Comparison of electronic structures of orthorhombic and hexagonal manganites studied by X-ray absorption spectroscopy

Dong, Chung‐Li; Bao, C. W.; Tsai, H. M.; Chiou, J. W.; Chang, C. L.; Pong, W. F.; Durán, P.; Moure, C.; Peña, O.

doi:10.1016/j.ssc.2005.03.030

Cited by 14 publications

(9 citation statements)

References 20 publications

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“…6,7 Recently, the electronic structure of YMnO 3 has been extensively studied both theoretically and experimentally. 8,9 YMnO 3 is a FE, antiferromagnetic compound with a very low electrical conductivity. Upon doping with Me, it exhibits semiconducting behavior and good electrical conductivity.…”

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confidence: 99%

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

Chen

Pao

Tsai

et al. 2009

Applied Physics Letters

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X-ray absorption spectroscopy measurements have been performed to elucidate local electronic and atomic structures of orthorhombic 3d-transition metal-doped yttrium manganites ͑YMnO 3 ͒ with chemical formulae YMn 2/3 Me 1/3 O 3 ͑Me= Co, Ni, and Cu͒. The Mn L 3 -and K-edges x-ray absorption near-edge structure ͑XANES͒ demonstrate the direct substitution of Me 2+ for Mn 3+ , so that the positive effective charge of Mn ions are increased. Me-doping is also found to induce substantial broadening of the Mn L 3 -edge feature, which suggests enhancement of the delocalization of Mn 3d e g subbands and conductivity. Local spin density approximation ͑LSDA͒ +U ͑Hubbard U parameter͒ calculations were used to understand their electronic structures.

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confidence: 99%

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

Chen

Pao

Tsai

et al. 2009

Applied Physics Letters

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“…However, the signals are broadened in contrast to spectra from a single-crystalline hexagonal manganate. 70,71 Temperature-(Figure 10a) and field-dependent (Figure 10b) magnetization measurements at lower temperatures of phase pure InFeO 3 powders revealed Curie-like paramagnetism and a signal around 160 K (Figure 10, left, red box) in the zero-fieldcooled (ZFC) curve with a drop-in magnetization during fieldcooled (FC) measurements, that indicates a first-order magnetic phase transition. During cooling, the decrease in magnetization was seen at 175 K, while the very same phase transition was observed at 200 K during heating.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Molecular Level Synthesis of InFeO₃ and InFeO₃/Fe₂O₃ Nanocomposites

et al. 2021

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New heterometallic In−Fe alkoxides [InFe-(O t Bu) 4 (PyTFP) 2 ] (1), [InFe 2 (O neo Pen) 9 (Py)] (2), and [In-Fe 3 (O neo Pen) 12 ](3) were synthesized and structurally characterized. The arrangement of metal centers in mixed-metal framework was governed by the In:Fe ratio and the coordination preferences of Fe(III) and In(III) centers to be in tetrahedral and octahedral environments, respectively. 3 displayed a star-shaped socalled "Mitsubishi" motif with the central In atom coordinated with three tetrahedral {Fe(O neo Pen) 4 } − anionic units. The deterministic structural influence of the larger In atom was evident in 1 and 2 which displayed the coordination of neutral coligands to achieve the desired coordination number. Thermal decomposition studies of compounds 1−3 under inert conditions with subsequent powder diffraction studies revealed the formation of Fe 2 O 3 and In 2 O 3 in the case of 3 and 2, whereas 1 intriguingly produced elemental In and Fe. In contrary, the thermal decomposition of 1−3 under ambient conditions produced a ternary oxide, InFeO 3 , with additional Fe 2 O 3 present as a secondary phase in a different stoichiometric ratio predetermined through the In:Fe ratio in 2 and 3. The intimate mixing of different phases in InFeO 3 /Fe 2 O 3 nanocomposites was confirmed by transmission electron microscopy of solid residues obtained after the decomposition of 1 and 2. The pure InFeO 3 particles demonstrated ferromagnetic anomalies around 170 K as determined by temperature-dependent fieldcooled and zero-field-cooled magnetization experiments. A first-order magnetic transition with an increase in the ZFC measurements was explained by temperature-induced reduction of the Fe−Fe distance and the corresponding increase in superexchange.

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“…The EELS analysis of oxygen K-edge was performed on selected samples to disclose the effect of cation vacancies on the electronic structure of h-LuMn x O 3±δ ceramics. The oxygen K-edge around 532 eV contains hybridization of the O (2p) orbitals to unoccupied states of the Lu (5d) and Mn (3d) orbitals. ,,,, Figure a shows the oxygen K-edge of EELS spectra of three samples with different composition exhibiting differences in the peaks corresponding to Mn-3d/4sp and to Lu-5d/6sp bonds to oxygen ions. Published XAS spectra of O K-edge of YMnO 3 , HoMnO 3 , and TbMnO 3 ,,,, provide guidance to interpret the features observed in EELS spectra of the O K-edge in Figure a.…”

Section: Resultsmentioning

confidence: 99%

“…The oxygen K-edge around 532 eV contains hybridization of the O (2p) orbitals to unoccupied states of the Lu (5d) and Mn (3d) orbitals. ,,,, Figure a shows the oxygen K-edge of EELS spectra of three samples with different composition exhibiting differences in the peaks corresponding to Mn-3d/4sp and to Lu-5d/6sp bonds to oxygen ions. Published XAS spectra of O K-edge of YMnO 3 , HoMnO 3 , and TbMnO 3 ,,,, provide guidance to interpret the features observed in EELS spectra of the O K-edge in Figure a. Accordingly, peaks “a” and “b” correspond to bonding of Mn (3d) orbitals to apical and planar oxygen ions, and their intensities give a scale of the population of the unoccupied states for each sample.…”

Section: Resultsmentioning

confidence: 99%

“…10 The microstructure of selected LuMn x O 3±δ samples was studied in detail in this paper aiming to establish the role of Lu and Mn vacancies on lattice extended defects, dislocations, and other forms of chemical inhomogeneity inside the crystalline grains of bulk LuMn x O 3±δ ceramics. Since defects in the lattice will also affect the local crystal field of the Mn 3+ and Lu 3+ ions in the unit cell, 11,12 the electronic structure in off-stoichiometric LuMn x O 3±δ samples is also investigated. Combined with lattice images, EELS spectra of features with relevance for the study were taken looking at the O K-edge and Mn L 3,2 -edges.…”

Section: ■ Introductionmentioning

confidence: 99%

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Nanodomains Coupled to Ferroelectric Domains Induced by Lattice Distortion in Self-Doped LuMn_xO_3±δ Hexagonal Ceramics

Baghizadeh¹,

Vieira²,

Gonçalves³

et al. 2016

J. Phys. Chem. C

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Self-doped h-LuMn x O3±δ multiferroic ceramics with 0.92 ≤ x ≤ 1.12 were studied for the dependence of magnetic properties on x. Interlocking of lattice distortion at the nanoscale with ferroelectric (FE) domains in bulk RMnO3 materials is mostly unknown. Here we report occurrence of nanodomains in transmission electron microscopy (TEM) images with the presence of antiphase boundaries/ferroelectric domain walls separating nano-FE domains. Observed chemical inhomogeneity across the crystalline grains of the ceramics causes distortion in the lattice. Formation of nanostructural domains revealed across particles of Mn deficient or Lu deficient samples includes bands of strained atomic planes, structural antiphase boundaries, and planar defects similar to stacking fault ribbons. Nanotwins exist in the basal plane, the twin boundary representing disorder of the stacking of atomic planes along the [110] direction. Image contrast in high resolution HRTEM images and TEM image simulation confirm the role of planar defects on switching of electrical polarization, which cause topology breaking of sixfold vortices of FE domains in h-RMnO3 oxides. The local orbital arrangements of ions are investigated by EELS spectroscopy of O K-edge supported by theoretical analysis. Irreversibility in magnetization below the Néel temperature of antiferromagnetic ordering of the h-LuMn x O3±δ multiferroic solid solution is found for all ceramics showing dependence on cation vacancy type and nominal content. The main features observed in the irreversibility of magnetization were correlated to defects and inhomogeneity in the nanoscale images of the lattice of ceramics. The interplay of lattice distortion linked to extended defects and magnetic/ferroelectric properties of multiferroic ceramics is further discussed.

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Comparison of electronic structures of orthorhombic and hexagonal manganites studied by X-ray absorption spectroscopy

Cited by 14 publications

References 20 publications

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

Molecular Level Synthesis of InFeO₃ and InFeO₃/Fe₂O₃ Nanocomposites

Nanodomains Coupled to Ferroelectric Domains Induced by Lattice Distortion in Self-Doped LuMn_xO_3±δ Hexagonal Ceramics

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Comparison of electronic structures of orthorhombic and hexagonal manganites studied by X-ray absorption spectroscopy

Cited by 14 publications

References 20 publications

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

Molecular Level Synthesis of InFeO3 and InFeO3/Fe2O3 Nanocomposites

Nanodomains Coupled to Ferroelectric Domains Induced by Lattice Distortion in Self-Doped LuMnxO3±δ Hexagonal Ceramics

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Molecular Level Synthesis of InFeO₃ and InFeO₃/Fe₂O₃ Nanocomposites

Nanodomains Coupled to Ferroelectric Domains Induced by Lattice Distortion in Self-Doped LuMn_xO_3±δ Hexagonal Ceramics