• Title/Summary/Keyword: Nucleation and Growth

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New Ruthenium Complexes for Semiconductor Device Using Atomic Layer Deposition

  • Jung, Eun Ae;Han, Jeong Hwan;Park, Bo Keun;Jeon, Dong Ju;Kim, Chang Gyoun;Chung, Taek-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.363-363
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    • 2014
  • Ruthenium (Ru) has attractive material properties due to its promising characteristics such as a low resistivity ($7.1{\mu}{\Omega}{\cdot}cm$ in the bulk), a high work function of 4.7 eV, and feasibility for the dry etch process. These properties make Ru films appropriate for various applications in the state-of-art semiconductor device technologies. Thus, it has been widely investigated as an electrode for capacitor in the dynamic random access memory (DRAM), a metal gate for metal-oxide semiconductor field effect transistor (MOSFET), and a seed layer for Cu metallization. Due to the continuous shrinkage of microelectronic devices, better deposition processes for Ru thin films are critically required with excellent step coverages in high aspect ratio (AR) structures. In these respects, atomic layer deposition (ALD) is a viable solution for preparing Ru thin films because it enables atomic-scale control of the film thickness with excellent conformality. A recent investigation reported that the nucleation of ALD-Ru film was enhanced considerably by using a zero-valent metallorganic precursor, compared to the utilization of precursors with higher metal valences. In this study, we will present our research results on the synthesis and characterization of novel ruthenium complexes. The ruthenium compounds were easy synthesized by the reaction of ruthenium halide with appropriate organic ligands in protic solvent, and characterized by NMR, elemental analysis and thermogravimetric analysis. The molecular structures of the complexes were studied by single crystal diffraction. ALD of Ru film was demonstrated using the new Ru metallorganic precursor and O2 as the Ru source and reactant, respectively, at the deposition temperatures of $300-350^{\circ}C$. Self-limited reaction behavior was observed as increasing Ru precursor and O2 pulse time, suggesting that newly developed Ru precursor is applicable for ALD process. Detailed discussions on the chemical and structural properties of Ru thin films as well as its growth behavior using new Ru precursor will be also presented.

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Numerical Assessment of Tensile Strain Capacity for X80 Line Pipe Using GTN Model (GTN 모델을 이용한 X80 라인파이프의 인장 변형성능 해석)

  • Yoon, Young-Cheol;Kim, Ki-Seok;Lee, Jae Hyuk;Cho, Woo-Yeon
    • KSCE Journal of Civil and Environmental Engineering Research
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    • v.36 no.6
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    • pp.979-990
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    • 2016
  • This study presents a nonlinear finite element procedure involving a phenomenological model to validate the tensile strain capacity of the X80 line pipe developed for the strain-based design purpose. The procedure is based on the Gurson-Tvergaard-Needleman (GTN) model, which models nucleation, growth and coalescence of void volume fraction occurred inside a metal. In this study, the user-defined material module (UMAT) is implemented in the commercial finite element platform ABAQUS and is applied to the nonlinear damage analysis of steel specimens. Material parameters for the nonlinear damage analysis of base and weld metals are calibrated from numerical simulations for the tensile tests of round bar and full thickness specimens. They are then employed in the numerical simulations for SENT (Single Edge Notch Tension) test and CWPT (Curved Wide Plate Test) and in the simulations, the tensile strain capacities are naturally evaluated. Comparison of the numerical results with the experimental results and the conventional empirical formulae shows that the proposed numerical procedure can fairly well predict the tensile strain capacity of X80 line pipe. So, it is readily expected to be effectively applied to the strain-based design procedure.

Study of NIR in-line Monitoring of Physicochemical Changes during the Crystallization Process of Aspirin (Aspirin 결정화 과정 중 특성변화의 NIR 인라인 모니터링 연구)

  • Lee, Hea-Eun;Wang, In-Chun;Lee, Min-Jeong;Seo, Da-Young;Shin, Sangmun;Choi, Yongsun;Choi, Guang-Jin
    • Korean Chemical Engineering Research
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    • v.48 no.6
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    • pp.757-762
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    • 2010
  • Since the quality and performance of medicinal products are heavily dependent upon the size, shape and polymorphism of active pharmaceutical ingredients(APIs), their crystallization has been regarded as one of the most important pharmaceutical processes. In this study, NIR-based inline measurements were employed to monitor key attributes of API particles real-time during the crystallization process. Principal component analysis(PCA) method was selected to correlate inline NIR spectra while the well-known aspirin was studied as a model drug. According to our characterization results, the ratio of ethanol to acetone did not cause any change in polymorphism, but resulted in a significant difference in the nucleation time, crystal growth and crystal shape. These phenomenological changes were well correlated with the PCA's implications. It turned out that the NIR-based inline monitoring technology can be employed well in observing and predicting key quality attributes such as crystal size during pharmaceutical crystallization processes.

A New process for the Solid phase Crystallization of a-Si by the thin film heaters (박막히터를 사용한 비정질 실리콘의 고상결정화)

  • 김병동;정인영;송남규;주승기
    • Journal of the Korean Vacuum Society
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    • v.12 no.3
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    • pp.168-173
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    • 2003
  • Recently, according to the rapid progress in Flat-panel-display industry, there has been a growing interest in the poly-Si process. Compared with a-Si, poly-Si offers significantly high carrier mobility, so it has many advantages to high response rate in Thin Film Transistors (TFT's). We have investigated a new process for the high temperature Solid Phase Crystallization (SPC) of a-Si films without any damages on glass substrates using thin film heater. because the thin film heater annealing method is a very rapid thermal process, it has very low thermal budget compared to the conventional furnace annealing. therefore it has some characteristics such as selective area crystallization, high temperature annealing using glass substrates. A 500 $\AA$-thick a-Si film was crystallized by the heat transferred from the resistively heated thin film heaters through $SiO_2$ intermediate layer. a 1000 $\AA$-thick $TiSi_2$ thin film confined to have 15 $\textrm{mm}^{-1}$ length and various line width from 200 to 400 $\mu\textrm{m}$ was used as the thin film heater. By this method, we successfully crystallized 500 $\AA$-thick a-Si thin films at a high temperature estimated above $850^{\circ}C$ in a few seconds without any thermal deformation of g1ass substrates. These surprising results were due to the very small thermal budget of the thin film heaters and rapid thermal behavior such as fast heating and cooling. Moreover, we investigated the time dependency of the SPC of a-Si films by observing the crystallization phenomena at every 20 seconds during annealing process. We suggests the individual managements of nucleation and grain growth steps of poly-Si in SPC of a-Si with the precise control of annealing temperature. In conclusion, we show the SPC of a-Si by the thin film heaters and many advantages of the thin film heater annealing over other processes

Preparation of Dextran Microparticles by Using the SAS Process (초임계 반용매 재결정 공정을 이용한 Dextran 입자의 제조)

  • Kang, Dong-Yuk;Min, Byoung-Jun;Rho, Seon-Gyun;Kang, Choon-Hyoung
    • Korean Chemical Engineering Research
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    • v.46 no.5
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    • pp.958-964
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    • 2008
  • In this work, micro-sized dextran particles, which have recently been focused as one of the candidate materials for the Drug Delivery System(DDS), were prepared by means of the Supercritical Antisolvent (SAS) process with $CO_2$. With dimethyl sulfoxide(DMSO) as the solvent, effects of the operating variables such as temperature (308.15~323.15 K), pressure(90~130 bar), solute concentration(10~20 mg/ml), and the molecular weight of the solute(Mw=37,500, 450,000) on the size and morphology of the resulting particles were thoroughly observed. The higher solute concentration led to the larger particles, however, the injection velocity of the solution and pressure did not show significant effects on the resulting particle size. With dextran of the lower molecular weight, the smallest particles were obtained at 313.15 K. On the other hand, the size of the particles from the high molecular weight dextran ranged between $0.1{\sim}0.5{\mu}m$ with an incremental effect of the temperature and pressure. For the solute concentration of 5 mg/ml, the lower molecular weight dextran did not form discrete particles while aggregation of the particles appeared when the solute concentration exceeded 15 mg/ml for the higher molecular weight dextran. It is believed that if the solute concentration is too low, the degree of the supersaturation in the recrystallization chamber would not be sufficient for initiation of the nucleation and growth mechanism. Instead, the spinodal decomposition mechanism leads to formation of the island-like phase separation which appears similar to aggregation of the discrete particles. This effect would be more pronounced for the smaller molecular weight polymer system due to the narrower phase-splitting region.

Petrology of Host Body of Feldspar Deposits in Jechon Ganites (장석광상 모암인 제천반상화강암의 암석학적 특성)

  • Lee, Han-Yeang;Kim, Dai-Oap;Park, Joong-Kwon
    • Journal of the Korean earth science society
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    • v.22 no.5
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    • pp.405-414
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    • 2001
  • Jecheon granite can be divided into two types; porphyritic granite (K-feldspar megacryst bearing) and medium-grained biotite granite. Porphyritic granite, host body of feldspar deposits, is 8${\sim}$11 km in diameter and about 80 $km^{2}$ in area. It mainly contains K-feldspar, plagioclase, biotite and quartz, and magnetite, zircon, sphene and apatite are accessary minerals. Enclosed minerals in K-feldspar megacryst with 3${\sim}$10 cm in diameter are hornblende, plagioclase, quartz, magnetite, apatite, sphene and zircon. Mafic enclaves mainly consisting of hornblende, plagioclase and quartz are frequently observed in porphrytic granite. Medium-grained biotite granite consists of K-feldspar, plagioclase, biotite and hornblende as main, and hematite, muscovite, apatite and zircon as accessary minerals. Core and rim An contents of plagioclase from porphyritic granite, medium biotite granite, K-feldspar megacryst, and mafic enclave are 36 and 21, 40 and 32, 37 and 32, and 43 and 36, respectively. $X_{Fe}$ values of hornblende are 0.57 at biotite granite, 0.51 at K-feldspar mehacryst and 0.45 at mafic enclave. $X_{Fe}$ values of biotite and hornblende are homogeneous without chemical zonation. K-feldspar megacryst shows end member of pure composition with exsolved thin lamellar pure albites. Characteristics of mineral compositions and petrography indicate porphyritic granite is igneous origin and medium-grained biotite granite comes from the same source of magma; biotite granite is initiated to solidly and from residual melt porphyritic granite can be formed. Possibly K-feldspar megacrysts are formde under H$_{2}$O undersaturation condition and near K-feldspar solidus curve temperature; growth rate is faster than nucleation rate. Mafic enclaves are thought to be mingled mafic magma in felsic magma, which is formed from compositional stratigraphy. Estimated equilibrium temperature and pressure for medium-grained biotite granite are about $800^{\circ}C$ and 4.83${\sim}$5.27 Kb, respectively.

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Evaluation of Hydrate Inhibition Performance of Water-soluble Polymers using Torque Measurement and Differential Scanning Calorimeter (토크 측정과 시차주사열량계를 이용한 수용성 고분자 화합물의 하이드레이트 저해 성능 평가)

  • Shin, Kyuchul;Park, Juwoon;Kim, Jakyung;Kim, Hyunho;Lee, Yohan;Seo, Yongwon;Seo, Yutaek
    • Korean Chemical Engineering Research
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    • v.52 no.6
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    • pp.814-820
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    • 2014
  • In this work, hydrate inhibition performance of water-soluble polymers including pyrrolidone, caprolactam, acrylamide types were evaluated using torque measurement and high pressure differential scanning calorimeter (HP ${\mu}$-DSC). The obtained experimental results suggest that the studied polymers represent the kinetic hydrate inhibition (KHI) performance. 0.5 wt% polyvinylcaprolactam (PVCap) solution shows the hydrate onset time of 34.4 min and subcooling temperature of 15.9 K, which is better KHI performance than that of pure water - hydrate onset time of 12.3 min and subcooling temperature of 6.0 K. 0.5 wt% polyvinylpyrrolidone (PVP) solution shows the hydrate onset time of 27.6 min and the subcooling temperature of 13.2 K while polyacrylamide-co-acrylic acid partial sodium salt (PAM-co-AA) solution shows less KHI performance than PVP solution at both 0.5 and 5.0 wt%. However, PAM-co-AA solution shows slow growth rate and low hydrate amount than PVCap. In addition to hydrate onset and growth condition, torque change with time was investigated as one of KHI evaluation methods. 0.5 wt% PVCap solution shows the lowest average torque of 6.4 N cm and 0.5 wt% PAM-co-AA solution shows the average torque of 7.2 N cm. For 0.5 wt% PVP solution, it increases 11.5 N cm and 5.0 wt% PAM-co-AA solution shows the maximum average torque of 13.4 N cm, which is similar to the average torque of pure water, 15.2 N cm. Judging from the experimental results obtained by both an autoclave and a HP ${\mu}$-DSC, the PVCap solution shows the best performance among the KHIs in terms of delaying hydrate nucleation. From these results, it can be concluded that the torque change with time is useful to identify the flow ability of tested solution, and the further research on the inhibition of hydrate formation can be approached in various aspects using a HP ${\mu}$-DSC.

Research of Diffusion Bonding of Tungsten/Copper and Their Properties under High Heat Flux

  • Li, Jun;Yang, Jianfeng
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.05a
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    • pp.14-14
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    • 2011
  • W (tungsten)-alloys will be the most promising plasma facing armor materials in highly loaded plasma interactive components of the next step fusion reactors due to its high melting point, high sputtering resistance and low deuterium/tritium retention. The bonding technology of tungsten to Cu alloy was one of the key issues. In this paper, W/CuCrZr diffusion bonding has been performed successfully by inserting pure metal interlay. The joint microstructure, interfacial elements migration and phase composition were analyzed by SEM, EDS, XRD, and the joint shear strength and micro-hardness were investigated. The mock-ups were fabricated successfully with diffusion bonding and the cladding technology respectively, and the high heat flux test and thermal fatigue test were carried out under actively cooling condition. When Ni foil was used for the bonding of tungsten to CuCrZr, two reaction layers, Ni4W and Ni(W) layer, appeared between the tungsten and Ni interlayer with the optimized condition. Even though Ni4W is hard and brittle, and the strength of the joint was oppositely increased (217 MPa) due primarily to extremely small thicknesses (2~3 ${\mu}m$). When Ti foil was selected as the interlayer, the Ti foil diffused quickly with Cu and was transformed into liquid phase at $1,000^{\circ}C$. Almost all of the liquid was extruded out of the interface zone under bonding pressure, and an extremely thin residual layer (1~2 ${\mu}m$) of the liquid phase was retained between the tungsten and CuCrZr, which shear strength exceeded 160 MPa. When Ni/Ti/Ni multiple interlayers were used for bonding of tungsten to CuCrZr, a large number of intermetallic compound ($Ni_4W/NiTi_2/NiTi/Ni_3T$) were formed for the interdiffusion among W, Ni and Ti. Therefore, the shear strength of the joint was low and just about 85 MPa. The residual stresses in the clad samples with flat, arc, rectangle and trapezoid interface were estimated by Finite Element Analysis. The simulation results show that the flat clad sample was subjected maximum residual stress at the edge of the interface, which could be cracked at the edge and propagated along the interface. As for the rectangle and trapezoid interface, the residual stresses of the interface were lower than that of the flat interface, and the interface of the arc clad sample have lowest residual stress and all of the residual stress with arc interface were divided into different grooved zones, so the probabilities of cracking and propagation were lower than other interfaces. The residual stresses of the mock-ups under high heat flux of 10 $MW/m^2$ were estimated by Finite Element Analysis. The tungsten of the flat interfaces was subjected to tensile stresses (positive $S_x$), and the CuCrZr was subjected to compressive stresses (negative $S_x$). If the interface have a little microcrack, the tungsten of joint was more liable to propagate than the CuCrZr due to the brittle of the tungsten. However, when the flat interface was substituted by arc interfaces, the periodical residual stresses in the joining region were either released or formed a stress field prohibiting the growth or nucleation of the interfacial cracks. Thermal fatigue tests were performed on the mock-ups of flat and arc interface under the heat flux of 10 $MW/m^2$ with the cooling water velocity of 10 m/s. After thermal cycle experiments, a large number of microcracks appeared at the tungsten substrate due to large radial tensile stress on the flat mock-up. The defects would largely affect the heat transfer capability and the structure reliability of the mock-up. As for the arc mock-up, even though some microcracks were found at the interface of the regions, all microcracks with arc interface were divided into different arc-grooved zones, so the propagation of microcracks is difficult.

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