On the Control of Plasma Chemistry and Silicon Etching Kinetics in Ternary HBr + Cl2 + O2 Gas System: Effects of HBr/O2 and Cl2/O2 Mixing Ratios

2020 ◽  
Vol 12 (5) ◽  
pp. 628-640
Author(s):  
Byung Jun Lee ◽  
Alexander Efremov ◽  
Yunho Nam ◽  
Kwang-Ho Kwon
Keyword(s):  
Etching Rate ◽  
Plasma Chemistry ◽  
Active Species ◽  
Reaction Products ◽  
Mixing Ratios ◽  
Adsorption Sites ◽  
Gas System ◽  
Molecular Reaction ◽  
Oh Reactions ◽  
Kinetics Of

The influences of both HBr/O2 (at constant Cl2 fraction) and Cl2/O2 (at constant HBr fraction) ratios in HBr + Cl 2 + O2 gas mixture on bulk plasma characteristics, active species densities and etching kinetics of silicon were studied. The results indicated that an increase in O2 content in a feed gas at constant Cl2 fraction in a processing gas (1) produces the stronger impact on plasma chemistry by the influence on the kinetics of electron-impact and atom-molecular reaction; and (2) provides the wider adjustments for both halogen atom flux and ion flux with the opposite tendencies with those for variable Cl2/O2 mixing ratio. The experiments demonstrated that the transition toward more oxygenated plasmas in both cases lowers the Si etching rate as well as result is decreasing effective reaction probability and etching yield. These effects may be associated with decreasing amount of adsorption sites for Cl/Br atoms as well as increasing sputtering (ion-stimulated desorption) threshold for reaction products due to the formation of the low-volatile silicon oxy-chlorides and-bromides in heterogeneous SiClx + O/OH and SiBrx + O/OH reactions.

scholarly journals ON MECHANISMS OF OXYGEN INFLUENCE ON GAS-PHASE PARAMETERS AND SILICON REACTIVE-ION ETCHING KINETICS IN HBr + Cl2 + O2 PLASMA

2019 ◽  
Vol 62 (10) ◽  
pp. 76-83
Author(s):  
Aleksandr M. Efremov ◽  
Vladimir V. Rybkin ◽  
Vladimir B. Betelin ◽  
Kwang-Ho Kwon
Keyword(s):  
Steady State ◽  
Halogen Atom ◽  
Etching Rate ◽  
Reactive Ion Etching ◽  
Oh Radicals ◽  
Plasma Parameters ◽  
Ion Etching ◽  
Bias Power ◽  
Mixing Ratios ◽  
Adsorption Sites

The effects of both HBr/O2 and Cl2/O2 mixing ratios in HBr+Cl2+O2 gas mixture on plasma parameters, steady-state densities of active species and Si etching kinetics were studied under the typical conditions of reactive ion etching process: total gas pressure (p = 10 mTorr), input power (W = 500 W), bias power (Wdc = 200 W). The data on internal plasma parameters and plasma chemistry were obtained using a combination of Langmuir probe diagnostics and 0-dimensional (global) plasma modeling. It was found that the variation in HBr/O2 mixing ratio at constant Cl2 fraction in a feed gas is characterized by the stronger impact on the steady-state plasma composition through both electron-impact and atom-molecular reaction kinetics as well as allows one to obtain the wider change in the total halogen atom density. It was shown that changes in both HBr/O2 and Cl2/O2 mixing ratios toward O2-rich plasmas lowers the Si etching rate that exhibits no evident correlations with total halogen atom flux and ion energy flux. The model-based analysis of Si etching kinetics allowed one to conclude that the effective reaction probability for Si + Cl/Br heterogeneous reaction depends on the flux of oxidative species – oxygen atoms and OH radicals. The reasons may be 1) the oxidation of silicon resulting in higher reaction threshold energy; and 2) the decreasing fraction of free adsorption sites for Cl/Br atoms due to the oxidation of reaction products into the lower volatile SiBrxOy and SiClxOy compounds.

The Kinetics of Inhibition of the Action of Thrombin by the Fibrinopeptides Formed during the Clotting of Fibrinogen

1966 ◽  
Vol 16 (01/02) ◽  
pp. 277-295 ◽  
Author(s):  
A Silver ◽  
M Murray
Keyword(s):  
Amino Acids ◽  
Competitive Inhibition ◽  
Amorphous Material ◽  
Peptide Bond ◽  
Initial Reaction ◽  
Reaction Products ◽  
Coagulation Mechanism ◽  
Kinetics Of ◽  
Kinetics Of Inhibition ◽  
Burk Plot

SummaryVarious investigators have separated the coagulation products formed when fibrinogen is clotted with thrombin and identified fibrinopeptides A and B. Two other peaks are observed in the chromatogram of the products of coagulation, but these have mostly been dismissed by other workers. They have been identified by us as amino acids, smaller peptides and amorphous material (37). We have re-chromatographed these peaks and identified several amino acids. In a closed system of fibrinogen and thrombin, the only reaction products should be fibrin and peptide A and peptide B. This reasoning has come about because thrombin has been reported to be specific for the glycyl-arginyl peptide bond. It is suggested that thrombin also breaks other peptide linkages and the Peptide A and Peptide B are attacked by thrombin to yield proteolytic products. Thrombin is therefore probably not specific for the glycyl-arginyl bond but will react on other linkages as well.If the aforementioned is correct then the fibrinopeptides A and B would cause an inhibition with the coagulation mechanism itself. We have shown that an inhibition does occur. We suggest that there is an autoinhibition to the clotting mechanism that might be a control mechanism in the human body.The experiment was designed for coagulation to occur under controlled conditions of temperature and time. Purified reactants were used. We assembled an apparatus to record visually the speed of the initial reaction, the rate of the reaction, and the density of the final clot formed after a specific time.The figures we derived made available to us data whereby we could calculate and plot the information to show the mechanism and suggest that such an inhibition does exist and also further suggest that it might be competitive.In order to prove true competitive inhibition it is necessary to fulfill the criteria of the Lineweaver-Burk plot. This has been done. We have also satisfied other criteria of Dixon (29) and Bergman (31) that suggest true competitive inhibition.

Kinetics of the catalytic hydrodesulphurization reaction system; hydrogenolysis of thiophene

1980 ◽  
Vol 45 (10) ◽  
pp. 2728-2741 ◽  
Author(s):  
Pavel Fott ◽  
Petr Schneider
Keyword(s):  
Atmospheric Pressure ◽  
Active Sites ◽  
Flow Reactor ◽  
Kinetic Equations ◽  
Reaction System ◽  
Reaction Products ◽  
Molybdenum Catalyst ◽  
Cobalt Molybdenum Catalyst ◽  
Kinetics Of ◽  
Reaction Schemes

Kinetics have been studied of the reaction system taking place during the reaction of thiophene on the cobalt-molybdenum catalyst in a gradientless circulation flow reactor at 360 °C and atmospheric pressure. Butane has been found present in a small amount in the reaction products even at very low conversion. In view of this, consecutive and parallel-consecutive (triangular) reaction schemes have been proposed. In the former scheme the appearance of butane is accounted for by rate of desorption of butene being comparable with the rate of its hydrogenation. According to the latter scheme part of the butane originates from thiophene via a different route than through hydrogenation of butene. Analysis of the kinetic data has revealed that the reaction of thiophene should be considered to take place on other active sites than that of butene. Kinetic equations derived on this assumption for the consecutive and the triangular reaction schemes correlate experimental data with acceptable accuracy.

Kinetics of carbon monoxide methanation on a Ni/SiO2 catalyst

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček
Keyword(s):  
Carbon Monoxide ◽  
Reaction Rate ◽  
Catalyst Activity ◽  
Adsorbed Hydrogen ◽  
Reaction Products ◽  
Co Methanation ◽  
Molar Ratios ◽  
Rate Determining Step ◽  
Higher Temperature ◽  
Kinetics Of

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.

Study of kinetics of reaction of lignin model compounds with propylene oxide

Holzforschung ◽  
2008 ◽  
Vol 62 (2) ◽  
pp. 169-175 ◽  
Author(s):  
Krishna K. Pandey ◽  
Tapani Vuorinen
Keyword(s):  
Chemical Reaction ◽  
Propylene Oxide ◽  
Aqueous Media ◽  
Reaction Products ◽  
Model Compounds ◽  
Rapid Reduction ◽  
Visible Absorption ◽  
Lignin Model Compounds ◽  
Lignin Model ◽  
Kinetics Of

Abstract The etherification of phenolic groups has been found to inhibit photodegradation in wood and lignin rich pulps. The precise understanding of kinetics of chemical reaction between lignins or their model compounds and the etherifying agent is the first step for developing a viable modification procedure. In this study, we have investigated the reaction of lignin model compounds (namely, phenol and guaiacol) with propylene oxide in aqueous media. The kinetics of etherification reaction was studied under varying pH conditions in the temperature range 30–60°C. The etherified reaction products were characterized by gas chromatogram-mass spectrum (GC-MS). The extent of etherification of phenols and the rate of chemical reaction was followed by UV-Visible absorption spectroscopy. The reaction between lignin model compounds and propylene oxide was indicated by a rapid reduction in the absorbance accompanied by the development of a new band corresponding to etherified products. The reaction kinetics was investigated at pH ∼12 under the condition of excess concentration of propylene oxide. The reaction followed first order kinetics and rate constants increased linearly with an increase in the temperature and concentration of propylene oxide. The MS fragment data of reaction product support the proposed reaction scheme. The activation energy of the reaction of propylene oxide with phenol and guaiacol, calculated with the Arrhenius equation, was 56.2 kJ mol-1 and 45.4 kJ mol-1, respectively.

scholarly journals Morphological and Elemental Investigations on Co–Fe–B–O Thin Films Deposited by Pulsed Laser Deposition for Alkaline Water Oxidation: Charge Exchange Efficiency as the Prevailing Factor in Comparison with the Adsorption Process

2021 ◽  
Author(s):  
Y. Popat ◽  
M. Orlandi ◽  
S. Gupta ◽  
N. Bazzanella ◽  
S. Pillai ◽  
...  
Keyword(s):  
Pulsed Laser Deposition ◽  
Water Oxidation ◽  
Active Sites ◽  
High Surface ◽  
Pulsed Laser ◽  
Industrial Applications ◽  
Active Species ◽  
Laser Deposition ◽  
Core Shell ◽  
Adsorption Sites

Abstract Mixed transition-metals oxide electrocatalysts have shown huge potential for electrochemical water oxidation due to their earth abundance, low cost and excellent electrocatalytic activity. Here we present Co–Fe–B–O coatings as oxygen evolution catalyst synthesized by Pulsed Laser Deposition (PLD) which provided flexibility to investigate the effect of morphology and structural transformation on the catalytic activity. As an unusual behaviour, nanomorphology of 3D-urchin-like particles assembled with crystallized CoFe2O4 nanowires, acquiring high surface area, displayed inferior performance as compared to core–shell particles with partially crystalline shell containing boron. The best electrochemical activity towards water oxidation in alkaline medium with an overpotential of 315 mV at 10 mA/cm2 along with a Tafel slope of 31.5 mV/dec was recorded with core–shell particle morphology. Systematic comparison with control samples highlighted the role of all the elements, with Co being the active element, boron prevents the complete oxidation of Co to form Co3+ active species (CoOOH), while Fe assists in reducing Co3+ to Co2+ so that these species are regenerated in the successive cycles. Thorough observation of results also indicates that the activity of the active sites play a dominating role in determining the performance of the electrocatalyst over the number of adsorption sites. The synthesized Co–Fe–B–O coatings displayed good stability and recyclability thereby showcasing potential for industrial applications. Graphic Abstract

The kinetics of the photo-induced solid-state chemical reaction in Ag/As33S67bilayers and its reaction products

1999 ◽  
Vol 79 (2) ◽  
pp. 223-237 ◽  
Author(s):  
T. Wagner ◽  
E. Márquez ◽  
J. Fernández-Pena ◽  
J. M. González-Leal ◽  
P. J. S. Ewen ◽  
...  
Keyword(s):  
Solid State ◽  
Chemical Reaction ◽  
Reaction Products ◽  
State Chemical ◽  
Solid State Chemical Reaction ◽  
Kinetics Of

Kinetics of reactions of acyl isothiocyanates with amines

1980 ◽  
Vol 45 (8) ◽  
pp. 2334-2342 ◽  
Author(s):  
Ján Imrich ◽  
Pavol Kristian ◽  
Dušan Podhradský ◽  
Milan Dzurilla
Keyword(s):  
Solvent Polarity ◽  
Uv Spectra ◽  
Spectroscopic Methods ◽  
Stopped Flow ◽  
Analogous Reaction ◽  
Reaction Products ◽  
Experimental Conditions ◽  
Glycine Ethyl Ester ◽  
Nucleophilic Reagents ◽  
Kinetics Of

The kinetics of reactions of 4-substituted benzoyl, cinnamoyl and phenyl isothiocyanates with aliphatic amines and glycine ethyl ester in organic solvents was studied by the stopped-flow and UV spectroscopic methods. The reaction of acyl isothiocyanates with the nucleophilic reagents employed proved to be 103 - 104 times faster than analogous reaction of phenyl isothiocyanates. A linear correlation between logk and σp constants with positive ρ slope was found. The solvent polarity has only a negligible effect on the reaction. UV spectra as well as gas chromatography of the reaction products proved that under the employed experimental conditions N,N'-disubstituted thioureas are the sole reaction products.

Reaction Kinetics of Poly-Si Etching in TMAH Solution

2021 ◽  
Vol 314 ◽  
pp. 60-65
Author(s):  
Taegun Park ◽  
Sangwoo Lim
Keyword(s):  
Reaction Kinetics ◽  
Alkaline Solution ◽  
Etching Rate ◽  
Tetramethylammonium Hydroxide ◽  
Dissolved Gas ◽  
Metal Free ◽  
Effect Of Water ◽  
Detailed Kinetics ◽  
Kinetics Of ◽  
Tmah Solution

Tetramethylammonium hydroxide (TMAH) is a metal-free strong alkaline solution which can etch poly-Si. The concentration of dissolved gas as well as the concentration of TMAH affects etching rate of poly-Si. The detailed kinetics of poly-Si etching in TMAH solution is investigated in this study. The effect of water and TMAH concentration on the etching kinetics of poly-Si was investigated by using various concentrations of TMAH solution. It is found that H2O in TMAH solution plays an important role in etching poly-Si. Presence of dissolved CO2 and O2 in TMAH solution tends to inhibit etching of poly-Si. The concentration of dissolved CO2 and O2 in TMAH were reduced by Ar bubbling, thereby the poly-Si etching rate increased.

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