Why MnIn{sub 2}O{sub 4} spinel is not a transparent conducting oxide?

• Published in: Journal of solid state chemistry 2012-03, Vol.187
• Main Authors: Martinez-Lope, M.J., Retuerto, M., Department of Chemistry, Rutgers State University of New Jersey, Piscataway, NJ 08854-8087, Calle, C. de la, Porcher, Florence, Alonso, J.A.
• Format: Article
• Language: English
• Subjects: ANTIFERROMAGNETISM; CATIONS; CHARGE CARRIERS; CHARGE DISTRIBUTION; CITRATES; CRYSTALLOGRAPHY; CUBIC LATTICES; DISTRIBUTION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; INTERACTIONS; MANGANESE IONS; NEUTRON DIFFRACTION; OXIDES; SPACE GROUPS; SPINELS
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/J.JSSC.2012.01.009

The title compound has been synthesized by a citrate technique. The crystal structure has been investigated at room temperature from high-resolution neutron powder diffraction (NPD) data. It crystallizes in a cubic spinel structure, space group Fd3-bar m, Z=8, with a=9.0008(1) A at 295 K. It exhibits a crystallographic formula (Mn{sub 0.924(2)}In{sub 0.076(2)}){sub 8a}(In{sub 1.804(2)}Mn{sub 0.196(2)}){sub 16d}O{sub 4}, where 8a and 16d stand for the tetrahedral and octahedral sites of the spinel structure, respectively, with a slight degree of inversion, {lambda}=0.08. MnIn{sub 2}O{sub 4} shows antiferromagnetic interactions below T{sub N} Almost-Equal-To 40 K, due to the statistical distribution of Mn ions over the two available sites. Unlike the related MgIn{sub 2}O{sub 4} and CdIn{sub 2}O{sub 4} spinels, well known as transparent conducting oxides, MnIn{sub 2}O{sub 4} is not transparent and shows a poor conductivity ({sigma}=0.38 S cm{sup -1} at 1123 K): the presence of Mn ions, able to adopt mixed valence states, localizes the charges that, otherwise, would be delocalized in the spinel conduction band. - Graphical Abstract: From NPD data the crystallographic formula (Mn{sub 0.924(2)}In{sub 0.076(2)}){sub 8a}(In{sub 1.804(2)}Mn{sub 0.196(2)}){sub 16d}O{sub 4}, shows a slight degree of inversion, {lambda}=0.08 and a certain In deficiency. The presence of Mn ions, able to adopt mixed oxidation states, localize the charges that, otherwise, would be delocalized in the spinel conduction band; the presence of localized Mn{sup 2+} and Mn{sup 3+} ions provides the characteristic brown color. Highlights: Black-Right-Pointing-Pointer Accurate structural determination from NPD data: inversion degree (8%), and In deficiency. Black-Right-Pointing-Pointer Bond-valence indicates Mn{sup 2+}-Mn{sup 3+} ions; edge-sharing octahedra contain 90% In{sup 3+}+10% Mn{sup 3+} cations. Black-Right-Pointing-Pointer Conductivity several orders of magnitude lower than those of MgIn{sub 2}O{sub 4} or CdIn{sub 2}O{sub 4}. Black-Right-Pointing-Pointer Variability of Mn oxidation states cancels any electron-doping effect, emptying conduction band of mobile charge carriers. Black-Right-Pointing-Pointer Curie-Weiss behavior confirming the determined charge distribution.