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Quantum Mechanical Simulation for the Analysis, Optimization and Accelerated Development of Precursors and Processes for Atomic Layer Deposition (ALD)

  • Mustard, Thomas Jeffrey Lomax;Kwak, Hyunwook Shaun;Goldberg, Alexander;Gavartin, Jacob;Morisato, Tsuguo;Yoshidome, Daisuke;Halls, Mathew David
    • Journal of the Korean Ceramic Society
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    • v.53 no.3
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    • pp.317-324
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    • 2016
  • Continued miniaturization and increasingly exact requirements for thin film deposition in the semiconductor industry is driving the search for new effective, efficient, selective precursors and processes. The requirements of defect-free, conformal films, and precise thickness control have focused attention on atomic layer deposition (ALD). ALD precursors so far have been developed through a trial-and-error experimental approach, leveraging the expertise and tribal knowledge of individual research groups. Precursors can show significant variation in performance, depending on specific choice of co-reactant, deposition stage, and processing conditions. The chemical design space for reactive thin film precursors is enormous and there is urgent need for the development of computational approaches to help identify new ligand-metal architectures and functional co-reactants that deliver the required surface activity for next-generation thin-film deposition processes. In this paper we discuss quantum mechanical simulation (e.g. density functional theory, DFT) applied to ALD precursor reactivity and state-of-the-art automated screening approaches to assist experimental efforts leading toward optimized precursors for next-generation ALD processes.

Ru and $RuO_2$ Thin Films Grown by Atomic Layer Deposition

  • Shin, Woong-Chul;Choi, Kyu-Jeong;Jung, Hyun-June;Yoon, Soon-Gil;Kim, Soo-Hyun
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.149-149
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    • 2008
  • Metal-Insulator-Metal(MIM) capacitors have been studied extensively for next generation of high-density dynamic random access memory (DRAM) devices. Of several candidates for metal electrodes, Ru or its conducting oxide $RuO_2$ is the most promising material due to process maturity, feasibility, and reliability. ALD can be used to form the Ru and RuO2 electrode because of its inherent ability to achieve high level of conformality and step coverage. Moreover, it enables precise control of film thickness at atomic dimensions as a result of self-limited surface reactions. Recently, ALD processes for Ru and $RuO_2$, including plasma-enhanced ALD, have been studied for various semiconductor applications, such as gate metal electrodes, Cu interconnections, and capacitor electrodes. We investigated Ru/$RuO_2$ thin films by thermal ALD with various deposition parameters such as deposition temperature, oxygen flow rate, and source pulse time. Ru and $RuO_2$ thin films were grown by ALD(Lucida D150, NCD Co.) using RuDi as precursor and O2 gas as a reactant at $200\sim350^{\circ}C$.

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Involvement of Hepatic Innate Immunity in Alcoholic Liver Disease

  • Byun, Jin-Seok;Jeong, Won-Il
    • IMMUNE NETWORK
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    • v.10 no.6
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    • pp.181-187
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    • 2010
  • Excessive alcohol consumption is one of the critical causative factors leading to alcoholic liver disease (ALD). ALD is characterized by a wide spectrum of liver damage, ranging from simple uncomplicated liver steatosis (fatty liver) to steatohepatitis and liver fibrosis/cirrhosis. It has been believed that the obvious underlying cause for ALD is due to hepatocyte death induced by alcohol itself. However, recent sparkling studies have shown that diverse immune responses contribute to ALD because liver is enriched with numerous immune cells. Especially, a line of evidence has suggested that innate immune cells such as Kupffer cells and natural killer (NK)/NKT cells are significantly involved in the pathogenesis of ALD via production of pro-inflammatory cytokines and other mediators. Indeed, more interestingly, hepatic stellate cells (HSCs), known as a major cell inducing liver steatosis and fibrosis, can be killed by liver NK cells, which could be suppressed by chronic alcohol consumption. In this review, with the view of liver as predominant innate immune organ, we describe the pathogenesis of ALD in which what roles of innate immune cells are and how they are interacting with HSCs.

ALD와 PEALD 공정에서의 파티클 형성과 박막 특성 비교

  • Gang, Go-Ru;Kim, Jin-Tae;Cha, Deok-Jun;Yun, Ju-Yeong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.253-253
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    • 2013
  • 본 실험에서는 전구체(Precursor)로 TMA (Tris methyl Aluminum)를 사용한 ALD (Atomic Layer Deposition)와 PEALD (Plasma Enhanced Atomic Layer Deposition) 공정 중 발생하는 입자(particle)를 ISPM (In-Situ Particle Mornitor)로 관찰하였다. ALD과 PEALD 공정에서 Al2O3 박막을 형성하기 위해서 반응가스(Reactant)로 각 각 H2O와 O2 plasma를 사용하였다. 이러한 차이로 인해서 진공 챔버(Vacuum Chamber) 안에서의 각기 다른 매커니즘에 의해서 Al2O3의 박막이 형성된다. 또한 공정 중 발생할 수 있는 파티클(Particle) 생성 매커니즘의 차이점을 가진다. ALD의 경우 전구체와 반응가스 사이에 충분한 purge가 이루어지지 않거나 dead zone이 존재할 경우 라인과 챔버 상에 잔류한 전구체와 반응가스에 의해서 불완전한 반응물로 파티클이 생성될 수 있다. 반면 PEALD 경우는 반응가스(Reactant)로 O2 plasma를 극부(localization)적으로 형성하여 박막을 형성하므로 반응가스의 잔류의 영향은 없으나 고에너지의 플라즈마에 의해서 물리적 영향에 의한 파티클이 생성될 수 있다. 공정 중 발생하는 입자(Particle)은 수율 감소와 박막의 물성에 영향을 미칠 수 있다. 그러므로 두 공정 중 발생하는 파티클을 ISPM으로 관찰하였고, 각 공정에서 형성된 박막의 두께 균일도, 표면의 형상(morphology), 화학적 조성 및 전기적 특성을 측정하였다. 이를 통해서 ALD와 PEALD의 파티클과 박막특성을 비교하였다.

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Effects of Substrate Temperature on the Microstructure and Photoluminescence Properties of ZnO Thin Films by Atomic Layer Deposition (ZnO 성장을 위한 Atomic Layer Deposition법에서 공정온도가 박막의 구조적 및 광학적 특성에 미치는 영향)

  • Lim, Jong-Min;Lee, Chong-Mu
    • Korean Journal of Materials Research
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    • v.15 no.11
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    • pp.741-744
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    • 2005
  • Atomic layer deposition (ALD) is a very promising deposition technique for ZnO thin films. However, there have been very few reports on ZnO grown by ALD. Effects of substrate temperature in both ALD and post annealing on the microstructure and PL properties of ZnO thin films were investigated using X-ray diffraction, photoluminescence, and scanning electron microscopy. The temperature window of ALD is found to be between $130-180^{\circ}C$. The growth rate of ZnO thin film increases as the substrate temperature increases in the temperature range except the temperature window. The crystal quality depends most strongly on the substrate temperature among all the growth parameters of ALD. The crystallinity of the film is improved by increasing the growth thine per ALD cycle or doing post-annealing treatment. The grain size of the film tends to increase and the grain shape tends to change from a worm-like longish shape to a round one as the annealing temperature increases from $600^{\circ}C\;to\;1,000^{\circ}C$.

Growth of Atomic Layer Deposition Platinum on TiO2 (이산화 티타늄 위에서의 원자층 증착법 백금의 성장 특성)

  • Kim, Hyun Gu;Lee, Han-Bo-Ram
    • Journal of the Korean institute of surface engineering
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    • v.48 no.2
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    • pp.38-42
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    • 2015
  • Atomic layer deposition (ALD) is essential for the fabrication of nanoscale electronic devices because it has excellent conformality, atomic scale thickness control, and large area uniformity. Metal thin films are one of the important material components for electronic devices as a conductor. As the size of electronic devices shrinks, the thickness of metal thin films is decreased down to few nanometers, and the metal films become non-continuous due to inherent island growth of metal below a critical thickness. So, fabrication of continuous metal thin films by ALD is fundamentally and practically important. Since ALD films are grown through self-saturated reactions between precursors on surface, initial growth characteristics significantly depend on the surface properties and the selection of precursors. In this work, we investigated ALD Pt on $TiO_2$ substrate by using trimethyl-methyl-cyclopentadienyl-Platinum ($MeCpPtMe_3$) precursor and $O_3$ reactant. By using $O_3$ instead of $O_2$, initial nucleation rate of ALD Pt was increased on $TiO_2$ surface, resulting in formation of continuous thin Pt films. Morphologies of ALD Pt on $TiO_2$ were characterized by using Scanning Electron Microscope (SEM) and Energy-Dispersive X-ray Spectroscopy (EDS). Crystallinity of ALD Pt on $TiO_2$ correlated with its growth characteristics was analyzed by X-Ray Diffraction (XRD).

Study on the characteristics of ALD, ZrO2 thin film for next-generation high-density MOS devices (차세대 고집적 MOS 소자를 위한 ALD ZrO2 박막의 특성 연구)

  • Ahn, Seong-Joon;Ahn, Seung-Joon
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.9 no.1
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    • pp.47-52
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    • 2008
  • As the packing density of IC devices gets ever higher, the thickness of the gate $SiO_2$ layer of the MOS devices is now required to be reduced down to 1 nm. For such a thin $SiO_2$ layer, the MOS device cannot operate properly because of tunneling current and threshold voltage shift. Hence there has been much effort to develop new dielectric materials which have higher dielectric constants than $SiO_2$ and is free from such undesirable effects. In this work, the physical and electrical characteristics of ALD $ZrO_2$ film have been studied. After deposition of a thin ALD $ZrO_2$ film, it went through thermal treatment in the presence of argon gas at $800^{\circ}C$ for 1 hr. The characteristics of morphology, crystallization kinetics, and interfacial layer of $Pt/ZrO_2/Si$ samples have been investigated by using the analyzing instruments like XRD, TEM and C-V plots. It has been found that the characteristics of the $Pt/ZrO_2/Si$ device was enhanced by the thermal treatment.

Effect of Non-lattice Oxygen Concentration on Non-linear Interfacial Resistive Switching Characteristic in Ultra-thin HfO2 Films

  • Kim, Yeong-Jae;Kim, Jong-Gi;Mok, In-Su;Lee, Gyu-Min;Son, Hyeon-Cheol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.359-360
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    • 2013
  • The effect of electrode and deposition methods on non-linear interfacial resistive switching in HfO2 based $250{\times}250$ nm2 cross-point device was studied. HfO2 based device has the interfacial resistive switching properties of non-linearity and self-compliance current switching. The operating current in HfO2 based device was increased with negatively increasing the heat of formation energy in top electrode. Also, it was investigated that the operating current in HfO2 based device was changed with deposition methods of O3 reactant ALD, H2O reactant ALD and dc reactive sputtering, resulting the magnitude of the operating current and on/off ratio in order of HfO2 films deposited by dc reactive sputtering, H2O reactant ALD, and O3 reactant ALD. To investigate the effect of electrode and deposition methods on operating current of non-linear interfacial resistive switching in the cross-point device, X-ray photoelectron spectroscopy was measured. Through the analysis of O 1s spectra, non-lattice oxygen concentration, which is closely related to oxygen vacancies, was increased in order of Pt, TiN, and Ti top electrodes and in order of O3 reactant ALD, H2O reactant ALD, and O3 reactant ALD, and dc reactive sputtering deposition method. From all results, non-lattice oxygen concentration in ultra-thin HfO2 films play a crucial role in the operating current and memory states (LRS & HRS) in the non-linear interfacial resistive switching.

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High Quality Nickel Atomic Layer Deposition for Nanoscale Contact Applications

  • Kim, Woo-Hee;Lee, Han-Bo-Ram;Heo, Kwang;Hong, Seung-Hun;Kim, Hyung-Jun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2009.05a
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    • pp.22.2-22.2
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    • 2009
  • Currently, metal silicides become increasingly more essential part as a contact material in complimentary metal-oxide-semiconductor (CMOS). Among various silicides, NiSi has several advantages such as low resistivity against narrow line width and low Si consumption. Generally, metal silicides are formed through physical vapor deposition (PVD) of metal film, followed by annealing. Nanoscale devices require formation of contact in the inside of deep contact holes, especially for memory device. However, PVD may suffer from poor conformality in deep contact holes. Therefore, Atomic layer deposition (ALD) can be a promising method since it can produce thin films with excellent conformality and atomic scale thickness controllability through the self-saturated surface reaction. In this study, Ni thin films were deposited by thermal ALD using bis(dimethylamino-2-methyl-2-butoxo)nickel [Ni(dmamb)2] as a precursor and NH3 gas as a reactant. The Ni ALD produced pure metallic Ni films with low resistivity of 25 $\mu{\Omega}cm$. In addition, it showed the excellent conformality in nanoscale contact holes as well as on Si nanowires. Meanwhile, the Ni ALD was applied to area-selective ALD using octadecyltrichlorosilane (OTS) self-assembled monolayer as a blocking layer. Due to the differences of the nucleation on OTS modified surfaces toward ALD reaction, ALD Ni films were selectively deposited on un-coated OTS region, producing 3 ${\mu}m$-width Ni line patterns without expensive patterning process.

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Fabrication of TiO2 Thin Films Using UV-enhanced Atomic Layer Deposition at Room Temperature (자외선 활성화 원자층 성장 기술을 이용한 상온에서 TiO2 박막의 제조)

  • Lee, Byoung-H.;Sung, Myung-M.
    • Journal of the Korean Vacuum Society
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    • v.19 no.2
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    • pp.91-95
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    • 2010
  • A UV-enhanced atomic layer deposition (UV-ALD) process was developed to deposit $TiO_2$ thin films on Si substrates using titanium isopropoxide(TIP) and $H_2O$ as precursors with UV light. In the UV-ALD process, the surface reactions were found to be self-limiting and complementary enough to yield a uniform, conformal, pure $TiO_2$ thin film on Si substrates at room temperature. The UV light was very effective to obtain the high-quality $TiO_2$ thin films with good adhesive strength on Si substrates. The UV-ALD process was applied to produce uniform and conformal $TiO_2$ coats into deep trenches with high aspect ratio.