• Journal of the Korean Ceramic Society
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• v.52 no.5
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• pp.331-337
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• 2015

$LaBO_3$ (B = Cr, Mn, Fe, Co, and Ni) perovskites, the most common perovskite-type mixed ionic-electronic conductors (MIECs), are promising candidates for intermediate-temperature solid oxide fuel cell (IT-SOFC) cathodes. The catalytic activity on MIEC-based cathodes is closely related to the bulk ionic conductivity. Doping B-site cations with other metals may be one way to enhance the ionic conductivity, which would also be sensitively influenced by the chemical composition of the dopants. Here, using density functional theory (DFT) calculations, we quantitatively assess the activation energies of bulk oxide ion diffusion in $LaBO_3$ perovskites with a wide range of combinations of B-site cations by calculating the oxygen vacancy formation and migration energies. Our results show that bulk oxide ion diffusion dominantly depends on oxygen vacancy formation energy rather than on the migration energy. As a result, we suggest that the late transition metal-based perovskites have relatively low oxygen vacancy formation energies, and thereby exhibit low activation energy barriers. Our results will provide useful insight into the design of new cathode materials with better performance.

• Korean Journal of Materials Research
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• v.18 no.12
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• pp.673-677
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• 2008

Calcia (CaO) stabilized cubic-$HfO_2$ is studied by density functional theory (DFT) with generalized gradient approximation (GGA). When a Ca atom is substituted for a Hf atom, an oxygen vacancy is produced to satisfy the charge neutrality. The lattice parameter of a $2{\times}2{\times}2$ cubic $HfO_2$ supercell then increases by $0.02\;{\AA}$. The oxygen atoms closest to the oxygen vacancy are attracted to the vacancy as the vacancy is positive compared to the oxygen ion. When the oxygen vacancy is located at the site closest to the Ca atom, the total energy of $HfO_2$ reaches its minimum. The energy barriers for the migration of the oxygen vacancy were calculated. The energy barriers between the first and the second nearest sites, the second and the third nearest sites, and the third and fourth nearest sites are 0.2, 0.5, and 0.24 eV, respectively. The oxygen vacancies at the third and fourth nearest sites relative to the Ca atom represent the oxygen vacancies in undoped $HfO_2$. Therefore, the energy barrier for oxygen migration in the $HfO_2$ gate dielectric is 0.24 eV, which can explain the origin of gate dielectric leakage.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.293-294
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• 2008

CaO stabilized cubic-$HfO_2$ is studied by using Density Functional Theory with GGA. When a Ca atom is substituted for a Hf atom, an oxygen vacancy is produced to satisfy the charge neutrality condition. When the oxygen vacancy is located at the first nearest site from the Ca atom, the total energy of $HfO_2$ is the most favorable. We calculate the energy barriers for the oxygen vacancy migration. The energy barriers between the first and the second nearest sites, the second and the third nearest sites, and the third and fourth nearest sites are 0.2, 0.5, 0.24 eV, respectively. The oxygen vacancies at the third and fourth nearest sites from the Ca atom represent the oxygen vacancies in undoped $HfO_2$. Therefore, the energy barrier for oxygen migration in $HfO_2$ gate dielectricis is 0.24eV, which can explain a leakage origin of gate dielectric.

• Journal of the Korean Ceramic Society
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• v.46 no.2
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• pp.155-160
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• 2009

The reliability could be one of the essential properties for multilayer ceramic capacitor (MLCC) using in various electronic devices and the concentration and mobility of oxygen vacancy would play important role in the reliability. To investigate the migration behavior of oxygen vacancies, thermally stimulated depolarization current (TSDC) is adopted. In dielectric material of X5R MLCC, the TSD-Current peak observed around 150$^{\circ}C$ and 200$^{\circ}C$ which represented the migration of oxygen vacancy. Substituting Yttrium for Dysprosium in X5R MLCC showed higher migration activation energy and lower TSD current density.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.1 no.1
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• pp.5-16
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• 1991

It was grown Cubic $ZrO_2(10 mol% Y_2O_3)$ single crystals doped with 1 wt% rare earth metal oxides (RE=Ce, Pr, Nd, Eu, Er) by Skull method. It was investigated electrical properties on (111) plane of grown single crystals by Impedance Spectroscopy. It was potted relation between temperature and electrical conductivities and observed the transition at $약300-400^{\circ}$ It was obtained activation energy on the migration of oxygen vacancy between low temperature (before the transition) and high temperature (after the transition till ${\11}500^{\circ}$) and its difference can be seen the activation energy of the formation of oxygen vacancies by break up defect complexes. It was obtained the activation energy according as add yttria and rare earth metal oxides and discussed ionic conduction mechanism. Grown single crystals showed Ce: orange - red, Pr: golden - yellow, Nd: lilac, Eu: light pink, Er: pink due to dopant effect from the light absorption data in the visible range.

• Journal of the Korean Ceramic Society
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• v.37 no.3
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• pp.271-279
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• 2000

5 m/o Yb-doped SrCeO3 proton conductor was prepared by a solid state reaction method and its total electriccal conductivity measured as a function of both oxygen partial pressure and water vapor partial pressure in the temperature range of 500~100$0^{\circ}C$. From the total conductivity have been deconvoluted the partial conductivities of oxide ions, protons, and holes, respectively, on the basis of the defect model proposed. The equilibrium constant of hydrogen-dissolution reaction, proton concentration, and mobilities of oxygen vacancies and protons have subsequently been evaluated. It is verified that SrCe1-xYbxO3 is a mixed conductor of holes, protons and oxide ions and the proton conduction prevails as temperature decreases and water vapor pressure increases. The heat of water dissolution takes a representative value of $\Delta$HoH=-(140$\pm$20) kJ/mol-H2O, but tends to be less negative with increasing temperature. Migration enthalpies of proton and oxygen vacancy are extracted as 0.83$\pm$0.10 eV and 0.81$\pm$0.01 eV, respectively.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.301-305
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• 2016

We investigate proton conduction in a nonstoichiometric ${\Sigma}3$ $BaZrO_3$ (210)[001] tilt grain boundary using density functional theory (DFT). We employ the space charge layer (SCL) and structural disorder (SD) models with the introduction of protons and oxygen vacancies into the system. The segregation energies of proton and oxygen vacancy are determined as -0.70 and -0.54 eV, respectively. Based on this data, we obtain a Schottky barrier height of 0.52 V and defect concentrations at 600K, in agreement with the reported experimental values. We calculate the energy barrier for proton migration across the grain boundary core as 0.61 eV, from which we derive proton mobility. We also obtain the proton conductivity from the knowledge of proton concentration and mobility. We find that the calculated conductivity of the nonstoichiometric grain boundary is similar to those of the stoichiometric ones in the literature.

• Journal of the Korean Ceramic Society
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• v.25 no.4
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• pp.390-398
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• 1988

Effects of atmospheres and adidtives on the grain growth of TiO2 ceramics were investigated. In the range of 1300~140$0^{\circ}C$, grain growth was increased in CO2 as compared with O2 atmosphere and the grain boundary migration activation energy was lower than the diffusion activation energy of oxygen ion in TiO2. Also, in the case of addition of oxides, the grain growth was increased by oxides acting as a acceptor andinhibited by oxides acting as a donor. From the above results, when the oxygen vacancy concentration was increased, the intrinsic grain boundary mobility was increased and the pore drag force was decreased due to the rapid densification. Also it seems that the pore was migrated by the surface diffusion rather than lattice diffusion.

• Korean Journal of Materials Research
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• v.17 no.9
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• pp.453-457
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• 2007

Interest in use of ink-jet printing for pattern-on-demand fabrication of metal interconnects without complicated and wasteful etching process has been on rapid increase. However, ink-jet printing is a wet process and needs an additional thermal treatment such as an annealing process. Since a metal ink is a suspension containing metal nanoparticles and organic capping molecules to prevent aggregation of them, the microstructure of an ink-jet printed metal interconnect 'as dried' can be characterized as a stack of loosely packed nanoparticles. Therefore, during being treated thermally, an inkjet-printed interconnect is likely to evolve a characteristic microstructure, different from that of the conventionally vacuum-deposited metal films. Microstructure characteristics can significantly affect the corresponding electrical and mechanical properties. The characteristics of change in microstructure and electrical resistivity of inkjet-printed silver (Ag) films when annealed isothermally at a temperature between 170 and $240^{\circ}C$ were analyzed. The change in electrical resistivity was described using the first-order exponential decay kinetics. The corresponding activation energy of 0.44 eV was explained in terms of a thermally-activated mechanism, i.e., migration of point defects such as vacancy-oxygen pairs, rather than microstructure evolution such as grain growth or change in porosity.