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Bond strength dependent superionic phase transformation in the solid solution series Cu_2ZnGeSe_(4-x)S_x

Zeier, Wolfgang G. and Heinrich, Christophe P. and Day, Tristan and Panithipongwut, Chatr and Kieslich, Gregor and Brunklaus, Gunther and Snyder, G. Jeffrey and Tremel, Wolfgang (2013) Bond strength dependent superionic phase transformation in the solid solution series Cu_2ZnGeSe_(4-x)S_x. Journal of Materials Chemistry A, 2 (6). pp. 1790-1794. ISSN 2050-7488. http://resolver.caltech.edu/CaltechAUTHORS:20140228-085101535

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Abstract

Recently, copper selenides have shown to be promising thermoelectric materials due to their possible superionic character resulting from mobile copper cations. Inspired by this recent development in the class of quaternary copper selenides we have focused on the structure-to-property relationships in the solid solution series Cu_2ZnGeSe_(4-x)S_x. The material exhibits an insulator-to-metal transition at higher temperatures, with a transition temperature dependent on the sulfur content. However, the lattice parameters show linear thermal expansion at elevated temperatures only and therefore no indication of a structural phase transformation. ^(63)Cu nuclear magnetic resonance shows clear indications of Cu located on at least two distinct sites, which eventually merge into one (apparent) site above the phase transformation. In this manuscript the temperature dependent lattice parameters and electronic properties of the solid solution Cu_2ZnGeSe_(4-x)S_x are reported in combination with ^(63)Cu NMR, and an attempt will be made to relate the nature of the electronic phase transformation to a superionic phase transformation and a changing covalent character of the lattice upon anion substitution in this class of materials.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://pubs.rsc.org/en/Content/ArticleLanding/2014/TA/c3ta13007j#!divAbstractPublisherArticle
http://dx.doi.org/10.1039/c3ta13007jDOIArticle
ORCID:
AuthorORCID
Snyder, G. Jeffrey0000-0003-1414-8682
Additional Information:© 2014 The Royal Society of Chemistry. Received 1st August 2013; Accepted 23rd November 2013. First published online 25 Nov 2013. Financial support through the Excellence Initiative (DFG/GSC 266) is acknowledged by W. G. Z., C. P. H. and G. K. W. G. Z. is a recipient of a fellowship from the Carl Zeiss-Stiftung. G.K. is a recipient of a fellowship from the Konrad Adenauer Stiftung. T.D. acknowledges support from the U.S. Air Force Office of Scientific Research.
Funders:
Funding AgencyGrant Number
Excellence InitiativeDFG/GSC 266
Carl Zeiss-StiftungUNSPECIFIED
Konrad Adenauer StiftungUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Record Number:CaltechAUTHORS:20140228-085101535
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140228-085101535
Official Citation:J. Mater. Chem. A, 2014, 2, 1790
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44049
Collection:CaltechAUTHORS
Deposited By: John Wade
Deposited On:28 Feb 2014 17:28
Last Modified:18 Nov 2016 17:46

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