibility, AC susceptibility, and neutron scattering data for single crystals of Co1xFexSn with 0<x<1 including the data from Ref. [9] and the present work highlighted in the inset. The regions labeled “planar” or “axial” correspond to A-type antiferromagnetic order with the Fe spins aligned in the kagome planes or along the c axis, respectively. In the purple area of the phase diagram, the spins are in a “tilted” configuration. The spin-glass transition is labeled Tg in Fig. 1 and is defined as the temperature where the zero-field cooled and field-cooled susceptibility data diverge in an applied field of 100 Oe. A possible quantum critical point near x=0.4 is avoided by the emergence of the spin-glass phase. For compositions 0.4<x<0.6, there are two magnetic transitions. The spin-glass phase disappears near the percolation threshold for a kagome lattice of pc=x=0.524 [20], although long-range antiferromagnetic order persists to lower values of x0.4.

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  • Figure 3
    Figure 3

    (a) Magnetic susceptibility vs temperature for a series of Fe-doped CoSn crystals from 15 to 300 K, where xnom refers to the amount of Fe added relative to Co at the start of the crystal growth process. (b) If the data in (a) are fit to a Curie-Weiss law, C/(T+θ)+χ0, the Curie constant, C, should be proportional to the Fe concentration if only the Fe dopant atoms are magnetic. Assuming S=1 for each iron, this gives an effective moment of 2.82μB for each Fe atom and the red points in (b). The blue points are the actual Fe content as determined from careful EDX measurements on the same crystals used to produce the data shown in (a). The agreement between the two sets of data are within experimental error. The fitted values for C, θ, and χ0 are given in Table 1.

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  • Figure 4
    Figure 4

    Room-temperature lattice constants for Fe-, In-, and Ni-doped crystals, as determined from x-ray powder diffraction. The value x is the EDX measured atomic fraction of each dopant, i.e., Co1xFexSn, Co1xNixSn, or CoSn1xInx. The lattice constants for pure CoSn are shown by the filled black circle.

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  • Figure 5
    Figure 5

    (a) ZFC and FC magnetic susceptibility data for crystals of Co1xFexSn with H=100Oe applied along the c axis. (b) Magnetic susceptibility data for a second Co0.83Fe0.17Sn crystal with the field applied along both the c and the a axis. The larger susceptibility for Hc may indicate that the Fe spins tend to lie in the plane, as is the case for pure FeSn. (c) Magnetization data for Co1xFexSn crystals with x=0.02, 0.08, 0.17 with Hc at temperatures below the temperature, Tg. The magnetization data for Ha are the same within experimental error. Also shown (dashed line) is the expected magnetization curve at 0.4 K for noninteracting spins with S=1 and g=2.

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  • Figure 6
    Figure 6

    (a) Specific heat divided by temperature vs temperature for CoSn and three iron-doped alloys. Inset: Magnetic specific heat vs temperature for x=0.02 illustrating the linear temperature dependence near and below Tg1K. (b) Magnetic entropy removed due to magnetic order vs temperature. For a concentration x of Fe spins with S=1 the expected entropy is xRln(3). The measured entropy release is about 60% of this value, which is close to the value of xRln(2), as noted by the second dashed line. (c) Specific heat divided by temperature vs temperature for a CoSn crystal and a CoSn crystal doped with x=0.02, in applied magnetic fields of H=0, 40, and 80 kOe.

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  • Figure 7
    Figure 7

    (a) Real part of AC susceptibility vs temperature and frequency for a Co0.83Fe0.17Sn crystal. The shift of the maximum with frequency (black arrows) is indicative of glassy behavior. (b) Imaginary part of the susceptibility near Tg. Note the magnitude is much smaller than the real part. (c) Change in magnetization vs time for temperatures below glass transition temperature. In this time interval the relaxation can be fit to a stretched exponential. The crystal was cooled from 20 K in a field of 10 kOe to the desired temperature and then the field was set to 0. The magnetization continued to drift downwards, implying some glassy response. For temperatures above Tg, the magnetization was essentially independent of time.

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  • Figure 8
    Figure 8

    (a) Comparison of the magnetic susceptibility data from CoSn, Co0.987Fe0.013Sn, CoSn0.95In0.05, CoSn0.90In0.1, and CoSn0.8In0.2 with H=10kOe. Notice that the room-temperature susceptibility of all of the In-doped samples are larger than the value for pure CoSn. This suggests a larger Pauli susceptibility with indium doping and presumably a corresponding larger density of states at EF. (b) C/T vs T for three In-doped crystals and CoSn.

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  • Figure 9
    Figure 9

    Comparison of the magnetic susceptibility of pure CoSn and a Ni-doped CoSn crystal, Co0.93Ni0.07Sn taken with H=10kOe. Low-temperature specific-heat data are shown in the inset for the same two crystals, with the green data corresponding to the Ni-doped crystal.

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  • Figure 10
    Figure 10

    Resistivity vs temperature for CoSn crystals doped with Fe, In, or Ni.

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