• Proceedings of the Materials Research Society of Korea Conference
• /
• 2001.11a
• /
• pp.161-161
• /
• 2001

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2002.11a
• /
• pp.91-91
• /
• 2002

• Proceedings of the Korean Vacuum Society Conference
• /
• 2014.02a
• /
• pp.363-363
• /
• 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.

• Applied Chemistry for Engineering
• /
• v.10 no.3
• /
• pp.331-335
• /
• 1999

The transition metal oxides have been of interest as bifunctional electrocatalysts for bifunctional air electrodes. The amorphous citrate precursor (ACP) process has been optimized to prepare perovskite (La0.6Ca0.4CoO3) and pyrochlore (Pb2Ru2O6) powders with high surface area, and consequent improvement of The electrocatalytic performance in an air electrode with thermal treatment. PTFE -bonded gas diffusion electrodes loaded with perovskitc and pyrochlore catalysts showed good bifunctional performances. The electrodes were fairly stable up to 100 hour in the galvanostatic mode at ${\pm}25mA/cm^2$, from which these electrodes offer promise as practical bifunctional air electrodes.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.10
• /
• pp.3331-3337
• /
• 2012

Ru-modified Pt nanoparticles of various sizes on platelet carbon nanofiber toward methanol oxidation were investigated in terms of particle size effect. The sizes of Pt nanoparticles, prepared by polyol method, were in the range of 1.5-7.5 nm and Ru was spontaneously deposited by contacting Pt nanoparticles with the Ru precursor solutions of 2 and 5 mM. The Ru-modified Pt nanoparticles were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The methanol oxidation activities of Ru-modified Pt nanoparticles, measured using cyclic voltammetry and chronoamperometry, revealed that when the Pt particle size was less than 4.3 nm, the mass specific activity was fairly constant with an enhancement factor of more than 2 at 0.4 V. However, the surface area specific activity was maximized on Pt nanoparticles of 4.3 nm modified with 5 mM Ru precursor solution. The observations were discussed in terms of the enhancement of poison oxidation by Ru and the population variation of Pt atoms at vertices and edges of Pt nanoparticles due to selective deposition of Ru on the facets of (111) and (100).

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.08a
• /
• pp.78-78
• /
• 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.

• Journal of the Korean Electrochemical Society
• /
• v.7 no.4
• /
• pp.201-205
• /
• 2004

The Pt-Ru electrocatalyst was Prepared on Nafion membrane modified with Polypyrrole by chemical reduction of $H_2PtCI_6\;and\;RuCl_3$ solution ai precursor. From the electron dispersive microanalysis spectroscope(EDS), the Pt-Ru catalyst was located on the surface of Ppy/Nafion composite. The electrochemical oxidation of methanol on Pt-Ru catalyst deposited in Polypyrrole-impregnated Nafion was investigated by cyclic voltammetry (CV) and chronoamperometry. The onset potential of methanol oxidation was shifted to negative potential as the $RuCI_3$ concentration in deposition solution. Also, it was known that the Pt-Ru binary catalyst on Nafion could be directly deposited by using Polypyrrole and resulting Pt-Ru/PPy/Nafion was available for methanol oxidation.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2008.11a
• /
• pp.149-149
• /
• 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 $200\sim350^{\circ}C$.

• Korean Journal of Materials Research
• /
• v.22 no.4
• /
• pp.202-206
• /
• 2012

$CoSi_2$ was formed through annealing of atomic layer deposition Co thin films. Co ALD was carried out using bis(N,N'-diisopropylacetamidinato) cobalt ($Co(iPr-AMD)_2$) as a precursor and $NH_3$ as a reactant; this reaction produced a highly conformal Co film with low resistivity ($50\;{\mu}{\Omega}cm$). To prevent oxygen contamination, $ex-situ$ sputtered Ti and $in-situ$ ALD Ru were used as capping layers, and the silicide formation prepared by rapid thermal annealing (RTA) was used for comparison. Ru ALD was carried out with (Dimethylcyclopendienyl)(Ethylcyclopentadienyl) Ruthenium ((DMPD)(EtCp)Ru) and $O_2$ as a precursor and reactant, respectively; the resulting material has good conformality of as much as 90% in structure of high aspect ratio. X-ray diffraction showed that $CoSi_2$ was in a poly-crystalline state and formed at over $800^{\circ}C$ of annealing temperature for both cases. To investigate the as-deposited and annealed sample with each capping layer, high resolution scanning transmission electron microscopy (STEM) was employed with electron energy loss spectroscopy (EELS). After annealing, in the case of the Ti capping layer, $CoSi_2$ about 40 nm thick was formed while the $SiO_x$ interlayer, which is the native oxide, became thinner due to oxygen scavenging property of Ti. Although Si diffusion toward the outside occurred in the Ru capping layer case, and the Ru layer was not as good as the sputtered Ti layer, in terms of the lack of scavenging oxygen, the Ru layer prepared by the ALD process, with high conformality, acted as a capping layer, resulting in the prevention of oxidation and the formation of $CoSi_2$.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2014.02a
• /
• pp.357.2-357.2
• /
• 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.