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

Abstract

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 tomore » 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.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [1]
  1. Instituto de Ciencia de Materiales de Madrid, C.S.I.C., Cantoblanco E-28049 Madrid (Spain)
  2. (United States)
  3. Laboratoire Leon Brillouin, CEA/Saclay, 91191 Gif Sur Ivette Cedex, France. (France)
Publication Date:
OSTI Identifier:
22012056
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: . 187; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; CATIONS; CHARGE CARRIERS; CHARGE DISTRIBUTION; CITRATES; CRYSTALLOGRAPHY; CUBIC LATTICES; DISTRIBUTION; INTERACTIONS; MANGANESE IONS; NEUTRON DIFFRACTION; OXIDES; SPACE GROUPS; SPINELS

Citation Formats

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, and Alonso, J.A., E-mail: ja.alonso@icmm.csic.es. Why MnIn{sub 2}O{sub 4} spinel is not a transparent conducting oxide?. United States: N. p., 2012. Web. doi:10.1016/J.JSSC.2012.01.009.
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., E-mail: ja.alonso@icmm.csic.es. Why MnIn{sub 2}O{sub 4} spinel is not a transparent conducting oxide?. United States. doi:10.1016/J.JSSC.2012.01.009.
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, and Alonso, J.A., E-mail: ja.alonso@icmm.csic.es. Thu . "Why MnIn{sub 2}O{sub 4} spinel is not a transparent conducting oxide?". United States. doi:10.1016/J.JSSC.2012.01.009.
@article{osti_22012056,
title = {Why MnIn{sub 2}O{sub 4} spinel is not a transparent conducting oxide?},
author = {Martinez-Lope, M.J. and Retuerto, M. and Department of Chemistry, Rutgers State University of New Jersey, Piscataway, NJ 08854-8087 and Calle, C. de la and Porcher, Florence and Alonso, J.A., E-mail: ja.alonso@icmm.csic.es},
abstractNote = {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.},
doi = {10.1016/J.JSSC.2012.01.009},
journal = {Journal of Solid State Chemistry},
number = ,
volume = . 187,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2012},
month = {Thu Mar 15 00:00:00 EDT 2012}
}
  • Thin films of a transparent conducting oxide solid solution Cd{sub 1+x}In{sub 2-2x}Sn{sub x}O{sub 4} (x=0.15, 0.45, and 0.70) were deposited via rf magnetron sputtering. X-ray diffraction indicated the films consisted of a polycrystalline spinel phase. Atomic force microscopy measurements revealed a surface root mean square roughness between 1.3 and 6.0 nm. Optical absorption was 10% or less in the visible for x=0.15, 0.45, and 0.70. Optical gaps averaged near 3.5, 3.70, and 3.65 eV for films annealed in Ar/CdS of compositions corresponding to x=0.15, 0.45, and 0.70. Conductivity exceeded 2000 S/cm for x=0.15 and 4000 S/cm for x=0.45 and 0.70.more » Mobilities of 43, 50, and 56 cm{sup 2}/Vs were measured for films annealed in Ar/CdS of compositions corresponding to x=0.15, 0.45, and 0.70, respectively. Composition data obtained via electron probe microanalysis indicate the films are becoming Cd deficient during the annealing process. This suggests an excess of In{sup +3} and/or Sn{sup +4} on Cd{sup +2} sites may play a role in carrier production in these films. The Cd volatilization may also inhibit crystallization and decrease mobility.« less
  • A new transparent conducting oxide (TCO), which can be expressed as Ga{sub 3{minus}x}In{sub 5+x}Sn{sub 2}O{sub 16}; 0.2{le}x{le}1.6, has been identified. The equilibrium phase relationships of this new material with respect to three other TCOs in Ga{sub 2}O{sub 3}{endash}In{sub 2}O{sub 3}{endash}SnO{sub 2} are reported. The optical properties of this phase are slightly superior to Sn-doped indium oxide (ITO) and depend on composition. A room-temperature conductivity of 375 {Omega}cm{sup {minus}1} was obtained for H{sub 2}-reduced Ga{sub 2.4}In{sub 5.6}Sn{sub 2}O{sub 16}. This value is an order of magnitude lower than commercial ITO films, but comparable to values reported for bulk, polycrystalline Sn-doped In{submore » 2}O{sub 3}. {copyright} {ital 1997 American Institute of Physics.}« less
  • The formation of mixed lithium-cobalt spinel oxide Li{sub x}Co{sub 3{minus}x}O{sub 4} by solid-state reaction in air at low temperature between Li{sub 2}CO{sub 3} and Co{sub 3}O{sub 4} in the atomic ratio Li/Co 1.0 has been investigated by DTG, DTA, and X-ray diffraction measurements. Lithiated Co{sub 3}O{sub 4} was formed around 220 C. As at this temperature the diffusion rate of lithium ions into Co{sub 3}O{sub 4} lattice is very low, it can be assumed that only the surface of Co{sub 3}O{sub 4} particles was lithiated. By increasing the temperature above 380 C, LiCoO{sub 2} formation occurred.
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