Azimuthal ion movement in HiPIMS plasmas -- Part I: velocity distribution function

Magnetron sputtering discharges feature complex magnetic field configurations to confine the electrons close to the cathode surface. This magnetic field configuration gives rise to a strong electron drift in azimuthal direction, with typical drift velocities on the order of \SI{100}{\kilo\meter\per\second}. In high power impulse magnetron sputtering (HiPIMS) plasmas, the ions have also been observed to follow the movement of electrons with velocities of a few \si{\kilo\meter\per\second}, despite being unmagnetized. In this work, we report on measurements of the azimuthal ion velocity using spatially resolved optical emission spectroscopy, allowing for a more direct measurement compared to experiments performed using mass spectrometry. The azimuthal ion velocities increase with target distance, peaking at about \SI{1.55}{\kilo\meter\per\second} for argon ions and \SI{1.25}{\kilo\meter\per\second} for titanium ions. Titanium neutrals are also found to follow the azimuthal ion movement which is explained with resonant charge exchange collisions. The experiments are then compared to a simple test-particle simulation of the titanium ion movement, yielding good agreement to the experiments when only considering the momentum transfer from electrons to ions via Coulomb collisions as the only source of acceleration in azimuthal direction. Based on these results, we propose this momentum transfer as the primary source for ion acceleration in azimuthal direction

High power impulse magnetron sputtering discharges: Instabilities and plasma self-organization

We report on instabilities in high power impulse magnetron sputtering plasmas which are likely to be of the generalized drift wave type. They are characterized by well defined regions of high and low plasma emissivity along the racetrack of the magnetron and cause periodic shifts in floating potential. The azimuthal mode number m depends on plasma current, plasma density, and gas pressure. The structures rotate in × direction at velocities of ∼10 km s−1 and frequencies up to 200 kHz. Collisions with residual gas atoms slow down the rotating wave, whereas increasing ionization degree of the gas and plasma conductivity speeds it up

Ionization wave propagation on a micro cavity plasma array

Microcavity plasma arrays of inverse pyramidal cavities have been fabricated in p-Si wafers. Each cavity acts as a microscopic dielectric barrier discharge. Operated at atmospheric pressure in argon and excited with high voltage at about 10 kHz, each cavity develops a localized microplasma. Experiments have shown a strong interaction of individual cavities, leading to the propagation of wave-like optical emission structures along the surface of the array. This phenomenon is numerically investigated using computer simulation. The observed ionization wave propagates with a speed of about 5 km/s, which agrees well the experimental findings. It is found that the wave propagation is due to sequential contributions of a drift of electrons followed by drift of ions between cavities seeded by photoemission of electrons by the plasma in adjacent cavities

Nitrosylation vs. oxidation – How to modulate cold physical plasmas for biological applications

Thiol moieties are major targets for cold plasma-derived nitrogen and oxygen species, making CAPs convenient tools to modulate redox-signaling pathways in cells and tissues. The underlying biochemical pathways are currently under investigation but especially the role of CAP derived RNS is barely understood. Their potential role in protein thiol nitrosylation would be relevant in inflammatory processes such as wound healing and improving their specific production by CAP would allow for enhanced treatment options beyond the current application. The impact of a modified kINPen 09 argon plasma jet with nitrogen shielding on cysteine as a thiol-carrying model substance was investigated by FTIR spectroscopy and high-resolution mass spectrometry. The deposition of short-lived radical species was measured by electron paramagnetic resonance spectroscopy, long-lived species were quantified by ion chromatography (NO2-, NO3-) and xylenol orange assay (H2O2). Product profiles were compared to samples treated with the so-called COST jet, being introduced by a European COST initiative as a reference device, using both reference conditions as well as conditions adjusted to kINPen gas mixtures. While thiol oxidation was dominant under all tested conditions, an Ar + N2/O2 gas compositions combined with a nitrogen curtain fostered nitric oxide deposition and the desired generation of S-nitrosocysteine. Interestingly, the COST-jet revealed significant differences in its chemical properties in comparison to the kINPen by showing a more stable production of RNS with different gas admixtures, indicating a different •NO production pathway. Taken together, results indicate various chemical properties of kINPen and COST-jet as well as highlight the potential of plasma tuning not only by gas admixtures alone but by adjusting the surrounding atmosphere as well

Chemical fingerprints of cold physical plasmas – an experimental and computational study using cysteine as tracer compound

Reactive oxygen and nitrogen species released by cold physical plasma are being proposed as effectors in various clinical conditions connected to inflammatory processes. As these plasmas can be tailored in a wide range, models to compare and control their biochemical footprint are desired to infer on the molecular mechanisms underlying the observed effects and to enable the discrimination between different plasma sources. Here, an improved model to trace short-lived reactive species is presented. Using FTIR, high-resolution mass spectrometry, and molecular dynamics computational simulation, covalent modifications of cysteine treated with different plasmas were deciphered and the respective product pattern used to generate a fingerprint of each plasma source. Such, our experimental model allows a fast and reliable grading of the chemical potential of plasmas used for medical purposes. Major reaction products were identified to be cysteine sulfonic acid, cystine, and cysteine fragments. Less-abundant products, such as oxidized cystine derivatives or S-nitrosylated cysteines, were unique to different plasma sources or operating conditions. The data collected point at hydroxyl radicals, atomic O, and singlet oxygen as major contributing species that enable an impact on cellular thiol groups when applying cold plasma in vitro or in vivo

Concepts and characteristics of the 'COST Reference Microplasma Jet'

Biomedical applications of non-equilibrium atmospheric pressure plasmas have attracted intense interest in the past few years. Many plasma sources of diverse design have been proposed for these applications, but the relationship between source characteristics and application performance is not well-understood, and indeed many sources are poorly characterized. This circumstance is an impediment to progress in application development. A reference source with well-understood and highly reproducible characteristics may be an important tool in this context. Researchers around the world should be able to compare the characteristics of their own sources and also their results with this device. In this paper, we describe such a reference source, developed from the simple and robust micro-scaled atmospheric pressure plasma jet (μ-APPJ) concept. This development occurred under the auspices of COST Action MP1101 'Biomedical Applications of Atmospheric Pressure Plasmas'. Gas contamination and power measurement are shown to be major causes of irreproducible results in earlier source designs. These problems are resolved in the reference source by refinement of the mechanical and electrical design and by specifying an operating protocol. These measures are shown to be absolutely necessary for reproducible operation. They include the integration of current and voltage probes into the jet. The usual combination of matching unit and power supply is replaced by an integrated LC power coupling circuit and a 5 W single frequency generator. The design specification and operating protocol for the reference source are being made freely available

Helium metastable species generation in atmospheric pressure RF plasma jets driven by tailored voltage waveforms in mixtures of He and N2

Spatially resolved tunable diode-laser absorption measurements of the absolute densities of He-I (23S1) metastables in a micro atmospheric pressure plasma jet operated in He/N2 and driven by 'peaks'- and 'valleys'-type tailored voltage waveforms are presented. The measurements are performed at different nitrogen admixture concentrations and peak-to-peak voltages with waveforms that consist of up to four consecutive harmonics of the fundamental frequency of 13.56 MHz. Comparisons of the measured metastable densities with those obtained from particle-in-cell/Monte Carlo collision simulations show a good quantitative agreement. The density of helium metastables is found to be significantly enhanced by increasing the number of consecutive driving harmonics. Their generation can be further optimized by tuning the peak-to-peak voltage amplitude and the concentration of the reactive gas admixture. These findings are understood based on detailed fundamental insights into the spatio-temporal electron dynamics gained from the simulations, which show that voltage waveform tailoring allows to control the electron energy distribution function to optimize the metastable generation. A high degree of correlation between the metastable creation rate and the electron impact excitation rate from the helium ground state into the He-I ((3s)3S1) level is observed for some conditions which may facilitate an estimation of the metastable densities based on phase resolved optical emission spectroscopy measurements of the 706.5 nm He-I line originating from the above level and metastable density values at proper reference conditions