• Title/Summary/Keyword: Grain boundaries

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Crystal Growth of rutiles doped with Impurity Ions by Floating Zone Method (부유대용융법에 의한 불순이온 주입된 $TiO_2$단결정 성장 연구)

  • 이성영;유영문;김병호
    • Proceedings of the Korea Crystallographic Association Conference
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    • 1999.04a
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    • pp.1-1
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    • 1999
  • 부유대용융법에 의하여 불순이온의 종류와 각 이온의 주입 농도를 달리하는 Rutile 단결정을 성장하였다. 성장된 결정으로부터 제조한 박편시료를 이용하여 결정결함과 광투과도에 미치는 각 불순이온의 영향을 조사하였다. 결정성장용 주원료로 99.99%의 TiO2를 사용하고, 불순이온 주입을 위한 원료로서 99.99%의 Al2O3, H3BO3, Ga2O3, Sc2O3, V2O5, Fe2O3, ZrO2, Er2O3, Cr2O3를 각각 사용하였다. 불순이온의 종류에 따르는 영향을 조사하기 위하여 TiO2 99.8 atomic%-불순이온 0.2atomic%의 조성이 되도록 각 이온별로 원료를 정밀하게 평량하고 균일 혼합하였다. 불순 이온의 첨가량에 따르는 영향을 조사하기 위하여 Al2O3는 각각 pure, 0.2, 0.4, 0.6 atomic%를, Cr2O3는 pure, 0.003, 0.05, 0.2 atomic%를 각각 치환하여 원료를 조합하였다. 균일 혼합된 원료를 직경 8mm의 고무 튜브에 넣고 CIP(Cold Isostatic Press0에서 2000kg/$\textrm{cm}^2$의 압력으로 성형한 후 150$0^{\circ}C$에서 1시간 소결함으로서 결정성장용 다결정 원료를 합성하였다. 합성된 다결정을 double ellipsoidal mirror 내에 설치하고,halogen lamp로 가열하여 원료의 한쪽 끝을 용융한 다음, 20rpm의 회전속도, 3-5mm/hr의 성장속도로 하는 유속 1$\ell$/min의 O2 분위기속에서 부유대용융법에 의하여 결정을 성장하였다. 성장된 결정을 성장축에 수직한 방향으로 각각 절단, 연삭, 연마한 박편을 이용하여 편광하에서 low-angle grain boundaries 및 기타의 결정결함을 관찰하였으며, 0.3$\mu\textrm{m}$~0.8$\mu\textrm{m}$ 범위 및 0.6$\mu\textrm{m}$~3.4$\mu\textrm{m}$ 범위에서의 투과 및 흡수 스펙트럼을 측정하였다. 결정 성장 결과 B3+, Er3+, Cr3+ 이온은 Ti4+ 이온과 이온의 크기 차이가 심하여 결정의 정상적인 성장을 방해하는 물성을 나타냈고, V5+, Cr3+ 이온은 흑색의 결정, Fe3+ 이온은 적갈색의 결정으로 성장되었다. Al3+, Zr4+, Al3+의 순서로 투과도가 높아지는 것이 관찰되었다. 불순이온의 농도에 따른 영향으로서 Al3+ 이온의 경우 주입농도가 높아질수록 low angle boundary와 oxygen deficiency가 감소하였고, 투과율은 조금 감소하거나 큰 차이가 없는 것으로 나타났다. 반면에 Cr3+ 이온을 주입한 경우 0.003 atomic%에서 최적의 물성을 보였으며, 주입농도가 높아질수록 결정성장이 어려워지고 광의 투과도가 급격히 저하되었다.

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The Effect of Solidification Rate on Solidification Behavior in IN792+Hf Superalloy (IN792+Hf 초내열합금의 응고거동에 미치는 응고속도의 영향)

  • Bae, Jae-Sik;Kim, Hyeon-Cheol;Lee, Jae-Hyeon;Yu, Yeong-Su;Jo, Chang-Yong
    • Korean Journal of Materials Research
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    • v.11 no.6
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    • pp.502-507
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    • 2001
  • The effect of solidification rate on the microstructure of directionally solidified IN792+ Hf superalloy has been studied. Solidification sequence and precipitation behavior of the alloy have been analysed by microstructural observation. The script carbide transformed to faceted carbide with decreasing solidification rates. The incorporation of ${\gamma}$ phase into the faceted carbide was due to dendritic growth of carbides. Some elongated carbide bars formed along the grain boundaries at a solidification rate of 0.5$\mu\textrm{m}$/s. Two zones, ${\gamma}$' forming elements enriched zone and depleted zone, were found in the residual liquid area. Eutectic ${\gamma}$/${\gamma}$' nucleated in the f forming elements enriched zone. Formation of eutectic ${\gamma}$/${\gamma}$' increased the ratio of (Ti+Hf+Ta+W)/Al and induced η phase precipitation. The ratio of (Ti+Hf+Ta+W)/Al decreased at lower solidification rates due to sufficient back diffusion in the residual liquid area. Hence, the Precipitation of the η Phase efficiently suppressed at the lower solidification rate.

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Investigation of Corrosion Mechanism by Analyses of Spent Chromia Refractory fvom a Coal Gasifier (석탄 가스화기에서의 크로미아 내화물 분석을 통한 화학적 침식 기구 규명)

  • Kim Han Bom;Oh Myongsook
    • Journal of Energy Engineering
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    • v.13 no.4
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    • pp.281-290
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    • 2004
  • Spent refractories from a coal gasifier after 1000 hours of operation were analyzed for crystalline phases, chemical composition and microstructures as a function of slag penetration depth, and the slag corrosion mechanism was determined. The chemical corrosion of chromia refractory occurred via reaction between Cr$_2$O$_3$ of the refractory and FeO and A1$_2$O$_3$ in the slag. The FeO reacted with Cr$_2$O$_3$ at the slare/refractory interface and formed FeCr$_2$O$_4$. After all FeO were consumed, Al in the penetrating slag substituted Cr in Cr$_2$O$_3$, forming (Al, Cr)$_2$O$_3$, at the edges of the particle, which were broken to form fragments rich in Al. The corrosion resistance of Cr$_2$O$_3$ varied with the particle size and the extent of sintering, and the higher resistance was observed in the larger and more sintered particles. There was no chemical change in ZrO$_2$, but showed the effects of physical corrosion: the grain boundaries became more wavy, and ZrO$_2$ grains were split in the corroded area. The slag penetration depth increased in the refractory samples farther down from the feed nozzles.

Development of Novel Materials for Reduction of Greenhouse Gases and Environmental Monitoring Through Interface Engineering

  • Hirano, Shin-Ichi;Gang, Seok-Jung L.;Nowotny, Janusz-Nowotny;Smart, Roger-St.C.Smart;Scrrell, Charles-C.Sorrell;Sugihara, Sunao;Taniguchi, Tomihiroi;Yamawaki, Michio;Yoo
    • Korean Journal of Materials Research
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    • v.9 no.6
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    • pp.635-653
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    • 1999
  • The present work considers work considers research strategies to address global warming. Specifically, this work considers the development of technologies of importance for the reduction of greenhouse gas emission and, especially, the materials that are critical to these technologies. It is argued that novel materials that are essential for the production of environmentally friendly energy may be developed through a special kind of engineering: interface engineering, rather than through classical bulk chemistry. Progress on the interface engineering requires to increase the present state of understanding on the local properties of materials interfaces and interfaces processes. This, consequently, requires coordinated international efforts in order to establish a strong background in the science of materials interfaces. This paper considers the impact of interfaces, such as surfaces and grain boundaries, on the functional properties of materials. This work provides evidence that interfaces exhibit outstanding properties that are not displayed by the bulk phase. It is shown that the local interface chemistry and structure and entirely different than those of the bulk phase. In consequence the transport of both charge and matter along and across interfaces, that is so important for energy conversion, is different than that in the bulk. Despite that the thickness of interfaces is of an order to a nanometer, their impact on materials properties is substantial and, in many cases, controlling. This leads to the conclusion that the development of novel materials with desired properties for specific industrial applications will be possible through controlled interface chemistry. Specifically, this will concern materials of importance for energy conversion and environmental monitoring. Therefore, there is a need to increase the present state of understanding of the local properties of materials interfaces and the relationship between interfaces and the functional properties of materials. In order to accomplish this task coordinated international efforts of specialized research centres are required. These efforts are specifically urgent regarding the development of materials of importance for the reduction of greenhouse gases. Success of research in this area depends critically on financial support that can be provided for projects on materials of importance for a sustainable environment, and these must be considered priorities for all of the global economies. The authors of the present work represent an international research group economies. The authors of the present work represent an international research group that has entered into a collaboration on the development of the materials that are critical for the reduction of greenhouse gas emissions.

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Mechanical Properties of The CO2 Free Vacuum Carburized in SCM415H (CO2 무 배출 침탄 열처리된 SCM415H 소재의 기계적 성질)

  • Byun, Jae-Hyuk;Ro, Seung-Hoon;Lee, Jong-Hyung;Lee, Chang-Hun;Yang, Seong-Hyeon
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.36 no.9
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    • pp.971-978
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    • 2012
  • Vacuum carburizing is supposed to be the superior process to the gas carburizing. However, the vacuum carburizing has the stage in which hydrocarbon gas is supplied into the furnace to be pyrolysis, and consequently the stable heat treatment is hard to achieve due to the soot from the hydrocarbon pyrolysis. Recently, many studies have been made which utilize acetylene gas to overcome this defects. In this paper, the carburizing and the diffusion periods have been selected based on the Harris experimental formula, and the mechanical properties of the vacuum carburized specimen have been compared with those of the gas carburized SCM415H specimen to identify the feasibility of the $CO_2$ free vacuum carburizing process. The result showed that the vacuum carburized materials used have no oxidization of the grain boundaries, and show the 29.8% higher effective hardness depth and the acceptable tensile strength.

A study on the electrolytic properties of $CaF_2$ crystals with $YF_3$ addition ($YF_3 $ 첨가에 따른 $CaF_2 $ 결정의 고체전해질 특성에 관한 연구)

  • Cha, Y.W.;Park, D.C.;Orr, K.K.
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.4 no.1
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    • pp.21-32
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    • 1994
  • $CaF_2$ crystals were grown with various growth rates by Bridgman method, and the electrical properties of these were studied to examine the changes of ionic conductivities with growth rates by AC Impedance Analyzer. As the growth rates were higher, $CaF_2$ crystals were grown to polycrystals from single crystal. And as grain boundaries and various defects were altered, the ionic conductivities were changed dramatically. $YF_3$ added to $CaF_2$ for disorderizing $CaF_2$ structure and improving the number of $F^-$ carriers and vacancies in $CaF_2$ crystals. Then $Ca_{1-x}Y_XF_{2+X}$ crystals were gained. And the ionic conductivities of $Ca_{1-x}Y_XF_{2+X}$ crystals were investigated with $YF_3$ addition. The ionic conductivities of $CaF_2$ and $Ca_{1-x}Y_XF_{2+X}$ crystals with temperatures were compared. In addition, the effects of clusterings and defects on the electrical properties of solid electrolytes were researched.

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Textural Implications of Fine-Grained Peridotite Xenoliths in Basaltic Rocks from Jeju Island (제주도 현무암에 포획된 세립질 맨틀 페리도타이트 포획암의 조직적 특성)

  • Yang, Kyoung-Hee;Nam, Bok-Hyun;Kim, Jin-Seop;Szabo, Csaba
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.1
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    • pp.1-11
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    • 2009
  • Fine-grained peridotite xenoliths are rarely trapped in the basaltic rocks from the southeastern part of Jeju Island. Based on textural characteristics of the constituent phases showing uniform-sized, fine-grained tabular to mosaic grains with rare porphyroclastic relics, the studied samples can be defined as fine-grained, foliated porphyroclastic peridotites (FPP). Almost no significant difference among the FPPs in textures and major element compositions implies that the FPPs were derived from a structural domain, experiencing similar deformation events and deformation patterns. Moreover, the bimodal distribution with kink-banded porphyroclasts ($2{\sim}3mm$) and stain-free neoblasts ($200{\sim}300{\mu}m$), straight to gently curved grain boundaries with triple junctions, interstitial melt pockets, and microstructures for migrating grain boundary suggest that the studied samples went through dynamic recrystallization (${\pm}$ static recrystallization) in the presence of melt/fluid movement along foliation planes. No notable difference between the FPP and common protogranular xenoliths in major element compositions and geochemical evolution also implies that the FPP and protogranular xenoliths were from a similar horizon. Thus, the textural and geochemical characteristics of the FPPs reflects deformation events occurred at a localized and narrow zone within the lithospheric mantle beneath the Jeju Island. Although further detailed studies are necessary to define deformation events, the most possible process which could trigger deformation in the FPP in the rigid upper mantle was the ascending basaltic magma forming high-stress deformation zones. The suggested high-stress deformation zones in the lithosphere beneath the Jeju Island may be produced by paleo-faulting events related to the ascent of basalt magma before Jeju Island was formed.

New Approaches for Overcoming Current Issues of Plasma Sputtering Process During Organic-electronics Device Fabrication: Plasma Damage Free and Room Temperature Process for High Quality Metal Oxide Thin Film

  • Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.100-101
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    • 2012
  • The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

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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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Geoacoustic characteristics of Quaternary stratigraphic sequences in the mid-eastern Yellow Sea (황해 중동부 제4기 퇴적층의 지음향 특성)

  • Jin, Jae-Hwa;Jang, Seong-Hyeong;Kim, Seong-Pil;Kim, Hyeon-Tae;Lee, Chi-Won;Chang, Jeong-Hae;Choi, Jin-Hyeok;Ryang, Woo-Heon
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.6 no.2
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    • pp.81-92
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    • 2001
  • According to analyses of high-resolution seismic profiles (air gun, sparker, and SBP) and a deep-drill core(YSDP 105) in the mid-eastern Yellow Sea, stratigraphic and geoacoustic models have been established and seismo-acoustic modeling has been fulfilled using ray tracing of finite element method. Stratigraphic model reflects seismo-, litho-, and chrono-stratigraphic sequences formed under a significant influence of Quaternary glacio-eustatic sea-level fluctuations. Each sequence consists of terrestrial to very-shallow-marine coarse-grained lowstand systems tract and tidal fine-grained transgressive to highstand systems tract. Based on mean grain-size data (121 samples) of the drill core, bulk density and P-wave velocity of depositional units have been inferred and extrapolated down to a depth of the recovery using the Hamilton's regression equations. As goo-acoustic parameters, the 121 pairs of bulk density and P-wave velocity have been averaged on each unit of the stratigraphic model. As a result of computer ray-tracing simulation of the subsurface strata, we have found that there are complex ray paths and many acoustic-shadow zones owing to the presence of irregular layer boundaries and low-velocity layers.

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