• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 추계학술대회 논문집 Vol.21
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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 $200\sim350^{\circ}C$.

• E2M - 전기 전자와 첨단 소재
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• 제28권2호
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• pp.25-33
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• 2015

Ruthenium (Ru) thin films were grown on thermally-grown $SiO_2$ substrates by atomic layer deposition (ALD) using a sequential supply of four kinds of novel zero-valent Ru precursors, isopropyl-methylbenzene-cyclohexadiene Ru(0) (IMBCHDRu, $C_{16}H_{22}Ru$), ethylbenzen-cyclohexadiene Ru(0) (EBCHDRu, $C_{14}H_{18}Ru$), ethylbenzen-ethyl-cyclohexadiene Ru(0) (EBECHDRu, $C_{16}H_{22}Ru$), and (ethylbenzene)(1,3-butadiene)Ru(0) (EBBDRu, $C_{12}H_{16}Ru$) and molecular oxygen (O2) as a reactant at substrate temperatures ranging from 140 to $350^{\circ}C$. It was shown that little incubation cycles were observed for ALD-Ru processes using these new novel zero-valent Ru precursors, indicating of the improved nucleation as compared to the use of typical higher-valent Ru precursors such as cyclopentadienyl-based Ru (II) or ${\beta}$-diketonate Ru (III) metallorganic precursors. It was also shown that Ru nuclei were formed after very short cycles (only 3 ALD cycles) and the maximum nuclei densities were almost 2 order of magnitude higher than that obtained using higher-valent Ru precursors. The step coverage of ALD-Ru was excellent, around 100% at on a hole-type contact with an ultra-high aspect ratio (~32) and ultra-small trench with an aspect ratio of ~ 4.5 (top-opening diameter: ~ 25 nm). The developed ALD-Ru film was successfully used as a seed layer for Cu electroplating.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.78-78
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• 2013

Recently, many platinoid metals like platinum and ruthenium have been used as an electrode of microelectronic devices because of their low resistivity and high work-function. However the material cost of Ru is very expensive and it usually takes long initial nucleation time on SiO2 during chemical deposition. Therefore many researchers have focused on how to enhance the initial growth rate on SiO2 surface. There are two methods to deposit Ru film with atomic layer deposition (ALD); the one is thermal ALD using dilute oxygen gas as a reactant, and the other is plasma enhanced ALD (PEALD) using NH3 plasma as a reactant. Generally, the film roughness of Ru film deposited by PEALD is smoother than that deposited by thermal ALD. However, the plasma is not favorable in the application of high aspect ratio structure. In this study, we used a bis(ethylcyclopentadienyl)ruthenium [Ru(EtCp)2] as a metal organic precursor for both thermal and plasma enhanced ALDs. In order to reduce initial nucleation time, we use several methods such as Ar plasma pre-treatment for PEALD and usage of sacrificial RuO2 under layer for thermal ALD. In case of PEALD, some of surface hydroxyls were removed from SiO2 substrate during the Ar plasma treatment. And relatively high surface nitrogen concentration after first NH3 plasma exposure step in ALD process was observed with in-situ Auger electron spectroscopy (AES). This means that surface amine filled the hydroxyl removed sites by the NH3 plasma. Surface amine played a role as a reduction site but not a nucleation site. Therefore, the precursor reduction was enhanced but the adhesion property was degraded. In case of thermal ALD, a Ru film was deposited from Ru precursors on the surface of RuO2 and the RuO2 film was reduced from RuO2/SiO2 interface to Ru during the deposition. The reduction process was controlled by oxygen partial pressure in ambient. Under high oxygen partial pressure, RuO2 was deposited on RuO2/SiO2, and under medium oxygen partial pressure, RuO2 was partially reduced and oxygen concentration in RuO2 film was decreased. Under low oxygen partial pressure, finally RuO2 was disappeared and about 3% of oxygen was remained. Usually rough surface was observed with longer initial nucleation time. However, the Ru deposited with reduction of RuO2 exhibits smooth surface and was deposited quickly because the sacrificial RuO2 has no initial nucleation time on SiO2 and played a role as a buffer layer between Ru and SiO2.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 하계학술대회 논문집 Vol.9
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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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.357.2-357.2
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• 2014

Ruthenium (Ru) 박막은 우수한 화학적 열적 안정성 및 높은 일함수(4.7eV) 특성으로 인해 20 nm급 이하의 차세대 DRAM capacitor의 전극 물질 및 Cu metalization을 위한 seed layer로 각광을 받고 있다. Ru박막의 나노스케일 정보전자소자로의 적용을 위해서는 두께제어가 용이하고 3D 구조에서 우수한 단차 피복 특성을 갖는 atomic layer deposition (ALD)을 이용한 박막 형성이 필수적이다. 이에 본 연구에서는 ALD 방법을 이용하여 0가의(cymene) (1,5-hexadiene) Ru (0) (C16H24Ru) 전구체를 합성, ALD 방법을 이용하여 우수한 초기성장거동을 갖는 Ru 박막을 증착 하였다. 형성된 Ru 박막의 표면 형상, 두께, 밀도를 주사전자현미경(Scanning electron microscopy)과 X-선 반사율 측정(X-ray reflectometer)으로 조사하였다. 또한 전기적 특성을 4침법(four-point-probe)으로 측정하였고, 박막의 화학적 조성과 결정성의 정보를 X-선 광전자분광법(X-ray photoelectron spectroscopy)과 X-선 회절(X-ray diffraction)을 이용하여 확인하였다.

• 마이크로전자및패키징학회지
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• 제25권3호
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• pp.7-12
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• 2018

차세대 초미세 Cu 배선 적용을 위한 원자층증착법(atomic layer deposition, ALD)을 이용하여 증착된 Ru확산 방지층과 Cu 박막 사이의 계면 신뢰성을 평가하기 위해, Ru 공정온도 및 $200^{\circ}C$ 후속 열처리 시간에 따라 4점굽힘시험으로 정량적인 계면접착에너지를 평가하였고, 박리계면을 분석하였다. 225, 270, $310^{\circ}C$ 세 가지 ALD Ru 공정온도에 따른 계면접착에너지는 각각 8.55, 9.37, $8.96J/m^2$로 유사한 값을 보였는데, 이는 증착온도 변화에 따라 Ru 결정립 크기 등 미세조직 및 비저항의 차이가 적어서, 계면 특성도 거의 차이가 없는 것으로 판단된다. $225^{\circ}C$의 공정온도에서 증착된 Ru 박막의 계면접착에너지는 $200^{\circ}C$ 후속 열처리시 250시간까지는 $7.59J/m^2$ 이상으로 유지되었으나, 500시간 후에는 $1.40J/m^2$로 급격히 감소하였다. 박리계면에 대한 X-선 광전자 분광기 분석 결과, 500시간 후 Cu 계면 산화로 인하여 계면접착 에너지가 감소한 것으로 확인되었다. 따라서 ALD Ru 박막은 계면신뢰성이 양호한 차세대 Cu 배선용 확산방지층 후보가 된다고 판단된다.

• 대한금속재료학회지
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• 제50권8호
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• pp.557-562
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• 2012

Self-organized ruthenium (Ru) dots were fabricated by $400^{\circ}C$ RTA (rapid thermal annealing) and ALD (atomic layer deposition). The dots were produced under the $400^{\circ}C$ RTA conditions for 10, 30 and 60 seconds on all Si(100)/200 nm-SiO2, glass, and glass/fluorine-doped tin oxide (FTO) substrates. Electrical sheet resistance, and surface microstructure were examined using a 4-point probe and FE-SEM (field emission scanning electron microscopy). Ru dots were observed when a 30 nm-Ru layer on a Si(100)/200 nm-SiO2 substrate was annealed for 10, 30 and 60 seconds, whereas the dots were only observed on a glass substrate when a 50 nm-Ru layer was annealed on glass. For a glass/FTO substrate, RTA <30 seconds was needed for 30 nm Ru thick films. Those dots can increase the effective surface area for silicon and glass substrates by up to 5-44%, and by 300% for the FTO substrate with a < $20^{\circ}$ wetting angle.

• 마이크로전자및패키징학회지
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• 제23권2호
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• pp.49-55
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• 2016

차세대 반도체의 초미세 Cu 배선 확산방지층 적용을 위해 원자층증착법(atomic layer deposition, ALD) 공정을 이용하여 증착한 RuAlO 확산방지층과 Cu 박막 계면의 계면접착에너지를 정량적으로 측정하였고, 환경 신뢰성 평가를 수행하였다. 접합 직후 4점굽힘시험으로 평가된 계면접착에너지는 약 $7.60J/m^2$으로 측정되었다. $85^{\circ}C$/85% 상대습도의 고온고습조건에서 500시간이 지난 후 측정된 계면접착에너지는 $5.65J/m^2$로 감소하였으나, $200^{\circ}C$에서 500시간 동안 후속 열처리한 후에는 $24.05J/m^2$으로 계면접착에너지가 크게 증가한 것으로 평가되었다. 4점굽힘시험 후 박리된 계면은 접합 직후와 고온고습조건의 시편의 경우 RuAlO/$SiO_2$ 계면이었고, 500시간 후속 열처리 조건에서는 Cu/RuAlO 계면인 것으로 확인되었다. X-선 광전자 분광법 분석 결과, 고온고습조건에서는 흡습으로 인하여 강한 Al-O-Si 계면 결합이 부분적으로 분리되어 계면접착에너지가 약간 낮아진 반면, 적절한 후속 열처리 조건에서는 효과적인 산소의 계면 유입으로 인하여 강한 Al-O-Si 결합이 크게 증가하여 계면접착에너지도 크게 증가한 것으로 판단된다. 따라서, ALD Ru 확산방지층에 비해 ALD RuAlO 확산방지층은 동시에 Cu 씨앗층 역할을 하면서도 전기적 및 기계적 신뢰성이 우수할 것으로 판단된다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2005년도 하계학술대회 논문집 Vol.6
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• pp.143-144
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• 2005

Recently, MIM(metal-insulator-metal) capacitor is one of the essential device for DRAM device. In this thesis, $Al_2O_3$ thin film which has a relatively high dielectric constant was deposited by ALD(atomic layer deposition) using MPTMA and $H_2O$ source. Deposition temperature of $Al_2O_3$ thin film was $200^{\circ}C$ and its thickness was 300 ${\AA}$. $RuO_2$ bottom electrode was deposited by RF-magnetron sputtering using $RuO_2$ target. The physical characteristics of $Al_2O_3$ films were investigated by AES, TEM and Ellipsometry. Electrical characteristics were analyzed by C-V and I-V measurement.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.363-363
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• 2014

Ruthenium (Ru) has attractive material properties due to its promising characteristics such as a low resistivity ($7.1{\mu}{\Omega}{\cdot}cm$ in the bulk), a high work function of 4.7 eV, and feasibility for the dry etch process. These properties make Ru films appropriate for various applications in the state-of-art semiconductor device technologies. Thus, it has been widely investigated as an electrode for capacitor in the dynamic random access memory (DRAM), a metal gate for metal-oxide semiconductor field effect transistor (MOSFET), and a seed layer for Cu metallization. Due to the continuous shrinkage of microelectronic devices, better deposition processes for Ru thin films are critically required with excellent step coverages in high aspect ratio (AR) structures. In these respects, atomic layer deposition (ALD) is a viable solution for preparing Ru thin films because it enables atomic-scale control of the film thickness with excellent conformality. A recent investigation reported that the nucleation of ALD-Ru film was enhanced considerably by using a zero-valent metallorganic precursor, compared to the utilization of precursors with higher metal valences. In this study, we will present our research results on the synthesis and characterization of novel ruthenium complexes. The ruthenium compounds were easy synthesized by the reaction of ruthenium halide with appropriate organic ligands in protic solvent, and characterized by NMR, elemental analysis and thermogravimetric analysis. The molecular structures of the complexes were studied by single crystal diffraction. ALD of Ru film was demonstrated using the new Ru metallorganic precursor and O2 as the Ru source and reactant, respectively, at the deposition temperatures of $300-350^{\circ}C$. Self-limited reaction behavior was observed as increasing Ru precursor and O2 pulse time, suggesting that newly developed Ru precursor is applicable for ALD process. Detailed discussions on the chemical and structural properties of Ru thin films as well as its growth behavior using new Ru precursor will be also presented.