• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.70.1-70.1
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• 2012

In-situ X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy studies of SOFC cathode materials will be discussed in this presentation. The mixed conducting perovskites (ABO3) containing rare and alkaline earth metals on the A-site and a transition metal on the B-site are commonly used as cathodes for solid oxide fuel cells (SOFC). However, the details of the oxygen reduction reaction are still not clearly understood. The information about the type of adsorbed oxygen species and their concentration is important for a mechanistic understanding of the oxygen incorporation into these cathode materials. XPS has been widely used for the analysis of adsorbed species and surface structure. However, the conventional XPS experiments have the severe drawback to operate at room temperature and with the sample under ultrahigh vacuum (UHV) conditions, which is far from the relevant conditions of SOFC operation. The disadvantages of conventional XPS can be overcome to a large extent with a "high pressure" XPS setup installed at the BESSY II synchrotron. It allows sample depth profiling over 2 nm without sputtering by variation of the excitation energy, and most importantly measurements under a residual gas pressure in the mbar range. It is also well known that the catalytic activity for the oxygen reduction is very sensitive to their electrical conductivity and oxygen nonstoichiometry. Although the electrical conductivity of perovskite oxides has been intensively studied as a function of temperature or oxygen partial pressure (Po2), in-situ measurements of the conductivity of these materials in contact with the electrolyte as a SOFC configuration have little been reported. In order to measure the in-plane conductivity of an electrode film on the electrolyte, a substrate with high resistance is required for excluding the leakage current of the substrate. It is also hardly possible to measure the conductivity of cracked thin film by electrical methods. In this study, we report the electrical conductivity of perovskite $La_{0.6}Sr_{0.4}CoO_{3-{\delta}}$ (LSC) thin films on yttria-stabilized zirconia (YSZ) electrolyte quantitatively obtained by in-situ IR spectroscopy. This method enables a reliable measurement of the electronic conductivity of the electrodes as part of the SOFC configuration regardless of leakage current to the substrate and cracks in the film.

• Journal of the Korean Magnetics Society
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• v.8 no.3
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• pp.111-117
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• 1998

Recent discovery of colossal magnetoresistance (CMR) phenomena in perovskite manganese oxides has evoked great interest for its physical peculiarity and the possible industrial application. Besides manganese oxides, CMR phenomena is also observed in $Tl_2Mn_2O_7$ with pyrochlore structure and in Cr-based chalcogenide with spinel structure. In this paper, we have studied electronic structures of Cr-based chalcogenide spindles $Fe_{1-x}Cu_xCr_2S_4$ at x=0.0, 0.5, 1.0 using the linearized muffin-tin orbital (LMTO) band method within the local density approximation (LDA). The characteristic resistivity for x=0.0, 0.5 could be explained qualitatively in terms of the half-metalic electronic structure and the Jahn-Teller effect. Especially, the half-metallic nature appearing in the metallic temperature regime is well descibed by the proposed conduction model for x=0.0, 0.5, 1.0. We have suggested, based on the conduction model, that the CMR phenomena observed in these compounds are closely correlated with the obtained half-metallic electronic structure.

• Economic and Environmental Geology
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• v.37 no.6 s.169
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• pp.603-612
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• 2004

Pyrochlore is known as one of the most promising materials for the immobilization of radionuclide in high level waste. This study included the synthesis, phase relation and characteristics of $pyrochlore(CaCeZr_xTi_{2-x}O_{7,\;x=0.2\~2.0)$ in the system of Ca-Ce-Zr-Ti-O. Using the CPS(Cold pressing and sintering) method, the mixtures of $CaCO3_,\;CeO_2,\;ZrO_2\;and\;TiO_2$ oxides were pressed, and sintered at $1100\~1600^{\circ}C$ for 20 hours. The optimal synthetic conditions at various compositions were differed from 1300 to $1600^{\circ}C$ Even in the optimal temperatures, pyrochlore or fluorite coexisted with minor amount of perovskite, $CeO_2\;or\;Ce_{0.75}Zr_{0.25}O_2$. It was confirmed that pyrochlore and fluorite structures were stable at $x\leq0.6\;and\;x\geq1.0$, respectively. Especially, the compositions of pyrochlore or fluorite showed non-stoichiometric compositions in that contents of Ca and Ti were more deficient and those of Zr and Ce were more excess than batch compositions with the increase of x value. These characteristics stemmed from the behavior of elements occupied at eight- and six-coordinated site, and then caused the coexistence of perovskite, $CeO_2\;or\;Ce_{0.75}Zr_{0.25}O_2$ along with pyrochlore or fluorite.

• Journal of the Korean Electrochemical Society
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• v.11 no.2
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• pp.89-94
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• 2008

We synthesized and investigated $(La_{0.75}Sr_{0.25})_{1-x}FeO_{3-\delta}$ perovskite oxides having different stoichiomety (x = 0, 0.02, 0.04, 0.06, 0.08) as cathode materials. SEM images and XRD patterns reveal that the synthesized powder has uniform size distribution and high degree of crystallinity. The electrochemical performances of the synthesized powders were investigated by AC impedance spectroscopy. Both the electric conductivity and the electrochemical performance showed the highest properties at the stoichiometry x = 0.02. Finally, we concluded that the variation of A-site deficiency results in the variation of the amount of oxygen vacancy and micro structure, which leads to the variation of electric conductivity and polarization resistance.

• Applied Chemistry for Engineering
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• v.19 no.4
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• pp.382-387
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• 2008

$Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-{\delta}}$ oxide was synthesized by polymerized complex method. Dense membrane of perovskite oxide was prepared using as-prepared powder by pressing and sintering at $1080^{\circ}C$. Leakage test was conducted on the membrane sealed by gold ring, Pyrex ring or Pyrex powder as a sealing material. The oxygen permeation flux of $Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-{\delta}}$ membrane increased with increasing temperature and was $0.74mL/min{\cdot}cm^2$ at $900^{\circ}C$. In the case of the membrane applied by sealing material, oxygen permeation flux of the membrane using gold ring at $950^{\circ}C$ was higher than that using Pyrex materials because the undesired spreading of Pyrex glass materials in the membrane led to the reduction of effective permeation area. Microphotograph analysis results for the membrane after permeation test confirmedthe diffusion of Pyrex glass seal into the membrane.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1679-1683
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• 2013

Intergrowth perovskite type complex oxides $La_{0.8}Ln_{0.2}Sr_2MnCrO_{7-{\delta}}$ (Ln=La, Nd, Gd, and Dy) have been synthesized by sol-gel method. Rietveld profile analysis shows that the phases crystallize with tetragonal unit cell in the space group I4/mmm. The unit cell parameters a and c decrease with decreasing effective ionic radius of the lanthanide ion. The magnetic studies suggest that the ferromagnetic interactions are dominant due to $Mn^{3+}$-O-$Mn^{4+}$ and $Mn^{3+}$-O-$Cr^{3+}$ double exchange interactions. Both Weiss constant (${\theta}$) and Curie temperature ($T_C$) increase with decreasing ionic radius of lanthanide ion. It was found that the transport mechanism is dominated by Mott's variable range hopping (VRH) model with an increase of Mott localization energy.

• The Korean Journal of Ceramics
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• v.4 no.3
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• pp.213-221
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• 1998

$BaCe_{0.9}Gd_{0.1_O_{2.95}$ powder was synthesized by oxalate coprecipitation method. Precipitate with a stoichimetric ratio of the cations was prepared by adding a mixture of Ba, Ce and Gd nitrate solution to an oxalic acid solution at pH 4. Reaction between the constituent oxides to form a perovskite phase was initiated at $800^{\circ}C$ and a single phase $BaCe_{0.9}Gd_{0.1_O_{2.95}$ powder having good sinterability was obtained after calcination at $1000^{\circ}C$. Sintering green compacts of this powder for 6 h showed a considerable densification to start at $1100^{\circ}C$ and resulted in 93% and 97% relative densities at $1300^{\circ}$ and at $1450^{\circ}C$, respectively. Whereas the power compacts prepared by solid state reaction had lower relative densities, 78% at $1300^{\circ}$and 90% at $1450^{\circ}C$. Fine particles of $CeO_2$ second phase were observed in the surface of the sintered compacts. This was attributed to the evaporation of BaO from the surface that had been exposed during thermal etching.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.211.2-211.2
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• 2014

Epitaxial complex oxide thin film heterostructures have attracted a great attention for their multifunctional properties, such as ferroelectricity, and ferromagnetism. Two dimensional electron gas (2DEG) confined at the interface between two insulating perovskite oxides such as LaAlO3/SrTiO3 interface, provides opportunities to expand various electronic and memory devices in nano-scale. Recently, it was reported that the conductivity of 2DEG could be controlled by external electric field. However, the switched conductivity of 2DEG was not stable with time, resulting in relaxation due to the reaction between charged surface on LaAlO3 layer and atmospheric conditions. In this report, we demonstrated a way to control the conductivity of 2DEG in non-volatile way integrating ferroelectric materials into LAO/STO heterostructure. We fabricated epitaxial Pb(Zr0.2Ti0.8)O3 films on LAO/STO heterostructure by pulsed laser deposition. The conductivity of 2DEG was reproducibly controlled with 3-order magnitude by switching the spontaneous polarization of PZT layer. The controlled conductivity was stable with time without relaxation over 60 hours. This is also consistent with robust polarization state of PZT layer confirmed by piezoresponse force microscopy. This work demonstrates a model system to combine ferroelectric material and 2DEG, which guides a way to realize novel multifunctional electronic devices.

• Coupled systems mechanics
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• v.6 no.1
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• pp.29-40
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• 2017

This work employed density functional theory to investigate the structural and ferroelectric properties of the Ruddlesden-Popper (RP) phase of lead titanate, $Pb_2TiO_4$, as well as its phase transitions with epitaxial strain. A wealth of novel structural instabilities, which are absent in the host $PbTiO_3$ material, were identified in the RP phase through phonon soft-mode analysis. Our calculations showed that the ground state of $Pb_2TiO_4$ is antiferroelectric, distinct from the dominant ferroelectric phase in the corresponding host material. In addition, applied epitaxial strain was found to play a key role in the interactions among the instabilities. The induction of a sequence of antiferroelectric and antiferrodistortive (AFD) phase transitions by epitaxial strain was demonstrated, in which the ferroic instability and AFD distortion were cooperative rather than competitive, as is the case in the host $PbTiO_3$. The RP phase in conjunction with strain engineering thus represents a new approach to creating ferroic orders and modifying the interplay among structural instabilities in the same constituent materials, enabling us to tailor the functionality of perovskite oxides for novel device applications.

• Journal of the Korean Magnetics Society
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• v.9 no.3
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• pp.131-135
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• 1999

The electronic structures and properties of layered perovskite $LaSrMnO_4$ and $SR^2MnO_4$ have been determined using the local-density full potential Imearized augmented plane wave method. The total energy calculations show that the antiterromagnetic state has lower energy than the ferromagnetic state in $LaSrMnO_4$. The jahn-Teller distortion of Mn-O octahedron produces the energy gap and the $3z^2-r^2$ orbital ordering, which stabilizes 2 dimensional antiferromagnetis state.