Quantitative analyses of oxidation states for cubic SrMnO3 and orthorhombic SrMnO2.5 with electron energy loss spectroscopy

Kobayashi, Shunsuke; Tokuda, Yasutaka; Mizoguchi, Teruyasu; Shibata, Naoya; Satô, Yukio; Ikuhara, Yuichi; Yamamoto, Takahisa

doi:10.1063/1.3520655

Cited by 34 publications

(40 citation statements)

References 21 publications

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“…This is consistent with prior reports on the reduction of undoped SrMnO 3 to Sr 2 Mn 2 O 5 . 38 The original oxygen content and average Mn oxidation state then was determined from the mass loss observed.…”

Section: Methodsmentioning

confidence: 99%

Investigation into the effect of Si doping on the performance of Sr1−yCayMnO3−δ SOFC cathode materials

et al. 2013

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In this paper we report the successful incorporation of silicon into Sr1-yCayMnO3-δ perovskite materials for potential applications in cathodes for solid oxide fuel cells. The Si substitution onto the B site of a (29)Si enriched Sr1-yCayMn1-xSixO3-δ perovskite system is confirmed by (29)Si MAS NMR measurements at low B0 field. The very large paramagnetic shift (~3000-3500 ppm) and anisotropy (span ~4000 ppm) suggests that the Si(4+) species experiences both Fermi contact and electron-nuclear dipolar contributions to the paramagnetic interaction with the Mn(3+/4+) centres. An improvement in the conductivity is observed for low level Si doping, which can be attributed to two factors. The first of these is attributed to the tetrahedral coordination preference of Si leading to the introduction of oxide ion vacancies, and hence a partial reduction of Mn(4+) to give mixed valence Mn. Secondly, for samples with high Sr levels, the undoped systems adopt a hexagonal perovskite structure containing face sharing of MnO6 octahedra, while Si doping is shown to help to stabilise the more highly conducting cubic perovskite containing corner linked octahedra. The level of Si, x, required to stabilise the cubic Sr1-yCayMn1-xSixO3-δ perovskite in these cases is shown to decrease with increasing Ca content; thus cubic symmetry is achieved at x = 0.05 for the Sr0.5Ca0.5Mn1-xSixO3-δ series; x = 0.075 for Sr0.7Ca0.3Mn1-xSixO3-δ; x = 0.10 for Sr0.8Ca0.2Mn1-xSixO3-δ; and x = 0.15 for SrMn1-xSixO3-δ. Composites with 50% Ce0.9Gd0.1O1.95 were examined on dense Ce0.9Gd0.1O1.95 pellets. For all series an improvement in the area specific resistances (ASR) values is observed for the Si-doped samples. Thus these preliminary results show that silicon can be incorporated into perovskite cathode materials and can have a beneficial effect on the performance.

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Section: Methodsmentioning

confidence: 99%

Investigation into the effect of Si doping on the performance of Sr1−yCayMnO3−δ SOFC cathode materials

et al. 2013

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“…By doing so, the O-K b peak in all spectra is aligned at 537 eV, while the positions and intensity of the adjacent O-K a and O-K c peaks change steadily with strain as indicated with dashed lines. According to previous reports, since the O-K a prepeak has a very strong contribution from the Mn 3d e g band occupancy, it can be used to extract information on the Mn oxidation state [36,37].…”

Section: B Eel Spectroscopy Studiesmentioning

confidence: 99%

“…have been thoroughly addressed [36][37][38][39]. Nevertheless, the determination of the energy difference between the oxygen O-K b main peak and the O-K a prepeak appears to be the most accurate method and less dependent on spectral noise [36,38], and has been successfully applied to SrMnO 3 thin films [9,17].…”

Section: Mn-l 3 and Mn-l 2 Edges And The O-k A And Mn-l 3 Edgesmentioning

confidence: 99%

Strain-driven oxygen deficiency in multiferroicSrMnO3thin films

Agrawal

Guo

et al. 2016

Phys. Rev. B

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The structural and electronic properties of a series of SrMnO 3 thin films grown on different substrates leading to different biaxial strains are examined by means of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS). Here, we report a comprehensive theoretical investigation on the impact of oxygen nonstoichiometry and strain on the O-K and Mn-L 2,3 electron energy-loss near-edge structures of SrMnO 3 with the aid of the all-electron density functional theory code WIEN2K. Our experimental and theoretical EELS data reveal pronounced peak-height changes and energy shifts as a function of strain, which are ascribed to differences in the oxygen vacancy density rather than to a direct effect of lattice distortions. In addition, we find that the formation of oxygen vacancies in SrMnO 3 is likely to be enhanced by tensile strain. Compared to the unstrained material, the vacancy formation energy is reduced by 0.25 eV under 3.78% tensile strain.

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“…XAS of the Mn L 2,3 edges shows a significant increase of the L 3 /L 2 ratio in x =1 SLs compared to SrMnO 3 films (Fig. S3), thus indicating a transfer of electrons from Ir 4+ to Mn 4+ [28,29]. In order to show the evolution of PMA, magnetization loops were measured along both in-plane ([100]) and outof-plane ([001]) directions and the representative results are shown in Fig.…”

mentioning

confidence: 97%

Tuning Perpendicular Magnetic Anisotropy by Oxygen Octahedral Rotations in (La1−xSrxMnO
Yi
¹
,
Flint
²
,
Balakrishnan
³

et al. 2017
Phys. Rev. Lett.
115
9
91
1
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Perpendicular magnetic anisotropy (PMA) plays a critical role in the development of spintronics, thereby demanding new strategies to control PMA. Here we demonstrate a conceptually new type of interface induced PMA that is controlled by oxygen octahedral rotation. In superlattices comprised of La1−xSrxMnO3 and SrIrO3, we find that all superlattices (0≤x ≤1) exhibit ferromagnetism despite the fact that La1−xSrxMnO3 is antiferromagnetic for x >0.5. PMA as high as 4×10 6 erg/cm 3 is observed by increasing x and attributed to a decrease of oxygen octahedral rotation at interfaces. We also demonstrate that oxygen octahedral deformation cannot explain the trend in PMA. These results reveal a new degree of freedom to control PMA, enabling discovery of emergent magnetic textures and topological phenomena.

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Quantitative analyses of oxidation states for cubic SrMnO3 and orthorhombic SrMnO2.5 with electron energy loss spectroscopy

Cited by 34 publications

References 21 publications

Investigation into the effect of Si doping on the performance of Sr1−yCayMnO3−δ SOFC cathode materials

Investigation into the effect of Si doping on the performance of Sr1−yCayMnO3−δ SOFC cathode materials

Strain-driven oxygen deficiency in multiferroicSrMnO3thin films

Tuning Perpendicular Magnetic Anisotropy by Oxygen Octahedral Rotations in (La1−xSrxMnO
Yi
¹
,
Flint
²
,
Balakrishnan
³

et al. 2017
Phys. Rev. Lett.
115
9
91
1
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Quantitative analyses of oxidation states for cubic SrMnO3 and orthorhombic SrMnO2.5 with electron energy loss spectroscopy

Cited by 34 publications

References 21 publications

Investigation into the effect of Si doping on the performance of Sr1−yCayMnO3−δ SOFC cathode materials

Investigation into the effect of Si doping on the performance of Sr1−yCayMnO3−δ SOFC cathode materials

Strain-driven oxygen deficiency in multiferroicSrMnO3thin films

Tuning Perpendicular Magnetic Anisotropy by Oxygen Octahedral Rotations in (La1−xSrxMnOYi1, Flint2, Balakrishnan3 et al. 2017Phys. Rev. Lett.1159911View full textAdd to dashboardCite

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Tuning Perpendicular Magnetic Anisotropy by Oxygen Octahedral Rotations in (La1−xSrxMnO
Yi
¹
,
Flint
²
,
Balakrishnan
³

et al. 2017
Phys. Rev. Lett.
115
9
91
1
View full text Add to dashboard Cite