• Title/Summary/Keyword: Transition-metal

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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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Mineralogical and Geochemical Characteristics of the Precipitates in Acid Mine Drainage of the Heungjin-Taemaek Coal Mine (흥진태맥 석탄광 산성광산배수 침전물의 광물학적 및 지구화학적 특성)

  • Shin, Ji-Hwan;Park, Ji-Yeon;Kim, Yeongkyoo
    • Economic and Environmental Geology
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    • v.54 no.2
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    • pp.299-308
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    • 2021
  • Fe(II) released from mining activities is precipitated as various Fe(III)-oxyhydroxides when exposed to an oxidizing environment including mine drainage. Ferrihydrite, one of the representative precipitated Fe(III) minerals, is easy to adsorb heavy metals and other pollutants due to the large specific surface area caused by very low crystallinity. Ferrihydrite is transformed to thermodynamically more stable goethite in the natural environment. Hence, information on the transformation of ferrihydrite to goethite and the related mobility of heavy metals in the acid mine drainage is important to predict the behaviors of those elements during ferrihydrite to goethite transition. The behaviors of heavy metals during the transformation of ferrihydrite to goethite were investigated for core samples collected from an AMD treatment system in the Heungjin-Taemaek coal mine by using X-ray diffraction (XRD), chemical analysis, and statistical analysis. XRD results showed that ferrihydrite gradually transformed to goethite from the top to the bottom of the core samples. Chemical analysis showed that the relative concentration of As was significantly high in the core samples compared with that in the drainage, indicating that As was likely to be adsorbed strongly on or coprecipitated with iron oxyhydroxide. Correlation analysis also indicated that As can be easily removed from mine drainage during iron mineral precipitation due to its high affinity to Fe. The concentration ratio of As, Cd, Co, Ni, and Zn to Fe generally decreased with depth in the core samples, suggesting that mineral transformation can increase those concentrations in the drainage. In contrast, the concentration ratio of Cr to Fe increased with depth, which can be explained by the chemical bond of iron oxide and chromate, and surface charge of ferrihydrite and goethite.

Preservation of World Records Heritage in Korea and Further Registry (한국의 세계기록유산 보존 현황 및 과제)

  • Kim, Sung-Soo
    • Journal of Korean Society of Archives and Records Management
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    • v.5 no.2
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    • pp.27-48
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    • 2005
  • This study investigates the current preservation and management of four records and documentary heritage in Korea that is in the UNESCO's Memory of the World Register. The study analyzes their problems and corresponding solutions in digitizing those world records heritages. This study also reviews additional four documentary books in Korea that are in the wish list to add to UNESCO's Memory of the World Register. This study is organized as the following: Chapter 2 examines the value and meanings of world records and documentary heritage in Korea. The registry requirements and procedures of UNESCO's Memory of the World Register are examined. The currently registered records of Korea include Hunmin-Chongum, the Annals of the Choson Dynasty, the Diaries of the Royal Secretariat (Seungjeongwon Ilgi), and Buljo- Jikji-Simche-Yojeol (vol. II). These records heritage's worth and significance are carefully analyzed. For example, Hunmin-Chongum("訓民正音") is consisted of unique and systematic letters. Letters were delicately explained with examples in its original manual at the time of letter's creation, which is an unparalleled case in the world documentary history. The Annals of the Choson Dynasty("朝鮮王朝實錄") are the most comprehensive historic documents that contain the longest period of time in history. Their truthfulness and reliability in describing history give credits to the annals. The Royal Secretariat Diary (called Seungjeongwon-Ilgi("承政院日記")) is the most voluminous primary resources in history, superior to the Annals of Choson Dynasty and Twenty Five Histories in China. Jikji("直指") is the oldest existing book published by movable metal print sets in the world. It evidences the beginning of metal printing in the world printing history and is worthy of being as world heritage. The review of the four registered records confirms that they are valuable world documentary heritage that transfers culture of mankind to next generations and should be preserved carefully and safely without deterioration or loss. Chapter 3 investigates the current status of preservation and management of three repositories that store the four registered records in Korea. The repositories include Kyujanggak Archives in Seoul National University, Pusan Records and Information Center of National Records and Archives Service, and Gansong Art Museum. The quality of their preservation and management are excellent in all of three institutions by the following aspects: 1) detailed security measures are close to perfection 2) archiving practices are very careful by using a special stack room in steady temperature and humidity and depositing it in stack or archival box made of paulownia tree and 3) fire prevention, lighting, and fumigation are thoroughly prepared. Chapter 4 summarizes the status quo of digitization projects of records heritage in Korea. The most important issue related to digitization and database construction on Korean records heritage is likely to set up the standardization of digitization processes and facilities. It is urgently necessary to develop comprehensive standard systems for digitization. Two institutions are closely interested in these tasks: 1) the National Records and Archives Service experienced in developing government records management systems; and 2) the Cultural Heritage Administration interested in digitization of Korean old documents. In collaboration of these two institutions, a new standard system will be designed for digitizing records heritage on Korean Studies. Chapter 5 deals with additional Korean records heritage in the wish list for UNESCO's Memory of the World Register, including: 1) Wooden Printing Blocks(經板) of Koryo-Taejangkyong(高麗大藏經) in Haein Temple(海印寺); 2) Dongui-Bogam("東醫寶鑑") 3) Samguk-Yusa("三國遺事") and 4) Mugujeonggwangdaedaranigyeong. Their world value and importance are examined as followings. Wooden Printing Blocks of Koryo-Taejangkyong in Haein Temple is the worldly oldest wooden printing block of cannon of Buddhism that still exist and was created over 750 years ago. It needs a special conservation treatment to disinfect germs residing in surface and inside of wooden plates. Otherwise, it may be damaged seriously. For its effective conservation and preservation, we hope that UNESCO and Government will schedule special care and budget and join the list of Memory of the Word Register. Dongui-Bogam is the most comprehensive and well-written medical book in the Korean history, summarizing all medical books in Korea and China from the Ancient Times through the early 17th century and concentrating on Korean herb medicine and prescriptions. It is proved as the best clinical guidebook in the 17th century for doctors and practitioners to easily use. The book was also published in China and Japan in the 18th century and greatly influenced the development of practical clinic and medical research in Asia at that time. This is why Dongui Bogam is in the wish list to register to the Memory of the World. Samguk-Yusa is evaluated as one of the most comprehensive history books and treasure sources in Korea, which illustrates foundations of Korean people and covers histories and cultures of ancient Korean peninsula and nearby countries. The book contains the oldest fixed form verse, called Hyang-Ka(鄕歌), and became the origin of Korean literature. In particular, the section of Gi-ee(紀異篇) describes the historical processes of dynasty transition from the first dynasty Gochosun(古朝鮮) to Goguryeo(高句麗) and illustrates the identity of Korean people from its historical origin. This book is worthy of adding to the Memory of the World Register. Mugujeonggwangdaedaranigyeong is the oldest book printed by wooden type plates, and it is estimated to print in between 706 and 751. It contains several reasons and evidence to be worthy of adding to the list of the Memory of the World. It is the greatest documentary heritage that represents the first wooden printing book that still exists in the world as well as illustrates the history of wooden printing in Korea.

The Effect of Nitric Oxide Donor or Nitric Oxide Synthase Inhibitor on Oxidant Injury to Cultured Rat Lung Microvascular Endothelial Cells (산화질소 공여물과 산화질소 합성효소 길항제가 백서 폐미세혈관 내피세포 산화제 손상에 미치는 영향)

  • Chang, Joon;Michael, John R.;Kim, Se-Kyu;Kim, Sung-Kyu;Lee, Won-Young;Kang, Kyung-Ho;Yoo, Se-Hwa;Chae, Yang-Seok
    • Tuberculosis and Respiratory Diseases
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    • v.45 no.6
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    • pp.1265-1276
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    • 1998
  • Background : Nitric oxide(NO) is an endogenously produced free radical that plays an important role in regulating vascular tone, inhibition of platelet aggregation and white blood cell adhesion to endothelial cells, and host defense against infection. The highly reactive nature of NO with oxygen radicals suggests that it may either promote or reduce oxidant-induced cell injury in several biological pathways. Oxidant injury and interactions between pulmonary vascular endothelium and leukocytes are important in the pathogenesis of acute lung injury, including acute respiratory distress syndrome(ARDS). In ARDS, therapeutic administration of NO is a clinical condition providing exogenous NO in oxidant-induced endothelial injury. The role of exogenous NO from NO donor or the suppression of endogenous NO production was evaluated in oxidant-induced endothelial injury. Method : The oxidant injury in cultured rat lung microvascular endothelial cells(RLMVC) was induced by hydrogen peroxide generated from glucose oxidase(GO). Cell injury was evaluated by $^{51}$chromium($^{51}Cr$) release technique. NO donor, such as S-nitroso-N-acetylpenicillamine(SNAP) or sodium nitroprusside(SNP), was added to the endothelial cells as a source of exogenous NO. Endogenous production of NO was suppressed with N-monomethyl-L-arginine(L-NMMA) which is an NO synthase inhibitor. L-NMMA was also used in increased endogenous NO production induced by combined stimulation with interferon-$\gamma$(INF-$\gamma$), tumor necrosis factor-$\alpha$(TNF-$\alpha$), and lipopolysaccharide(LPS). NO generation from NO donor or from the endothelial cells was evaluated by measuring nitrite concentration. Result : $^{51}Cr$ release was $8.7{\pm}0.5%$ in GO 5 mU/ml, $14.4{\pm}2.9%$ in GO 10 mU/ml, $32.3{\pm}2.9%$ in GO 15 mU/ml, $55.5{\pm}0.3%$ in GO 20 mU/ml and $67.8{\pm}0.9%$ in GO 30 mU/ml ; it was significantly increased in GO 15 mU/ml or higher concentrations when compared with $9.6{\pm}0.7%$ in control(p < 0.05; n=6). L-NMMA(0.5 mM) did not affect the $^{51}Cr$ release by GO. Nitrite concentration was increased to $3.9{\pm}0.3\;{\mu}M$ in culture media of RLMVC treated with INF-$\gamma$ (500 U/ml), TNF-$\alpha$(150 U/ml) and LPS($1\;{\mu}g/ml$) for 24 hours ; it was significantly suppressed by the addition of L-NMMA. The presence of L-NMMA did not affect $^{51}Cr$ release induced by GO in RLMVC pretreated with INF-$\gamma$, TNF-$\alpha$ and LPS. The increase of $^{51}Cr$ release with GO(20 mU/ml) was prevented completely by adding 100 ${\mu}M$ SNAP. But the add of SNP, potassium ferrocyanate or potassium ferricyanate did not protect the oxidant injury. Nitrite accumulation was $23{\pm}1.0\;{\mu}M$ from 100 ${\mu}M$ SNAP at 4 hours in phenol red free Hanks' balanced salt solution. But nitrite was not detectable from SNP upto 1 mM The presence of SNAP did not affect the time dependent generation of hydrogen peroxide by GO in phenol red free Hanks' balanced salt solution. Conclusion : Hydrogen peroxide generated by GO causes oxidant injury in RLMVC. Exogenous NO from NO donor prevents oxidant injury, and the protective effect may be related to the ability to release NO. These results suggest that the exogenous NO may be protective on oxidant injury to the endothelium.

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