Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide

Takafumi Yamamoto; Hiroshi Ohkubo; Cédric Tassel; Naoaki Hayashi; Shota Kawasaki; Taku Okada; Takehiko Yagi; James Hester; Maxim Avdeev; Yoji Kobayashi; Hiroshi Kageyama

doi:10.1021/acs.inorgchem.6b02513

Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide

Takafumi Yamamoto, Hiroshi Ohkubo, Cédric Tassel, Naoaki Hayashi, Shota Kawasaki, Taku Okada, Takehiko Yagi, James Hester, Maxim Avdeev, Yoji Kobayashi, Hiroshi Kageyama

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7 Scopus citations

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.

Original language	English (US)
Pages (from-to)	12093-12099
Number of pages	7
Journal	Inorganic Chemistry
Volume	55
Issue number	22
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02513
State	Published - Nov 21 2016
Externally published	Yes

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Generated from Scopus record by KAUST IRTS on 2022-09-13

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{be93669de5734338bbb7fc899f02af29,

title = "Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide",

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 M{\"o}ssbauer 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 N{\'e}el 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.",

author = "Takafumi Yamamoto and Hiroshi Ohkubo and C{\'e}dric Tassel and Naoaki Hayashi and Shota Kawasaki and Taku Okada and Takehiko Yagi and James Hester and Maxim Avdeev and Yoji Kobayashi and Hiroshi Kageyama",

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doi = "10.1021/acs.inorgchem.6b02513",

language = "English (US)",

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T1 - Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide

AU - Yamamoto, Takafumi

AU - Ohkubo, Hiroshi

AU - Tassel, Cédric

AU - Hayashi, Naoaki

AU - Kawasaki, Shota

AU - Okada, Taku

AU - Yagi, Takehiko

AU - Hester, James

AU - Avdeev, Maxim

AU - Kobayashi, Yoji

AU - Kageyama, Hiroshi

N1 - Generated from Scopus record by KAUST IRTS on 2022-09-13

PY - 2016/11/21

Y1 - 2016/11/21

N2 - 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.

AB - 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.

UR - https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b02513

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DO - 10.1021/acs.inorgchem.6b02513

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SP - 12093

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Impact of lanthanoid substitution on the structural and physical properties of an infinite-layer iron oxide

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