Journal
JOURNAL OF SOLID STATE CHEMISTRY
Volume 198, Issue -, Pages 210-217Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jssc.2012.09.040
Keywords
Hexagonal perovskites; Face-sharing tetramers; Oxohalides; Manganese cobalt mixed oxides; Mixed valence; Shallow donors
Funding
- Fonds Europe'en de De'veloppement Re'gional (FEDER)
- CNRS
- Re'gion Nord Pas-de-Calais
- Ministe're de l'Enseignement Supe'rieur et de la Recherche
- ANR (Agence Nationale de la Recherche)
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We show here that the incorporation of Mn in Ba-Co-oxohalide, BaCoX0.2-xO3-delta, hexagonal perovskite stabilizes the 6H-form (stacking sequence (chhhch'); c, h=[BaO3] and h'=[BaOX] layers), with tetramers of face-sharing octahedra) rather than the trimeric 10H-form. On the contrary to previous results on the Fe incorporation in similar system leading to more reduced 10H-compounds, the Mn effect is to increase the mean (Co/Mn) valence better suited to the 6H form. We experienced a poor Mn/Co miscibility during our syntheses leading to great difficulties to isolate mixed Co/Mn single phase materials and/or weak reproducibility. Powder neutron diffraction data shows a mixed Mn/Co octahedral occupancy, while the tetrahedra are filled by Co3+ cations. Anionic vacancies were refined in the h'-[BaO1-zX1-x] layer and the next c-[BaO3-z] layers, while the h-[BaO3] layers are not oxygen deficient. Magnetic properties suggest that a part of Mn cations remain paramagnetic until low temperature, while isolated spin clusters (probably driven by AFM Co tetrahedral dimers) behave as low-dimensional AFM systems. Transport measurements reveal a transition from high-temperature metallic to low-temperature semi-conducting states that could occur from defect shallow donor upon the Mn for Co substitution. (C) 2012 Elsevier Inc. All rights reserved.
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