Proceedings of the Korean Vacuum Society Conference
/
2011.02a
/
pp.17-18
/
2011
Plasma in liquid phase has attracted great attention in the last few years by the wide domain of applications in material processing, decomposition of organic and inorganic chemical compounds and sterilization of water. The plasma in liquid is characterized by three main regions which interact each - other during the plasma operation: the liquid phase, which supply the plasma gas phase with various chemical compounds and ions, the plasma in the gas phase at atmospheric pressure and the interface between these two regions. The most complex region, but extremely interesting from the fundamental, chemical and physical processes which occur here, is the boundary between the liquid phase and the plasma gas phase. In our laboratory, plasma in liquid which behaves as a glow discharge type, is generated by using a bipolar pulsed power supply, with variable pulse width, in the range of 0.5~10 ${\mu}s$ and 10 to 30 kHz repetition rate. Plasma in water and other different solutions was characterized by electrical and optical measurements. Strong emissions of OH and H radicals dominate the optical spectra. Generally water with 500 ${\mu}S/cm$ conductivity has a breakdown voltage around 2 kV, depending on the pulse width and the repetition rate of the power supply. The characteristics of the plasma initiated in ultrapure water between pairs of different materials used for electrodes (W and Ta) were investigated by the time-resolved optical emission and the broad-band absorption spectroscopy. The deexcitation processes of the reactive species formed in the water plasma depend on the electrode material, but have been independent on the polarity of the applied voltage pulses. Recently, Coherent anti-Stokes Raman Spectroscopy method was employed to investigate the chemistry in the liquid phase and at the interface between the gas and the liquid phases of the solution plasma system. The use of the solution plasma allows rapid fabrication of the metal nanoparticles without being necessary the addition of different reducing agents, because plasma in the liquid phase provides a reaction field with a highly excited energy radicals. We successfully synthesized gold nanoparticles using a glow discharge in aqueous solution. Nanoparticles with an average size of less than 10 nm were obtained using chlorauric acid solutions as the metal source. Carbon/Pt hybrid nanostructures have been obtained by treating carbon balls, synthesized in a CVD chamber, with hexachloro- platinum acid in a solution plasma system. The solution plasma was successfully used to remove the template remained after the mesoporous silica synthesis. Surface functionalization of the carbon structures and the silica surface with different chemical groups and nanoparticles, was also performed by processing these materials in the liquid plasma.
$(Pb_{0.98}La_{0.08})(Zr_{0.65}Ti_{0.35})O_3$ (PLZT) thin films with $TiO_2$ buffer layers were deposited on Pt/Ti/$SiO_2$/Si substrates by an R.F. magnetron sputtering method in order to improve the ferroelectric characteristics of the films. And the ferroelectric properties and crystallinities of the PLZT thin films were investigated in terms of the effects of the post annealing temperatures of $TiO_2$ buffer layers between a platinum bottom electrode and PLZT thin film. The ferroelectric properties of the PLZT thin films improved as increasing of the post annealing temperatures of $TiO_2$ layers, thereby reaching their maximum at $600^{\circ}C$.
Park, Jingyu;Jeon, Heeyoung;Kim, Hyunjung;Kim, Jinho;Jeon, Hyeongtag
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.
A gold amalgam voltammetric microelectrode (GAVM) system was developed for the quantification of dissolved biogeochemical species, such as O2, Fe2+, Mn2+, and HS- in sediment porewater. Commercially available Ag/AgCl and platinum electrodes were used as the reference and counter electrode, respectively, and a gold amalgam microelectrode was fabricated in the laboratory using 150-um diameter gold wire and a borosilicate capillary tube with a 1.6-mm diameter. A portable potentiostat (Metrohm, DropSens) was used for the application of voltage sweeping and to acquire the electric current. For sediment profiling, a commercially available actuator was customized and modified. The analysis method used in the system used the most widely used analysis method among the electrochemical analysis currently used The GAVM system was successively calibrated with the species and applied to estuarine sediments. The porewater analysis showed that the oxygen concentration was decreased to zero at a depth of 0.6 mm, and maximum Mn2+ and Fe2+ concentrations of 50 uM and 20 uM were detected at 2 and 3-cm depths, respectively. Maximum HS- concentrations of 10 uM were detected at 4 cm in the deeper sediments. The GAVM system was successfully developed and applied to the sediment and can be used to better understand biogeochemical reactions.
A study on the application of impedance phase angle for redox titration, acid-base titration, chelate titration and precipitation titration has been carried out. A constant alternating current was passed between two platinum electrodes. One of them was a polarizable micro-electrode of $0.1cm^2$ or $0.026cm^2$ surface area and the other a non-polarizable large electrode of $1cm^2$ surface area dipped in the solution to be titrated. The impedance and the phase angle of the titration cell were measured with lock-in amplifier to obtain well behaved titration curve respectively. In titration of oxalic acid vs. potassium permanganate, the end-point was obtained successfully from the phase angle titration curve. In this experiment, the concentration of 0.0005 M to 0.05 M, the current of $50{\mu}A$ and the frequency of near 50 Hz were used. In titration of phosphoric acid vs. sodium hydroxide, the first end-point was obtained successfully on the optimum experimental condition of 0.001 M concentration, $50{\mu}A$ current and 25~97 Hz frequency. However, the end-point in titration of cupric sulfate vs. disodium-EDTA couldn't be obtained clearly. The end-point was obtained with the out-of-phase impedance curve on the experimental condition of 0.01 M concentration, $100{\mu}A$ current, 5~35 Hz frequency range. In titration of sodium chloride vs. silver nitrate, the end-point was obtained successfully on the experimental condition of 0.1 M concentration, $100{\mu}A$ current and 5~47 Hz frequency range. This study showed that the impedance phase angle was applicable for the detection of the end-points in redox titration curve, acid-base titration curve, chelate titration curve and precipitation titration curve.
Background: During movement the major inputs to nervous system come from firstly the muscle and joint to maintain posture and motion and secondly the chemoreceptors and baroreceptors to adjust the cardiovascular and respiratory function. Their complex relationships are generally studied for many years but the direct relation between the joint and respiratory system is not studied thoroughly until now. So this experiment was performed to determine whether the natural movement of knee joint can cause the enhancement of respiratory function by observation of the changes of respiratory rate, phrenic nerve activity and inspiratory neuron activity during the stimulation of knee joint in cat anesthetized with $\alpha$-chloralose. Method: Twenty six male adult cats were used and the extracelluar recording using bipolar platinum electrode and carbon filament electrode was done to record the changes in the activities of phrenic nerve and inspiratory neuron movement of knee joint, injection of chemicals into the joint cavity and electrical stimulation of articular nerve were done. Results: The 60 Hz. could not but 120 Hz. flexion-extension movement of knee joint increased respiratory rate(R.R.), tidal neural activity(TNA) and minute neural activity(MNA). Intra-articular injection of lactate could not increase R.R. but significantly increase TNA and MNA which represented the enhanced respiratory function. Injection of potassium chloride showed similar effects with the case of lactate but the duration of effect was shorter. The electrical stimulation of medial articular nerve with IV strength which could activate only group I and II afferents showed increased TNA and MNA during stimulation but 20 V stimulation which could activate all the afferents increased all the respiratory parameters. The changes of inspiratory neuron activity by knee joint stimulation was similar to that of phrenic nerve. Conclusion: The respiratory center could be directly stimulated by the activation of group I and II articular afferents and it seemed that the magnitude of the respiratory center enhancement is proportional to the amount of sensory information from the knee joint. These facts might suggest that the respiratory function could be enhanced even by the normal movement of knee joint.
The effects of ouabain on the contractile and electrical activities were investigated in the isolated preparations of guinea-pig taenia coli, and compared with those of vanadate. Spontaneous contractions were recorded with force transducer, and electrical activites were measured by use of suction electrode, or single sucrose-gap technique. The contractions were induced by the electrical stimulation for 5 seconds every 1 minute with alternating current (60 Hz, 3.0 V/cm) through the platinum electrodes located in parallel with the long axis of the preparation. All experiments were performed in tris-buffered Tyrode solution which was aerated with $100%{\;}O_2$ and kept at $35^{\circ}C$. The results obtained were as follows: 1) Responses of spontaneous contractions to ouabain were concentration-dependent; $10^{-7}M$ ouabain caused a rise of basal tone. Above the concentration of $10^{-6}M$ ouabain, an initial increase followed by a decrease in tension was observed. 2) A continuous spike discharge was induced by the administration of $10^{-7}M$ ouabain. Above $10^{-6}M$ ouabain, a transient initial increase followed by a decrease in spike frequency and amplitude was produced, and finally membrane potential was sustained at a certain level without a spike discharge. 3) The characteristic response to $10^{-7}M$ ouabain was not blocked by the pretreatment with $10^{-7}M$ atropine. 4) The electrically induced contractions were completely suppressed at the concentration of $2{\times}10^{-7}M$ ouabain. These contractions were blocked more rapidly in paralled with the increase in ouabain concentration. 5) Effects of vanadate on the spontaneous activities were quite different from those of ouabain; $10^{-6}M$ vanadate increased the amplitude of contractions and $10^{-5}M$ vanadate increased slightly both amplitude and frequency of spontaneous contractions. $10^{-4}M$ vanadate showed irregular phasic contractions superimposed on the increased basal tone. 6) $10^{-5}M$ vanadate depolarized the membrane potential and shortened the interval between the bursts of spike discharge, whereas $10^{-4}M$ vanadate induced continuous spike discharge with membrane depolarization. 7) Vanadate caused a characteristic inhibitory response to the contractions induced by electrical stimulation; An initial rapid inhibition of tension development and then gradual recovery to a certain level. From the above results, the following conclusions could be made: 1) The rise of basal tone at $10^{-7}M$ ouabain is due to continuous spike discharge without a silent period. The continuous spike discharge is likely to be associated with a slight membrane depolarization caused by the blockage of Na pump. 2) The biphasic response induced by above $10^{-6}M$ ouabain seems to occur by the different mechanisms. The initial increase in tension is associated with depolarization along with an increase in spike frquency, whereas the subsequent relaxation occurs through a non-electrical mechanism. 3) The characteristic response to $10^{-7}M$ ouabain is resulted not from the action on intrinsic nerve terminal, but from its direct action on the membrane of smooth muscle cells. 4) The phasic contractions superimposed on the increased basal tone at the concentration of $10^{-4}M$ vanadate is resulted from the continuous spike discharge with membrane depolarization, of which mechanism remains unknown. 5) The inhibitory action of ouabain on the electrically induced contractions suggests that the increasein intracellular Na in some way inhibits the electrically induced $Ca^{2+}$ influx. The mechanism of vanadate action on the induced contractions remains unknown.
Even traces of CO in the hydrogen-rich feed gas to proton exchange membrane fuel cells (PEMFC) poison the platinum anode electrode and dramatically decrease the power output. In this work, a variety of catalytic materials consisting of $Cu/Ce_xZr_{1-x}O_2$, (x = 0.0-1.0) were synthesised, characterized and tested for CO oxidation and preferential oxidation of CO (PROX). These catalysts prepared by hydrothermal and deposition-precipitation methods. The catalysts were characterized by XRD, XRF, SEM, BET, $N_2O$ titration and oxygen storage capacity (OSC) measurement. The effects of composition of the support and degree of excess oxygen were investigated fur activity and $CO_2$ selectivity with different temperatures. The composition of the support markedly influenced the PROX activity. Among the various $Cu/Ce_xZr_{1-x}O_2$ catalysts having different composition, $Cu/Ce_{0.9}Zr_{0.1}O_2$ and $Cu/Ce_{0.7}Zr_{0.3}O_2$ showed the highest activities (>99%) and selectivities (ca.50%) in the temperature range of $150{\sim}160^{\circ}C$. It was found that by using of $Ce_xZr_{1-x}O_2$ mixed oxide support which possesses a high oxygen storage capacity, oxidation-reduction activity of Cu-based catalyst was improved, which resulted in the increase of catalytic activity and selectivity of CO oxidation in excess $H_2$ environments.
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