• Title/Summary/Keyword: Surface coverage

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Determination of Adsorption Isotherms of Hydrogen at an Ir Electrode Interface Using the Phase-Shift Method and Correlation Constants (Ir 전극 계면에서 위상이동 방법 및 상관계수를 이용한 수소의 흡착동온식 결정)

  • Jeon, Sang-K.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.132-140
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    • 2007
  • The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

A bilayer diffusion barrier of atomic layer deposited (ALD)-Ru/ALD-TaCN for direct plating of Cu

  • Kim, Soo-Hyun;Yim, Sung-Soo;Lee, Do-Joong;Kim, Ki-Su;Kim, Hyun-Mi;Kim, Ki-Bum;Sohn, Hyun-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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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.

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The Ecological Characteristics and Conservation Counterplan of Menyanthes trifoliata Habitat in Floating Mat in Korean East Coastal Lagoon, Sunyoodam (조름나물이 서식하는 동해안 석호 습지인 선유담의 생태적 특성 및 보전방안)

  • Kim, Heung-Tae;Lee, Gwang-Moon;Kim, Jae Geun
    • Journal of Wetlands Research
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    • v.15 no.1
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    • pp.25-34
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    • 2013
  • The purpose of this study is to investigate the properties of Menyanthes trifoliata habitat in coastal lagoons. To characterize plant composition in the habitats in the lagoon, the plot sampling method was applied. The depths of water and floating mat were measured. Surface water quality factors including pH, electrical conductivity (EC), dissolved oxygen (DO), and total dissolved solids (TDS) were measured in the sites. Phosphate, nitrate, ammonium, and major cations were measured in laboratory. The wetland has 78 taxa of wetland plants. The average coverage and density of M. trifoliata was 62.6% and $71.2/m^2$, respectively and Phragmites australis is important associate in Sunyoodam lagoon. The average depths of floating mats were 26.5cm in M. trifoliata and 68.9cm in the P. australis-M. trifoliata communities, and the water depth below the mat was 106.5cm and 17.7cm, respectively. The values of pH, DO, EC and TDS in the water were 5.06, 46.1%, 59.4 ${\mu}s/cm$, and 29.3 mg/L, respectively. The concentrations of phosphate, nitrate, and ammonium showed 47.2, 9321, and 15.9 ${\mu}g/L$, respectively. The concentrations of Ca, K, Na, and Mg had 11.1, 1.5, 15.1, and 11.3 mg/L, respectively. The habitats of M. trifoliata in the lagoon corresponds to a kind of lowland communities in Hewett's classification. To conserve the habitats of M. trifoliata in Sunyoodam lagoon, the supply of open water area, the construction of observation deck, and the block of inflow from the surrounding paddy fields are needed in the future.

Changes in Distribution of Debris Slopes and Vegetation Characteristics in Mudeungsan National Park (무등산국립공원의 암설사면 분포변화 및 식생 특성)

  • Seok-Gon Park;Dong-Hyo Kim
    • Korean Journal of Environment and Ecology
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    • v.37 no.1
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    • pp.1-12
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    • 2023
  • We analyzed the distribution area of debris slopes in Mudeungsan (Mt. Mudeung) National Park by comparing aerial photos of the past (1966) and the present (2017) and identified the vegetation characteristics that affect the change in the area of the debris slopes by investigating the vegetation status of the debris slopes and the surrounding areas. The area of debris slopes in Mt. Mudeung appears to have been reduced to a quarter of what it used to be. Debris slopes here have decreased at an average rate of 2.3 ha/yr over 51 years by vegetation covers. Notably, most of the small-area debris slopes in the low-inclination slopes disappeared due to active vegetation coverage. However, there are still west-facing, south-west-facing, south-facing, and large-area debris slopes remaining because the sun's radiant heat rapidly raises the surface temperature of rock blocks and dries moisture, making tree growth unfavorable. Because of these locational characteristics, the small-scale vegetation in the middle of Deoksan Stony Slope, which is the broadest area, showed distinct characteristics from the adjacent forest areas. Sunny places and tree species with excellent drying resistance were observed frequently in Deoksan Stony Slope. However, tree species with high hygropreference that grow well in valleys with good soil conditions also prevailed. In some of these places, the soil layer has been well developed due to the accumulation of fine materials and organic matter between the crevices of the rock blocks, which is likely to have provided favorable conditions for such tree species to settle and grow. At the top of Mt. Mudeung, on the other hand, the forest covered the debris slopes, where Mongolian oaks (Quercus mongolica) and royal azaleas (Rhododendron schlippenbachii), which typically grow in the highlands, prevailed. This area was considered favorable for the development of vegetation for the highlands because the density of rock blocks was lower than in Deoksan Stony Slope, and the soil was exposed. Moreover, ash trees (Fraxinus rhynchophylla) and Korean maple trees (Acer pseudosieboldianum) that commonly appear in the valley areas were dominant here. It is probably due to the increased moisture content in the soil, which resulted from creating a depressive landform with a concave shape that is easy to collect rainwater as rock blocks in some areas fell and piled up in the lower region. In conclusion, the area, density of the rock blocks, and distribution pattern of rock block slopes would have affected the vegetation development and species composition in the debris slope landform.