• Korean Journal of Materials Research
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• v.30 no.2
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• pp.99-104
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• 2020

Recent discoveries of ferroelectric properties in ultrathin doped hafnium oxide (HfO₂) have led to the expectation that HfO₂ could overcome the shortcomings of perovskite materials and be applied to electron devices such as Fe-Random access memory (RAM), ferroelectric tunnel junction (FTJ) and negative capacitance field effect transistor (NC-FET) device. As research on hafnium oxide ferroelectrics accelerates, several models to analyze the polarization switching characteristics of hafnium oxide ferroelectrics have been proposed from the domain or energy point of view. However, there is still a lack of in-depth consideration of models that can fully express the polarization switching properties of ferroelectrics. In this paper, a Zr-doped HfO₂ thin film based metal-ferroelectric-metal (MFM) capacitor was implemented and the polarization switching dynamics, along with the ferroelectric characteristics, of the device were analyzed. In addition, a study was conducted to propose an applicable model of HfO₂-based MFM capacitors by applying various ferroelectric switching characteristics models.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.381-381
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• 2010

$(ZrO_2)_{0.66}(HfO_2)_{0.34}$ thin films as gate dielectrics have been proposed to overcome the problems of tunneling current and degradation mobility inachieving a thin equivalent oxide thickness. An extremely thin $SiO_2$ layer is used in order to separate the carrier in MOSFET channel from the dielectric field fluctuation caused by phonons in the dielectric which decreases the carrier mobility. The electronic and optical properties influenced the device performance to a great extent. $(ZrO_2)_{0.66}(HfO_2)_{0.34}$ dielectric films on p-Si (100) were grown by atomic layer deposition method, for which the conduction band offsets, valence band offsets and band gapswere obtained by using X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. The band gap, valence and conduction band offset values for $(ZrO_2)_{0.66}(HfO_2)_{0.34}$ dielectric thin film, grown on Si substrate were about 5.34, 2.35 and 1.87 eV respectively. This band alignment was similar to that of $ZrO_2$. In addition, The dielectric function (k, $\omega$), index of refraction n and the extinction coefficient k for the $(ZrO_2)_{0.66}(HfO_2)_{0.34}$ thin films were obtained from a quantitative analysis of REELS data by comparison to detailed dielectric response model calculations using the QUEELS-$\varepsilon$(k, $\omega$)-REELS software package. These optical properties are similar with $ZrO_2$ dielectric thin films.

• Bulletin of the Korean Chemical Society
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• v.23 no.8
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• pp.1067-1072
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• 2002

A new polystyrene-divinylbenzene resin containing 2-(2-thiazolylazo)-5-dimethylamino-phenol (TAM) functional groups has been synthesized and its sorption behavior for nineteen metal ions, including Zr(Ⅳ),Hf(Ⅳ) and U(Ⅵ) has been investigated by batch and column methods. The chelating resin showed high sorption affinity for Zr(Ⅳ) at pH 1-5 and U(Ⅵ) at pH 4. Some parameters affecting the sorption of the metal ions have been detailed. The breakthrough and overall capacities were measured under optimized conditions. The overall capacities of Zr(Ⅳ), Th(Ⅳ) and U(Ⅵ), which showed higher than the other metal ions, were 0.90,0.84 and 0.80 mmol/g, respectively. The elution order of metal ions at pH 4 was evaluated as Zr(Ⅳ) > Th(Ⅳ) > U(Ⅵ) > Cu(Ⅱ) > Hf(Ⅳ) > W(Ⅵ) > Mo(Ⅵ) > In(Ⅲ) > Sn(Ⅳ) > Cr(Ⅲ) > V(Ⅴ) > Fe(Ⅲ). Quantitative recovery of most metal ions except Zr(Ⅳ) was achieved using 2M HNO3. Desorption and recovery of Zr(Ⅳ) was successfully performed with 2 M HClO4 and 2 M HCl.

• Journal of the Korean Ceramic Society
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• v.22 no.6
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• pp.42-52
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• 1985

Several $Al_2O_3$-based polycrystalline which had different dopant ratio in the range of 0.5mol% were prepared by doping pure $Cr_2O_3$ $HfO_2$. Single crystalline which had same composition with above polycrystalline were made by means of floating zone method. This study examined the role of each dopant for enhancing the mechanical properties of $Al_2O_3$-based Ceramics. Optical micrographs $({ imes}200)$ of $Al_2O_3-Cr_2O_3$ single crystal showing not only radial crack (rc) on the specimen surface but median crack(mc) and lateral crack(lc) under surface at the edge of indentation mark. Fracture toughness of Al2O3-based Ceramics was increased with $ZrO_2$ content. Alloying effect of $Cr_2O_3$ contributed to the hardness of $Al_2O_3$ based ceramics.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.3
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• pp.195-214
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• 2020

The Samgwang Au-Ag deposit has been one of the largest deposits in Korea. The deposit consists of eight lens-shaped quartz veins which filled fractures along fault zones in Precambrian metasedimentary rock, which feature suggest that it is an orogenic-type deposit. The Ti-bearing minerals occur in wallrock (titanite, ilmenite and rutile) and laminated quartz vein (rutile). They occur minerals including biotite, muscovite, chlorite, white mica, monazite, zircon, apatite in wallrock and white mica, chlorite, arsenopyrite in laminated quartz vein. Chemical composition of titanite has maximum vaules of 3.94 wt.% (Al₂O₃), 0.49 wt.% (FeO), 0.52 wt.% (Nb₂O₅), 0.46 wt.% (Y₂O₃) and 0.43 wt.% (V₂O₅). Titanite with 0.06~0.14 (Fe/Al ratio) and 0.06~0.15 (X_Al (=Al/Al+Fe³⁺+Ti)) corresponds with metamorphic origin and low-Al variety. Chemical composition of ilmenite has maximum values of 0.07 wt.% (ZrO₂), 0.12 wt.% (HfO₂), 0.26 wt.% (Nb₂O₅), 0.04 wt.% (Sb₂O₅), 0.13 wt.% (Ta₂O₅), 2.62 wt.% (As₂O₅), 0.29 wt.% (V₂O₅), 0.12 wt.% (Al₂O₃) and 1.59 wt.% (ZnO). Chemical composition of rutile in wallrock and laminated quartz vein has maximum values of 0.35 wt.%, 0.65 wt.% (HfO₂), 2.52 wt.%, 0.19 wt.% (WO₃), 1.28 wt.%, 1.71 wt.% (Nb₂O₃), 0.03 wt.%, 0.07 wt.% (Sb₂O₃), 0.28 wt.%, 0.21 wt.% (As₂O₅), 0.68 wt.%, 0.70 wt.% (V₂O₃), 0.48 wt.%, 0.59 wt.% (Cr₂O₃), 0.70 wt.%, 1.90 wt.% (Al₂O₃) and 4.76 wt.%, 3.17 wt.% (FeO), respectively. Rutile in laminated quartz vein is higher contents (HfO₂, Nb₂O₃, As₂O₅, Cr₂O₃, Al₂O₃ and FeO) and lower content (WO₃) than rutile in wallrock. The substitutions of rutile in wallrock and laminated quatz vein are as followed : rutile in wallrock [(Fe³⁺, Al³⁺, Cr³⁺) + Hf⁴⁺ + (W⁵⁺, As⁵⁺, Nb⁵⁺) ⟵⟶ 2Ti⁴⁺ + V⁴⁺, 2Fe²⁺ + (Al³⁺, Cr³⁺) + Hf⁴⁺ + (W⁵⁺, As⁵⁺, Nb⁵⁺) ⟵⟶ 2Ti⁴⁺ + 2V⁴⁺], rutile in laminated quartz vein [(Fe³⁺, Al³⁺) + As⁵⁺ ⟵⟶ Ti⁴⁺ + V⁴⁺, (Fe³⁺, Al³⁺) + As⁵⁺ ⟵⟶ Ti⁴⁺ + Hf⁴⁺, 4(Fe³⁺, Al³⁺) ⟵⟶ Ti⁴⁺ + (W⁵⁺, Nb⁵⁺) + Cr³⁺], respectively. Based on these data, titanite, ilmenite and rutile in wallrock were formed by resolution and reconcentration of cations (W⁵⁺, Nb⁵⁺, As⁵⁺, Hf⁴⁺, V⁴⁺, Cr³⁺, Al³⁺, Fe³⁺, Fe²⁺) in minerals of wallrock during regional metamorphism. And then rutile in laminated quartz vein was formed by reconcentration of cations (Nb⁵⁺, As⁵⁺, Hf⁴⁺, Cr³⁺, Al³⁺, Fe³⁺, Fe²⁺) in alteration minerals (white mica, chlorite) and Ti-bearing minerals reaction between hydrothermal fluid originated during ductile shear and Ti-bearing minerals (titanite, ilmenite and rutile) in wallrock.

• Journal of the Korean Ceramic Society
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• v.22 no.6
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• pp.37-41
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• 1985

Several $Al_2O_3$-based polycrystalline which had different dopant ratio in the range of 0.5mol% were prepared by doping pure $Cr_2O_3$, $ZrO_2$, $HfO_3$ Single crystalline which had same composition with above polycrystalline were made by means of floating zone method. This study examined the role of each dopant for enhancing the mefchanical properties of $Al_2O_3$-based Ceramics. Optical micrographs $({\times}200)$ of $Al_2O_3-Cr_2O_3$ single crystal showing not only radial crack (rc) on the specimen surface but median crack (mc) and lateral crack (lc) under surface at the edge of indentation mark. Fracture toughness of $Al_2O_3$-based Ceramics was increased with $ZrO_2$ content. Alloying effect of $Cr_2O_3$ contributed to the hardness of $Al_2O_3$ based ceramics.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.36 no.1
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• pp.88-92
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• 2023

The ferroelectricity in Hf_0.5Zr_0.5O₂ (HZO) thin films is one of the most interesting topics for next-generation nonvolatile memory applications. It is known that a crystallization process is required at a temperature of 400℃ or higher to form an orthorhombic phase that results in the ferroelectric properties of the HZO film. However, to realize the integration of ferroelectric HZO films in the back-end-of-line, it is necessary to reduce the annealing temperature below 400℃. This study aims to comprehensively analyze the ferroelectric properties according to the annealing temperature (350-500℃) and time (1-5 h) using a furnace as a crystallization method for HZO films. As a result, the ferroelectric behaviors of the HZO films were achieved at a temperature of 400℃ or higher regardless of the annealing time. At the annealing temperature of 350℃, the ferroelectric properties appeared only when the annealing time was sufficiently increased (4 h or more). Based on these results, it was experimentally confirmed that the optimization of the annealing temperature and time is very important for the ferroelectric phase crystallization of HZO films and the improvement of their ferroelectric properties.

• Journal of the Korean earth science society
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• v.27 no.1
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• pp.49-60
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• 2006

The purpose of this study is to investigate geochemical characteristics for stream sediments in the Naju area. We collected 139 stream sediments samples from primary channels. Samples were dried slowly in the laboratory and chemical analysis was carried out using XRF. ICP-AES and NAA. In order to investigate geochemical characteristics, the geological groups categorized into granitic gneiss area, schist area, granite area, arenaceous rock area, tuff area, andesite area, and rhyolite area. Average contents of major elements for geological groups are $SiO_2\;58.37{\sim}66.06wt.%,\;Al_2O_3\;13.98{\sim}18.41wt.%,\;Fe_2O_3\;4.09{\sim}6.10wt.%,\;CaO\;0.54{\sim}1.33wt.%,\;MgO\;0.86{\sim}1.34wt.%,\;K_2O\;2.38{\sim}4.01wt.%,\;Na_2O\;0.90{\sim}1.32wt.%,\;TiO_2\;0.82{\sim}1.03wt.%,\;MnO\;0.09{\sim}0.15wt.%,\;P_2O_5\;0.11{\sim}0.18wt.%$. According to the comparison of average contents of major elements, $Al_2O_3\;and\;K_2O$ are higher in granitic gneiss area, $Fe_2O_3,\;CaO,\;P_2O_5$ are higher in tuff area, MgO and $TiO_2$ are higher in andesite area, $Na_2O_$ is higher in rhyolite area, $SiO_2$, and MnO are higher in arenaceous rock area. Average contents of minor and rare earth elements for geological groups are $Ba\;1278{\sim}1469ppm,\;Be\;1.1{\sim}1.5ppm,\;Cu\;18{\sim}25ppm,\;Nb\;25{\sim}37ppm,\;Ni\;16{\sim}25ppm,\;Pb\;21{\sim}28ppm,\;Sr\;83{\sim}155ppm,\;V\;64{\sim}98ppm,\;Zr\;83{\sim}146ppm,\;Li\;32{\sim}45ppm,\;Co\;7.2{\sim}12.7ppm,\;Cr\;37{\sim}76ppm,\;Cs\;4.8{\sim}9.1ppm,\;Hf\;7.5{\sim}25ppm,\;Rb\;88{\sim}178ppm,\;Sc\;7.7{\sim}12.6ppm,\;Zn\;83{\sim}143ppm,\;Pa\;11.3{\sim}37ppm,\;Ce\;69{\sim}206ppm,\;Eu\;1.1{\sim}1.5ppm,\;Yb\;1.8{\sim}4.4ppm$. According to the comparison of average contents of minor and rare earth elements for geological groups, Pb, Li, Cs, Hf, Rb, Sb, Pa, Ce, Eu, and Yb are higher in granitic gneiss area; Ba, Co, and Cr in schist area; Nb, Ni, and Zr in arenaceous rock area; Sr in tuff area: and Be, Cu, V, Sc, and Zn are such in andesite area.

• Proceedings of the Korean Vacuum Society Conference
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• 2000.02a
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• pp.106-106
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• 2000

반도체 소자가 미세화 됨에 따라 게이트 유전막으로 사용되는 SiO2의 박막화가 요구되나, boron penetration에 의한 Vt shift, 게이트 누설전류, 다결정 실리콘 게이트의 depletion effect 그리고 quantum mechanical effect 때문에 ~20 급에서 한계를 나타내고 있다. 이에 0.1$\mu\textrm{m}$이상의 design rule을 갖는 logic이나 memory 소자에서 요구되어지는 ~10 급 게이트 산화막은 SiO2(K=3.9)를 대신하여 고유전율을 갖는 재료의 채택이 필수 불가결하게 되었다. 고유전 박막 재료를 사용하면, 두께를 두껍게 해도 동일한 inversion 특성이 유지되고 carrier tunneling 이 덜하여 등가 산화막의 두께를 줄일 수 있다. 이러한 고유전박막 재료중 가장 활발히 연구되고 있는 재료는 Ta2O5, Al2O3, STO 그리고 BST 등이 있으나 Ta2O5, STO, BST 등은 실리콘 기판과 직접 반응을 한다는 문제를 가지고 있으며, Al2O3는 유전율이 낮의 재료가 최근 주목받고 있다. 본 실험에서는 ZrO2, HfO2 또는 그 silicates 등의 재료가 최근 주목 받고 있다. 본 실험에서는 ZrO2 박막의 증착조건에 따른 물리적, 전기적 특성 변화에 대하여 연구하였다. RCA 방식으로 세정한 P-type (100) 실리콘 기판위에 reactive DC sputtering 방법으로 압력 5mtorr, power 100~400W, 기판온도는 100-50$0^{\circ}C$로 변화시켜 ZrO2 박막을 증착한 후 산소와 아르곤 분위기에서 400-80$0^{\circ}C$, 10-120min으로 열처리하였다. 증착직후의 시편들과 열처리한 ZrO2 박막의 미세구조와 전기적 특성 변화를 관찰하였다. 우선 굴절율(RI)를 이용해 ZrO2 박막의 밀도를 예측하여 power와 기판온도에 따라 이론값 2.0-2.2 에 근접한 구조를 얻은 후 XRD, XPS, AFM, 그리고 TEM을 사용하여 ZrO2 박막의 chemical bonding, surface roughness 그리고 interfacial layer의 특성을 관찰하였다. 그리고 C-V, I-V measurement를 이용해 capacitance, 유전율, 누설전류 등의 전기적 특성을 관찰해 최적 조건을 설정하였다.

• The Journal of the Petrological Society of Korea
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• v.27 no.1
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• pp.37-47
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• 2018

Volcanic ash samples of historical eruptions from Mt. Baekdu were analyzed for major oxides, trace and rare earth elements by a variety of analytical techniques. The results indicate that the ashes consist of approximately 58.8~71.1 wt.% $SiO_2$, 9.6~16.8 wt.% $Al_2O_3$, 4.5~6.9 wt.% $Fe_2O_{3t}$, 0.1~1.7 wt.% MgO, 0.3~1.6 wt.% CaO, 5.2~6.3 wt.% $Na_2O$, 4.3~5.9 wt.% $K_2O$ and less than 1.2 wt.% $TiO_2$. Thirty two trace metals including Ba, Cu, Cr. Co, Ni, Sr, V, Zn, and Zr were analyzed. The ashes can be divided two groups: group A(1 ka Millennium pumice, 1668 and $190{\underline{3}}$ pumice) and group B(1702 pumice) according to the relative enrichment of HREEs. The abundances of heavy metals such as Cu, Co, Mn, and Zn were relatively low. As compared to the Sakurajima volcanic ash, Baekdusan volcanic ash has low concentrations of Y, Nb, Pb, U, Sc, V, Ni and Cu and high concentrations of Zr, Ba, Hf, Cr, Co, Zn and rare-earth (except Eu).