Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states

Rebecca W. Smaha; Wei He; Jack Mingde Jiang; Jiajia Wen; Yi Fan Jiang; John P. Sheckelton; Charles J. Titus; Suyin Grass Wang; Yu Sheng Chen; Simon J. Teat; Adam A. Aczel; Yang Zhao; Guangyong Xu; Jeffrey W. Lynn; Hong Chen Jiang; Young S. Lee

doi:10.1038/s41535-020-0222-8

Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states

Rebecca W. Smaha, Wei He, Jack Mingde Jiang, Jiajia Wen, Yi Fan Jiang, John P. Sheckelton, Charles J. Titus, Suyin Grass Wang, Yu Sheng Chen, Simon J. Teat, Adam A. Aczel, Yang Zhao, Guangyong Xu, Jeffrey W. Lynn, Hong Chen Jiang, Young S. Lee

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Abstract

The spin-12 kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu₄(OH)₆FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin-12 kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q = 0 magnetic order. Partially Zn-substituted barlowite (Cu_3.44Zn_0.56(OH)₆FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu²⁺ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.

Original language	English
Article number	23
Journal	npj Quantum Materials
Volume	5
Issue number	1
DOIs	https://doi.org/10.1038/s41535-020-0222-8
State	Published - Dec 1 2020

Funding

The work at Stanford and SLAC was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-76SF00515; this includes the synthesis, physical property measurements, neutron scattering, X-ray scattering, and numerical simulations. A portion of this research used resources at the HFIR, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. We acknowledge the support of the National Institute of Standards and Technology, U. S. Department of Commerce, in providing the neutron research facilities used in this work. This research used resources of the ALS, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Use of the APS, an Office of Science User Facility operated for the U.S. DOE Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under contract no. DE-AC02-06CH11357. NSF’s ChemMatCARS Sector 15 is supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/ CHE-1834750. Use of the PILATUS3 X CdTe 1M detector is supported by the National Science Foundation under grant number NSF/DMR-1531283. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the NSF under award ECCS-1542152. R.W.S. was supported by the Department of Defense through the NDSEG Fellowship Program and by an NSF Graduate Research Fellowship (DGE-1656518). We thank S. Lapidus for assistance at APS beamline 11-BM; C.M. Brown for assistance at NCNR beamline BT-1; I.R. Fisher for use of the MPMS and dilution refrigerator; A.T. Hristov for help with the dilution refrigerator; and S. Raghu, T. Senthil, and G. Chen for helpful discussion. The identification of any commercial product or trade name does not imply endorsement or recommendation by the National Institute of Standards and Technology.

Funders	Funder number
DOE Office of Science
Divisions of Chemistry
Materials Research
U. S. Department of Commerce
U.S. DOE
National Science Foundation	NSF/ CHE-1834750, 1542152, NSF/DMR-1531283, 1531283, 1834750, ECCS-1542152
U.S. Department of Defense	DGE-1656518
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Argonne National Laboratory
American Pain Society
Division of Materials Sciences and Engineering

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Smaha, R. W., He, W., Jiang, J. M., Wen, J., Jiang, Y. F., Sheckelton, J. P., Titus, C. J., Wang, S. G., Chen, Y. S., Teat, S. J., Aczel, A. A., Zhao, Y., Xu, G., Lynn, J. W., Jiang, H. C., & Lee, Y. S. (2020). Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states. npj Quantum Materials, 5(1), Article 23. https://doi.org/10.1038/s41535-020-0222-8

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title = "Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states",

abstract = "The spin-12 kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu4(OH)6FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin-12 kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q = 0 magnetic order. Partially Zn-substituted barlowite (Cu3.44Zn0.56(OH)6FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu2+ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.",

author = "Smaha, {Rebecca W.} and Wei He and Jiang, {Jack Mingde} and Jiajia Wen and Jiang, {Yi Fan} and Sheckelton, {John P.} and Titus, {Charles J.} and Wang, {Suyin Grass} and Chen, {Yu Sheng} and Teat, {Simon J.} and Aczel, {Adam A.} and Yang Zhao and Guangyong Xu and Lynn, {Jeffrey W.} and Jiang, {Hong Chen} and Lee, {Young S.}",

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doi = "10.1038/s41535-020-0222-8",

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Smaha, RW, He, W, Jiang, JM, Wen, J, Jiang, YF, Sheckelton, JP, Titus, CJ, Wang, SG, Chen, YS, Teat, SJ, Aczel, AA, Zhao, Y, Xu, G, Lynn, JW, Jiang, HC & Lee, YS 2020, 'Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states', npj Quantum Materials, vol. 5, no. 1, 23. https://doi.org/10.1038/s41535-020-0222-8

TY - JOUR

T1 - Materializing rival ground states in the barlowite family of kagome magnets

T2 - quantum spin liquid, spin ordered, and valence bond crystal states

AU - Smaha, Rebecca W.

AU - He, Wei

AU - Jiang, Jack Mingde

AU - Wen, Jiajia

AU - Jiang, Yi Fan

AU - Sheckelton, John P.

AU - Titus, Charles J.

AU - Wang, Suyin Grass

AU - Chen, Yu Sheng

AU - Teat, Simon J.

AU - Aczel, Adam A.

AU - Zhao, Yang

AU - Xu, Guangyong

AU - Lynn, Jeffrey W.

AU - Jiang, Hong Chen

AU - Lee, Young S.

PY - 2020/12/1

Y1 - 2020/12/1

N2 - The spin-12 kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu4(OH)6FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin-12 kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q = 0 magnetic order. Partially Zn-substituted barlowite (Cu3.44Zn0.56(OH)6FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu2+ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.

AB - The spin-12 kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu4(OH)6FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin-12 kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q = 0 magnetic order. Partially Zn-substituted barlowite (Cu3.44Zn0.56(OH)6FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu2+ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.

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JO - npj Quantum Materials

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Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states

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