3D Transition Metal Ordering and Rietveld Stacking Fault Quantification in the New Oxychalcogenides La2O2Cu2–4xCd2xSe2

Ainsworth, C.M.; Lewis, J.W.; Wang, C.H.; Coelho, A.A.; Johnson, H.E.; Brand, H.E.A.; Evans, J.S.O.

doi:10.1021/acs.chemmater.6b00924

3D Transition Metal Ordering and Rietveld Stacking Fault Quantification in the New Oxychalcogenides La2O2Cu2–4xCd2xSe2

Ainsworth, C.M.; Lewis, J.W.; Wang, C.H.; Coelho, A.A.; Johnson, H.E.; Brand, H.E.A.; Evans, J.S.O.

Authors

C.M. Ainsworth

J.W. Lewis

C.H. Wang

A.A. Coelho

H.E. Johnson

H.E.A. Brand

Professor John Evans john.evans@durham.ac.uk
Professor

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.

Citation

Ainsworth, C., Lewis, J., Wang, C., Coelho, A., Johnson, H., Brand, H., & Evans, J. (2016). 3D Transition Metal Ordering and Rietveld Stacking Fault Quantification in the New Oxychalcogenides La2O2Cu2–4xCd2xSe2. Chemistry of Materials, 28(9), 3184-3195. https://doi.org/10.1021/acs.chemmater.6b00924

Journal Article Type	Article
Acceptance Date	Mar 31, 2016
Online Publication Date	Apr 27, 2016
Publication Date	May 10, 2016
Deposit Date	Sep 27, 2016
Publicly Available Date	Apr 4, 2017
Journal	Chemistry of Materials
Print ISSN	0897-4756
Electronic ISSN	1520-5002
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	28
Issue	9
Pages	3184-3195
DOI	https://doi.org/10.1021/acs.chemmater.6b00924
Public URL	https://durham-repository.worktribe.com/output/1404364

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/acs.chemmater.6b00924].