• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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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.

• Korean Journal of Materials Research
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• v.20 no.12
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• pp.676-680
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• 2010

Most TCOs such as ITO, AZO(Al-doped ZnO), FTO(F-doped $SnO_2$) etc., which have been widely used in LCD, touch panel, solar cell, and organic LEDs etc. as transparent electrode material reveal n-type conductivity. But in order to realize transparent circuit, transparent p-n junction, and introduction of transparent p-type materials are prerequisite. Additional prerequisite condition is optical transparency in visible spectral region. Oxide based materials usually have a wide optical bandgap more than ~3.0 eV. In this study, single-phase transparent semiconductor of $SrCu_2O_2$, which shows p-type conductivity, have been synthesized by 2-step solid state reaction at $950^{\circ}C$ under $N_2$ atmosphere, and single-phase $SrCu_2O_2$ thin films of p-type TCOs have been deposited by RF magnetron sputtering on alkali-free glass substrate from single-phase target at $500^{\circ}C$, 1% $H_2$/(Ar + $H_2$) atmosphere. 3% $H_2$/(Ar + $H_2$) resulted in formation of second phases. Hall measurements confirmed the p-type nature of the fabricated $SrCu_2O_2$ thin films. The electrical conductivity, mobility of carrier and carrier density $5.27{\times}10^{-2}S/cm$, $2.2cm^2$/Vs, $1.53{\times}10^{17}/cm^3$ a room temperature, respectively. Transmittance and optical band-gap of the $SrCu_2O_2$ thin films revealed 62% at 550 nm and 3.28 eV. The electrical and optical properties of the obtained $SrCu_2O_2$ thin films deposited by RF magnetron sputtering were compared with those deposited by PLD and e-beam.

• 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.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.12
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• pp.647-655
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• 2016

Lead dioxide ($PbO_2$) is an electrode material that is effective for organic pollutant degradation based on hydroxyl radical ($^{\bullet}OH$) attack. Representative parameters for $PbO_2$ electrodeposition are summarized to current, temperature, reaction time, concentration of Pb(II) and electrolyte agent. In this study, $Ti/PbO_2$ electrodes were fabricated by electrodeposition method under controlled reaction time, current density, temperature, concentration of $HNO_3$ electrolyte. Effects of deposition parameters on $^{\bullet}OH$ evolution were investigated in terms of electrochemical bleaching of p-Nitrosodimethylaniline (RNO). As major results, the $^{\bullet}OH$ evolution was promoted at the $PbO_2$ that was deposited in longer reaction time (1-90 min), lower current density ($0.5-50mA/cm^2$), higher temperature ($5-65^{\circ}C$) and lower $HNO_3$ concentration (0.01-1.0 M). Especially, the $PbO_2$ which was deposited in 0.01 M of lowest $HNO_3$ concentration by applying $20mA/cm^2$ for above 10 min was most effective on $^{\bullet}OH$ evolution. The performance gap between $PbO_2$s that was best and worst in $^{\bullet}OH$ evolution was about 41%. Among the properties of $PbO_2$ related on $^{\bullet}OH$ evolution performance, conductivity of $Ti/PbO_2$ significantly influenced on $^{\bullet}OH$ evolution. The increase in conductivity promoted $^{\bullet}OH$ evolution. In addition, the increase in crystal size of $PbO_2$ interfered $^{\bullet}OH$ evolution at surface of some $PbO_2$ deposits.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.131-137
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• 2012

Polyaniline (PANI) and polypyrrole (Ppy) hollow sphere structures with controlled shell thicknesses can be easily synthesized than those of using a layer-by-layer method for cathode active material of lithium-ion batteries. Polystyrene (PS) core was synthesized by emulsion polymerization using an anion surfactant. The shell thicknesses of PANI and Ppy were controlled by amounts of aniline and pyrrole monomers. PS was removed by an organic solution. This structure increased in contact with an electrolyte and a specific capacity in lithium-ion batteries. But polymers have disadvantages such as the difficult control of molecular weights and low densities. These disadvantages were completed by controlled shell thicknesses. The amount of aniline monomer increased from 1.2, 2.4, 3.6, 4.8 to 6.0 mL, and the shell thicknesses were 30.2, 38.0, 42.2, 48.2, and 52.4 nm, respectively. And the amount of pyrrole monomer was 0.6, 1.2, 2.4 and 3.6 mL, the shell thicknesses were 16.0, 22.0, 27.0 and 34.0 nm, respectively. In the cathode materials with controlled shell thicknesses, shell thicknesses of the PANI hollow spheres were 30.2, 42.2, and 52.4 nm, and discharge specific capacities of after 10 cycle were ~18, ~29, and ~62 mAh/g, respectively. The shell thicknesses of the Ppy hollow spheres were 16.0, 22.0, 27.0 and 34.0 nm, and discharge specific capacities of after 15 cycle were ~15, ~36, ~56, and ~77 mAh/g, respectively. Thus, shell thicknesses of PANI and Ppy increased, the specific capacities increased.