Spatially resolved diagnostics on a micro atmospheric pressure plasma jet

Despite enormous potential for technological applications, fundamentals of stable non-equilibrium micro-plasmas at ambient pressure are still only partly understood. Micro-plasma jets are one sub-group of these plasma sources. For an understanding it is particularly important to analyse transport phenomena of energy and particles within and between the core and effluent of the discharge. The complexity of the problem requires the combination and correlation of various highly sophisticated diagnostics yielding different information with an extremely high temporal and spatial resolution. A specially designed rf microscale atmospheric pressure plasma jet (µ-APPJ) provides excellent access for optical diagnostics to the discharge volume and the effluent region. This allows detailed investigations of the discharge dynamics and energy transport mechanisms from the discharge to the effluent. Here we present examples for diagnostics applicable to different regions and combine the results. The diagnostics applied are optical emission spectroscopy (OES) in the visible and ultraviolet and two-photon absorption laser-induced fluorescence spectroscopy. By the latter spatially resolved absolutely calibrated density maps of atomic oxygen have been determined for the effluent. OES yields an insight into energy transport mechanisms from the core into the effluent. The first results of spatially and phase-resolved OES measurements of the discharge dynamics of the core are presented.

A DFT study of the chain growth probability in Fischer-Tropsch synthesis

The chain growth probability (alpha value) is one of the most significant parameters in Fischer-Tropsch (FT) synthesis. To gain insight into the chain growth probability, we systematically studied the hydrogenation and C-C coupling reactions with different chain lengths on the stepped Co(0001) surface using density functional theory calculations. Our findings elucidate the relationship between the barriers of these elementary reactions and the chain length. Moreover, we derived a general expression of the chain growth probability and investigated the behavior of the alpha value observed experimentally. The high methane yield results from the lower chain growth rate for C-1 + C-1 coupling compared with the other coupling reactions. After C-1, the deviation of product distribution in FT synthesis from the Anderson-Schulz-Flory distribution is due to the chain length-dependent paraffin/olefin ratio. (C) 2008 Elsevier Inc. All rights reserved.

Absolute Calibration of Atomic Density Measurements by Laser-Induced Fluorescence Spectroscopy with Two-Photon Excitation (TALIF)

The two-photon resonances of atomic hydrogen (? = 2 × 205.1 nm), atomic nitrogen (? = 2 × 206.6 nm) and atomic oxygen (? = 2 × 225.6 nm) are investigated together with two selected transitions in krypton (? = 2×204.2 nm) and xenon (? = 2×225.5 nm). The natural lifetimes of the excited states, quenching coefficients for the most important collisions partners, and the relevant ratios of the two-photon excitation cross sections are measured. These data can be applied to provide a calibration for two-photon laser-induced fluorescence measurements based on comparisons with spectrally neighbouring noble gas resonances.

Laser-Induced Fluorescence Measurements of Absolute Atomic Densities: Concepts and Limitations

The potential of laser-induced fluorescence spectroscopy of atoms is reviewed with emphasis on the determination of absolute densities. Examples of experiments with single-photon and two-photon excitation are presented. Calibration methods applicable with the different schemes are discussed. A new method is presented that has the potential to allow absolute measurement in plasmas of elevated pressure where collisional depletion of the excited state is present.

Absolute Atomic Oxygen Density Measurements by Two-Photon Absorption Laser-induced Fluorescence Spectroscopy in an RF-Excited Atmospheric Pressure Plasma Jet

The atmospheric pressure plasma jet is a capacitively coupled radio frequency discharge (13.56 MHz) running with a high helium flux (2m3 h-1) between concentric electrodes. Small amounts (0.5%) of admixed molecular oxygen do not disturb the homogeneous plasma discharge. The jet effluent leaving the discharge through the ring-shaped nozzle contains high concentrations of radicals at a low gas temperature—the key property for a variety of applications aiming at treatment of thermally sensitive surfaces. We report on absolute atomic oxygen density measurements by two-photon absorption laser-induced fluorescence (TALIF) spectroscopy in the jet effluent. Calibration is performed with the aid of a comparative TALIF measurement with xenon. An excitation scheme (different from the one earlier published) providing spectral matching of both the two-photon resonances and the fluorescence transitions is applied.

Absolute Atomic Oxygen Density Distributions in the Effluent of a Micro Scale Atmospheric Pressure Plasma Jet

The coplanar microscale atmospheric pressure plasma jet (µ-APPJ) is a capacitively coupled radio frequency discharge (13.56 MHz, ~15W rf power) designed for optimized optical diagnostic access. It is operated in a homogeneous glow mode with a noble gas flow (1.4 slm He) containing a small admixture of molecular oxygen (~0.5%). Ground state atomic oxygen densities in the effluent up to 2 × 1014 cm-3 are measured by two-photon absorption laser-induced fluorescence spectroscopy (TALIF) providing space resolved density maps. The quantitative calibration of the TALIF setup is performed by comparative measurements with xenon. A maximum of the atomic oxygen density is observed for 0.6% molecular oxygen admixture. Furthermore, an increase in the rf power up to about 15W (depending on gas flow and mixture) leads to an increase in the effluent’s atomic oxygen density, then reaching a constant level for higher powers.

Absolute atomic oxygen density profiles in the discharge core of a microscale atmospheric pressure plasma jet

The micro atmospheric pressure plasma jet is an rf driven (13.56 MHz, ~20 W) capacitively coupled discharge producing a homogeneous plasma at ambient pressure when fed with a gas flow of helium (1.4 slm) containing small admixtures of oxygen (~0.5%). The design provides excellent optical access to the plasma core. Ground state atomic oxygen densities up to 3x1016 cm-3 are measured spatially resolved in the discharge core by absolutely calibrated two-photon absorption laser-induced fluorescence spectroscopy. The atomic oxygen density builds up over the first 8 mm of the discharge channel before saturating at a maximum level. The absolute value increases linearly with applied power.

Generation of Atomic Oxygen in the Effluent of an Atmospheric Pressure Plasma Jet

The planar 13.56MHz RF-excited low temperature atmospheric pressure plasma jet (APPJ) investigated in this study is operated with helium feed gas and a small molecular oxygen admixture. The effluent leaving the discharge through the jet’s nozzle contains very few charged particles and a high reactive oxygen species’ density. As its main reactive radical, essential for numerous applications, the ground state atomic oxygen density in the APPJ’s effluent is measured spatially resolved with two-photon absorption laser induced fluorescence spectroscopy. The atomic oxygen density at the nozzle reaches a value of ~1016 cm-3. Even at several centimetres distance still 1% of this initial atomic oxygen density can be detected. Optical emission spectroscopy (OES) reveals the presence of short living excited oxygen atoms up to 10 cm distance from the jet’s nozzle. The measured high ground state atomic oxygen density and the unaccounted for presence of excited atomic oxygen require further investigations on a possible energy transfer from the APPJ’s discharge region into the effluent: energetic vacuum ultraviolet radiation, measured by OES down to 110 nm, reaches far into the effluent where it is presumed to be responsible for the generation of atomic oxygen.

Measurement of Quenching Coefficients and Developement of Calibration Methods for Quantitative Spectroscopy of Plasma at Elevated Pressures

Measurements of collisional de-excitation (quenching) coefficients required for the interpretation of emission and fluorescence spectroscopic measurements are reported. Particular attention is turned on argon transitions which are of interest for actinometric determinations of atomic ground state populations and on fluorescence lines originating from excited atoms and noble gases in connection with two-photon excitation (TALIF) of atomic radicals. A novel method is described which allows to infer quenching coefficients for collisions with molecular hydrogen of noble gas states in the energy range up to 24 eV. The excitation is performed in these experiments by collisions of energetic electrons in the sheath of an RF excited hydrogen plasma during the field reversal phase which lasts about 10 ns. We describe in addition a calibration method - including quenching effects - for the determination by TALIF of absolute atomic radical densities of hydrogen, nitrogen and oxygen using two-photon resonances in noble gases close by the resonances of the species mentioned. The paper closes with first ideas on a novel technique to bypass quenching effects in TALIF by introducing an additional, controllable loss by photoionization that will allow quenching-free determination of absolute atomic densities with prevalent nanosecond laser systems in situations where collisional de-excitation dominates over spontaneous emission.

The dynamics of radio-frequency driven atmospheric pressure plasma jets

The complex dynamics of radio-frequency driven atmospheric pressure plasma jets is investigated using various optical diagnostic techniques and numerical simulations. Absolute number densities of ground state atomic oxygen radicals in the plasma effluent are measured by two-photon absorption laser induced fluorescence spectroscopy (TALIF). Spatial profiles are compared with (vacuum) ultra-violet radiation from excited states of atomic oxygen and molecular oxygen, respectively. The excitation and ionization dynamics in the plasma core are dominated by electron impact and observed by space and phase resolved optical emission spectroscopy (PROES). The electron dynamics is governed through the motion of the plasma boundary sheaths in front of the electrodes as illustrated in numerical simulations using a hybrid code based on fluid equations and kinetic treatment of electrons.

Bis(trifluoromethyl)mercury(II) complexes with purine and 3,5-dimethyl-4 '-amino-triazole as ligands, [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2)

Colourless single crystals of [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2) were obtained from aqueous and etheric solutions of the respective components Purine, (imidazo[4,5-d]pyrimidine, Pur), 3,5-dimethyl-4 '-amino-triazole (Dat) and bis(trifluoromethyl)mercury(II), Hg(CF3)(2). [Hg(CF3)(2)(Pur)](4) crystallizes with the tetragonal system (P-4, Z = 8, a = 1486.8(2), c = 1026.2(l) pm, R-all = 0.0657) with tetrameric molecules consisting of four purine molecules bridged by slightly bent Hg(CF3)2 molecules forming a cage with the CF3 ligands surrounding this cage. The two modifications of [Hg(Dat)(CF3)2]2 (1: 170 K, triclinic, P-1, Z = 2, a 814.9(2), b = 845.4(2), c = 968.4(3) pm, alpha = 106.55(2)degrees, beta= 103.41(2)degrees, gamma = 110.79(2)degrees, R-all = 0.1189; II: monoclinic, P2(1)/c, Z = 8, a = 879.8(2), b = 1731.0(3), c = 1593.9(3) pm, beta = 106.89(2)degrees, R-all = 0.1199) both contain dimeric molecules that are stacked parallel to one crystal axis to strands which are arranged in a parallel fashion in I and rotated against each other in 11 by 110 degrees. In both, the tetrameric [Hg(CF3)(2)(Pur)](4) and the dimeric [Hg(CF3)(2)(Dat)](2) the Hg(CF3)(2) molecules are slightly bent (around 167 and 170 degrees) and rather weakly attached to the N-donor ligands Pur and Dat with Hg-N distances around 272 pm, although in both cases the Hg atoms bridge between two ligand molecules.

Diagnostic based modelling of radio-frequency driven atmospheric pressure plasmas

Diagnostic based modelling (DBM) actively combines complementary advantages of numerical plasma simulations and relatively simple optical emission spectroscopy (OES). DBM is employed to determine absolute atomic oxygen ground state densities in a helium–oxygen radio-frequency driven atmospheric pressure plasma jet. A comparatively simple one-dimensional simulation yields detailed information on electron properties governing the population dynamics of excited states. Important characteristics of the electron dynamics are found to be largely insensitive to details of the chemical composition and to be in very good agreement with space and phase-resolved OES. Benchmarking the time and space resolved simulation allows us to subsequently derive effective excitation rates as the basis for DBM with simple space and time integrated OES. The population dynamics of the upper O 3p 3P (? = 844 nm) atomic oxygen state is governed by direct electron impact excitation, dissociative excitation, radiation losses and collisional induced quenching. Absolute values for atomic oxygen densities are obtained through tracer comparison with the upper Ar 2p1 (? = 750.4 nm) state. The presented results for the atomic oxygen density show excellent quantitative agreement with independent two-photon laser-induced fluorescence measurements.

Diagnostic-based modeling on a micro-scale atmospheric-pressure plasma jet

Diagnostic-based modeling (DBM) actively combines complementary advantages of numerical plasma simulations and relatively simple optical emission spectroscopy (OES). DBM is applied to determine spatial absolute atomic oxygen ground-state density profiles in a micro atmospheric-pressure plasma jet operated in He–O2. A 1D fluid model with semi-kinetic treatment of the electrons yields detailed information on the electron dynamics and the corresponding spatio-temporal electron energy distribution function. Benchmarking this time- and space-resolved simulation with phase-resolved OES (PROES) allows subsequent derivation of effective excitation rates as the basis for DBM. The population dynamics of the upper O(3p3P) oxygen state (? = 844 nm) is governed by direct electron impact excitation, dissociative excitation, radiation losses, and collisional induced quenching. Absolute values for atomic oxygen densities are obtained through tracer comparison with the upper Ar(2p1) state (? = 750.4 nm). The resulting spatial profile for the absolute atomic oxygen density shows an excellent quantitative agreement to a density profile obtained by two-photon absorption laser-induced fluorescence spectroscopy.

The challenge of revealing and tailoring the dynamics of radio-frequency plasmas

The complex dynamics of ionization and excitation mechanisms in capacitively coupled radio-frequency plasmas is discussed for single- and dual-frequency operations in low-pressure and atmospheric pressure plasmas. Electrons are energized through the dynamics of electric fields in the vicinity of the plasma boundary sheaths. Distinctly different power dissipation mechanisms can either co-exist or initiate mode transitions exhibiting characteristic spatio-temporal ionization structures. Phase resolved optical emission spectroscopy, in combination with adequate modelling of the population dynamics of excited states, and numerical simulations reveal dissipation associated with sheath expansion, sheath collapse, transient electron avalanches and wave–particle interactions. In dual-frequency systems the relative phase between the two frequency components provides additional strategies to tailor the plasma dynamics.