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|Title:||Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide|
|Publisher:||American Chemical Society|
|Citation:||Yamamoto, T., Ohkubo, H., Tassel, C., Hayashi, N., Kawasaki, S., Okada, T., Yagi, T., Hester, J., Avdeev, M., Kobayashi, Y., & Kageyama, H. (2016). Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide. Inorganic Chemistry, 55(22), 12093-12099. doi:10.1021/acs.inorgchem.6b02513|
|Abstract:||The effect of lanthanoid (Ln = Nd, Sm, Ho) substitution on the structural and physical properties of the infinite-layer iron oxide SrFeO2 was investigated by X-ray diffraction (XRD) at ambient and high pressure, neutron diffraction, and 57Fe Mössbauer spectroscopy. Ln for Sr substituted samples up to ∼30% were synthesized by topochemical reduction using CaH2. While the introduction of the smaller Ln3+ ion reduces the a axis as expected, we found an unusual expansion of the c axis as well as the volume. Rietveld refinements along with pair distribution function analysis revealed the incorporation of oxygen atoms between FeO2 layers with a charge-compensated composition of (Sr1–xLnx)FeO2+x/2, which accounts for the failed electron doping to the FeO2 layer. The incorporated partial apical oxygen or the pyramidal coordination induces incoherent buckling of the FeO2 sheet, leading to a significant reduction of the Néel temperature. High-pressure XRD experiments for (Sr0.75Ho0.25)FeO2.125 suggest a possible stabilization of an intermediate spin state in comparison with SrFeO2, revealing a certain contribution of the in-plane Fe–O distance to the pressure-induced transition. © 2016 American Chemical Society|
|Appears in Collections:||Journal Articles|
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