3D transition metal ordering and Rietveld stacking fault quantification in the new oxychalcogenides La2O2Cu2–4xCd2xSe2
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Date
2016-04-04
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Publisher
American Chemical Society
Abstract
A number of LnOCuCh (Ln = La-Nd, Bi; Ch = S, Se, Te) compounds have been reported in the literature built from alternating layers of fluorite-like [Ln2O2]2+ sheets and antifluorite-like [M2Se2]2- sheets, where M is in the +1 oxidation state leading to full occupancy of available MSe4/2 tetrahedral sites. There is also a family of related LnOM0.5Se (Ln = La & Ce, M = Fe, Zn, Mn & Cd) compounds built from alternating layers of [Ln2O2]2+ sheets and [MSe2]2- sheets, where M is in the +2 oxidation state with half occupancy of available tetrahedral sites and complex ordering schemes in two dimensions. This paper reports a new family of compounds containing both +1 and +2 metal ions in the La2O2Cu2-4xCd2xSe2 family. We show how Cu1+ and Cd2+ ions segregate into distinct fully occupied and half occupied checkerboard-like layers respectively, leading to complex long-range superstructures in the third (stacking) dimension. To understand the structure and microstructure of these new materials we have developed and implemented a new methodology for studying low and high probability stacking faults using a Rietveld-compatible supercell approach capable of analyzing systems with thousands of layers. We believe this method will be widely applicable. © 2016 American Chemical Society.
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Keywords
Defects, Materials, Layers, Transition elements, Oxidation, Ions, Calculation methods
Citation
Ainsworth, C. M., Lewis, J. W., Wang, C.-H., Coelho, A. A., Johnston, H. E. A., Brand, H. E. & Evans, J. S. O.(2016). 3D transition metal ordering and Rietveld stacking fault quantification in the new oxychalcogenides La2O2Cu2–4 x Cd2 x Se2. Chemistry of Materials, 28(9), 3184-3195.doi:10.1021/acs.chemmater.6b00924