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Title: Synthesis-dependent properties of barlowite and Zn-substituted barlowite

Abstract

The mineral barlowite, Cu4(OH)6FBr, has been the focus of recent attention due to the possibility of substituting the interlayer Cu2+ 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 (Cu3ZnxCu1–x(OH)6FBr). 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.

Authors:
 [1];  [1];  [2];  [2];  [1]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1490829
Alternate Identifier(s):
OSTI ID: 1490749; OSTI ID: 1691652
Grant/Contract Number:  
AC02-76SF00515; AC02-06CH11357; NSF/CHE-1346572; NSF/DMR-1531283; DGE-1656518; ECCS-1542152
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 268; Journal Issue: C; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Crystal growth; Quantum spin liquid; Magnetic properties; Crystal structure determination; Spectroscopy; Heat capacity

Citation Formats

Smaha, Rebecca W., He, Wei, Sheckelton, John P., Wen, Jiajia, and Lee, Young S. Synthesis-dependent properties of barlowite and Zn-substituted barlowite. United States: N. p., 2018. Web. doi:10.1016/j.jssc.2018.08.016.
Smaha, Rebecca W., He, Wei, Sheckelton, John P., Wen, Jiajia, & Lee, Young S. Synthesis-dependent properties of barlowite and Zn-substituted barlowite. United States. doi:https://doi.org/10.1016/j.jssc.2018.08.016
Smaha, Rebecca W., He, Wei, Sheckelton, John P., Wen, Jiajia, and Lee, Young S. Sat . "Synthesis-dependent properties of barlowite and Zn-substituted barlowite". United States. doi:https://doi.org/10.1016/j.jssc.2018.08.016. https://www.osti.gov/servlets/purl/1490829.
@article{osti_1490829,
title = {Synthesis-dependent properties of barlowite and Zn-substituted barlowite},
author = {Smaha, Rebecca W. and He, Wei and Sheckelton, John P. and Wen, Jiajia and Lee, Young S.},
abstractNote = {The mineral barlowite, Cu4(OH)6FBr, has been the focus of recent attention due to the possibility of substituting the interlayer Cu2+ 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 (Cu3ZnxCu1–x(OH)6FBr). 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.},
doi = {10.1016/j.jssc.2018.08.016},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 268,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

CSD 1839945: Experimental Crystal Structure Determination: Non-CSD Structure
dataset, April 2018


CSD 1839946: Experimental Crystal Structure Determination: Non-CSD Structure
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CSD 1839947: Experimental Crystal Structure Determination: Non-CSD Structure
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CSD 1861924: Experimental Crystal Structure Determination: Non-CSD Structure
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Order–disorder transition in the S = ½ kagome antiferromagnets claringbullite and barlowite
journal, January 2019

  • Henderson, Alyssa; Dong, Lianyang; Biswas, Sananda
  • Chemical Communications, Vol. 55, Issue 77
  • DOI: 10.1039/c9cc04930d

Order–disorder transition in the S = ½ kagome antiferromagnets claringbullite and barlowite
journal, January 2019

  • Henderson, Alyssa; Dong, Lianyang; Biswas, Sananda
  • Chemical Communications, Vol. 55, Issue 77
  • DOI: 10.1039/c9cc04930d

From Claringbullite to a New Spin Liquid Candidate Cu 3 Zn(OH) 6 FCl
journal, December 2018


Nuclear and magnetic structures of the frustrated quantum antiferromagnet barlowite, Cu 4 ( OH ) 6 FBr
journal, November 2018


Quantum magnetism in minerals
journal, July 2018