• Journal of Powder Materials
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• v.20 no.1
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• pp.19-23
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• 2013

Ru films were successfully prepared by plasma-enhanced atomic layer deposition (PEALD) using $Ru(EtCp)_2$ and $NH_3$ plasma. To optimize Ru PEALD process, the effect of growth temperature, $NH_3$ plasma power and $NH_3$ plasma time on the growth rate and preferred orientation of the deposited film was systemically investigated. At a growth temperature of $270^{\circ}C$ and $NH_3$ plasma power of 100W, the saturated growth rate of 0.038 nm/cycle was obtained on the flat $SiO_2$/Si substrate when the $Ru(EtCp)_2$ and $NH_3$ plasma time was 7 and 10 sec, respectively. When the growth temperature was decreased, however, an increased $NH_3$ plasma time was required to obtain a saturated growth rate of 0.038 nm/cycle. Also, $NH_3$ plasma power higher than 40 W was required to obtain a saturated growth rate of 0.038 nm/cycle even at a growth temperature of $270^{\circ}C$. However, (002) preferred orientation of Ru film was only observed at higher plasma power than 100W. Moreover, the saturation condition obtained on the flat $SiO_2$/Si substrate resulted in poor step coverage of Ru on the trench pattern with an aspect ratio of 8:1, and longer $NH_3$ plasma time improved the step coverage.

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.99-105
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• 2006

Polyamine dendrimers functionalized with electrochemiluminescent (ECL) polypyridyl Ru(II) complexes, dend-$[CO-(CH_2)_3-mbpy{\cdot}Ru(L)_2]_3(PF_6)_6$ (dend: N$(CH_2CH_2NH)_3$-, L: bpy, o-phen, phen-Cl, DTDP), were synthesized through the complexation of dendritic polypyridyl ligands to Ru(II) complexes. Their electrochemical redox potentials, photoluminescence (PL), and relative ECL intensities were studied. The ECL emissions produced by the reaction between the electro-oxidized $Ru^{3+}$ species of polyamine dendrimers and tripropylamine as a coreactant were measured in a static system with potential cycles between 0.8 and 1.3 V or through flow injection analysis with a potential of +1.3 V, and were compared to that of $[Ru(o-phen)_3](PF_6)_2{\cdot}Dend-[CO-(CH_2)_3-mbpy{\cdot}Ru(bpy)_2]_3(PF_6)_6$ showed an ECL intensity that was two-fold greater than that of the reference complex $[Ru(o-phen)_3](PF_6)_2$.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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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.

• Applied Chemistry for Engineering
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• v.17 no.1
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• pp.87-92
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• 2006

The steam reforming of methane over Ru-promoted $Ni/Al_2O_3$ was carried out. Compared with $Ni/Al_2O_3$, which needs pre-reduction by $H_2$, $Ru/Ni/Al_2O_3$ catalysts exhibited relatively higher activity than conventional $Ni/Al_2O_3$. According to $H_2-TPR$ of reduced or used catalysts and $CH_4-TPR$, it was revealed that the reduction of $RuO_x$ by $CH_4$ decomposition begins at a lower temperature ($220^{\circ}C$) and the reduced Ru facilitates the reduction of NiO, and leads to self-activation. To improve metal dispersion, the catalyst was soaked in 7 M aqueous $NH_4OH$ for 2 h at $45^{\circ}C$ while stirring. As a result, $Ru/Ni/Al_2O_3$ catalysts with aqueous $NH_4OH$ treatment have higher activity, larger metal surface area (by $H_2$-chemisorption), and small particle size (by XRD and XPS). It is noted that the amount of noble metal could be reduced by aqueous $NH_4OH$ treatment.

• Journal of the Korean Vacuum Society
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• v.11 no.1
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• pp.35-42
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• 2002

We fabricate thermally stable and low resistance Ru ohmic contacts to $n-ZnO:Al(3\times10^{18}\textrm{cm}^{-3})$, grown by specially designed dual target sputtering system. It is shown that the as-deposited Ru contact produces a specific contact resistance of $2.1{\times}10^{-3}{\Omega}\textrm{cm}^2$. Annealing of the Ru contacts leads to the improvement of current-voltage characteristics. For example, annealing of the contact at $700^{\circ}C$ for 1 min produces a contact resistance of $3.2{\times}10^{-5}}{\Omega}\textrm{cm}^2$. furthermore, the metallisation scheme is found to be thermally stable: the surface of the contact is fairly smooth with a rms roughness of 1.4 nm upon annealing at $700^{\circ}C$. These results strongly indicate that the Ru contact represents a suitable metallisation scheme for fabrication of high-performance ZnO-based optical devices and high-temperature devices. In addition, possible mechanisms are suggested to describe the annealing temperature dependence of the specific contact resistance.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1615-1620
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• 2010

Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.228.1-228.1
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• 2010

선택적 CO 산화반응(PrOx)을 위한 Ru이 고분산 담지된 $Ru/{\alpha}-Al_2O_3$ 촉매를 증착-침전법(deposition-precipitation)으로 제조하였다. 용액의 pH와 aging 시간에 따른 Ru 입자의 크기 변화와 분산도의 영향을 살펴보았으며 함침법(impregnation)으로 비교 촉매를 제조하였다. 촉매의 특성분석은 BET, TPR, CO-Chemisorption분석을 수행하여 촉매의 비표면적, 환원특성, 분산도를 알 수 있었다. 특성분석결과, 증착-침전법으로 제조한 $Ru/{\alpha}-Al_2O_3$ 촉매가 함침법으로 제조한 촉매에 비해 분산도가 높았으며, pH별 촉매 제조에서는 pH6.5로 제조한 촉매가 22.06%로 가장 높은 분산도를 보였다. 또한, 담체의 비표면적 영향에 따른 Ru 입자의 분산도를 살펴보기 위해 ${\gamma}-Al_2O_3$와 ${\alpha}-Al_2O_3$ 담체를 적용한 결과, 비표면적이 작은 ${\alpha}-Al_2O_3$ 담체 표면에서 Ru 분산도가 ${\gamma}-Al_2O_3$ 담체에 비해 높았다. 이는 기공이 발달하여 비표면적이 넓은 ${\gamma}-Al_2O_3$ 담체는 소량의 Ru을 고분산 담지 시 담체 표면보다는 기공 내에 담지 되는 양이 많아 실제 반응 시 반응에 참여하는 표면 활성 금속양이 적음을 알 수 있다. 특히, 선택적 산화반응과 같이 표면에서 빠른 반응이 일어나는 경우, 기공 내부의 활성금속이 반응에 참여하기 어려워 반응 활성이 낮음을 PrOx 반응실험을 통해 확인할 수 있었다. PrOx test 조건은 GHSV 250000~60000, 온도는 80~200도, 람다값은 2~4로 성능 비교하여 실험 하였다. PrOx의 성능평가 결과 담체를 ${\alpha}-Al_2O_3$를 사용하여 deposition-precipitation방법으로 제조한 pH6.5 촉매에서 $100{\sim}160^{\circ}C$에서 90%의 가장 높은 CO conversion을 가지고 18%의 선택도를 가졌다.

• Korean Journal of Metals and Materials
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• v.47 no.6
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• pp.349-355
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• 2009

In the solvent extraction of Ru(IV) with Alamine336, it was found that Ru took part in the reaction as $RuCl_{6}_^{2-}$ in the HCl concentration range of 1 to 5 M. Interaction parameter between hydrogen ion and $RuCl_{6}_^{2-}$ was estimated by applying Bromley equation to the extraction data. From the mixed solutions of Pd(II) and Ru(IV), the distribution coefficients of Pd were found to be higher than those of Ru in the experimental ranges. Separation factor between Pd and Ru rapidly increased with the decrease of Alamine336 concentration. About 60% of the Ru from the mixed solutions was extracted by TBP at 8.3 M HCl, while Pd was not extracted in the HCl concentration range of 1.6 to 8.3 M.

• Transactions of the Korean hydrogen and new energy society
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• v.30 no.3
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• pp.193-200
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• 2019

$RuO_2$, $PtO_2$, and various $(Ru,Pt)O_2$ colloidal solution were prepared using modified Watanabe method. Electrodes were manufactured by dipping of Ni mesh into the colloidal solution. Manufactured electrodes were characterized by XRD, SEM, and EDS. $(Ru,Pt)O_2$ electrodes showed $RuO_2$ crystal structure and high roughness. The hydrogen evolution reaction (HER) activities were evaluated by Linear Sweep Voltammetry. 1Ru2Pt electrode showed similar activity with commercial electrode, HER potentials are -0.9 V for both.

• Clean Technology
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• v.19 no.3
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• pp.320-326
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• 2013

Nano-sized PtRu-Ni/VC and PtRu-Sn/VC electrocatalysts were synthesized by a one-step radiation-induced reduction (RIR) (30 kGy) process using distilled water as the solvent and Vulcan XC-72 as the supporting material. The obtained electrocatalysts were characterized by transmission electron microscopy (TEM), scanning electron microscope energy dispersive spectroscopic (SEM-EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The catalytic efficiency of electrocatalysts was examined for oxygen reduction, MeOH oxidation and CO stripping decreased in the following order, Hydrogen stripping : PtRu-Sn/VC > PtRu-Ni/VC > PtRu/VC$^{(R)}$ (E-TEK). MeOH oxidation : PtRu-Sn/VC > PtRu-Ni/VC > PtRu/ VC$^{(R)}$ (E-TEK). Unit cell performance : PtRu-Sn/VC > PtRu-Ni/VC > PtRu/VC$^{(R)}$ (E-TEK) catalysts.