• Title/Summary/Keyword: metal plating

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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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An Improvement in the Properties of MH Electrode of Ni/MH Battery by the Copper Coating (Ni/MH 전지에서 Cu 도금에 의한 음극활물질의 전극 특성 향상)

  • Cho, Jin Hun;Kim, In Jung;Lee, Yun Sung;Nahm, Kee Suk;Kim, Ki Ju;Lee, Hong Ki
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.568-574
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    • 1997
  • The effect of microencapsulation of maetal hydride (MH) with copper on the electrode performance of a Ni/MH battery has been investigated. The MH electrodes were prepared with a combination of cold press and paste methods. The discharge capacity of the electrode increased with an addition of small amounts if CMC into the electrode, but decreased when heat-treated in an oxygen-free nitrogen flow. The capacity of a Cu-coated $LaNi_5$ electrode was higher than that of LaNi5electrode. The discharge capacity of the electrode prepared with Cu-coated $LaNi_5$ increased with the increase of copper content in the electrode. It is considered that the increase of copper content enhanced the current density on the electrode surface, leading to the increase of the discharge capacity The MH electrode coated by an acidic electroless plating method showed much higher discharge capacity than that using an alkaline electroless plating method. The discharge capacity of the $LaNi_{4.5}Al_{0.5}$ electrode was higher than that of the $LaNi_5$ electrode. Also, the effect of microencapsulation on the deactivation of $LaNi_5$ was studied using an absorption-desorption cycle in CO-containing hydrogen.

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Characteristics of MOCVD Cobalt on ALD Tantalum Nitride Layer Using $H_2/NH_3$ Gas as a Reactant

  • Park, Jae-Hyeong;Han, Dong-Seok;Mun, Dae-Yong;Yun, Don-Gyu;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.377-377
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    • 2012
  • Microprocessor technology now relies on copper for most of its electrical interconnections. Because of the high diffusivity of copper, Atomic layer deposition (ALD) $TaN_x$ is used as a diffusion barrier to prevent copper diffusion into the Si or $SiO_2$. Another problem with copper is that it has weak adhesion to most materials. Strong adhesion to copper is an essential characteristic for the new barrier layer because copper films prepared by electroplating peel off easily in the damascene process. Thus adhesion-enhancing layer of cobalt is placed between the $TaN_x$ and the copper. Because, cobalt has strong adhesion to the copper layer and possible seedless electro-plating of copper. Until now, metal film has generally been deposited by physical vapor deposition. However, one draw-back of this method is poor step coverage in applications of ultralarge-scale integration metallization technology. Metal organic chemical vapor deposition (MOCVD) is a good approach to address this problem. In addition, the MOCVD method has several advantages, such as conformal coverage, uniform deposition over large substrate areas and less substrate damage. For this reasons, cobalt films have been studied using MOCVD and various metal-organic precursors. In this study, we used $C_{12}H_{10}O_6(Co)_2$ (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) as a cobalt precursor because of its high vapor pressure and volatility, a liquid state and its excellent thermal stability under normal conditions. Furthermore, the cobalt film was also deposited at various $H_2/NH_3$ gas ratio(1, 1:1,2,6,8) producing pure cobalt thin films with excellent conformality. Compared to MOCVD cobalt using $H_2$ gas as a reactant, the cobalt thin film deposited by MOCVD using $H_2$ with $NH_3$ showed a low roughness, a low resistivity, and a low carbon impurity. It was found that Co/$TaN_x$ film can achieve a low resistivity of $90{\mu}{\Omega}-cm$, a low root-mean-square roughness of 0.97 nm at a growth temperature of $150^{\circ}C$ and a low carbon impurity of 4~6% carbon concentration.

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A STUDY ON METAL RELEASE OF TIN ION-PLATED STAINLESS STEEL ORTHODONTIC APPLIANCES (TiN 피막 처리된 스테인레스강 교정용 장치물의 금속 유리에 대한 연구)

  • KIM, Myung-Sook;Sung, Jae-Hyun;Kwon, Oh-Won
    • The korean journal of orthodontics
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    • v.25 no.1 s.48
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    • pp.43-54
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    • 1995
  • This study was conducted to examine the metal release of TiN-plated stainless steel orthodontic appliances by constructing the simulated orthodontic appliances equivalent to maxillary half arch, by dividing into TiN-plated and TiN-nonplated Bloops and by dividing again these groups into welded and nonwelded groups. And then, the total quantity of metal release was obtained by measuring the amounts of both soluble and precipitated nickel and chromium after immersing in artificial saliva for 15 days. And then, the corrosion appearance of surface structure was observed by using SEM. The results of this study were summarized as follows. 1. The total amounts of released nickel and chromium showed that the TiN-plated group after welding(Group 1) was 25.46 ${\mu}g$, respectively, and 17.4 ${\mu}g$, while the TiN-nonplated group after welding(Group III) was 54.69 ${\mu}g$, respectively, and 85.27 ${\mu}g$. Then, the TiN-Plated group indicated less amounts of metal release(p<0.05). 2. The total amounts of the TiN-plated group without welding(Group II) was 0.05${\mu}g$ and 0.34${\mu}g$, respectively. Then, it was shown that the TiN-plated group without welding(Group II) indicated less metal release than that of the TiN-Plated group after welding(Group I)(p<0.01, p<0.05). 3. When observing their surface structure, there were a lot of precipitate and pitting corrosion in the groups with welding(Group I & III), when the TiN-plated group(Group I) showed lower level than the TiN-nonplated group(Group IIII). On the other hand, the groups without welding(Group II & IV) indicated a little of pitting corrosion. 4. In case of observation with the naked eyes, it was shown that there were significant disco1oration and corrosion in the groups with welding(Group I & III), while there was no any remarkable change in the groups without welding(Group II & IV).

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The Electrochemical Characteristics of Mercapto Compounds on the Copper Electroplating (전기구리도금에 미치는 Mercapto화합물의 전기화학적 특성)

  • Son Sang Ki;Lee Yoo Yong;Cho Byung Won;Lee Jae Bong;Lee Tae Hee
    • Journal of the Korean Electrochemical Society
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    • v.4 no.4
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    • pp.160-165
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    • 2001
  • The eletrochemical charateristics of mercapto compound additives on the copper electroplating for semi conductor metalization were investigated. Mercapto compounds including sulfur atom is known that they activate deposition rate in eletroplating. Four different types of mercapto compounds were chosen with different concentration and both the characteristics of plating and throwing power were investigated by electrochemical experiments such as Hull cell test, Haring-Blum cell, cathodic polarization, EQCM(Electrochemical Quartz Crystal Microbalance). 3-Mercapto-1-propanesulfonic acid among 4 different mercapto compounds was regarded as the most proper activator with the results of the mass change of Cu metal deposited on eletrode by cathodic polarization and EQCM. The overpotential was more shifted to 100 mV in the concentration of 20 ppm than the solution with only $Cl^-$ in cathodic scan.

Corrosion and Surface Resistance of Ni-C Composite by Electrodeposition (전해도금에 의한 Ni-C 복합층의 내식성 및 표면 전기저항)

  • Park, Je-Sik;Lee, Sung-Hyung;Jeong, Goo-Jin;Lee, Churl-Kyoung
    • Korean Journal of Materials Research
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    • v.21 no.5
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    • pp.288-294
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    • 2011
  • Simultaneous Ni and C codeposition by electrolysis was investigated with the aim of obtaining better corrosion resistivity and surface conductivity of a metallic bipolar plate for application in fuel cells and redox flow batteries. The carbon content in the Ni-C composite plate fell in a range of 9.2~26.2 at.% as the amount of carbon in the Ni Watt bath and the roughness of the composite were increased. The Ni-C composite with more than 21.6 at.% C content did not show uniformly dispersed carbon. It also displayed micro-sized defects such as cracks and crevices, which result in pitting or crevice corrosion. The corrosion resistance of the Ni-C composite in sulfuric acid is similar with that of pure Ni. Electrochemical test results such as passivation were not satisfactory; however, the Ni-C composite still displayed less than $10^{-4}$ $A/cm^2$ passivation current density. Passivation by an anodizing technique could yield better corrosion resistance in the Ni-C composite, approaching that of pure Ni plating. Surface resistivity of pure Ni after passivation was increased by about 8% compared to pure Ni. On the other hand, the surface resistivity of the Ni-C composite with 13 at.% C content was increased by only 1%. It can be confirmed that the metal plate electrodeposited Ni-C composite can be applied as a bipolar plate for fuel cells and redox flow batteries.

Design of very fast acting fuse element using the Ag-Cu alloy (Ag-Cu 합금을 이용한 매우 빠른 동작 특성의 퓨즈 엘리멘트 설계)

  • Kim, Eun-Min;Lee, Seung-Hwan;Cho, Dae-Kweon;Kim, Shin-Hyo
    • The Transactions of The Korean Institute of Electrical Engineers
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    • v.63 no.8
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    • pp.1070-1074
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    • 2014
  • With the development of the electronics industry and widespread supply of many different electrical appliances, the factors of the electrical fires are also diversified. For this reason, the fuse, safety-critical component, needs accurate and stable operating characteristics for preventing various fire factor, and also needs various operating characteristics. Especially when the all electrical resistance are dropped by internal short of circuit, high current inrushes and makes the fire. In order to prevent this, very fast acting fuses should be applied. However, existing very fast acting characteristics fuse has less wire dimension of element Ag100% metal than that of fast acting fuse, and it is made of plating with low melting point metals, so it satisfy very fast acting but it can't satisfy durability and safety. For this reason, in this study, through the analyzing fusing characteristics of Ag-Cu alloy composition, the new alloy composition, which implement to very fast acting fuse without decrease of fuse elements dimension, is suggested. And this study classify the operating characteristics changes, a resistance change, and the rated current of the fuse in the overall composition change of Ag-Cu alloying. and it can be utilized for designing fuse.

Corrosion Analysis of Materials by High Temperature and Zn Fume (고온 및 Zn Fume에 의한 소재들의 부식성 분석)

  • Baek, Min Sook
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.5
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    • pp.551-556
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    • 2018
  • The material normally used in hot dip galvanizing facilities is SM45C (carbon steel for mechanical structure, KS standard), mainly because of its price. During this process, the oxidation of the plating facility occurs due to the heat of the Zn fumes coming from the molten zinc. Since the cycle time of the current facilities is 6 months, much time and money are wasted. In this study, the corrosive properties of various materials (Inconel625, STS304, SM45C) were investigated by oxidation in a high temperature and Zn fumes environment. The possibility of applying the hot-dip galvanizing equipment was investigated for each material. The Zn fumes were generated by directly bubbling Ar gas into Zn molten metal in a 650 degree furnace. High-temperature, Zn fumes corrosion was conducted for 30 days. The sample was removed after 30 days and the oxidation of the surface was confirmed with EDS and SEM, and the corrosion properties were examined using potentiodynamic polarization tests.

A Study on the PEM Electrolysis Characteristics Using Ti Mesh Coated with Electrocatalysts (Ti Mesh 처리 촉매전극을 이용한 고체고분자 전해질 전기분해 특성연구)

  • Sim, Kyu-Sung;Kim, Youn-Soon;Kim, Jong-Won;Han, Sang-Do
    • Transactions of the Korean hydrogen and new energy society
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    • v.7 no.1
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    • pp.29-37
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    • 1996
  • Alkaline water electrolysis has been commercialized as the only large-scale method for a long time to produce hydrogen and the technology is superior to other methods such as photochemical, thermochemical water splitting, and thermal decomposition method in view of efficiency and related technical problem. However, such conventional electrolyzer do not have high electric efficiency and productivity to apply to large scale hydrogen production for energy or chemical feedstocks. Solid polymer electrolyte water electrolysis using a perfluorocation exchange membrane as an $H^+$ ion conductor is considered to be a promising method, because of capability for operating at high current densities and low cell voltages. So, this is a good technology for the storage of electricity generated by photovoltaic power plants, wind generators and other energy conversion systems. One of the most important R&D topics in electrolyser is how to minimize cell voltage and maximize current density in order to increase the productivity of the electrolyzer. A commercialized technology is the hot press method which the film type electrocatalyst is hot-pressed to soild polymer membrane in order to eliminate the contact resistance. Various technologies, electrocatalyst formed over Nafion membrane surface by means of nonelectrolytic plating process, porous sintered metal(titanium powder) or titanium mesh coated with electrocatalyst, have been studied for preparation of membrane-electrocatalyst composites. In this study some experiments have been conducted at a solid polymer electrolyte water electrolyzer, which consisted of single cell stack with an electrode area of $25cm^2$ in a unipolar arrangement using titanium mesh coated with electrocatalyst.

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Study on the coating weight and corrosion resistance of Zinc phosphate for surface treatment of ammunition (탄약 표면 처리용 아연계 인산염 피막의 중량 및 내식성에 관한 연구)

  • Kim, Myung-Hyun;Lee, Seung-Yong;Lee, Hyun-Hee;Lee, Young-Tae
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.18 no.10
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    • pp.603-610
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    • 2017
  • Steel used for various industrial fields including ammunition is vulnerable to corrosion so surface treatments are required such as plating, painting and chemical conversion coating. Zinc phosphate, used for ammunition manufacturing, is used to stick the stable compound on the surface by chemical conversion of metal. The quality of phosphate coating depends on many factors such as total acidity and iron content. In this study, we studied the influence of total acidity and iron content on coating weight and corrosion resistance of phosphate coating. The surface structure of the coating becomes dense and corrosion resistance is improved with increasing iron content. However, total acidity influences only the thickness and phosphate coating weight. In conclusion, this study suggests the optimal range of total acidity and iron content to manufacture the ammunition.