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

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
• 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
• Contract Date: Dec 1, 2016