• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1704-1710
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• 2010

The structure of a 2D grid-like copper(II) complex [Cu$(NCO)_2$(pyz)](pyz=pyrazine) (1) consists of 1D chains of Cu-pyz units connected by double end-on (EO) cyanato bridges. Each Cu(II) ion has a distorted octahedral coordination, completed by the four EO cyanato and two pyrazine ligands. Magnetic interactions through EO cyanato and pyrazine bridges in 1 are discussed on the basis of DFT broken-symmetry calculations at the B3LYP level. For model dicopper(II) complexes I (bridged by cyanato) and II (bridged by pyrazine), electronic structure calculations reproduce very well the experimental couplings for the S = 1/2 ferromagnetic and antiferromagnetic exchange-coupled 2D system: the calculated exchange parameters J are +1.25 $cm^{-1}$ and -3.07 $cm^{-1}$ for I and II, respectively. The $\sigma$ orbital interactions between the Cu $x^2-y^2$ magnetic orbitals and the nitrogen lone-pair orbitals of pyrazine are analyzed from the viewpoint of through-bond interaction. The energy splitting of 0.106 eV between two SOMOs indicates that the superexchange interaction should be antiferromagnetic in II. On the other hand, there are no bridging orbitals that efficiently connect the two copper(II) magnetic orbitals in I because the HOMOs of the basal-apical NCO bridge do not play a role in the formation of overlap interaction pathway. The energy separation in the pair of SOMOs of I is calculated to be very small (0.054 eV). This result is consistent with the occurrence of weakly ferromagnetic properties in I.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.34 no.5
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• pp.386-392
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• 2021

Multiferroics exhibiting the coexistence and a possible coupling of ferromagnetic and ferroelectric order are attracting widespread interest in terms of academic interests and possible applications. However, room-temperature single-phase multiferroics with soft ferromagnetic and displacive ferroelectric properties are still rare owing to the contradiction in the origin of ferromagnetism and ferroelectricity. In this study, we demonstrated that sizable ferromagnetic properties are induced in the ferroelectric bismuth ferrite-barium titanate system simply by introducing Co ions into the A-site. It is noted that all modified compositions exhibit well-saturated magnetic hysteresis loops at room temperature. Especially, 70Bi_0.95Co_0.05FeO₃-30Ba_0.95Co_0.05TiO₃ manifests noticeable ferroelectric and ferromagnetic properties; the spontaneous polarization and the saturation magnetization are 42 µC/cm² and 3.6 emu/g, respectively. We expect that our methodology will be widely used in the development of perovskite-structured multiferroic oxides.

• Journal of the Korean Magnetics Society
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• v.21 no.1
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• pp.1-4
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• 2011

We have studied magnetic structure and magnetic anisotropy energy of cubic transition metal mono-oxide cluster FeO and MnO using OpenMX method based on density functional method. The calculation results show that the antiferromagnetic spin arrangement has the lowest energy for FeO and MnO due to the superexchange interactions. The magnetic anisotropy is only found for antiferromagnetically ordered FeO cluster, since occupied electron of 3d down-spin level induces the spin-orbit couplings with <111> directed angular momentum.

• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.91-97
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• 1997

In the course of magnetic study on several perovskite-type oxides, A2Fe(Ⅲ)BO6 (A = Ca, Sr, Ba and B = Sb, Bi), we have observed a strong irreversibility in their dc-magnetizations. When the structural data and the Mossbauer spectra are considered, such an irreversibility is to be associated with some competitions between the nearest-neighbors (nn) and the next-nearest-neighbors (nnn) in their magnetic sublattices. Particularly, the Mossbauer spectra indicate that Sr2FeBiO6 of cubic perovskite-structure is apparently well ordered crystalline compound. Nontheless this antiferromagnet shows a magnetic property which resembles that of a spin-glass. The strong history dependence is observed below 91 K and the irreversible magnetic behavior is also observed from the measurement of hysteresis loops at 10 K after zero-field-cooled (zfc) and field-cooled (fc) processes. Considering the nn and the nnn superexchanges of almost same order in ordered perovskite, it is proposed that there exists a competition and cancellation of antiferromagnetic and ferromagnetic superexchange between the nearest-neighbors and the next-nearest-neighbors, thus introducing a certain degree of frustration.

• Korean Journal of Materials Research
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• v.14 no.8
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• pp.595-599
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• 2004

We investigated the structural, electrical and magnetic properties of Mn-doped $CuAlO_2$ delafossite ceramics ($CuAl_{1-x}Mn_{x}O_2,\;0\le\;x\;\le0.05$), synthesized by solid-state reaction method in an air atmosphere at a sintering temperature of $1150^{\circ}C$. The solubility limit of Mn ions in delafossite $CuAlO_2$ was found to be as low as about 3 $mol\%$. Positive Hall coefficient and the temperature dependence of conductivity established that non-doped $CuAlO_2$ ceramic is a variable-range hopping p-type semiconductor. It was found that the Mn-doping in $CuAlO_2$ rapidly reduced the hole concentration and conductivity, indicating compensation of free holes. The analysis of the magnetization data provided an evidence that antiferromagnetic superexchange interaction is the dominant mechanism of the exchange coupling between Mn ions in $CuAl_{1-x}Mn_{x}O$ alloy, leading to an almost paramagnetic behavior in this alloy.

• Journal of the Korean Magnetics Society
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• v.5 no.3
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• pp.171-174
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• 1995

We have studied the paramagnetic $CuF_{2}$ using the techniques of pulsed nuclear magnetic resonance(NMR). The powder sample revealed two well-separated lines from the distinct $^{19}F$ sites at room temperature and at 77 K. The distinct frequency shifts of the two lines appear to arise from electron transfers. Furthermore, the two sites have very short spin-lattice relaxation times ($T_{1}$). The frequency-shifted site has the shorter $T_{1}$ than the unshifted one, reflecting the difference of the electron environments of the two sites.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.218-218
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• 2012

Recently, hexagonal manganites have attracted much attention because of the coexistence of ferroelectricity and antiferromagnetic (AFM) order. The crystal structure of hexagonal manganites consists of $MnO_5$ polyhedra in which $Mn^{3+}$ ion is surrounded by three oxygen atoms in plane and two apical oxygen ions. The Mn ions within Mn-O plane form a triangular lattice and couple the spins through the AFM superexchange interaction. Due to incomplete AFM coupling between neighboring Mn ions in the triangular lattice, the system forms a geometrically-frustrated magnetic state. Among hexagonal manganites, $YMnO_3$, in particular, is the best known experimentally since the f states are empty. In addition, for applications, $YMnO_3$ thin films have been known as promising candidates for non-volatile ferroelectric random access memories. However, $YMnO_3$ has low magnetic order temperature (~70 K) and A-type AFM structure, which hinders its applications. We have synthesized $YMn1_{-x}Cr_xO_3$ (x = 0, 0.05 and 0.1) samples by the conventional solid-state reaction. The powders of stoichiometric proportions were mixed, and calcined at $900^{\circ}C$ for $YMn1_{-x}Cr_xO_3$ for 24 h. The obtained powders were ground, and pressed into 5-mm-thick disks of 1/2-inch diameter. The disks were directly put into the oven, and heated up to $1,300^{\circ}C$ and sintered in air for 24 h. The phase of samples was checked at room temperature by powder x-ray diffraction using a Rigaku Miniflex diffractometer with Cu $K{\alpha}$ radiation. All the magnetization measurements were carried out with a superconducting quantum-interference-device magnetometer. Our experiments point out that the Cr-doped samples show the characteristics of a spin-glass state at low temperatures.

• Journal of Magnetics
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• v.19 no.1
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• pp.59-63
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• 2014

Nano-sized nickel substituted cobalt ferrite powders, $Ni_xCo_{1-x}Fe_2O_4$ ($0.0{\leq}x{\leq}1.0$), were fabricated by the sol-gel method, and their crystallographic and magnetic properties were studied. All the ferrite powders showed a single spinel structure, and behaved ferrimagnetically. When the nickel substitution was increased, the lattice constants and the sizes of particles of the ferrite powders decreased. The M$\ddot{o}$ssbauer absorption spectra of $Ni_xCo_{1-x}Fe_2O_4$ ferrite powders could be fitted with two six-line subspectra, which were assigned to a tetrahedral A-site and octahedral B-sites of a typical spinel crystal structure. The increase in values of the magnetic hyperfine fields indicated that the superexchange interaction was stronger, with the increased nickel concentration in $Ni_xCo_{1-x}Fe_2O_4$. This could be explained using the cation distribution, which can be written as, $(Co_{0.28-0.28x}Fe_{0.72+0.28x})[Ni_xCo_{0.72-0.72x}Fe_{1.28-0.28x}]O_4$. The two values of the saturation magnetization and the coercivity decreased, as the rate of nickel substitution was increased. These decreases could be explained using the cation distribution, the magnetic moment, and the magneto crystalline anisotropy constant of the substituted ions.

• Korean Journal of Materials Research
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• v.28 no.7
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• pp.371-375
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• 2018

The manganese-, nickel-, and aluminum-doped cobalt ferrite powders, $Mn_{0.2}Co_{0.8}Fe_2O_4$, $Ni_{0.2}Co_{0.8}Fe_2O_4$, and $Al_{0.2}CoFe_{1.8}O_4$, are fabricated by the sol-gel method, and the crystallographic and magnetic properties of the powders are studied in comparison with those of $CoFe_2O_4$. All the ferrite powders are nano-sized and have a single spinel structure with the lattice constant increasing in $Mn_{0.2}Co_{0.8}Fe_2O_4$ but decreasing in $Ni_{0.2}Co_{0.8}Fe_2O_4$ and $Al_{0.2}CoFe_{1.8}O_4$. All the $M{\ddot{o}}ssbauer$ spectra are fitted as a superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. The values of the magnetic hyperfine fields of $Ni_{0.2}Co_{0.8}Fe_2O_4$ are somewhat increased in the A and B sites, while those of $Mn_{0.2}Co_{0.8}Fe_2O_4$ and $Al_{0.2}CoFe_{1.8}O_4$ are decreased. The variation of $M{\ddot{o}}ssbauer$ parameters is explained using the cation distribution equation, superexchange interaction and particle size. The hysteresis curves of the ferrite powders reveal a typical soft ferrite pattern. The variation in the values of saturation magnetization and coercivity are explained in terms of the site distributions, particle sizes and the spin magnetic moments of the doped ions.

• Journal of the Korean Magnetics Society
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• v.9 no.3
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• pp.143-148
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• 1999

Magnetic properties and crystallographic properties of $Cu_{1-x}Ge_{1-y}Fe_{x+y}O_3$ system were studied by using x-ray diffraction, superconducting quantum interference device (SQUID) and Mossbauer spectroscopy. All the samples have orthorhombic structure and the lattice constants some decreased as the substituted iron contents increasing. The spin-Peierls (SP) transition temperature of our samples are about 12.5 K and these temperatures lowered as increasing substituted iron contents. The Mossbauer spectra consisted with two Zeeman sextets and one doublet due to $Fe^{3+}$ ions. The jump up of magnetic hyperfine field of 2nd Zeeman sextet and the increasing of the values of quadrapole splitting and isomer shift of doublet below SP transition temperature could be interpreted with the variation of the superexchange interaction, the symmetry of lattice sites and the covalency of bonds due to the atomic displacements.