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Interplay between Cu and Fe Valences in BaR(Cu0.5Fe0.5)2O5+δ Double Perovskites with R=Lu, Yb, Y, Eu, Sm, Nd, and Pr

✍ Scribed by J. Lindén; M. Kochi; K. Lehmus; T. Pietari; M. Karppinen; H. Yamauchi


Publisher
Elsevier Science
Year
2002
Tongue
English
Weight
389 KB
Volume
166
Category
Article
ISSN
0022-4596

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✦ Synopsis


We have conducted a systematic 57 Fe MoK ssbauer study on BaR(Cu 0.5 Fe 0.5 ) 2 O 5؉ double perovskites with various oxygen contents and rare-earth elements (R ‫؍‬ Lu, Yb, Y, Eu, Sm, Nd, and Pr). In samples based on R ‫؍‬ Lu, Yb, Y, Eu, Sm the oxygen content remained at +0, upon reductive or oxidative heat treatments under normal pressure. The larger rare-earth elements, i.e. Nd or Pr, readily allowed for continuous oxygen content tuning up to +0.3. By employing high-pressure heat treatments higher oxygen contents were achieved for all samples. The NeH el temperature of the samples was found to decrease with increasing amounts of oxygen entering the lattice. In high-pressure oxygenated samples the decrease was less severe indicating that despite the incorporation of oxygen a large amount of Fe still remains in the high-spin trivalent state. By using chargeneutrality arguments together with the relative intensities of the MoK ssbauer spectral components the average valences of Fe and Cu were obtained. Oxygenation under normal pressure led to a corresponding increase of the valence of Fe, while Cu remained divalent. Upon high-pressure heat treatment equal amounts of Fe 3؉ and Cu 2؉ were found to be oxidized to Fe 5؉ and Cu 3؉ , respectively.


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