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Ba3Fe1.56Ir1.44O9: A Polar Semiconducting Triple Perovskite with Near Room Temperature Magnetic Ordering

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journal contribution
posted on 29.05.2018, 18:38 by Timothy Ferreira, Darren Carone, Amanda Huon, Andreas Herklotz, Sebastian A. Stoian, Steve M. Heald, Gregory Morrison, Mark D. Smith, Hans-Conrad zur Loye
The crystal chemistry and magnetic properties for two triple perovskites, Ba3Fe1.56Ir1.44O9 and Ba3NiIr2O9, grown as large, highly faceted single crystals from a molten strontium carbonate flux, are reported. Unlike the idealized A3MM2′O9 hexagonal symmetry characteristic of most triple perovskites, including Ba3NiIr2O9, Ba3Fe1.56Ir1.44O9 possesses significant site-disorder, resulting in a noncentrosymmetric polar structure with trigonal symmetry. The valence of iron and iridium in the heavily distorted Fe/Ir sites was determined to be Fe­(III) and Ir­(V) by X-ray absorption near edge spectroscopy (XANES). Density functional theory calculations were conducted to understand the effect of the trigonal distortion on the local Fe­(III)­O6 electronic structure, and the spin state of iron was determined to be S = 5/2 by Mössbauer spectroscopy. Conductivity measurements indicate thermally activated semiconducting behavior in the trigonal perovskite. Magnetic properties were measured and near room temperature magnetic ordering (TN = 270 K) was observed for Ba3Fe1.56Ir1.44O9.