• Electrical & Electronic Materials
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• v.28 no.2
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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.

• Korean Journal of Materials Research
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• v.8 no.12
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• pp.1090-1098
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• 1998

$RuO_2$ thin films were deposited on Si and Ru/Si substrates by rf magnetron reactive sputtering and annealed in oxygen atmosphere(1atm) to investigate their thermal stability and diffusion barrier property. $RuO_2$ thin films were thermally stable up to 700\ulcorner for 10min. in oxygen atmosphere and showed excellent barrier property against the interdiffusion of silicon and oxygen. After annealing at $750^{\circ}C$ , however, volatilization to higher oxide occurred at the surface and inside of $RuO_2$ thin film and diffusion barrier property was also deteriorated. When annealed at $800^{\circ}C$, $RuO_2$thin film showed a different microstructure from that of $RuO_2$ thin film annealed at 75$0^{\circ}C$. It is likely that surface defect structure of $RuO_2$, $RuO_3$, and excess oxygen had an influence on the mode of volatilization with increasing annealing temperature.

• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.286-290
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• 2008

Small amounts of CO in reformate fuel gas effectively block platinum catalysts by strong adsorption on the platinum surface at the operation temperature of $60{\sim}80^{\circ}C$ in PEMFC. To oxidate CO, Ru/C layer (CO filter) was placed between Pt/C layer and GDL (gas diffusion layer) in this study. Ru/C filter provided good CO-tolerant PEMFC anode, but decreased the performance of unit cell about 10% at 0.6 V due to mass transfer resistance from Ru/C filter thickness and increase of charge transfer resistance. Membrane degradation is one of the most important factors limiting the life-time of PEMFCs. Membrane durability would be dependent on the electrode catalyst type. It seemed that Ru catalyst layer would shorten the life time of PEMFC as enhanced the fluoride emission rate of membrane in acceleration test.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.86.2-86.2
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• 2011

저온형 연료전지인 직접 메탄올 연료전지(Direct Methanol Fuel Cells, DMFC)는 친환경적인 발전 시스템, 높은 에너지 효율의 장점 때문에 주목을 받고 있으나 연료극의 촉매로 사용되는 금속은 고가의 귀금속인 Pt와 Ru가 요구되어 제조비용이 비싸기 때문에 촉매의 양을 줄이고, 반응 도중 생성되는 CO에 의한 촉매의 피독 문제 등 해결하여야 할 점이 산적해 있어 연료전지 중 촉매의 활성을 높이는 연구들이 활발히 이루어지고 있다. 종래의 MEA의 촉매층 제조공정은 우선 환원석출법에 의해 Pt-Ru/C를 합성하고 Nafion 용액에 혼합하여 Pt-Ru/C 슬러리를 제조한다. 이 방법에서는 carbon sheet에 spray 방법으로 Pt-Ru/C 촉매층이 만들어지기 때문에, Pt-Ru 촉매가 Nafion에 의해 부분적으로 매몰되어 촉매의 전기화학적 활성이 떨어지는 문제점이 있다. 이를 해결하는 방안으로 펄스전류를 이용하여 Pt-Ru 합금입자를 carbon sheet에 전기화학적으로 담지 시켜 Nafion에 매몰되는 것을 방지하는 펄스전해법 연구가 진행되고 있다. 그러나 촉매의 입자크기가 일반적으로 50~70 nm 이상으 크기 때문에 촉매의 낮은 활성이 문제점으로 야기되고 있다. 본 연구에서는 Pt-Ru/C 촉매층 제조 문제점을 해결하고, 촉매의 전기화학적 활성을 증가시키기 위해서 2~4 nm Pt-Ru 콜로이드를 전해액으로 사용하고, 전기영동법을 이용하여 Pt-Ru 나노 입자를 carbon sheet($1{\times}1cm^2$) 에 담지 시켰다. 전기영동법에서 균일한 Pt-Ru 촉매층의 제조를 위해 전류인가 방법으로는 펄스전류를 사용하였고, 실험변수로는 전해액 pH, duty cycle, 담지시간을 선정하였다. 합성된 Pt-Ru 콜로이드를 TEM분석으로 나노입자의 크기와 분산성 분석하였고, 콜로이드 나노입자의 표면전하 상태를 분석하기 위해 zeta-potential을 분석하였다. Pt-Ru/C의 촉매의 전기화학적 활성을 분석하기 위하여 0.5 M H_2SO_4$ 와 1 M $CH_3OH$ 혼합용액에 CV(Cyclic Voltammetry)실시하였고, carbon sheet 전극 상 Pt-Ru의 분산성 확인을 위하여 FE-SEM분석을 수행하였다.

• The Transactions of the Korean Institute of Electrical Engineers C
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• v.53 no.4
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• pp.208-212
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• 2004

In this paper, the characteristics of co-sputtered Ru-Zr metal alloy as gate electrode of MOS capacitors have been investigated. The atomic compositions of alloy were varied by using the combinations of relative sputtering power of Ru and .Zr. C-V and I-Vcharacteristics of MOS capacitors were measured to find the effective oxide thickness and work function. The alloy made of about 50% of Ru and 50% of Zr exhibited an adequate work function for nMOS. C-V and I-V measurements after 600 and $700^{\circ}C$ rapid thermal annealing were performed to prove the thermal and chemical stability of the Ru-Zr alloy film. Negligible changes in the accumulated capacitance and work function before and after annealing were observed. Sheet resistance of Ru-Zr alloy was lower than that of poly-silicon. It can be concluded that the Ru-Zr alloy can be a possible substitute for the poly-silicon used as a gate of nMOS.

• Corrosion Science and Technology
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• v.2 no.4
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• pp.189-193
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• 2003

The Ru etching using $O_2/C_{12}$ plasmas has been studied by employing the helicon etcher. The changes of Ru etch rate, Ru to $SiO_2$ etch selectivity and Ru electrode etching slope with varied process variables were investigated. The Ru etching slope at the optimized etching condition was measured to be $84^{\circ}$. We reveal that the Ru etching using $O_2/C_{12}$ plasma generates the $RuO_2$ thin film. Possible mechanism of Ru etching is discussed.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1200-1204
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• 1999

The reactions of Ru(tpy)Cl3 (tpy = 2,2';6',2"-terpyridine) with new N,N,C-terdentate ligands, 3,2'-annulated-6-(2"-pyridyl)-2-phenylpyridines (1, HL) and the properties of their Ru(II) complexes are described. The distribution ratio of the two possible Ru(II) complexes, a pentaaza-coordinated complex [Ru(tpy)(1-N,N')Cl]+ and a cycloruthenated complex [Ru(tpy)(La-N,N',C)]+ are highly dependent on the length of the polymethylene unit. The trimethylene bridge of the N,N,C-terdentate in pentaaza-coordinated complex is rigid enough to induce an asymmetry in the complex.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.152-152
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• 1999

1Gb급 이상 기억소자의 캐패시터 재료로 주목받고 있는 (Ba,Sr)TiO3 [BST] 박막의 전극재료로는 Pt, Ru, Ir과 같은 금속전극과 RuO2, IrO2와 산화물 전도체가 유망한 것으로 알려져 있다. 그런데, DRAM의 집적도가 증가하게 되면, BST같은 고유전율 박막을 유전재료로 사용한다 하더라도, 3차원적인 구조가 불가피하게 때문에 기존의 sputtering 방법으로는 우수한 단차피복성을 얻기 힘들므로, MOCVD법이 필수적이다. 본 연구에서는 기존에 연구되었던 Pt에 비해 식각특성이 우수하고, 비교적 낮은 비저항을 갖는 Ru 박막증착에 대한 연구를 행하였다. 본 연구에서는 수직형의 반응기와 저항 가열 방식의 susceptor로 구성된 저압 유기금속 화학증착기를 사용하여 최대 6inch 직경을 갖는 기판 위에 Ru박막을 증착하였다. Precursor로는 기존에 연구된 적이 없는 bis-(ethyo-$\pi$-cyclopentadienyl)Ru (Ru(C5H4C2H5)2, [Ru(EtCp)2])를 사용하였으며, bubbler의 온도는 85$^{\circ}C$로 하였다. Si, SiO2/Si를 사용하였으며, 증착온도 25$0^{\circ}C$~40$0^{\circ}C$, 증착압력 3Torr의 조건에서 Ru 박막을 증착하였다. Presursor를 운반하는 수송기체로는 Ar을 사용하였으며, carbon과 같은 불순물의 제거를 위해 O2를 첨가하였다. 증착된 박막은 XRD, SEM, 4-point probe등을 통해 구조적, 전기적 특성을 평가하였으며, 열역학 계산을 위해서는 SOLGASMIX-PV프로그램을 사용하였다. Ru 박막의 증착에 있어서 산소의 첨가는 필수적이었으며, Ru 박막의 증착속도는 30$0^{\circ}C$~40$0^{\circ}C$의 온도 영역에서 200$\AA$/min으로 일정하였으며, 첨가된 산소의 양이 적을수록 더 치밀하고 평탄한 표면형상을 보였으며, 또한 더 낮은 전기 전도도를 보였다. 그리고 증착된 박막은 12~15$\mu$$\Omega$cm 정도의 낮은 비저항 값을 나타냈으며 이것은 기존의 sputtering 법에 의해 증착된 Ru 박막의 비저항 값들과 비교될만하다. 한편, 높은 온도, 높은 산소분압 조건에서 RuO2의 형성을 관찰하였으며, 이것은 열역학적인 계산을 통해서 잘 설명할 수 있었다.

• Bulletin of the Korean Chemical Society
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• v.26 no.10
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• pp.1525-1528
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• 2005

The synthesis and characterization of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O\;(C_2O_4}^{2-}$ = oxalato anoin) complex are described, and its redox properties (in buffer solution of pH = 12) have been investigated. This complex is used for in situ generation of oxoruthenates complexes which have been characterized by electronic spectroscopy. Reaction of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${S_2O_8}^{2-}$ in molar KOH generates trans-${[RuO_3(OH)_2]^{2-}/S_2O_8}^{2-}$ reagent while with excess ${BrO_3}^-$ in molar $Na_2CO_3$ generates ${[RuO_4]^-/BrO_3}^-$ reagent. Avoiding the direct use of [$RuO_4$] the organic-soluble $(n-Pr_4N)^+[RuO_4]^-$, (TPAP) has been isolated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${BrO_3}^-$ in molar carbonate and n-$Pr_4$NOH. In a mixture of $H_2O/CCl_4$ ruthenium tetraoxide can be generated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${IO_4}^-$. The catalytic activities of oxoruthenates that have been made from $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ towards the oxidation of benzyl alcohol, piperonyl alcohol, benzaldehyde and benzyl amine at room temperature have been studied.

• Journal of the Korean Ceramic Society
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• v.34 no.3
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• pp.241-248
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• 1997

RuO2 thin films were deposited on SiO2(1000$\AA$)/Si and MgO(100) single crystal substrates at low tem-peratures by hot-wall metalorganic chemical vapor deposition(MOCVD), and effects of deposition paramet-ers on the properties of the thin films were investigated. RuO2 single phase was obtained at lower de-position temperature of 25$0^{\circ}C$. RuO2 thin films deposited onto SiO2(1000$\AA$)/Si substrates showed a random orientation, and RuO2 films onto MgO(100) single crystals showed the (hk0) orientation. The crystallinity and resistivity of RuO2 thin films increased and decreased with increasing deposition temperature, respec-tively. The resistivity of RuO2 thin films decreased with decreasing the flow rate. The resistivity of the 2600$\AA$-thick RuO2 thin films deposited with O2 flow rate of 50 sccm at 35$0^{\circ}C$ was 52.7$\mu$$\Omega$-cm, and they could be applicable to bottom electrodes of high dielectric materals.