Hydrothermal synthesis, magnetism and resistivity of orthorhombic perovskite manganates Y1−xCaxMnO3 (x=0, 0.07, 0.55, 0.65)

Zhou, Zhiqiang; Guo, Li; Ye, Feng

doi:10.1016/j.jallcom.2013.03.220

Cited by 13 publications

(2 citation statements)

References 59 publications

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“…The original structures for the hexagonal , and orthorhombic YMnO 3 polymorphs were acquired from the Materials Project database . Initial calculations showed that the calculated material properties were particularly sensitive to the initialized magnetic ordering of the structures.…”

Section: Methodsmentioning

confidence: 99%

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

et al. 2020

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In the synthesis of complex oxides, solid-state metathesis provides low-temperature reactions where product selectivity can be achieved through simple changes in precursor composition. The influence of precursor structure, however, is less understood in solid-state synthesis. Here we present the ternary metathesis reaction (LiMnO 2 + YOCl → YMnO 3 + LiCl) to target two yttrium manganese oxide products, hexagonal and orthorhombic YMnO 3 , when starting from three different LiMnO 2 precursors. Using temperature-dependent synchrotron X-ray and neutron diffraction, we identify the relevant intermediates and temperature regimes of reactions along the pathway to YMnO 3. Manganesecontaining intermediates undergo a charge disproportionation into a reduced Mn(II,III) tetragonal spinel and oxidized Mn(III,IV) cubic spinel, which lead to hexagonal and orthorhombic YMnO 3 , respectively. Density functional theory calculations confirm that the presence of Mn(IV) caused by a small concentration of cation vacancies (∼2.2%) in YMnO 3 stabilizes the orthorhombic polymorph over the hexagonal. Reactions over the course of 2 weeks yield o-YMnO 3 as the majority product at temperatures below 600°C, which supports an equilibration of cation defects over time. Controlling the composition and structure of these defect-accommodating intermediates provides new strategies for selective synthesis of complex oxides at low temperatures.

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Section: Methodsmentioning

confidence: 99%

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

et al. 2020

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“…The Curie–Weiss temperatures θ c derived from Figure 5D–F are listed in Table 3, where their positive and negative values indicate FM and AFM exchange interactions, respectively, and their absolute values would reflect the strength of these exchange interactions 34 . It is noted that although the θ c of Ca 3 Ru x Mn 2− x O 7 ( x = 0.02, 0.06, 0.10) are negative, the absolute value decreases with increasing doping of Ru.…”

Section: Resultsmentioning

confidence: 99%

Enhanced magnetism in Ru‐doped hybrid improper perovskite Ca₃Mn₂O₇ via experimental and first‐principles study

Yuan

Zhang

et al. 2022

J Am Ceram Soc.

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The quasi‐2D Ruddlesden–Popper layered perovskites with single‐phase multiferroicity have attracted much attention in recent magnetoelectric memory applications. We have systematically investigated the optical and magnetic properties of Ru‐doped hybrid improper perovskite Ca3Mn2O7 both experimentally and using first‐principles calculations. The Ca3RuxMn2−xO7 (x = 0, 0.02, 0.06, 0.10) powders were successfully synthesized using the sol–gel method. Ru doping enhanced the ferromagnetism of Ca3Mn2O7. The quasi‐2D antiferromagnetic (AFM) fluctuation effect was observed in Ca3Mn2O7 and in certain doped samples. We also found that the optical bandgaps of the doped samples were reduced after doping, agreeing with the results of the first‐principles calculations. Infrared absorption spectra indicated the distortion of the Mn–O bonds was possibly due to the Jahn–Teller effect. To analyze the electronic structures and to understand the detailed atomic contributions of magnetic moments, the Crystal Orbital Hamilton Population (COHP) and Integrated COHP of the (Mn,Ru)O6 octahedra were also calculated. The Ru‐doped materials with the coexistence of ferromagnetic and AFM orderings are expected to be excellent candidates for magnetoelectric devices.

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A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO₃: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction

Marshall

Blichfeld

Skjærvø

et al. 2020

Chemistry A European J

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The reaction mechanisms, phase development and kinetics of the hydrothermal synthesis of hexagonal‐YMnO 3 from Y 2 O 3 and Mn 2 O 3 using in situ X‐ray diffraction are reported under different reaction conditions with temperatures ranging from 300 to 350 °C, and using 1, 5 and 10 m KOH, and 5 m NaOH mineraliser. Reactions initiated with Y 2 O 3 hydrating to Y(OH) 3 , which then dehydrated to YO(OH). Higher temperatures and KOH concentrations led to faster, more complete dehydrations. However, 1 m KOH led to YO(OH) forming concurrently with Y(OH) 3 before Y(OH) 3 fully dehydrated but yielded a very low phase purity of hexagonal‐YMnO 3 . Using NaOH mineraliser, no YO(OH) was observed. Dehydration also initiated at a higher temperature in the absence of Mn 2 O 3 . The evolution of Rietveld refined scale factors was used to determine kinetic information and approximate activation energies for the reaction. The described hydrothermal synthesis offers a fast, low‐temperature method for producing anisometric h‐YMnO 3 particles.

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Hydrothermal synthesis, magnetism and resistivity of orthorhombic perovskite manganates Y1−xCaxMnO3 (x=0, 0.07, 0.55, 0.65)

Cited by 13 publications

References 59 publications

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

Enhanced magnetism in Ru‐doped hybrid improper perovskite Ca₃Mn₂O₇ via experimental and first‐principles study

A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO₃: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction

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Hydrothermal synthesis, magnetism and resistivity of orthorhombic perovskite manganates Y1−xCaxMnO3 (x=0, 0.07, 0.55, 0.65)

Cited by 13 publications

References 59 publications

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO3 Polymorphs

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO3 Polymorphs

Enhanced magnetism in Ru‐doped hybrid improper perovskite Ca3Mn2O7 via experimental and first‐principles study

A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO3: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction

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Product

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Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

Defect-Accommodating Intermediates Yield Selective Low-Temperature Synthesis of YMnO₃ Polymorphs

Enhanced magnetism in Ru‐doped hybrid improper perovskite Ca₃Mn₂O₇ via experimental and first‐principles study

A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO₃: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction