Destabilization of the 6H-SrIrO3 polymorph through partial substitution of zinc and lithium

M. Bremholm; C. K. Yim; D. Hirai; E. Climent-Pascual; Q. Xu; H. W. Zandbergen; M. N. Ali; R. J. Cava

doi:10.1039/C2JM32558F

Destabilization of the 6H-SrIrO₃ polymorph through partial substitution of zinc and lithium

M. Bremholm,†*^ab C. K. Yim,†^a D. Hirai,^a E. Climent-Pascual,^a Q. Xu,^c H. W. Zandbergen,^c M. N. Ali^a and R. J. Cava^a

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* Corresponding authors

^a Department of Chemistry, Princeton University, Princeton, NJ 08544, USA

^b Center for Materials Crystallography, Department of Chemistry and iNANO, Aarhus University, Aarhus C, Denmark
E-mail: bremholm@chem.au.dk

^c National Centre for HREM, Laboratory of Materials Science, Delft University of Technology, Rotterdamseweg 137, 2628 AL Delft, The Netherlands

Abstract

We report on the destabilization of the 6H-SrIrO₃ polymorph through partial substitutions of zinc and lithium for iridium to form perovskites. The perovskites crystallize in the orthorhombic space group Pbnm: SrIr_1−xZn_xO₃ is found for 0.25 ≤ x ≤ 0.33, while SrIr_1−xLi_xO₃ is found only for x = 0.25. The Zn and Li ions are randomly distributed in the B-site lattice. Analysis shows that the perovskite stabilization is not driven by changes in average ionic size but rather is due to destabilization of the face-sharing octahedra that are present in 6H-type SrIrO₃. Magnetic susceptibility measurements show Curie–Weiss behavior, with relatively large temperature independent contributions, and that the iridium atoms have low effective moments, 0.52 to 1.08 μ_B per Ir. The resistivity of SrIr_0.67Zn_0.33O₃, characterized by Mott variable range hopping type semiconducting behavior, indicates that substituted Zn ions introduce significant disorder into the system. SrIr_0.75Li_0.25O₃ has a significant linear contribution to the specific heat at low temperatures.

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https://doi.org/10.1039/C2JM32558F

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Paper

Submitted

23 Apr 2012

Accepted

24 Jun 2012

First published

10 Jul 2012

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J. Mater. Chem., 2012,22, 16431-16436

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Destabilization of the 6H-SrIrO₃ polymorph through partial substitution of zinc and lithium

M. Bremholm, C. K. Yim, D. Hirai, E. Climent-Pascual, Q. Xu, H. W. Zandbergen, M. N. Ali and R. J. Cava, J. Mater. Chem., 2012, 22, 16431 DOI: 10.1039/C2JM32558F

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Journal of Materials Chemistry

Destabilization of the 6H-SrIrO₃ polymorph through partial substitution of zinc and lithium

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Destabilization of the 6H-SrIrO₃ polymorph through partial substitution of zinc and lithium

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