• Bulletin of the Korean Chemical Society
• /
• v.14 no.4
• /
• pp.439-444
• /
• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• Korean Journal of Materials Research
• /
• v.21 no.4
• /
• pp.216-219
• /
• 2011

Perovskite manganites such as $RE_{1-x}A_xMnO_3$ (RE = rare earth, A = Ca, Sr, Ba) have been the subject of intense research in the last few years, ever since the discovery that these systems demonstrate colossal magnetoresistance (CMR). The CMR is usually explained with the double-exchange (DE) mechanism, and CMR materials have potential applications for magnetic switching, recording devices, and more. However, the intrinsic CMR effect is usually found under the conditions of a magnetic field of several Teslas and a narrow temperature range near the Curie temperature ($T_c$). This magnetic field and temperature range make practical applications impossible. Recently, another type of MR, called the low-field magnetoresistance(LFMR), has also been a research focus. This MR is typically found in polycrystalline half-metallic ferromagnets, and is associated with the spin-dependent charge transport across grain boundaries. Composites with compositions $La_{0.7}(Ca_{1-x}Sr_x)_{0.3}MnO_3)]_{0.99}/(BaTiO_3)_{0.01}$ $[(LCSMO)_{0.99}/(BTO)_{0.01}]$were prepared with different Sr doping levels x by a standard ceramic technique, and their electrical transport and magnetoresistance (MR) properties were investigated. The structure and morphology of the composites were studied by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). BTO peaks could not be found in the XRD pattern because the amount of BTO in the composites was too small. As the content of x decreased, the crystal structure changed from orthorhombic to rhombohedral. This change can be explained by the fact that the crystal structure of pure LCMO is orthorhombic and the crystal structure of pure LSMO is rhombohedral. The SEM results indicate that LCSMO and BTO coexist in the composites and BTO mostly segregates at the grain boundaries of LCSMO, which are in accordance with the results of the magnetic measurements. The resistivity of all the composites was measured in the range of 90-400K at 0T, 0.5T magnetic field. The result indicates that the MR of the composites increases systematically as the Ca concentration increases, although the transition temperature $T_c$ shifts to a lower range.

• Proceedings of the Korean Institute of Surface Engineering Conference
• /
• 2016.11a
• /
• pp.181-181
• /
• 2016

Hydrogenated microcrystalline silicon (${\mu}c-Si:H$) films have attracted much attention as materials of the bottom-cells in Si thin film tandem photovoltaics due to their low bandgap and excellent stability against light soaking. However, in PECVD, the source gas $SiH_4$ must be highly diluted by $H_2$, which eventually results in low deposition rate. Moreover, it is known that high-rate ${\mu}c-Si:H$ growth is usually accompanied by a large number of dangling-bond (DB) defects in the resulting films, which act as recombination centers for photoexcited carriers, leading to a deterioration in the device performance. During film deposition, Si nanoparticles generated in $SiH_4$ discharges can be incorporated into films, and such incorporation may have effects on film properties depending on the size, structure, and volume fraction of nanoparticles incorporated into films. Here we report experimental results on the effects of nonoparticles incorporation at the different substrate temperature studied using a multi-hollow discharge plasma CVD method in which such incorporation can be significantly suppressed in upstream region by setting the gas flow velocity high enough to drive nanoparticles toward the downstream region. All experiments were performed with the multi-hollow discharge plasma CVD reactor at RT, 100, and $250^{\circ}C$, respectively. The gas flow rate ratio of $SiH_4$ to $H_2$ was 0.997. The total gas pressure P was kept at 2 Torr. The discharge frequency and power were 60 MHz, 180 W, respectively. Crystallinity Xc of resulting films was evaluated using Raman spectra. The defect densities of the films were measured with electron spin resonance (ESR). The defect density of fims deposited in the downstream region (with nonoparticles) is higher defect density than that in the upstream region (without nanoparticles) at low substrate temperature of RT and $100^{\circ}C$. This result indicates that nanoparticle incorporation can change considerably their film properties depending on the substrate temperature.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.27 no.4
• /
• pp.226-231
• /
• 2014

Thin thermistor films of solutions with nickel and manganese oxides were prepared by metal-organic decomposition (MOD). The structural properties of the thin films were investigated as a function of annealing temperature. Field emission scanning electron microscope (FE-SEM) results indicated that the thin films had a thin thickness, smooth and dense surface. The crystallization temperature of $414.9^{\circ}C$ was confirmed from thermogavimetric-differential thermal analysis (TG-DTA) curve. A single phase of cubic spinel structure was obtained for the thin film annealed from $700^{\circ}C$ to $800^{\circ}C$, which was confirmed from the X-ray diffraction (XRD). From the selected area electron diffraction (SAED) in high resolution transmission electron microscope (HRTEM), the nano grains (2~3 nm) of spinel phase with (311) and (222) planes were detected for the thin film annealed at $500^{\circ}C$, which could be applicable to read-out integrated circuit (ROIC) substrate of the uncooled microbolometer with low processing temperature.

• Korean Journal of Materials Research
• /
• v.14 no.10
• /
• pp.701-706
• /
• 2004

Bismuth layered structure ferroelectric thin films, La-substituted $Bi_{4}Ti_{3}O_{12}$ ($Bi_{1-x}La_{x}Ti_{3}O_{12}$, x=0.75, BLT) were prepared on the $Pt(111)/Ti/SiO_2/Si(100)$ substrates by a sol-gel spin coating process. The thin films were annealed in various conditions, i.e., oxygen, nitrogen and vacuum atmospheres for various annealing time. We investigated the annealing condition effects on the grain orientation and ferroelectric properties. The measured XRD patterns revealed that the BLT thin films showed only $Bi_{4}Ti_{3}O_{12}$-type phase with random orientation. $La^{3+}$ ion substitution for $Bi^{3+}$ ion in perovskite layers of $Bi_{4}Ti_{3}O_{12}$ decreased the degree of c-axis orientation and increased the remanent polarization ($2P_{r}$). The remanent polarization ($2P_{r}$) and the coercive field ($2E_{c}$) of the BLT thin film annealed at $650^{\circ}C$ for 5 min in oxygen atmosphere were $87{\mu}C/cm^2$ and 182 kV/cm, respectively, at an applied electric field of 240 kV/cm. For all of the BLT thin films annealed in various conditions, the fatigue resistance was shown. The improvement of ferroelectric properties with La substitution in $Bi_{4}Ti_{3}O_{12}$ could be attributed to the changes in space charge densities and grain orientation in the thin film.

• Journal of the Korean Magnetics Society
• /
• v.15 no.1
• /
• pp.7-11
• /
• 2005

A single slab in which one Ni(001) atom layer embedded between two of four Rh layers is considered to examine the oscillation of magnetic moment in each layer. The all electron total-energy full-potential linearized augmented plane wave(FLAPW) method was used to calculate the spin densities, magnetic moments, density of states(DOS), and the number of electrons within each muffin-tin(MT) sphere. The magnetic moment of the center layer Ni(C) in the system of 4Rh/Ni/4Rh is calculated to be 0.34${\mu}_B$, which is 40% have magnetic moment at the interface layers by strong band hybridization with Ni(C) when Ni(001) monolayers is inserted, and the magnetic moment shows a damped oscillation as we go from center Ni(C) layer to the surface Rh(S). From the calculated density of states, it is found that the Fermi level shifts inside the energy band of the Ni(C) in affection of Rh(001).

• Journal of the Korean Chemical Society
• /
• v.36 no.1
• /
• pp.44-50
• /
• 1992

The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.12 no.1
• /
• pp.36-41
• /
• 2002

Abstract The stoichiometric and double-ordered perovskite $Sr_2FeMoO_6$ (SFMO) polycrystalline ceramics were fabricated by sintering at above $900^{\circ}C$ in $H_2$(5%)/Ar reductive ambient. SMO polycrystals showed good ferromagnetic properties andmagnetrotesistqnce ratios of about 15 % at 8K and 3 % at room temperature. Amorphous SFMO thin films were deposited on $LaA1O_3$ and $SrTiO_3$ single crystal substrates using rf sputtering method with the SFMO polycrystalline ceramic target. Double-ordered perovskite polycrystalline SFMO thin films were fabricated by solid state crystallization by annealing the deposited amorphous films at above $680^{\circ}C$ in $H_2$(5%)/Ar reductive ambient. SFMO thin films exhibited ferromagnetic behavior. Their magnetroresistance ratios, however, were only 0.3~0.5% at 8K and disappeared with increasing the measuring temperature. This was attributed to the absence of magnetic spin tunneling between grains due to the porous structure and non-stoichiometric composition of the deposited films.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.12 no.1
• /
• pp.62-68
• /
• 1999

Ferroelectric $Sr_{0.7}/B_{2.3}(Ta_{1-x}Nb_x)_2O_9$(x=0, 0.1, 0.2, 0.3) thin films were deposited on $Pt/SiO_2/Si$ substrate by MOD(Metalorganic Decomposition) process. Metal carboxylate and metal alkoxide were used as precursors, and 2-methoxyethanol, xylene as solvents. After spin coating, thin films were pre-annealed at $400^{\circ}C$, followed by RTA(Rapid Thermal Annealing) and final annealing at $800^{\circ}C$ in oxygen atmosphere. These procedures were repeated three times to obtain thin films with the thickness of $2000{\AA}$. To enhance the nucleation and growth of layered-perovskite phase, thin films were rapid-thermally annealed above $720^{\circ}C$ in oxygen atmosphere. As RTA temperature increased, fluorite phase was transformed to layered-perovskite phase. And the change of Nb contents affected dielectric / electrical properties and microstructure. The ferroelectric characteristics of $Sr_{0.7}/B_{2.3}(Ta_{1-x}Nb_x)_2O_9$ thin film were Pr=8.67 $\mu{C}/cm^2$, Ec=62.4kV/cm and $I_{L}=1.4\times10^{-7}A/cm^2$ at the applied voltage of 5V, respectively.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.23 no.6
• /
• pp.283-290
• /
• 2013

A stoichiometric mixture of evaporating materials for $MgGa_2Se_4$ single crystal thin films was prepared from horizontal electric furnace. To obtain the single crystal thin films, $MgGa_2Se_4$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperatures were $610^{\circ}C$ and $400^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by double crystal X-ray diffraction (DCXD). The temperature dependence of the energy band gap of the $MgGa_2Se_4$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)=2.34 eV-(8.81{\times}10^{-4}eV/K)T^2/(T+251K)$. The crystal field and the spin-orbit splitting energies for the valence band of the $MgGa_2Se_4$ have been estimated to be 190.6 meV and 118.8 meV, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicate that the splitting of the ${\Delta}so$ definitely exists in the ${\Gamma}_5$ states of the valence band of the $MgGa_2Se_4$/GaAs epilayer. The three photocurrent peaks observed at 10 K are ascribed to the $A_{1^-}$, $B_{1^-}$exciton for n = 1 and $C_{27}-exciton$ peaks for n = 27.