Synthesis-Dependent Properties of Barlowite and Zn-Substituted Barlowite

Abstract

The mineral barlowite, Cu${}_4$(OH)${}_6$FBr, has been the focus of recent attention due to the possibility of substituting the interlayer Cu${}^{2+}$ site with non-magnetic ions to develop new quantum spin liquid materials. We re-examine previous methods of synthesizing barlowite and describe a novel hydrothermal synthesis method that produces large single crystals of barlowite and Zn-substituted barlowite (Cu${}_3$Zn${}_x$Cu${}_{1-x}$(OH)${}_6$FBr). The two synthesis techniques yield barlowite with indistinguishable crystal structures and spectroscopic properties at room temperature; however, the magnetic ordering temperatures differ by 4 K and the thermodynamic properties are clearly different. The dependence of properties upon synthetic conditions implies that the defect chemistry of barlowite and related materials is complex and significant. Zn-substituted barlowite exhibits a lack of magnetic order down to T = 2 K, characteristic of a quantum spin liquid, and we provide a synthetic route towards producing large crystals suitable for neutron scattering.

arXiv comment9 pages, 4 figures. Accepted to the Journal of Solid State Chemistry

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Cited by in corpus (15)

• The Chemistry of Quantum Spin Liquids
• Quantum Magnetism in Minerals
• From Claringbullite to a new spin liquid candidate Cu${}_3$Zn(OH)${}_6$FCl
• Materializing Rival Ground States in the Barlowite Family of Kagome Magnets: Quantum Spin Liquid, Spin Ordered, and Valence Bond Crystal States
• Dynamic fingerprint of fractionalized excitations in single-crystalline Cu${}_3$Zn(OH)${}_6$FBr
• From magnetic order to quantum disorder: a $\mu$SR study of the Zn-barlowite series of $S=\frac{1}{2}$ kagomé antiferromagnets, Zn${}_x$Cu${}_{4-x}$(OH)${}_6$FBr
• Site-Specific Structure at Multiple Length Scales in Kagome Quantum Spin Liquid Candidates
• Nuclear and Magnetic Structures of the Frustrated Quantum Antiferromagnet Barlowite, Cu${}_4$(OH)${}_6$FBr
• Antiferromagnetism in kagome $\alpha$-Cu${}_3$Mg(OH)${}_6$Br${}_2$
• High energy spin excitations in the quantum spin liquid candidate Zn-barlowite probed by resonant inelastic x-ray scattering
• Combinatorial exploration of quantum spin liquid candidates in the herbertsmithite material family
• Topological Aspects of Antiferromagnets
• Quantifying the Phase Diagram and Hamiltonian of $S=1/2$ Kagome Antiferromagnets: Bridging Theory and Experiment
• Magnetosynthesis effect on the structure and ground state of Cu${}^{2+}$-based antiferromagnets
• Local probe investigation of the spin dynamics in the kagome and inter-layers of orthorhombic barlowite Cu${}_4$(OD)${}_6$FBr: ${}^{79}$Br and ${}^{63}$Cu NQR study