Plasma ionization through wave-particle interaction in a capacitively coupled radio-frequency discharge

Phase resolved optical emission spectroscopy, with high temporal resolution, shows that wave-particle interactions play a fundamental role in sustaining capacitively coupled rf plasmas. The measurements are in excellent agreement with a simple particle-in-cell simulation. Excitation and ionization mechanisms are dominated by beam-like electrons, energized through the advancing and retreating electric fields of the rf sheath. The associated large-amplitude electron waves, driven by a form of two-stream instability, result in power dissipation through electron trapping and phase mixing. (c) 2007 American Institute of Physics.

Transition phenomena in a radio-frequency inductively coupled plasma

Changes of the electron dynamics during the mode transition (E- to H-mode) in a hydrogen radio-frequency (rf) inductively coupled plasma are investigated using space and phase resolved optical emission spectroscopy. The E- mode is characterized through relatively weak optical emission which is strongly modulated on a nanosecond time scale during the rf-cycle, with one pronounced maximum per cycle. The modulation in H-mode, with twice the rf-frequency, is significantly weaker while the emission intensities are about two orders of magnitude higher. In particular the transition between these two modes is studied under variations of rf-power input and gas pressure. Characteristic spatio-temporal structures are observed and can be understood in the frame of a simple model combining both coupling mechanisms in the transition regime.

Determination of the degree of dissociation in an inductively coupled hydrogen plasma using optical emission spectroscopy and laser diagnostics

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (~25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

Phase and space resolved optical emission spectroscopic investigations of an inductively coupled RF plasma using an imaging acousto-optic spectrometer

A novel acousto-optic spectrometer (IfU Diagnostic Systems GmbH) for 2-dimensional (2D) optical emission spectroscopy with high spectral resolution has been developed. The spectrometer is based on acousto-optic tuneable filter technology with fast random wavelength access. Measurements for characterisation of the imaging quality, the spatial resolution, and the spectral resolution are presented. The applicability for 2D-space and phase resolved optical emission spectroscopy (2D-PROES) is shown. 2D-PROES has been applied to an inductively coupled plasma with radio frequency excitation at 13.56 MHz.

Characterization of stationary and pulsed inductively coupled RF discharges for plasma sterilization

Sterilization of bio-medical materials using radio frequency (RF) excited inductively coupled plasmas (ICPs) has been investigated. A double ICP has been developed and studied for homogenous treatment of three-dimensional objects. Sterilization is achieved through a combination of ultraviolet light, ion bombardment and radical treatment. For temperature sensitive materials, the process temperature is a crucial parameter. Pulsing of the plasma reduces the time average heat strain and also provides additional control of the various sterilization mechanisms. Certain aspects of pulsed plasmas are, however, not yet fully understood. Phase resolved optical emission spectroscopy and time resolved ion energy analysis illustrate that a pulsed ICP ignites capacitively before reaching a stable inductive mode. Time resolved investigations of the post-discharge, after switching off the RF power, show that the plasma boundary sheath in front of a substrate does not fully collapse for the case of hydrogen discharges. This is explained by electron heating through super-elastic collisions with vibrationally excited hydrogen molecules.

Space and time resolved rotational state populations and gas temperatures in an inductively coupled hydrogen RF discharge

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (similar or equal to 25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

Observation of fast hydrogen atoms formed by ion bombarding of surfaces

We report on the observation of fast hydrogen atoms in a capacitively coupled RF reactor by optical emission spectroscopy. For the analysis we use the prominent H-alpha emission line of atomic hydrogen in combination with other lines from molecular hydrogen and argon. Several chaxacteristic emission structures can be identified. One of these structures is related to fast hydrogen atoms traveling from the surface of the powered electrode to the plasma bulk. From the appearance time within the RF period we conclude that this feature originates from ion bombardment of the electrode surface. Measured pressure dependencies and a simple model for the ion dynamics support this assumption.

Diagnostic studies of species concentrations in a capacitively coupled RF plasma containing CH4-H2-Ar

Three plasma diagnostic methods, tunable infrared diode laser absorption spectroscopy, optical emission spectroscopy and microwave interferometry have been used to monitor concentrations of transient and stable molecules, CH3, CH4, C2H2, C2H6, and of electrons in capacitively coupled CH4-H-2-Ar radiofrequency (RF) plasmas (f(RF) = 13.56 MHz, p = 100 Pa, phi (total)= 66 sccm) for various discharge power values (P = 10-100 W) and gas mixtures. The degree of dissociation of the methane precursor varied between 3% and 60%. The methyl radical concentration was found to be in the order of 10(12) molecules cm(-3) and the electron concentration in the order of loll cm(-3). The methyl radical concentration and the concentrations of the stable C-2 hydrocarbons, C2H2 and C2H6, produced in the plasma, increased with discharge power. The fragmentation rates of the methane precursor and conversion rates to the measured C-2 hydrocarbons were estimated in dependence on discharge power. Radial distributions of the electron and methyl radical concentrations, and of the gas temperature were measured for the first time simultaneously in the plasma region between the discharge electrodes. The measurements allow us to draw qualitative conclusions on the main chemical processes and the plasma chemical reaction paths.

The role of the relative voltage and phase for frequency coupling in a dual-frequency capacitively coupled plasma

Frequency coupling in multifrequency discharges is a complex nonlinear interaction of the different frequency components. An alpha-mode low pressure rf capacitively coupled plasma operated simultaneously with two frequencies is investigated and the coupling of the two frequencies is observed to greatly influence the excitation and ionization within the discharge. Through this, plasma production and sustainment are dictated by the corresponding electron dynamics and can be manipulated through the dual-frequency sheath. These mechanisms are influenced by the relative voltage and also the relative phase of the two frequencies.

Enrichment and analysis of nonenzymatically glycated peptides: Boronate affinity chromatography coupled with electron-transfer dissociation mass spectrometry

Nonenzymatic glycation of peptides and proteins by D-glucose has important implications in the pathogenesis of diabetes mellitus, particularly in the development of diabetic complications. However, no effective high-throughput methods exist for identifying proteins containing this low-abundance posttranslational modification in bottom-up proteomic studies. In this report, phenylboronate affinity chromatography was used in a two-step enrichment scheme to selectively isolate first glycated proteins and then glycated, tryptic peptides from human serum glycated in vitro. Enriched peptides were subsequently analyzed by alternating electron-transfer dissociation (ETD) and collision induced dissociation ( CID) tandem mass spectrometry. ETD fragmentation mode permitted identification of a significantly higher number of glycated peptides (87.6% of all identified peptides) versus CID mode (17.0% of all identified peptides), when utilizing enrichment on first the protein and then the peptide level. This study illustrates that phenylboronate affinity chromatography coupled with LC-MS/MS and using ETD as the fragmentation mode is an efficient approach for analysis of glycated proteins and may have broad application in studies of diabetes mellitus.

Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Comparison between fluid simulations and experiments in inductively coupled argon/chlorine plasmas

Comparisons of 2D fluid simulations with experimental measurements of Ar/Cl-2 plasmas in a low-pressure inductively coupled reactor are reported. Simulations show that the wall recombination coefficient of Cl atom (gamma) is a crucial parameter of the model and that neutral densities are very sensitive to its variations. The best agreement between model and experiment is obtained for gamma = 0.02, which is much lower than the value predicted for stainless steel walls (gamma = 0.6). This is consistent with reactor wall contaminations classically observed in such discharges. The electron density, negative ion fraction and Cl atom density have been investigated under various conditions of chlorine and argon concentrations, gas pressure and applied rf input power. The plasma electronegativity decreases with rf power and increases with chlorine concentration. At high pressure, the power absorption and distribution of charged particles become more localized below the quartz window. Although the experimental trends are well reproduced by the simulations, the calculated charged particle densities are systematically overestimated by a factor of 3-5. The reasons for this discrepancy are discussed in the paper.

Chitosan nanoparticle as protein delivery carrier - Systematic examination of fabrication conditions for efficient loading and release

Chitosan nanoparticles fabricated via different preparation protocols have been in recent years widely studied as carriers for therapeutic proteins and genes with varying degree of effectiveness and drawbacks. This work seeks to further explore the polyionic coacervation fabrication process, and associated processing conditions under which protein encapsulation and subsequent release can be systematically and predictably manipulated so as to obtain desired effectiveness. BSA was used as a model protein which was encapsulated by either incorporation or incubation method, using the polyanion tripolyphosphate (TPP) as the coacervation crosslink agent to form chitosan-BSA-TPP nanoparticles. The BSA-loaded chitosan-TPP nanoparticles were characterized for particle size, morphology, zeta potential, BSA encapsulation efficiency, and subsequent release kinetics, which were found predominantly dependent on the factors of chitosan molecular weight, chitosan concentration, BSA loading concentration, and chitosan/TPP mass ratio. The BSA loaded nanoparticles prepared under varying conditions were in the size range of 200-580 nm, and exhibit a high positive zeta potential. Detailed sequential time frame TEM imaging of morphological change of the BSA loaded particles showed a swelling and particle degradation process. Initial burst released due to surface protein desorption and diffusion from sublayers did not relate directly to change of particle size and shape, which was eminently apparent only after 6 h. It is also notable that later stage particle degradation and disintegration did not yield a substantial follow-on release, as the remaining protein molecules, with adaptable 3-D conformation, could be tightly bound and entangled with the cationic chitosan chains. In general, this study demonstrated that the polyionic coacervation process for fabricating protein loaded chitosan nanoparticles offers simple preparation conditions and a clear processing window for manipulation of physiochemical properties of the nanoparticles (e.g., size and surface charge), which can be conditioned to exert control over protein encapsulation efficiency and subsequent release profile. The weakness of the chitosan nanoparticle system lies typically with difficulties in controlling initial burst effect in releasing large quantities of protein molecules. (C) 2007 Elsevier B.V. All rights reserved.