Interplay of 3d and 4f Magnetism in Chiral Y6FeSi2S14 and Tb6FeSi2S14 Chalcogenides

Eranga H. Gamage; Nethmi W. Hewage; Ernesto Soto; Hafiz Zohaib Aslam; Jaeil Bai; Ahmad Alsaad; Gayatri Viswanathan; Philip Yox; V. Ovidiu Garlea; Saeed Kamali; Stuart Calder; Yaroslav Mudryk; Vladimir Antropov; Renat Sabirianov; Georgiy Akopov; Kirill Kovnir

doi:10.1021/acs.chemmater.4c03080

Interplay of 3d and 4f Magnetism in Chiral Y₆FeSi₂S₁₄ and Tb₆FeSi₂S₁₄ Chalcogenides

Eranga H. Gamage, Nethmi W. Hewage, Ernesto Soto, Hafiz Zohaib Aslam, Jaeil Bai, Ahmad Alsaad, Gayatri Viswanathan, Philip Yox, V. Ovidiu Garlea, Saeed Kamali, Stuart Calder, Yaroslav Mudryk, Vladimir Antropov, Renat Sabirianov, Georgiy Akopov, Kirill Kovnir

Research output: Contribution to journal › Article › peer-review

Abstract

The family of chiral, noncentrosymmetric, quaternary sulfides R₆(TM)_x(E)₂Q₁₄ (R = rare-earth metal; TM = transition metal; E = Si, Ge, Sn, Al, or Ga; and Q = S or Se) presents an exciting opportunity for exploration of their magnetic characteristics. The magnetic properties of these materials are directly influenced by the specific R and TM elements present in the sublattices. However, since the concentration of the TM is low (1 out of 23 atoms) with 50% partial occupancy, it is unclear whether and how TMs contribute to the overall magnetism of the compounds. To investigate the role of TM, two rare-earth Fe quaternary sulfide materials, R₆FeSi₂S₁₄ (R = Tb, Y), were synthesized through a solid-state reaction of arc-melted R₆FeSi₂ precursors with sulfur, and systematic studies were conducted on polycrystalline powders and single crystals. Y₆FeSi₂S₁₄ enables the exclusive study of Fe’s magnetic behavior due to the nonmagnetic nature of Y³⁺. Tb₆FeSi₂S₁₄ provides valuable insights into the interplay of 3d and 4f contributions in the presence of magnetic Tb. Magnetic measurements confirmed that both compounds exhibit a characteristic antiferromagnetic (AFM) peak. Y₆FeSi₂S₁₄ showed a Néel temperature, T_N, of ∼5 K, an effective magnetic moment, μ_eff, of 5.68 μ_B per Fe atom, and a negative Weiss constant, θ, of −19 K, confirming antiferromagnetic interactions of Fe magnetic moments. For Tb₆FeSi₂S₁₄, T_N increases with the introduction of Tb, reaching 14 K with a θ of −18 K. The derived μ_eff of 24.68 μ_B is higher than the contribution of 6 × Tb³⁺ ions (√6 × 9.72 = 23.81 μ_B) but close to the sum of the contribution of 6Tb + 1Fe. Magnetic structure refinement performed on neutron powder diffraction data indicates that the Fe moments in Y₆FeSi₂S₁₄ are aligned along the [001] direction in an AFM order, which agrees with single-crystal directional magnetization measurements. When Y is replaced with Tb, the Tb moments are ordered in a noncollinear configuration in the ab-plane, with the Tb triangles stacked to form buckled honeycombs, while the Fe moments maintain their collinearity along the c-axis. Consequently, the complex nature of magnetism in R₆(TM)_x(E)₂Q₁₄ quaternaries is due to a superposition of contributions from R³⁺ and TM magnetic sublattices.

Original language	English
Pages (from-to)	1160-1173
Number of pages	14
Journal	Chemistry of Materials
Volume	37
Issue number	3
DOIs	https://doi.org/10.1021/acs.chemmater.4c03080
State	Published - Feb 11 2025

Funding

We thank Prof. V. Pecharsky (deceased) (ISU and Ames National Laboratory) for access to the arc-melting setup and Professor Javier Vela (ISU) for the use of the diffuse reflectance setup. We also thank Allen Scheie (Los Alamos National Laboratory) for the helpful discussions and assistance in modeling the crystal field excitations. This work was primarily supported by the U.S. Department of Energy (DOE) Established Program to Stimulate Competitive Research (EPSCoR) Grant No. DE-SC0024284. Research at Rutgers was supported by a Rutgers University-Newark startup grant (G.A., H.Z.A.). Magnetic measurements (Y.M.) were supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The Ames National Laboratory is operated for the U.S. DOE by Iowa State University under contract #DE-AC02-07CH11358. A portion of this research used resources at the High Flux Isotope Reactor and Spallation Neutron Source, DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory. The beamtime was allocated to HB-2A (POWDER) on proposal nos. IPTS-27655 and IPTS-29003. This manuscript was authored by UT-Battelle, LLC under Contract #DE-AC05-00OR22725 with the U.S. Department of Energy. This work was primarily supported by the U.S. Department of Energy (DOE) Established Program to Stimulate Competitive Research (EPSCoR) Grant No. DE-SC0024284. Research at Rutgers was supported by a Rutgers University-Newark startup grant (G.A., H.Z.A.). Magnetic measurements (Y.M.) were supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The Ames National Laboratory is operated for the U.S. DOE by Iowa State University under contract #DE-AC02\u201307CH11358. A portion of this research used resources at the High Flux Isotope Reactor and Spallation Neutron Source, DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory. The beamtime was allocated to HB-2A (POWDER) on proposal nos. IPTS-27655 and IPTS-29003. This manuscript was authored by UT-Battelle, LLC under Contract #DE-AC05\u201300OR22725 with the U.S. Department of Energy.

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Gamage, E. H., Hewage, N. W., Soto, E., Aslam, H. Z., Bai, J., Alsaad, A., Viswanathan, G., Yox, P., Garlea, V. O., Kamali, S., Calder, S., Mudryk, Y., Antropov, V., Sabirianov, R., Akopov, G., & Kovnir, K. (2025). Interplay of 3d and 4f Magnetism in Chiral Y₆FeSi₂S₁₄ and Tb₆FeSi₂S₁₄ Chalcogenides. Chemistry of Materials, 37(3), 1160-1173. https://doi.org/10.1021/acs.chemmater.4c03080

@article{515e58a0b31c48ee954574fb577fe9df,

title = "Interplay of 3d and 4f Magnetism in Chiral Y6FeSi2S14 and Tb6FeSi2S14 Chalcogenides",

abstract = "The family of chiral, noncentrosymmetric, quaternary sulfides R6(TM)x(E)2Q14 (R = rare-earth metal; TM = transition metal; E = Si, Ge, Sn, Al, or Ga; and Q = S or Se) presents an exciting opportunity for exploration of their magnetic characteristics. The magnetic properties of these materials are directly influenced by the specific R and TM elements present in the sublattices. However, since the concentration of the TM is low (1 out of 23 atoms) with 50% partial occupancy, it is unclear whether and how TMs contribute to the overall magnetism of the compounds. To investigate the role of TM, two rare-earth Fe quaternary sulfide materials, R6FeSi2S14 (R = Tb, Y), were synthesized through a solid-state reaction of arc-melted R6FeSi2 precursors with sulfur, and systematic studies were conducted on polycrystalline powders and single crystals. Y6FeSi2S14 enables the exclusive study of Fe{\textquoteright}s magnetic behavior due to the nonmagnetic nature of Y3+. Tb6FeSi2S14 provides valuable insights into the interplay of 3d and 4f contributions in the presence of magnetic Tb. Magnetic measurements confirmed that both compounds exhibit a characteristic antiferromagnetic (AFM) peak. Y6FeSi2S14 showed a N{\'e}el temperature, TN, of ∼5 K, an effective magnetic moment, μeff, of 5.68 μB per Fe atom, and a negative Weiss constant, θ, of −19 K, confirming antiferromagnetic interactions of Fe magnetic moments. For Tb6FeSi2S14, TN increases with the introduction of Tb, reaching 14 K with a θ of −18 K. The derived μeff of 24.68 μB is higher than the contribution of 6 × Tb3+ ions (√6 × 9.72 = 23.81 μB) but close to the sum of the contribution of 6Tb + 1Fe. Magnetic structure refinement performed on neutron powder diffraction data indicates that the Fe moments in Y6FeSi2S14 are aligned along the [001] direction in an AFM order, which agrees with single-crystal directional magnetization measurements. When Y is replaced with Tb, the Tb moments are ordered in a noncollinear configuration in the ab-plane, with the Tb triangles stacked to form buckled honeycombs, while the Fe moments maintain their collinearity along the c-axis. Consequently, the complex nature of magnetism in R6(TM)x(E)2Q14 quaternaries is due to a superposition of contributions from R3+ and TM magnetic sublattices.",

author = "Gamage, {Eranga H.} and Hewage, {Nethmi W.} and Ernesto Soto and Aslam, {Hafiz Zohaib} and Jaeil Bai and Ahmad Alsaad and Gayatri Viswanathan and Philip Yox and Garlea, {V. Ovidiu} and Saeed Kamali and Stuart Calder and Yaroslav Mudryk and Vladimir Antropov and Renat Sabirianov and Georgiy Akopov and Kirill Kovnir",

note = "Publisher Copyright: {\textcopyright} 2025 American Chemical Society.",

year = "2025",

month = feb,

day = "11",

doi = "10.1021/acs.chemmater.4c03080",

language = "English",

volume = "37",

pages = "1160--1173",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "3",

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Gamage, EH, Hewage, NW, Soto, E, Aslam, HZ, Bai, J, Alsaad, A, Viswanathan, G, Yox, P, Garlea, VO, Kamali, S, Calder, S, Mudryk, Y, Antropov, V, Sabirianov, R, Akopov, G & Kovnir, K 2025, 'Interplay of 3d and 4f Magnetism in Chiral Y₆FeSi₂S₁₄ and Tb₆FeSi₂S₁₄ Chalcogenides', Chemistry of Materials, vol. 37, no. 3, pp. 1160-1173. https://doi.org/10.1021/acs.chemmater.4c03080

TY - JOUR

T1 - Interplay of 3d and 4f Magnetism in Chiral Y6FeSi2S14 and Tb6FeSi2S14 Chalcogenides

AU - Gamage, Eranga H.

AU - Hewage, Nethmi W.

AU - Soto, Ernesto

AU - Aslam, Hafiz Zohaib

AU - Bai, Jaeil

AU - Alsaad, Ahmad

AU - Viswanathan, Gayatri

AU - Yox, Philip

AU - Garlea, V. Ovidiu

AU - Kamali, Saeed

AU - Calder, Stuart

AU - Mudryk, Yaroslav

AU - Antropov, Vladimir

AU - Sabirianov, Renat

AU - Akopov, Georgiy

AU - Kovnir, Kirill

PY - 2025/2/11

Y1 - 2025/2/11

N2 - The family of chiral, noncentrosymmetric, quaternary sulfides R6(TM)x(E)2Q14 (R = rare-earth metal; TM = transition metal; E = Si, Ge, Sn, Al, or Ga; and Q = S or Se) presents an exciting opportunity for exploration of their magnetic characteristics. The magnetic properties of these materials are directly influenced by the specific R and TM elements present in the sublattices. However, since the concentration of the TM is low (1 out of 23 atoms) with 50% partial occupancy, it is unclear whether and how TMs contribute to the overall magnetism of the compounds. To investigate the role of TM, two rare-earth Fe quaternary sulfide materials, R6FeSi2S14 (R = Tb, Y), were synthesized through a solid-state reaction of arc-melted R6FeSi2 precursors with sulfur, and systematic studies were conducted on polycrystalline powders and single crystals. Y6FeSi2S14 enables the exclusive study of Fe’s magnetic behavior due to the nonmagnetic nature of Y3+. Tb6FeSi2S14 provides valuable insights into the interplay of 3d and 4f contributions in the presence of magnetic Tb. Magnetic measurements confirmed that both compounds exhibit a characteristic antiferromagnetic (AFM) peak. Y6FeSi2S14 showed a Néel temperature, TN, of ∼5 K, an effective magnetic moment, μeff, of 5.68 μB per Fe atom, and a negative Weiss constant, θ, of −19 K, confirming antiferromagnetic interactions of Fe magnetic moments. For Tb6FeSi2S14, TN increases with the introduction of Tb, reaching 14 K with a θ of −18 K. The derived μeff of 24.68 μB is higher than the contribution of 6 × Tb3+ ions (√6 × 9.72 = 23.81 μB) but close to the sum of the contribution of 6Tb + 1Fe. Magnetic structure refinement performed on neutron powder diffraction data indicates that the Fe moments in Y6FeSi2S14 are aligned along the [001] direction in an AFM order, which agrees with single-crystal directional magnetization measurements. When Y is replaced with Tb, the Tb moments are ordered in a noncollinear configuration in the ab-plane, with the Tb triangles stacked to form buckled honeycombs, while the Fe moments maintain their collinearity along the c-axis. Consequently, the complex nature of magnetism in R6(TM)x(E)2Q14 quaternaries is due to a superposition of contributions from R3+ and TM magnetic sublattices.

AB - The family of chiral, noncentrosymmetric, quaternary sulfides R6(TM)x(E)2Q14 (R = rare-earth metal; TM = transition metal; E = Si, Ge, Sn, Al, or Ga; and Q = S or Se) presents an exciting opportunity for exploration of their magnetic characteristics. The magnetic properties of these materials are directly influenced by the specific R and TM elements present in the sublattices. However, since the concentration of the TM is low (1 out of 23 atoms) with 50% partial occupancy, it is unclear whether and how TMs contribute to the overall magnetism of the compounds. To investigate the role of TM, two rare-earth Fe quaternary sulfide materials, R6FeSi2S14 (R = Tb, Y), were synthesized through a solid-state reaction of arc-melted R6FeSi2 precursors with sulfur, and systematic studies were conducted on polycrystalline powders and single crystals. Y6FeSi2S14 enables the exclusive study of Fe’s magnetic behavior due to the nonmagnetic nature of Y3+. Tb6FeSi2S14 provides valuable insights into the interplay of 3d and 4f contributions in the presence of magnetic Tb. Magnetic measurements confirmed that both compounds exhibit a characteristic antiferromagnetic (AFM) peak. Y6FeSi2S14 showed a Néel temperature, TN, of ∼5 K, an effective magnetic moment, μeff, of 5.68 μB per Fe atom, and a negative Weiss constant, θ, of −19 K, confirming antiferromagnetic interactions of Fe magnetic moments. For Tb6FeSi2S14, TN increases with the introduction of Tb, reaching 14 K with a θ of −18 K. The derived μeff of 24.68 μB is higher than the contribution of 6 × Tb3+ ions (√6 × 9.72 = 23.81 μB) but close to the sum of the contribution of 6Tb + 1Fe. Magnetic structure refinement performed on neutron powder diffraction data indicates that the Fe moments in Y6FeSi2S14 are aligned along the [001] direction in an AFM order, which agrees with single-crystal directional magnetization measurements. When Y is replaced with Tb, the Tb moments are ordered in a noncollinear configuration in the ab-plane, with the Tb triangles stacked to form buckled honeycombs, while the Fe moments maintain their collinearity along the c-axis. Consequently, the complex nature of magnetism in R6(TM)x(E)2Q14 quaternaries is due to a superposition of contributions from R3+ and TM magnetic sublattices.

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DO - 10.1021/acs.chemmater.4c03080

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Interplay of 3d and 4f Magnetism in Chiral Y₆FeSi₂S₁₄ and Tb₆FeSi₂S₁₄ Chalcogenides

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