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Structure and electronic properties of the quasi-one-dimensional Ba₂Co₁₋ₓZnₓS₃ series

Harrison, Mark R.; Maignan, Antoine; Hardy, Vincent; Lebedev, Oleg L.; Young, Nigel A.; Francesconi, M. Grazia

Authors

Mark R. Harrison

Antoine Maignan

Vincent Hardy

Oleg L. Lebedev

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Dr Nigel Young N.A.Young@hull.ac.uk
Senior Lecturer/ Director of Studies/ Deputy Head of Chemistry and Biochemistry/ Industrial Placements Coordinator



Abstract

This work focuses on the structure and physical properties of the solid solution Ba₂Co₁₋ₓZnₓS₃ (0 ≤ x ≤ 1), a family of quasi-one-dimensional sulfides with end members Ba₂CoS₃ and Ba₂ZnS₃. The structure of selected compounds with increasing Zn²⁺ content has been analysed using, neutron diffraction, TEM and EXAFS and the physical properties via magnetic susceptibility and resistivity measurements. The progressive substitution of the non-magnetic Zn²⁺ cation for Co²⁺ rapidly destroys the antiferromagnetic transition present at 46 K in the quasi one-dimensional Ba₂CoS₃, leading to paramagnetic behaviour down to the lowest investigated temperature (5K) for compounds with x > 0.25. For compounds with x ≥ 0.4, a pure CW regime is recovered around 300 K, yielding effective moments consistent with the g factor of the tetrahedrally coordinated Co²⁺ previously determined for Ba₂CoS₃. The Zn²⁺/Co²⁺ substitution also removes the metallic-like behaviour of Ba₂CoS₃ causing an increase in the value of the resistivity with all the Ba₂Co₁₋ₓZnₓS₃ compounds showing semiconducting behaviour. The negative magnetoresistance of Ba₂CoS₃ is improved by the Zn²⁺/Co²⁺ substitution, with values of – 6% for Ba₂Co₀.₇₅Zn₀.₂₅S₃, – 9% for Ba₂Co₀.₅Zn₀.₅S₃ and – 8% for Ba₂Co₀.₂₅Zn₀.₇₅S₃. However, there does not seem to be a correlation between the values of the resistivity and the magnetoresistance and the content of Zn²⁺, leading to the hypothesis that transport properties may be linked more closely to extrinsic properties.

Citation

Harrison, M. R., Maignan, A., Hardy, V., Lebedev, O. L., Young, N. A., & Francesconi, M. G. (2017). Structure and electronic properties of the quasi-one-dimensional Ba₂Co₁₋ₓZnₓS₃ series. Inorganic chemistry, 56(1), 213-223. https://doi.org/10.1021/acs.inorgchem.6b02014

Acceptance Date Nov 25, 2016
Online Publication Date Dec 16, 2016
Publication Date Jan 3, 2017
Deposit Date Dec 1, 2016
Publicly Available Date Dec 20, 2017
Journal Inorganic chemistry
Print ISSN 0020-1669
Electronic ISSN 1520-510X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 56
Issue 1
Pages 213-223
DOI https://doi.org/10.1021/acs.inorgchem.6b02014
Keywords Neutron diffraction; Ba₂Co₁₋ₓZnₓS₃ series
Public URL https://hull-repository.worktribe.com/output/445848
Publisher URL http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.6b02014
Copyright Statement This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see http://dx.doi.org/10.1021/acs.inorgchem.6b02014

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see http://dx.doi.org/10.1021/acs.inorgchem.6b02014






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