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Occupation sites and valence states of Co dopants in (La, Co)-codoped M-type Sr ferrite: Fe57 and Co59 nuclear magnetic resonance studies

H. Sakai, T. Hattori, Y. Tokunaga, S. Kambe, H. Ueda, Y. Tanioku, C. Michioka, K. Yoshimura, K. Takao, A. Shimoda, T. Waki, Y. Tabata, and H. Nakamura
Phys. Rev. B 98, 064403 – Published 2 August 2018

Abstract

To specify preferential occupation sites of Co substituents and to clarify charge and spin states of Co ions in (La, Co)-cosubstituted hexagonal magnetoplumbite-type (M-type) Sr ferrite Sr1xLaxFe12yCoyO19 (x,y0.4), Fe57 and Co59 nuclear magnetic resonance (NMR) spectra are measured under zero and external magnetic fields using powdered and single crystalline specimens. For comparison, NMR investigations of nondoped and La- or Co-doped M-type Sr ferrites are also performed. Ferrimagnetic M-type Sr ferrite contains the following five crystallographic Fe sites: the majority spin sites 12k, 2a, and 2b, and the minority spin sites 4f1 and 4f2. Based on Fe57 and Co59 NMR, a plausible model of (La, Co)-codoped Sr ferrite is deduced. To a considerable degree, the charge compensation between La3+ and Co2+ works in the equal (La, Co)-codoped case, where more than half of the Co ions are considered to be present in the minority spin 4f1 sites at the center of the oxygen tetrahedra, with the S=3/2 state carrying a small orbital moment owing to spin-orbit interaction. The remaining small number of high-spin Co2+ (S=3/2, L=1) ions with unquenched orbital moments would be distributed to the other octahedral 12k, 2a, and 4f2 sites.

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  • Received 10 November 2017
  • Revised 19 June 2018

DOI:https://doi.org/10.1103/PhysRevB.98.064403

©2018 American Physical Society

Physics Subject Headings (PhySH)

  1. Research Areas
  1. Physical Systems
Condensed Matter, Materials & Applied Physics

Authors & Affiliations

H. Sakai*, T. Hattori, Y. Tokunaga, and S. Kambe

  • Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195, Japan.

H. Ueda, Y. Tanioku, C. Michioka, and K. Yoshimura

  • Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan

K. Takao, A. Shimoda, T. Waki, Y. Tabata, and H. Nakamura

  • Department of Materials Science and Engineering, Kyoto University, Kyoto 606-8501, Japan

  • *sakai.hironori@jaea.go.jp
  • nakamura.hiroyuki.2w@kyoto-u.ac.jp

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Issue

Vol. 98, Iss. 6 — 1 August 2018

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Images

  • Figure 1
    Figure 1

    Crystal structure of M-type Sr ferrite SrFe12O19 (hexagonal, P63/mmc). Oxygen atoms, which are at the corner of each polyhedron, are omitted for clarity. Each iron atom is located at the center of a polyhedron. The five crystallographic iron sites are labeled by their Wyckoff notation.

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  • Figure 2
    Figure 2

    Frequency-swept Fe57 NMR spectra for powdered M-type Sr ferrite under zero field, which are taken with several separations of τ=15, 600, and 1200μs. The extrapolated intensities for τ0 are also shown.

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  • Figure 3
    Figure 3

    (a) Frequency-swept Fe57 NMR spectra of single crystals of M-type Sr ferrite under zero field. As schematically illustrated in the insets, two configurations are attempted with the oscillating field of H1 parallel and perpendicular to the magnetic easy c axis. The NMR intensities are normalized at the peak intensity for the 12k sites. Schematic illustrations are also shown for a magnetic domain wall and magnetic domains. The dotted rectangles indicate where NMR can occur for the cases of (b) H1c and (c) H1c. (d) Frequency-swept Fe57 NMR spectra of single crystal of M-type Sr ferrite in the case of H1c with applying external fields (H0) along the c axis.

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  • Figure 4
    Figure 4

    (a) External field dependence of Fe57 NMR spectra in the powdered M-type Sr ferrite under H0=0, 5, 10, 15, and 20 kOe. (b) Resonant frequencies versus H0 plot for the powdered M-type SrFe12O19.

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  • Figure 5
    Figure 5

    Zero field Fe57 NMR spectra of powdered polycrystalline La0.1, La0.2, La0.3, and La0.5-doped M-type Sr ferrites.

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  • Figure 6
    Figure 6

    Frequency-swept Fe57 and Co59 NMR spectra of single crystals of Co0.07-doped and nondoped M-type Sr ferrites under zero field with a setting of H1c.

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  • Figure 7
    Figure 7

    (a) External field dependence of low-frequency Co59 and 2bFe57 NMR spectra of a single crystal of Co0.07-doped M-type Sr ferrite. The size of single crystal was 5.3×2.1×0.27mm3. (b) Resonant frequencies versus H0 plot.

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  • Figure 8
    Figure 8

    (a) Zero field Fe57 NMR spectra of powdered (La, Co)0.1 and (La, Co)0.3-codoped M-type Sr ferrite. The spectra of pure M-type Sr ferrite are shown for comparison. (b) The spectra of (La, Co)0.3 are recorded with several magnitudes of H1. The magnitude of H1L is determined to maximize the 4f1Fe57 signal. (c) The spectra of (La, Co)0.3 obtained with a much reduced H1 (roughly, <10% of H1L) is superimposed, and its magnitude is adjusted to maximize the NMR signal at 80 MHz.

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  • Figure 9
    Figure 9

    (a) External field dependence of NMR spectra of powdered (La, Co)0.3-codoped M-type Sr ferrite sample around 80 MHz. (b) Resonant frequencies versus H0 plot of the (La, Co)0.3-codoped M-type Sr ferrite sample. In both plots, extrinsic NMR signals around the sample for H1, F19, and Cu63,65 are tagged as well, which originate from enamel insulation, fluorocarbon polymers, and copper coil.

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  • Figure 10
    Figure 10

    (a) Frequency-swept Fe57 NMR spectra for single crystals of (La0.24, Co0.11), (La0.29, Co0.15), (La, Co)0.4-codoped, and nondoped M-type Sr ferrites under zero field with a setting of H1c. The H1 magnitude is adjusted to maximize the 12k signal. (b) Spectral difference for (La, Co)0.4 codoped with different magnitudes of H1: One is for the Fe57-NMR with the larger magnitude of H1 and another is for Co59-NMR with a tiny magnitude of H1.

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  • Figure 11
    Figure 11

    (a) Zero field Co59 NMR spectra of powdered polycrystalline (La, Co)0.3-codoped M-type Sr ferrite taken with a fixed separation of τ=15μs. Co59 NMR spectra are labeled as S1, S2, and S3, respectively. (b) The magnified Co59 NMR spectra of S2 and S3 in the high-frequency region. The spectra are recorded with several separations of τ=15, 150, 800, and 1600μs. The extrapolated intensities of τ0 are also shown.

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  • Figure 12
    Figure 12

    (a) Zero field Co59 NMR spectra of single crystal of (La, Co)0.4-codoped M-type Sr ferrite with a setting of H1c. (b) Magnified Co59 NMR spectra S2 and S3 of single crystal in the high-frequency region.

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  • Figure 13
    Figure 13

    Bottom panel: Zero field Co59 NMR spectra of powdered (La, Co)0.1, (La, Co)0.2, and (La, Co)0.3-codoped M-type Sr ferrites recorded with a fixed separation of τ=15μs in the high-frequency region of S2 and S3. Upper panel: External field dependence of high-frequency Co59 NMR spectra labeled S2 and S3, of powdered (La, Co)0.3-codoped M-type Sr ferrite.

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  • Figure 14
    Figure 14

    Summary views of charge and spin states, and doping sites in (La, Co)-codoped M-type Sr ferrite. Two cases are illustrated: Main substitutions of Co2+ occur at (a) octahedral 4f2 sites, and (b) tetrahedral 4f1, which should correspond to S1.

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