• Title/Summary/Keyword: copper diffusion barrier

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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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Atomic Layer Depositied Tungsten Nitride Thin Films as Diffusion Barrier for Copper Metallization

  • Hwang, Yeong-Hyeon;Lee, In-Hwan;Jo, Byeong-Cheol;Kim, Yeong-Hwan;Jo, Won-Ju;Kim, Yong-Tae
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.145-145
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    • 2012
  • 반도체 집적회로의 집적도가 증가함에 따라 RC delay가 증가하며, 금속 배선의 spiking, electromigration 등의 문제로 인해 기존의 알루미늄 금속을 대체하기 위하여 구리를 배선재료로 사용하게 되었다. 하지만 구리는 실리콘 및 산화물 내에서 매우 빠른 확산도를 가지고 있으므로, 구리의 확산을 막아 줄 확산방지막이 필요로 하다. 이러한 확산방지막의 증착은, 소자의 크기가 작아짐에 따라 via/contact과 같은 고단차 구조에도 적용이 가능하도록 기존의 sputtering 증착 방법에서 이를 개선한 collimated sputter, long-throw sputter, ion-metal plasma 등의 방법으로 물리적인 증착법이 지속되어 왔지만, 근본적인 증착방법을 바꾸지 않는 한 한계에 도달하게 될 것이다. 원자층 증착법(ALD)은 CVD 증착법의 하나로, 소스와 반응물질을 주입하는 시간을 분리함으로써 증착하고자 하는 표면에서의 반응을 유도하여 원자층 단위로 원하는 박막을 얻을 수 있는 증착방법이다. 이를 이용하여 물리적 증기 증착법(PVD)보다 우수한 단차피복성과 함께 정교하게 증착두께를 컨트롤을 할 수 있다. 본 연구에서는 이러한 원자층 증착법을 이용하여 구리 배선을 위한 확산방지막으로 텅스텐질화막을 형성하였다. 텅스텐 질화막을 형성하기 위하여 금속-유기물 전구체와 함께 할라이드 계열인 WF6를 텅스텐 소스로 이용하였으며, 이에 대한 원자층 증착방법으로 이루어진 박막의 물성을 비교 평가하여 분석하였다.

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Ceramic barrier coated Pd hydrogen membrane on a porous nickel support (수소 분리용 팔라듐계 분리막의 세라믹 코팅 영향)

  • Lee, Chun-Boo;Lee, Sung-Wook;Park, Jin-Woo;Kim, Kwang-Ho;Hwang, Kyung-Ran;Park, Jong-Soo;Kim, Sung-Hyun
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.11a
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    • pp.114.1-114.1
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    • 2010
  • A highly performed Pd-based hydrogen membrane has prepared successfully on a modified porous nickel support. The porous nickel support modified by impregnation method of $Al(NO_3)_3{\cdot}9H_2O$ (Aldrich Co.) over the nickel powder showed a strong resistance to hydrogen embrittlement and thermal stability. Plasma surface modification treatment was introduced as a pre-treatment process instead of conventional HCl wet activation. Ceramic barrier was coated on the external surface of the prepared nickel supports to prevent intermetallic diffusion and to enhance the affinity between the support and membrane. Palladium and copper were deposited at thicknesses of $4\mu}m$ and $0.5{\mu}m$, respectively, on a barrier-coated support by DC sputtering process. The permeation measurement was performed in pure hydrogen at $400^{\circ}C$. The single gas permeation of our membrane was two times higher than that of the previous membrane which do not have ceramic barrier.

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A study on Electrical and Diffusion Barrier Properties of MgO Formed on Surface as well as at the Interface Between Cu(Mg) Alloy and $SiO_2$ (Cu(Mg) alloy의 표면과 계면에서 형성된 MgO의 확산방지능력 및 표면에 형성된 MgO의 전기적 특성 연구)

  • Jo, Heung-Ryeol;Jo, Beom-Seok;Lee, Jae-Gap
    • Korean Journal of Materials Research
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    • v.10 no.2
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    • pp.160-165
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    • 2000
  • We have investigated the electrical and diffusion barrier properties of MgO produced on the surface of Cu (Mg) alloy. Also the diffusion barrier property of the interfacial MgO between Cu alloy and $SiO_2$ has been examined. The results show that the $150\;{\AA}$-MgO layer on the surface remains stable up to $700^{\circ}C$, preventing the interdiffusion of C Cu and Si in Si/MgO/Cu(Mg) structure. It also has the breakdown voltage of 4.5V and leakage current density of $10^{-7}A/\textrm{cm}^2/$. In addition, the combined structure of $Si_3N4(100{\AA})/MgO(100{\AA})$ increases the breakdown voltage up to lOV and reduces the leakage current density to $8{\tiems}10^{-7}A/\textrm{cm}^2$. Furthermore, the interfacial MgO formed by the chemical reac­t tion of Mg and $SiO_2$ reduces the diffusion of copper into $SiO_2$ substrate. Consequently, Cu(Mg) alloy can be applied as a g gate electrode in TFT /LCDs, reducing the process steps.

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The Properties of Ta, Nb as Diffusion Barriers Against Copper Diffusion (구리 확산방지막으로서의 Ta와 Nb 박막의 특성에 관한 연구)

  • Choe, Jung-Il;Lee, Jong-Mu
    • Korean Journal of Materials Research
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    • v.6 no.10
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    • pp.1017-1024
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    • 1996
  • 본 연구에서는 여러 기판에 대한 Cu의 확산정도를 알기 위하여 Ta, Nb, Co/Ta이중층 및 Co/Nb 이중층 위에 기화법으로 증착하고 열처리를 실시하였다. 열처리한 Ta막은 열처리하지 않은 Ta막보다 Cu 확산방지막으로서의 성능이 더 떨어지는데, 이것은 열처리에 의하여 Ta막이 결정화되기 때문이다. Cu/Co/Ta/(001)Si 구조에서의 구리 실리사이드 생성온도는 Cu/Co/Ta(001)Si 구조에서의 그것보다 더 높다. 한편, nb의 Cu에 대한 barrier 특성은 Ta와 비슷한 수준이다. 또한 Cu막 도포 이전에 Pd+HF활성화 전처리나 N2플라즈마 전처리를 실시하면, Cu의 핵생성뿐만 아니라 기판에 대한 Cu막의 접착성도 향상된다.

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The Effects of Current Types on Through Via Hole Filling for 3D-SiP Application (전류인가 방법이 3D-SiP용 Through Via Hole의 Filling에 미치는 영향)

  • Chang, Gun-Ho;Lee, Jae-Ho
    • Journal of the Microelectronics and Packaging Society
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    • v.13 no.4
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    • pp.45-50
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    • 2006
  • Copper via filling is the important factor in 3-D stacking interconnection of SiP (system in package). As the packaging density is getting higher, the size of via is getting smaller. When DC electroplating is applied, a defect-free hole cannot be obtained in a small size via hole. To prevent the defects in holes, pulse and pulse reverse current was applied in copper via filling. The holes, $20\and\;50{\mu}m$ in diameter and $100{\sim}190\;{\mu}m$ in height. The holes were prepared by DRIE method. Ta was sputtered for copper diffusion barrier followed by copper seed layer IMP sputtering. Via specimen were filled by DC, pulse and pulse-reverse current electroplating methods. The effects of additives and current types on copper deposits were investigated. Vertical and horizontal cross section of via were observed by SEM to find the defects in via. When pulse-reverse electroplating method was used, defect free via were successfully obtained.

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Diffusion barrier properties of Mo compound thin films (Mo-화합물의 확산방지막으로서의 성질에 관한 연구)

  • 김지형;이용혁;권용성;염근영;송종한
    • Journal of the Korean Vacuum Society
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    • v.6 no.2
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    • pp.143-150
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    • 1997
  • In this study, doffusion barrier properties of 1000 $\AA$ thick molybdenum compound(Mo, Mo-N, $MoSi_2$, Mo-Si-N) films were investigated using sheet resistance measurement, X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), Scanning electron mircoscopy(SEM), and Rutherford back-scattering spectrometry(RBS). Each barrier material was deposited by the dc magnetron sputtering and annealed at 300-$800^{\circ}C$ for 30 min in vacuum. Mo and MoSi2 barrier were faied at low temperatures due to Cu diffusion through grain boundaries and defects in Mo thin film and the reaction of Cu with Si within $MoSi_2$, respectively. A failure temperature could be raised to $650^{\circ}C$-30 min in the Mo barrier system and to $700^{\circ}C$-30 min in the Mo-silicide system by replacing Mo and $MoSi_2$ with Mo-N and Mo-Si-N, respectively. The crystallization temperature in the Mo-silicide film was raised by the addition of $N_2$. It is considered that not only the $N_2$, stuffing effect but also the variation of crystallization temperature affects the reaction of Cu with Si within Mo-silicide. It is found that Mo-Si-N is the more effective barrier than Mo, $MoSi_2$, or Mo-N to copper penetraion preventing Cu reaction with the substrate for $30^{\circ}C$min at a temperature higher than $650^{\circ}C$.

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The Research of Solar Cells Applying Ni/Cu/Ag Contact for Low Cost & High Efficiency (태양전지의 저가격.고효율화를 위한 Ni/Cu/Ag 전극에 관한 연구)

  • Cho, Kyeong-Yeon;Lee, Ji-Hun;Lee, Soo-Hong
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2009.06a
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    • pp.444-445
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    • 2009
  • The metallic contact system of silicon solar cell must have several properties, such as low contact resistance, easy application and good adhesion. Ni is shown to be a suitable barrier to Cu diffusion as well as desirable contact metal to silicon. Nickel monosilicide(NiSi) has been suggested as a suitable silicide due to its lower resistivity, lower sintering temperature and lower layer stress than $TiSi_2$. Copper and Silver can be plated by electro & light-induced plating method. Light-induced plating makes use the photovoltaic effect of solar cell to deposit the metal on the front contact. The cell is immersed into the electrolytic plating bath and irradiated at the front side by light source, which leads to a current density in the front side grid. Electroless plated Ni/ Electro&light-induced plated Cu/ Light-induced plated Ag contact solar cells result in an energy conversion efficiency of 16.446 % on $0.2\sim0.6\;{\Omega}{\cdot}cm$, $20\;\times\;20\;mm^2$, CZ(Czochralski) wafer.

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Effect of pH Adjuster on Adhesion Strength between electroless copper film and Ta diffusion barrier (반도체 배선용 무전해 구리 도금액의 pH 조정제가 접합력에 미치는 영향)

  • Lee, Chang-Myeon;Lee, Hong-Gi;Heo, Jin-Yeong;Song, Dong-Ho
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2013.05a
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    • pp.186-186
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    • 2013
  • 반도체 배선용 무전해 구리 도금에서 pH조정제가 구리피막과 Ta 확산방지막 사이의 접합력에 미치는 영향에 대하여 연구하였다. TMAH로 pH가 조절된 경우 NaOH 사용시에 비하여 높은 접합력을 나타내었다. 면간거리 및 밀도 측정결과 TMAH를 사용한 경우 구리피막이 보다 치밀한 구조임을 확인할 수 있었다. TMAH 사용시의 높은 접합력은 NaOH을 사용 한 경우에 비하여 무전해 구리피막이 보다 낮은 내부응력을 갖기 때문으로 판단되었다. pH조정제에 따른 내부응력의 변화를 결정구조의 관점에서 자세히 고찰하였다.

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Ni/Cu Metallization for High Efficiency Silicon Solar Cells (Ni/Cu 전극을 적용한 고효율 실리콘 태양전지의 제작 및 특성 평가)

  • Lee, Eun-Joo;Lee, Soo-Hong
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.12
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    • pp.1352-1355
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    • 2004
  • We have applied front contact metallization of plated nickel and copper for high efficiency passivated emitter rear contact(PERC) solar cell. Ni is shown to be a suitable barrier to Cu diffusion as well as desirable contact metal to silicon. The plating technique is a preferred method for commercial solar cell fabrication because it is a room temperature process with high growth rates and good morphology. In this system, the electroless plated Ni is utilized as the contact to silicon and the plated Cu serves as the primary conductor layer instead of traditional solution that are based on Ti/Pd/Ag contact system. Experimental results are shown for over 20 % PERC cells with the Plated Ni/Cu contact system for good performance at low cost.