• Title/Summary/Keyword: Superexchange

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Synthesis and M$\ddot{o}$ssabuer Spectroscopy Studies of $Nd_{1-x}Bi_xY_2Fe_5O_{12}$ Nano-Particles

  • Uhm, Young Rang;Lee, Jae-Gwang;Kim, Chul Sung
    • Journal of Magnetics
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    • v.5 no.1
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    • pp.16-18
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    • 2000
  • The garnets $Nd_{1-x}Bi_xY_2Fe_5O_{12}$ ($\chi$=0.0, 0.25, 0.5, 0.75 and 1.0) have been studied by x-rays, electron microscopy, ferromagnetic resonance, vibrating sample magnetometer and Mossbauer spectroscopy, Ultra-fine polycrystalline cubic samples have been prepared by a melt-salt routed sol-gel method. The Mossbauer spectra consist of two sets of six-line patterns corresponding to $Fe^{3+}$ at the tetrahedral 24(d) and octahedral 16(a) sites. Magnetic hyperfine fields of $Nd_{0.5}Bi_{0.5}Y_2Fe_5O_{12}$ at 12 K are found to be 548 kOe (octahedral site) and 475 kOe (tetrahedral site), respectively, It is found that Debye temperatures for the tetrahedral and octahedral sites of $Nd_{0.75}Bi_{0.25}Y_2Fe_5O_{12}$ are $\theta_{tet}=436$ K and $\theta_{oct}=285$ K, respectively, The iron ions at both sites are highly covalent ferric. The Nel temperature decreases linearly with Bi concentration, from 630 K fur $\chi$=0.0 to 600 K for $\chi$=1.0, suggesting that the superexchange interaction for the Nd-O-Fe link is stronger than that for the Bi-O-Fe link. As a consequence, the coercivity of $Nd_{1-x}Bi_xY_2Fe_5O_{12}$ drastically decreases and the magnetization remains almost constant as x increases.

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Simultaneous regulation of photoabsorption and ferromagnetism of NaTaO3 by Fe doping

  • Yang, Huan;Zhang, Liguo;Yu, Lifang;Wang, Fang;Ma, Zhenzhen;Zhou, Jie;Xu, Xiaohong
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1422-1425
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    • 2018
  • $NaTa_{1-x}Fe_xO_3$ ($0{\leq}x{\leq}0.40$) nanocubes were synthesized by a relatively low temperature hydrothermal method, using $Ta_2O_5$, $FeCl_3$ and NaOH as the precursors. The UV-vis diffuse reflectance spectra showed that $NaTa_{1-x}Fe_xO_3$ had significant visible-light-absorbing capability, and the absorption edge of $NaTaO_3$ shifted to longer wavelength with the increase of Fe dopants. Moreover, $NaTa_{1-x}Fe_xO_3$ exhibited room-temperature ferromagnetism when $Fe^{3+}$ occupied $Ta^{5+}$ sites in $NaTaO_3$ crystal lattice. The ferromagnetism is mainly attributed to the superexchange interactions between doped $Fe^{3+}$, rather than the contribution of oxygen vacancies caused by Fe doping. Therefore, Fe doping can simultaneously regulate the optical and magnetic properties of $NaTaO_3$ semiconductor, which will enable its potential applications in multifunctional optical-electronics and opticalspintronics devices.

Crystallographic and Magnetic Properties of Co, Zn, Ni-Zn Substituted Nano-size Manganese Ferrites Synthesized by Sol-gel Method

  • Noh, Kwang Mo;Lee, Young Bae;Kwon, Woo Hyun;Kang, Jeoung Yun;Choi, Won-Ok;Chae, Kwang Pyo
    • Journal of Magnetics
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    • v.21 no.3
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    • pp.308-314
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    • 2016
  • Cobalt-, zinc-, and nickel-zinc-substituted nano-size manganese ferrite powders, $MnFe_2O_4$, $Mn_{0.8}Co_{0.2}Fe_2O_4$, $Mn_{0.8}Zn_{0.2}Fe_2O_4$ and $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$, were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently studied. The $MnFe_2O_4$ ferrite powder annealed at temperatures above 523 K exhibited a spinel structure, and the particle size increased as the annealing temperature increased. All ferrites annealed at 773 K showed a single spinel structure, and the lattice constants and particle size decreased with the substitution of Co, Zn, and Ni-Zn. The $M{\ddot{o}}ssbauer$ spectrum of the $MnFe_2O_4$ ferrite powder annealed at 523 K only showed a doublet due to its superparamagnetic phase, and the $M{\ddot{o}}ssbauer$ spectra of the $MnFe_2O_4$, $Mn_{0.8}Co_{0.2}Fe_2O_4$, and $Mn_{0.8}Zn_{0.2}Fe_2O_4$ ferrite powders annealed at 773 K could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of the $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$ ferrite powder annealed at 773 K consisted of two Zeeman sextets and one quadrupole doublet due to its ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explained the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. Relative to pure $MnFe_2O_4$, the saturation magnetizations and coercivities were larger in $Mn_{0.8}Co_{0.2}Fe_2O_4$ and smaller in $Mn_{0.8}Zn_{0.2}Fe_2O_4$, and $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$. These variations could be explained using the site distribution equations, particle sizes and magnetic moments of the substituted ions.

A Study on Mossbauer Spectra of the ${Ni_{1+x}}{Ti_x}{Fe_{2-2x}}O_4$ System (${Ni_{1+x}}{Ti_x}{Fe_{2-2x}}O_4$계의 $\M"{o}ssbauer$ 스펙트럼 연구)

  • Baek, Seung-Do;Ko, Jeong-Dae;Hong, Sung-Rak
    • Korean Journal of Materials Research
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    • v.11 no.1
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    • pp.3-7
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    • 2001
  • $M\"{o}ssbauer$ spectra of the $Ni_{1+x}Ti_xFe_{2-2x}O_4$ systems ($0{\leqq}x{\leqq}0.7$), which appear as single phase spinel structure, were examined at RT. The $M\"{o}ssbauer$ spectra reveal two sextet for $0{\leqq}x{\leqq}0.3$, two sextet and a doublet for $0.4{\leqq}x{\leqq}0.6$, and a doublet for x=0.7 As x increases, the area ratio of B-site and A-site($A_B/A_A$) of the sextet decreases, and the area ratio of the doublet and the total areas($A_{doublet}/A_{tot.}$) increases. The isomer shift(I.S.) of A-site slightly increases and magnetic hyperfine fields($H_{hf}$) of two sites decrease as the increasing x. From these results, we have obtained the cation distributions of the samples and concluded that the increasing x leads to the decrease of covalency of $Fe^{3+}-O^{2-}$ bond in A-sites and A-B superexchange interactions.eractions.

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Nickel Substitution Effects on Nano-sized Co, Mn and MnZn Ferrites Synthesized by Sol-gel Method

  • Choi, Won-Ok;Kwon, Woo Hyun;Chae, Kwang Pyo;Lee, Young Bae
    • Journal of Magnetics
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    • v.21 no.1
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    • pp.40-45
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    • 2016
  • Nickel substituted nano-sized ferrite powders, $Co_{1-x}Ni_xFe_2O_4$, $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$), were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently compared. The lattice constants decreased as quantity of nickel substitution increased, while the particle size decreased in $Co_{1-x}Ni_xFe_2O_4$ ferrite but increased for the $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites. For the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$) ferrite powders, the $M{\ddot{o}}ssbauer$ spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of $Mn_{0.8}Zn_{0.1}Ni_{0.1}Fe_2O_4$ consisted of two Zeeman sextets and one single quadrupole doublet due to the ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explain the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. The saturation magnetization decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. The coercivity decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. These variations could thus be explained by using the site distribution equations, particle sizes and spin magnetic moments of the substituted ions.

The development and the magnetic properties of sheet hexaferrite magnets (Hexaferrite 쉬트자석의 개발과 자기적 성질에 관한 연구)

  • 김철성;박승일;오영제
    • Journal of the Korean Magnetics Society
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    • v.5 no.4
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    • pp.281-286
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    • 1995
  • In order to study the effect of additives $SiO_{2}$ on the magnetic properties of hexaferrite sheet magnet, we used X-ray diffractometer, Mossbauer spectrometer, and VSM magnetometer. We have prepared $Ba_{0.25}Sr_{0.75}Fe_{12}O_{19}$ green sheets by the Dr. Blade method. Most of samples have a magnetoplurnbite crystal structure of typical M-type hexaferrite. The lattice parameters are found not to be affected by the addition of $SiO_{2}$. ${\alpha}-Fe_{2}O_{3}$ phase develops above $SiO_{2}$ 2.0 wt.%. Isomer shifts indicate that the valence of Fe ions is trivalent. Curie temperatures decrease slightly with increasing $SiO_{2}$ concentrations. It means that the $Si^{4+}$ subsitution for 12k-site $Fe^{3+}$ has an effect on the superexchange interactions Fe-O-Fe, which change the distance and the angle between cations and anions. It was suggested that ${\alpha}-Fe_{2}O_{3}$ phase results from the excessive Fe produced by subsituting $Si^{4+}$ for $Fe^{3+}$. Based upon the results of $Ba_{0.25}Sr_{0.75}Fe_{12}O_{19}$ added with $SiO_{2}$, we concluded that $H_{c}$, $M_{s}$ and $M_{r}$ depend more strongly on the microstructure chracteristics than on the cation substitution.

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Physical Properties of the Nonstoichiometric Perovskite $Dy_{1-x}Sr_xCoO_{3-y}$ System

  • 정수경;김민규;김규홍;여철현
    • Bulletin of the Korean Chemical Society
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    • v.17 no.9
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    • pp.794-798
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    • 1996
  • Solid solutions of the nonstoichiometric Dy1-xSrxCoO3-y system with the compositions of x=0.00, 0.25, 0.50, 0.75, and 1.00 have been synthesized by the solid state reaction at 1000 ℃ under atmospheric air pressure. The crystallographic structures of the solid solutions are analyzed by the powder X-ray diffraction patterns at room temperature. The analyses assign the compositions of x=0.00 and 0.25 to the orthorhombic system with space group of Pbnm/D2h16, the compositions of x=0.50 and 0.75 to the tetragonal system like a typical SrCoO2.86, and the composition of x=l.00 or SrCoO2.50 to the brownmillerite type system with space group of I**a. The reduced lattice volumes increase with x value due to the larger radius of Sr2+ ion than that of Dy3+ ion. The mole ratio of Co4+ ion to total Co ion with mixed valence state between Co3+ and Co4+ ions at B sites or τ value has been determined by an iodometric titration. All the samples except for the DyCoO3 compound show the mixed valnce state and thus the composition of x=0.50 has the maximum τ value in the system. The oxygen vacancies increasing with x value are randomly distributed over the crystal lattice except for the composition of x=l.00 which have the ordering of the oxygen vacancies. The nonstoichiometric chemical formulas of the Dy1-xSrxCo3+1-τCo4+τO3-(x-τ)/2 system are formulated from the x, τ, and y values. The electrical conductivity in the temperature range of 100 to 900 K increases with τ value linearly because of positive holes of the Co4+ ions in π* band as a conducting carrier. The activation energy of the x=0.50 as Ea=0.17 eV is minimum among other compouds. Broad and high order transition due to the overlap between σ* and π* bands broadened by the thermal activation is observed near 1000 K and shows a low temperature-semiconducting behavior. Magnetic properties following the Currie-Weiss law show the low to high spin transition in the cobaltate perovskite. Especially, the composition of x=0.75 presents weak ferromagnetic behavior due to the Co3+-O2--Co4+ indirect superexchange interaction.

Investigation on Ferroelectric and Magnetic Properties of Pb(Fe1/2Nb1/2)O3 Fe-Site Engineered with Antisymmetric Exchange Interaction (반대칭 교환 상호작용을 갖도록 Fe-Site가 제어된 PbFe1/2Nb1/2O3의 강유전/자기적 특성 연구)

  • Park, Ji-Hun;Lee, Ju-Hyeon;Cho, Jae-Hyeon;Jang, Jong Moon;Jo, Wook
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.35 no.3
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    • pp.297-302
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    • 2022
  • We investigated the origin of magnetic behaviors induced by an asymmetric spin exchange interaction in Fe-site engineered lead iron niobate [Pb(Fe1/2Nb1/2)O3, PFN], which exhibits a room-temperature multiferroicity. The magnitude of spin exchange interaction was regulated by the introduced transition metals with a distinct Bohr magneton, i.e., Cr, Co, and Ni. All compositions were found to have a single-phase perovskite structure keeping their ferroelectric order except for Cr introduction. We discovered that the incorporation of each transition metal imposes a distinct magnetic behavior on the lead iron niobate system; antiferro-, hard ferro-, and soft ferromagnetism for Cr, Co, and Ni, respectively. This indicates that orbital occupancy and interatomic distance play key roles in the determination of magnetic behavior rather than the magnitude of the individual Bohr magneton. Further investigations are planned, such as X-ray absorption spectroscopy, to clarify the origin of magnetic properties in this system.

Synthesis, Sytructure, and Magnetic Properties of One-Dimensional Thiophoshates, $Al_2NiP_2S_6$ (A=Rb, Cs) (1차원 구조를 갖는 Thiophoshates, $Al_2NiP_2S_6$ (A=Rb, Cs)의 합성, 구조 및 자기적 성질)

  • Dong, Yong Kwan;Lee, Kun Soo;Yun, Ho Seop;Hur, Nam Hwi
    • Journal of the Korean Chemical Society
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    • v.45 no.3
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    • pp.242-246
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    • 2001
  • The quaternary thiophosphates, $A_2NiP_2S_6$ (A=Rb, Cs), have been synthesized with halide fluxes and structurally characterized by single-crystal X-ray diffraction technique. These compounds crystallize in the space group $C_{2h}^5-P2_1/n$ of the monoclinic system with two formula units in a cell of dimensions a=5.960(2), b=12.323(4), $c=7.491(3)\AA$, $\beta=97.05(3)^{\circ}$, and $V=546.0(3)\AA^3$ for Rb2NiP2S6 and a=5.957(4), b=12.696(7), $c=7.679(4)\AA$, $b=93.60(5)^{\circ}$, and $V=579.7(5)\AA^3$ for $Cs_2NiP_2S_6.$ These compounds are isostructural. The structure of $Cs_2NiP_2S_6$ is made up of one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chains along the a axis and these chains are isolated by $Cs^+$ ions. The Ni atom is octahedrally coordinated by six S atoms. These Ni$S_6$ octahedral units are linked by sharing three m-S atoms of the $[P_2S_6^{4-}]$ anions to form the infinite one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chain. For $Cs_2NiP_2S_6$, the magnetic susceptibility reveals an antiferromagnetic exchange interaction below 8K,which corresponds to the Neel temperature ($T_N$). Above $T_N$, this compound obeys Curie-Weiss law. The magnetic moment, C, and ${\theta}forCs_2NiP_2S_6$ are 2.77 B.M., 0.9593 K, and -19.02 K, respectively. The effective magnetic moment obtained from the magnetic data is agreed with the spin-only value of $Ni^{2+}d^8$(2.83 B.M.) system.

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