• Title/Summary/Keyword: X-ray microscopy

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Mineralogy and Genesis of Bentonites from the Tertiary Formations in Geumgwangdong Area, Korea (제(第)3기층(紀層)에 부존(賦存)하는 점토광물(粘土鑛物)에 대(對)한 광물학적(鑛物學的) 및 성인적(成因的) 연구(硏究))

  • Kim, Soo Jin;Noh, Jin Hwan;Yu, Jae Young
    • Economic and Environmental Geology
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    • v.18 no.4
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    • pp.399-410
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    • 1985
  • Bentonites from the Janggi Group of the Lower Miocene age from the Geumgwangdong area, Korea, have been studied for mineralogical and genetic characterization. The Janggi Group is subdivided, in ascending order, into the Janggi Conglomerate, the Nuldaeri Tuff, the Geumgwangdong Shale, the Lower Coal-bearing Formation, the Basaltic Tuff, and the Upper Coalbearing Formation. Bentonites occur as thin or thick beds in all sedimentary units of the Janggi Group, except for the Janggi Conglomerate. Significant bentonite deposits are found in the Nuldaeri Tuff, the Lower Coal-bearing Formation and the Basaltic Tuff. Bentonites consist mainly of smectite (mainly montmorillonite), with minor quartz, cristobalite, opal-CT and feldspar. Occasionally, kaolinite, clinoptilolite or gypsum is associated with bentonites. Bentonites were studied by the methods of petrographic microscopy, X-ray diffraction, thermal analysis (DT A and TG), infrared absorption spectroscopic analysis, SEM, intercalation reaction, and chemical analysis. Smectites commonly occur as irregular boxwork-like masses with characteristic curled thin edges, but occasionally as smoothly curved to nearly flat thin flakes. Most of smectites have layer charge of 0.25-0.42, indicating typical montmorillonite. Crystal-chemical relations suggest that Fe is the dominant substituent for Al in the octahedral layer and there are generally no significant substituents for Si in the tetrahedral layer. Ca is the dominant interlayer cation in montmorillonite. Therefore, montmorillonite from the study area is dioctahedral Ca-montmorillonite. Occurrence and fabrics of bentonites suggest that smectites as well as cristobalite, opal-CT and zeolites have been formed diagenetically from tuffaceous materials. The precursor of smectites is trachytic or basaltic tuff. Smectites derived from the former contain relatively more $Al_2O$ a and less $Fe_2O_3$ than those from the latter.

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Phase Behavior Study of Fatty Acid Potassium Cream Soaps (지방산 칼륨 Cream Soaps 의 상거동 연구)

  • Noh, Min Joo;Yeo, Hye Lim;Lee, Ji Hyun;Park, Myeong Sam;Lee, Jun Bae;Yoon, Moung Seok
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.48 no.1
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    • pp.55-64
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    • 2022
  • The potassium cream soap with fatty acid called cleaning foam has a crystal gel structure, and unlike an emulsion system, it is weak to shear stress and shows characteristics that are easily separated under high temperature storage conditions. The crystal gel structure of cleansing foams is significantly influenced by the nature and proportion of fatty acids, degree of neutralization, and the nature and proportion of polyols. In order to investigate the effect of these parameters on the crystal gel structure, a ternary system consisting of water/KOH/fatty acid was investigated in this study. The investigation of differential scanning calorimeter (DSC) revealed that the eutectic point was found at the ratio of myristic acid (MA) : stearic acid (SA) = 3 : 1 and ternary systems were the most stable at the eutectic point. However, the increase in fatty acid content had little effect on stability. On the basis of viscosity and polarized optical microscopy (POM) measurements, the optimum degree of neutralization was found to be about 75%. The system was stable when the melting point (Tm) of the ternary system was higher than the storage temperature and the crystal phase was transferred to lamellar gel phase, but the increase in fatty acid content had little effect on stability. The addition of polyols to the ternary system played an important role in changing the Tm and causing phase transition. The structure of the cleansing foams were confirmed through cryogenic scanning electron microscope (Cryo-SEM), small and wide angle X-ray scattering (SAXS and WAXS) analysis. Since butylene glycol (BG), propylene glycol (PG), and dipropylene glycol (DPG) lowered the Tm and hindered the lamellar gel formation, they were unsuitable for the formation of stable cleansing foam. In contrast, glycerin, PEG-400, and sorbitol increased the Tm, and facilitated the formation of lamellar gel phase, which led to a stable ternary system. Glycerin was found to be the most optimal agent to prepare a cleansing foam with enhanced stability.

A Study of Coloration of Topaz(I): Mineralogical and Chemical Study on the Topaz Selected from Some Localities of the World (토파즈의 人工着色 處理를 위한 硏究(I) : 世界 主要 産地別 토파즈의 鑛物學的 및 化學的 特性)

  • Han, Yi-Kyeong;Park, Maeng-Eon;Jang, Yong-Nam
    • Journal of the Mineralogical Society of Korea
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    • v.5 no.2
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    • pp.109-121
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    • 1992
  • For the purpose of mineralogical and chemical study on the topazes from various localities of world(Brzail, China, India, Nigeria and Sri Lanka), electron microprobe analysis(EPMA), neutron activation analysis(NAA), X-ray diffractometry, Raman spectroscopy, etch test, scanning electron microscopy, refractive index, specific gravity, fluid inclusion were performed. The chemical composition in topaz was discussed along with its physical and structural properties. Variations in the unit-cell dimension and physical properties of topaz were found to have a close relations in the unit-cell dimension and physical properties of topaz were found to have a close relationship with extent of substitution of $OH^-\;for\;F^-$. According to neutron activation analyses, the trace elements had no effects on the physical properties of topaz. Raman spectra showed that the peaks of topaz were different in intensity from one locality to another. Etching defects in topaz includes negative crystal defect o point-bottom pit(India, Nigeria) and net work defect of curl-bottom pit(Brazil, China). Fluid inclusions in topaz may be classiffied into liquid $CO_2$-bearing inclusion, gaseous inclusion, halite, sylvite-bearing inclusion and liquid inclusion. The results of this study can be useful to devising artificial coloring methods for topaz with different mineralogical compositions.

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A Comparative Study on the Removals of 1-Naphthol by Natural Manganese Oxides and Birnessite (천연망간산화물과 버네사이트에 의한 1-Naphthol의 제거 특성 비교)

  • Lee, Doo-Hee;Harn, Yoon-I;Kang, Ki-Hoon;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.4
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    • pp.278-286
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    • 2009
  • In this study, four natural Mn oxides ($NMO_1-NMO_4$) was characterized using x-ray diffraction, scanning electron microscopy, and their removal efficiency for 1-naphthol (1-NP) in aqueous phase, using batch reactor, was investigated. The results were compared with one another and a synthetic manganese oxide, birnessite. The NMOs have a various Mn minerals including pyrolusite (${\beta}-MnO_2$), cryptomeltane (${\alpha}-MnO_2$) as well as birnessite (${\delta}-MnO_2$) depending on their sources, which results in different removal efficiencies (removals, kinetics) and reaction types (sorption or oxidative-transformation). The comparative study showed that $NMO_1$ (electrolytic Mn oxide) have a higher removal efficiency for 1-NP via oxidative-transformation compared to birnessite. The 1-NP removals by NMOs were followed by pseudo-first order reaction, and the surface area-normalized specific rate constants ($K_{surf},\;L/m^2$ min) determined were in order of $NMO_1(3.31{\times}10^{-3})$>${\delta}-MnO_2(1.48{\times}10^{-3}){\fallingdotseq}NMO_3(1.46{\times}10^{-3})$>$NMO_2(0.83{\times}10^{-3})$>$NMO_4(0.67{\times}10^{-3})$. From the solvent extraction experiments with the Mn oxide precipitates after reaction, it was observed that the oxidative-transformation rates of 1-NP were in order of $NMO_1{\fallingdotseq}{\delta}-MnO_2$>$NMO_3$>$NMO_4{\gg}NMO_2$ and the analysis of HPLC chromatogram and UV-Vis. absorption ratios ($A_{2/4}$, $A_{2/6}$) on the supernatant confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Results from this study proved that natural Mn oxide (except $NMO_2$) used in this experiment can be effectively applied for the removal of naphthols in aqueous phase, and the removal efficiencies are depending on the surface characters of the Mn oxides.

Improved Electrochemical Performance and Minimized Residual Li on LiNi0.6Co0.2Mn0.2O2 Active Material Using KCl (KCl을 사용한 LiNi0.6Co0.2Mn0.2O2계 양극활물질의 잔류리튬 저감 및 전기화학특성 개선)

  • Yoo, Gi-Won;Shin, Mi-Ra;Shin, Tae-Myung;Hong, Tae-Whan;Kim, Hong-kyeong
    • Journal of the Korean Electrochemical Society
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    • v.20 no.1
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    • pp.7-12
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    • 2017
  • Using a precursor of $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ as a starting material, a surface-modified cathode material was obtained by coating with KCl, where the added KCl reduces residual Li compounds such as $Li_2CO_3$ and LiOH, on the surface. The resulting electrochemical properties were investigated. The amounts of $Li_2CO_3$ and LiOH decreased from 8,464 ppm to 1,639 ppm and from 8,088 ppm to 6,287 ppm, respectively, with 1 wt% KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ that had been calcined at $800^{\circ}C$. X-ray diffraction results revealed that 1 wt% of KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ did not affect the parent structure but enhanced the development of hexagonal crystallites. Additionally, the charge transfer resistance ($R_{ct}$) decreased dramatically from $225{\Omega}$ to $99{\Omega}$, and the discharge capacity increased to 182.73mAh/g. Using atomic force microscopy, we observed that the surface area decreased by half because of the exothermic heat released by the Li residues. The reduced surface area protects the cathode material from reacting with the electrolyte and hinders the development of a solid electrolyte interphase (SEI) film on the surface of the oxide particles. Finally, we found that the introduction of KCl into $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ is a very effective method of enhancing the electrochemical properties of this active material by reducing the residual Li. To the best of our knowledge, this report is the first to demonstrate this phenomenon.

Microbial Leaching of Iron from Magnetite (미생물을 이용한 자철석으로부터 철 침출에 관한 연구)

  • Roh, Yul;Oh, Jong-Min;Seo, Yong-Jae;Jang, Hee-Dong
    • Journal of the Mineralogical Society of Korea
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    • v.19 no.4 s.50
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    • pp.265-275
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    • 2006
  • It is in its infancy to use bacteria as a novel biotechnology for leaching precious and heavy metals from raw materials. The objective of this study was to investigate biogeochemical processes of iron leaching from magnetite reduction by iron-reducing bacteria isolated from intertidal flat sediments, southwestern part of Korea. Microbial leaching experiments were performed using commercial magnetite, Aldrich magnetite, in well-defined mediums with and without bacteria. Water soluble Fe production was determined by ICP analysis of bioleached samples in comparison to uninoculated controls, and the resulting precipitated solids were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The extent of iron leaching from magnetite in the aerobic conditions (Fe = 107 ppm) was higher than that in the anaerobic environments (Fe = 94 ppm). In the anaerobic conditions, Fe(III) in commercial magnetite was also reduced to Fe(II), but no secondary mineral phases were observed. Amorphous iron oxides formed in the medium under aerobic conditions where there was sufficient supply of oxygen from the atmosphere. SEM observation suggests that the reduction process involves dissolution-precipitation mechanisms as opposed to solid state conversion of magnetite to amorphous iron oxides. The ability of bacteria to leach soluble iron and precipitate amorphous iron oxides from crystalline magnetite could have significant implications for biogeochemical processes in sediments where Fe(III) in magnetite plays an important role in the largest pool of electron acceptor as well as the tool as a novel biotechnology for leaching precious and heavy metals from raw materials.

Stellite bearings for liquid Zn-/Al-Systems with advanced chemical and physical properties by Mechanical Alloying and Standard-PM-Route

  • Zoz, H.;Benz, H.U.;Huettebraeucker, K.;Furken, L.;Ren, H.;Reichardt, R.
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2000.04a
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    • pp.9-10
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    • 2000
  • An important business-field of world-wide steel-industry is the coating of thin metal-sheets with zinc, zinc-aluminum and aluminum based materials. These products mostly go into automotive industry. in particular for the car-body. into building and construction industry as well as household appliances. Due to mass-production, the processing is done in large continuously operating plants where the mostly cold-rolled metal-strip as the substrate is handled in coils up to 40 tons unwind before and rolled up again after passing the processing plant which includes cleaning, annealing, hot-dip galvanizing / aluminizing and chemical treatment. In the liquid Zn, Zn-AI, AI-Zn and AI-Si bathes a combined action of corrosion and wear under high temperature and high stress onto the transfer components (rolls) accounts for major economic losses. Most critical here are the bearing systems of these rolls operating in the liquid system. Rolls in liquid system can not be avoided as they are needed to transfer the steel-strip into and out of the crucible. Since several years, ceramic roller bearings are tested here [1.2], however, in particular due to uncontrollable Slag-impurities within the hot bath [3], slide bearings are still expected to be of a higher potential [4]. The today's state of the art is the application of slide bearings based on Stellite\ulcorneragainst Stellite which is in general a 50-60 wt% Co-matrix with incorporated Cr- and W-carbides and other composites. Indeed Stellite is used as the bearing-material as of it's chemical properties (does not go into solution), the physical properties in particular with poor lubricating properties are not satisfying at all. To increase the Sliding behavior in the bearing system, about 0.15-0.2 wt% of lead has been added into the hot-bath in the past. Due to environmental regulations. this had to be reduced dramatically_ This together with the heavily increasing production rates expressed by increased velocity of the substrate-steel-band up to 200 m/min and increased tractate power up to 10 tons in modern plants. leads to life times of the bearings of a few up to several days only. To improve this situation. the Mechanical Alloying (MA) TeChnique [5.6.7.8] is used to prOduce advanced Stellite-based bearing materials. A lubricating phase is introduced into Stellite-powder-material by MA, the composite-powder-particles are coated by High Energy Milling (HEM) in order to produce bearing-bushes of approximately 12 kg by Sintering, Liquid Phase Sintering (LPS) and Hot Isostatic Pressing (HIP). The chemical and physical behavior of samples as well as the bearing systems in the hot galvanizing / aluminizing plant are discussed. DependenCies like lubricant material and composite, LPS-binder and composite, particle shape and PM-route with respect to achievable density. (temperature--) shock-reSistibility and corrosive-wear behavior will be described. The materials are characterized by particle size analysis (laser diffraction), scanning electron microscopy and X-ray diffraction. corrosive-wear behavior is determined using a special cylinder-in-bush apparatus (CIBA) as well as field-test in real production condition. Part I of this work describes the initial testing phase where different sample materials are produced, characterized, consolidated and tested in the CIBA under a common AI-Zn-system. The results are discussed and the material-system for the large components to be produced for the field test in real production condition is decided. Outlook: Part II of this work will describe the field test in a hot-dip-galvanizing/aluminizing plant of the mechanically alloyed bearing bushes under aluminum-rich liquid metal. Alter testing, the bushes will be characterized and obtained results with respect to wear. expected lifetime, surface roughness and infiltration will be discussed. Part III of this project will describe a second initial testing phase where the won results of part 1+11 will be transferred to the AI-Si system. Part IV of this project will describe the field test in a hot-dip-aluminizing plant of the mechanically alloyed bearing bushes under aluminum liquid metal. After testing. the bushes will be characterized and obtained results with respect to wear. expected lifetime, surface roughness and infiltration will be discussed.

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Identification of Active Agents for Reductive Dechlorination in Cement/Fe(II) Systems (시멘트와 Fe(II)을 이용한 환원성 탈염소화반응의 유효반응성분 규명)

  • Kim, Hong-Seok;Lee, Yu-Jung;Kim, Ha-Yan;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.11 no.6
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    • pp.35-42
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    • 2006
  • Experimental study was conducted to identify the active agent for reductive dechlorination of TCE in cement/Fe(II) systems. Several potential materials-hematite (${\alpha}-Fe_2O_3$), lepidocrocite (${\gamma}$-FeOOH), akaganeite (${\beta}$-FeOOH), ettringite ($Ca_6Al_2(SO_4)_3(OH)_{12}$)-that are cement components or parts of cement hydrates were tested if they could act as reducing agents by conducting TCE degradation experiments. From the initial degradation experiments, hematite was selected as a potential active agent. The pseudo-first-order degradation rate constant ($k\;=\;0.637\;day^{-1}$) for the system containing 200 mM Fe(II), hematite and CaO was close to that ($k\;=\;0.645\;day^{-1}$) obtained from the system containing cement and 200 mM Fe(II). CaO, which was originally added to simulate pH of the cement/Fe(II) system, was found to play an important role in degradation reactions. The reactivity of the hematite/CaO/Fe(II) system initially increased with increase of CaO dosage. However, the tendency declined in the higher CaO dosage region, implying a saturation type of behavior. The SEM analysis revealed that the hexagonal plane-shaped crystals were formed during the reaction with increasing degradation efficiency, which was brought about by increasing the CaO dosage. It was suspected that the crystals could be portlandite or green rust ($SO_4$) or Friedel's salt. The XRD analysis of the same sample identified the peaks of hematite, magnetite/maghemite, green rust ($SO_4$). Either instrumental analysis predicted the presence of the green rust ($SO_4$). Therefore, the green rust ($SO_4$) would potentially be a reactive agent for reductive dechlorination in cement/Fe(II) systems.

Characterization of InAs Quantum Dots in InGaAsP Quantum Well Grown by MOCVD for 1.55 ${\mu}m$

  • Choe, Jang-Hui;Han, Won-Seok;Song, Jeong-Ho;Lee, Dong-Han
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.134-135
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    • 2011
  • 양자점은 전자와 양공을 3차원으로 속박 시키므로 기존의 bulk나 양자우물보다 양자점을 이용한 레이저 다이오드의 경우 낮은 문턱 전류, 높은 미분이득 및 온도 안전성의 장점이 있을 거라 기대되고 있다. 그러나, 양자점은 낮은 areal coverage 때문에 높은 속박효율을 얻지 못하고 있다. 이러한 양자점의 문제점을 해결하기 위해 양자점을 양자우물 안에 성장시켜 운반자들의 포획을 향상시키는 방법들이 연구되고 있다. 양자우물 안에 양자점을 넣으면 양자우물이 운반자들의 포획을 증가 시키고, 열적 방출도 억제하여 온도 안정성이 향상 되는 것으로 알려져 있다. 광통신 대역의 1.3 ${\mu}m$ 경우, GaAs계를 이용하여 InAs 양자점을 strained InGaAs 박막을 우물층으로 한 dot-in-a-well 구조의 연구는 몇몇 보고된 바 있다. 그러나 InP계를 사용하는 1.55 ${\mu}m$ 대역에서 dot-in-a-well구조의 연구는 아직 미미하다. 본 연구에서는 유기 금속 화학 증착법(metal organic chemical vapor deposition)을 이용하여 InP 기판 위에 InAs 양자점을 자발성장법으로 성장하였으며 dot-in-a-well 구조에서 우물층으로 1.35 ${\mu}m$ 파장의 $In_{0.69}Ga_{0.31}As_{0.67}P_{0.33}$ (1.35Q)를, 장벽층으로는 1.1 ${\mu}m$ 파장의 $In_{0.85}Ga_{0.15}As_{0.32}P_{0.68}$(1.1Q)를 사용하였다. 양자우물층과 장벽층은 모두 InP 기판과 격자가 일치하는 조건으로 성장하였다. III족 원료로는 trimethylindium (TMI)와 trimethylgalium (TMGa)을 사용하였으며 V족 원료 가스로는 $PH_3$ 100%, $AsH_3$ 100%를, carrier gas로는 $H_2$를 사용하였다. InP buffer층의 성장 온도는 640$^{\circ}C$이며 양자점 성장 온도는 520$^{\circ}C$이다. 양자점 형성은 원자력간 현미경(Atomic force microscopy)를 이용하여 확인하였으며, 박막의 결정성은 쌍결정 회절분석(Double crystal x-ray deffractometry)를 이용하여 확인하였다. 확인된 성장 조건을 이용하여 양자점 시료를 성장하였으며 광여기분광법(Photoluminescence)을 이용하여 광특성을 분석하였다. Fig. 1은 dot in a barrier 와 dot-in-a-well 시료의 성장구조이다. Fig. 1(a)는 일반적인 dot-in-a-barrier 구조로 InP buffer층을 성장하고 1.1Q를 100 nm 성장한 후 양자점을 성장하였다. 그 후 1.1Q 100 nm와 InP 100 nm로 capping하였다. Fig. 1(b)는 dot-in-a-well 구조로 InP buffer층을 성장하고 1.1Q를 100 nm 성장 후 1.35Q 우물층을 4 nm 성장하였다. 그 위에 InAs 양자점을 성장하였다. 그 후에 1.35Q 우물층을 4 nm 성장하고 1.1Q 100 nm와 InP 100 nm로 capping하였다. Fig. 2는 dot-in-a-barrier 시료와 dot-in-a-well 시료의 상온 PL data이다. Dot-in-a-barrier 시료의 PL 파장은 1544 nm이며 반치폭은 79.70 meV이다. Dot-in-a-well 시료의 파장은 1546 nm이며 반치폭은 70.80 meV이다. 두 시료의 PL 파장 변화는 없으며, 반치폭은 dot-in-a-well 시료가 8.9 meV 감소하였다. Dot-in-a-well 시료의 PL peak 강도는 57% 증가하였으며 적분강도(integration intensity)는 45%가 증가하였다. PL 데이터에서 높은 에너지의 반치폭 변화는 없으며 낮은 에너지의 반치폭은 8 meV 감소하였다. 적분강도 증가에서 dot-in-a-well 구조가 dot-in-a-barrier 구조보다 전자-양공의 재결합이 증가한다는 것을 알 수 있으며, 반치폭 변화로부터 특히 높은 에너지를 갖는 작은 양자점에서의 재결합이 증가 된 것을 알 수 있다. 이는 양자우물이 장벽보다 전자-양공의 구속력을 증가시키기 때문에 양자점에 전자와 양공의 공급을 증가시키기 때문이다. 따라서 낮은 에너지를 가지는 양자점을 모두 채우고 높은 에너지를 가지는 양자점까지 채우게 되므로, 높은 에너지를 가지는 양자점에서의 전자-양공 재결합이 증가되었기 때문이다. 뿐만 아니라 파장 변화 없이 PL peak 강도와 적분강도가 증가하고 낮은 에너지 쪽의 반치폭이 감소한 것으로부터 에너지가 낮은 양자점보다는 에너지가 높은 양자점에서의 전자-양공 재결합율이 급증하였음을 알 수 있다. 우리는 이와 같은 연구에서 InP계를 이용해 1.55 ${\mu}m$에서도 dot in a well구조를 성장 하여 더 좋은 특성을 낼 수 있으며 앞으로 많은 연구가 필요할 것이라 생각한다.

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A bilayer diffusion barrier of atomic layer deposited (ALD)-Ru/ALD-TaCN for direct plating of Cu

  • Kim, Soo-Hyun;Yim, Sung-Soo;Lee, Do-Joong;Kim, Ki-Su;Kim, Hyun-Mi;Kim, Ki-Bum;Sohn, Hyun-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.239-240
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    • 2008
  • As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

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