[en] The initial polymerization reactions in particle forming Ar/He/C₂H₂ plasmas are studied by means of molecular beam mass spectrometry. The mass spectra are quantified with the help of Bayesian probability theory. The C_xH_y production in C₂H₂ plasma is studied by measuring the temporal evolution of the mass spectrometer signal under the influence of added C₂H₄ to the gas mixture. It is shown that C₄H₄ is very quickly formed after plasma ignition in reactions of C₂H₄ with C₂H radicals. Other C_nH₄ molecules, i.e. C₃H₄, C₅H₄ and C₆H₄, are formed in reactive pathways involving C₂H₄, as well. C₆H₆, which could not be uniquely identified as an aromatic or linear molecule, shows a similar trend with additional C₂H₄. But in this case more C₂H₄ is needed to detect the same relative change compared with C₄H₄. This is probably because more reaction steps are needed to form C₆H₆. It is shown that C₂H₄ is very likely produced in the acetylene plasma.

[en] Reactive plasmas are highly valued for their ability to produce large amounts of reactive radicals and of energetic ions bombarding surrounding surfaces. The non-equilibrium electron driven plasma chemistry is utilized in many applications such as anisotropic etching or deposition of thin films of high-quality materials with unique properties. However, the non-equilibrium character and the high power densities make plasmas very complex and hard to understand. Mass spectrometry (MS) is a very versatile diagnostic method, which has, therefore, a prominent role in the characterization of reactive plasmas. It can access almost all plasma generated species: stable gas-phase products, reactive radicals, positive and negative ions or even internally excited species such as metastables. It can provide absolute densities of neutral particles or energy distribution functions of energetic ions. In particular, plasmas with a rich chemistry, such as hydrocarbon plasmas, could not be understood without MS. This review focuses on quadrupole MS with an electron impact ionization ion source as the most common MS technique applied in plasma analysis. Necessary information for the understanding of this diagnostic and its application and for the proper design and calibration procedure of an MS diagnostic system for quantitative plasma analysis is provided. Important differences between measurements of neutral particles and energetic ions and between the analysis of low pressure and atmospheric pressure plasmas are described and discussed in detail. Moreover, MS-measured ion energy distribution functions in different discharges are discussed and the ability of MS to analyse these distribution functions with time resolution of several microseconds is presented.

[en] The velocity distribution function of titanium neutrals in the target region of a high power impulse magnetron sputtering discharge was investigated by optical emission spectroscopy. A high-resolution plane grating spectrograph combined with a fast, gated, intensified CCD camera was used to study the shape of selected optical emission lines. Doppler broadening and shift were analyzed to gain information about the velocity distribution of sputtered titanium neutrals. The velocity distribution function was found to depend on the discharge power for target power densities up to 0.6 kW cm⁻². Above that value, the velocity distribution was constant. The collision processes of sputtered neutrals close to the target were found to be describable using a modified version of the Krook collisional operator. Using this interpretation, evidence for strong scattering of the titanium neutrals in the target region was found. This scattering can be explained by resonant charge exchange with previously scattered titanium ions. (paper)

[en] Reactive high power impulse magnetron sputtering (HiPIMS) of metals is of paramount importance for the deposition of various oxides, nitrides and carbides. The addition of a reactive gas such as nitrogen to an argon HiPIMS plasma with a metal target allows the formation of the corresponding metal nitride on the substrate. The addition of a reactive gas introduces new dynamics into the plasma process, such as hysteresis, target poisoning and the rarefaction of two different plasma gases. We investigate the dynamics for the deposition of chromium nitride by a reactive HiPIMS plasma using energy- and time-resolved ion mass spectrometry, fast camera measurements and temporal and spatially resolved optical emission spectroscopy. It is shown that the addition of nitrogen to the argon plasma gas significantly changes the appearance of the localized ionization zones, the so-called spokes, in HiPIMS plasmas. In addition, a very strong modulation of the metal ion flux within each HiPIMS pulse is observed, with the metal ion flux being strongly suppressed and the nitrogen molecular ion flux being strongly enhanced in the high current phase of the pulse. This behavior is explained by a stronger return effect of the sputtered metal ions in the dense plasma above the racetrack. This is best observed in a pure nitrogen plasma, because the ionization zones are mostly confined, implying a very high local plasma density and consequently also an efficient scattering process. (paper)

[en] Nanosecond plasmas in liquids play an important role in the field of decontamination, electrolysis or plasma medicine. The understanding of these very dynamic plasmas requires information about the temporal variation of species densities and temperatures. This is analyzed by monitoring nanosecond pulsed plasmas that are generated by high voltages (HVs) between 14 and 26 kV and pulse lengths of 10 ns applied to a tungsten tip with 50 μm diameter immersed in water. Ignition of the plasma causes the formation of a cavitation bubble that is monitored by shadowgraphy to measure the dynamic of the created bubble and the sound speed of the emitted acoustic waves surrounding this tungsten tip. The temporal evolution of the bubble size is compared with cavitation theory yielding good agreement for an initial bubble radius of 25 μm with an initial pressure of 5 × 10⁸ Pa at a temperature of 1200 K for a HV of 20 kV. This yields an initial energy in the range of a few 10⁻⁵ J that varies with the applied HV. The dissipated energy by the plasma drives the adiabatic expansion of water vapor inside the bubble from its initial supercritical state to a low pressure, low temperature state at maximum bubble expansion reaching values of 10³ Pa and 50 K, respectively. These predictions from cavitation theory are corroborated by optical emission spectroscopy. After igniting the nanosecond plasma, the electrical power oscillates in the feed line between HV pulser and plasma chamber with a ring down time of the order of 60 ns. These reflected pulses re-ignite a plasma inside the expanding bubble periodically. Broadband emission due to recombination and Bremsstrahlung becomes visible within the first 30 ns. At later times, line emission dominates. Stark broadening of the spectral lines of H_α (656 nm) and OI (777 nm) is evaluated to determine both the electron density and the electron temperature in these re-ignited plasmas. (paper)

[en] High power impulse magnetron sputtering (HiPIMS) discharges have become an important tool for the deposition of thin, hard coatings. Such discharges are operated at a very low working gas pressure in the order of 1 Pa. Therefore, elastic collisions between ions and other heavy particles are often calculated to occur with low frequency, using the hard sphere approximation. However, inside the magnetic trap region of the discharge, a very dense plasma is created and Coulomb collisions become the dominant collision process for ions. In this article, we show that Coulomb collisions are a necessary part of a complete description of ion movement in the magnetic trap region of HiPIMS. To this end, the velocity distribution function (VDF) of chromium and titanium ions is measured using high-resolution optical emission spectroscopy. The VDF of those ions is then described using a simple simulation which employs a direct simulation Monte Carlo scheme. The simulation describes the self-relaxation of the VDF that is initially a Thompson distribution as being created during the sputtering process. Measurement positions inside the discharge are matched to the simulation results choosing an appropriate relaxation time. In this fashion, excellent agreement between simulation and measurement is obtained. We find, that the distribution quickly becomes mostly Maxwellian with a temperature of 9 eV for titanium ions and 4.5 eV in the case of chromium ions. Only the high energy tail of the VDF retains the shape of the initial Thompson distribution. The observed high temperature is explained with an energy redistribution from the highly energetic Thompson distribution into an partly-thermalized Maxwell-like distribution. Finally, the temperature resulting from this energy redistribution is calculated using a simple analytical model which shows good agreement with the measurements. (paper)

[en] Nanosecond plasmas in liquids are an important method to trigger the water chemistry for electrolysis or for biomedical applications in plasma medicine. The understanding of these chemical processes relies on knowing the variation of the temperatures in these dynamic plasmas. This is analyzed by monitoring nanosecond pulsed plasmas that are generated by high voltages at 20 kV and pulse lengths of 15 ns applied to a tungsten tip with 50 μm diameter immersed in water. Plasma emission is analyzed by optical emission spectroscopy ranging from UV wavelengths of 250 nm to visible wavelengths of 850 nm at a high temporal resolution of 2 ns. The spectra are dominated by the black body continuum from the hot tungsten surface and line emissions from the hydrogen Balmer series. Typical temperatures from 6000 K up to 8000 K are reached for the tungsten surface corresponding to the boiling temperature of tungsten at varying tungsten vapor pressures. The analysis of the ignition process and the concurrent spectral features indicate that the plasma is initiated by field ionization of water molecules at the electrode surface. At the end of the pulse, field emission of electrons can occur. During the plasma pulse, it is postulated that the plasma contracts locally at the electrode surface forming a hot spot. This causes a characteristic contribution to the continuum emission at small wavelengths. (paper)

[en] Nanosecond plasmas in liquids can initiate chemical processes that are exploited in the fields of water treatment, electrolysis or biomedical applications. The understanding of these chemical processes relies on unraveling the dynamics of the variation of pressures, temperatures and species densities during the different stages of plasma ignition and plasma propagation as well as the conversion of the liquid into the plasma state and the gas phase. This is analyzed by monitoring the emission of nanosecond pulsed plasmas that are generated by high voltages of 20 kV and pulse lengths of 10 ns applied to a tungsten tip with 50 μm diameter immersed in water. The spectra are acquired with a temporal resolution of 2 ns and the emission pattern is modelled by a combination of black body radiation from the hot tungsten tip and the pronounced emission lines of the hydrogen Balmer series. The data indicate two contributions of the hydrogen line radiation that differ with respect to the degree of self-absorption. It is postulated that one contribution originates from a recombination region showing strong self absorption and one contribution from an ionization region showing very little self-absorption. The emission lines from the ionization region are evaluated assuming Stark broadening, that yielded electron densities up to 5 × 10²⁵ m⁻³. The electron density evolution follows the same trend as the temporal evolution of the voltage applied to the tungsten tip. The propagation mechanism of the plasma is similar to that of a positive streamer in the gas phase, although in the liquid phase field effects such as electron transport by tunneling should play an important role. (paper)

[en] The excitation and dissociation of CO₂ admixed to argon and helium atmospheric pressure radio frequency plasmas is analyzed. The absorbed plasma power is determined by voltage and current probe measurements and the excitation and dissociation of CO₂ and CO by transmission mode Fourier-transform infrared spectroscopy (FTIR). It is shown, that the vibrational temperatures of CO₂ and CO are significantly higher in an argon compared to a helium plasma. The rotational temperatures remain in both cases close to room temperature. The conversion efficiency, expressed as a critical plasma power to reach almost complete depletion, is four times higher in the argon case. This is explained by the lower threshold for the generation of energetic particles (electrons or metastables) in argon as the main reactive collision partner, promoting excitation and dissociation of CO₂, by the less efficient quenching of vibrational excited states of CO and CO₂ by argon compared to helium and by a possible contribution of more energetic electrons in an argon plasma compared to helium. (paper)

[en] The rotation of localised ionisation zones, i.e. spokes, in magnetron discharge are frequently observed. The spokes are investigated by measuring floating potential oscillations with 12 flat probes placed azimuthally around a planar circular magnetron. The 12-probe setup provides sufficient temporal and spatial resolution to observe the properties of various spokes, such as rotation direction, mode number and angular velocity. The spokes are investigated as a function of discharge current, ranging from 10 mA (current density 0.5 mA cm⁻²) to 140 A (7 A cm⁻²). In the range from 10 mA to 600 mA the plasma was sustained in DC mode, and in the range from 1 A to 140 A the plasma was pulsed in high-power impulse magnetron sputtering mode. The presence of spokes throughout the complete discharge current range indicates that the spokes are an intrinsic property of a magnetron sputtering plasma discharge. The spokes may disappear at discharge currents above 80 A for Cr, as the plasma becomes homogeneously distributed over the racetrack. Up to discharge currents of several amperes (the exact value depends on the target material), the spokes rotate in a retrograde $\mathbf{E}\times <!--\; ??\; -->\mathbf{B}$ direction with angular velocity in the range of 0.2–4 km s⁻¹. Beyond a discharge current of several amperes, the spokes rotate in a $\mathbf{E}\times <!--\; ??\; -->\mathbf{B}$ direction with angular velocity in the range of 5–15 km s⁻¹. The spoke rotation reversal is explained by a transition from Ar-dominated to metal-dominated sputtering that shifts the plasma emission zone closer to the target. The spoke itself corresponds to a region of high electron density and therefore to a hump in the electrical potential. The electric field around the spoke dominates the spoke rotation direction. At low power, the plasma is further away from the target and it is dominated by the electric field to the anode, thus retrograde $\mathbf{E}\times <!--\; ??\; -->\mathbf{B}$ rotation. At high power, the plasma is closer to the target and it is dominated by the electric field pointing to the target, thus $\mathbf{E}\times <!--\; ??\; -->\mathbf{B}$ rotation. (paper)