Dirk Ellerweg

Characterization of the effluent of a He/O2 microscale atmospheric pressure plasma jet by quantitative molecular beam mass spectrometry

The effluent of a microscale atmospheric pressure plasma jet (μ-APPJ) operated in helium with a small admixture of molecular oxygen (<1.6%) has been analyzed by means of two independent diagnostics, quantitative molecular beam mass spectrometry (MBMS) and two-photon absorption laser-induced fluorescence spectroscopy (TALIF). The atomic oxygen density, the ozone density and the depletion of molecular oxygen have been measured by MBMS and the atomic oxygen density has been validated by TALIF. Absolute atomic oxygen densities in the effluent up to 4.7×1015 cm-3 could be measured with a very good agreement between both diagnostics. In addition, ozone densities in the effluent up to 1.4×1015 cm-3 and an O2 depletion up to 10% could be measured by MBMS. The atomic oxygen density shows a maximum value at an O2 admixture of 0.6%, whereas the ozone density continues to increase toward higher O2 admixtures. With increasing distance from the jet, the atomic oxygen density decreases but is still detectable at a distance of 30 mm. The ozone density increases with distance, saturating at a distance of 40 mm. By applying higher powers to the μ-APPJ, the atomic oxygen density increases linearly whereas the ozone density exhibits a maximum.

Quadrupole mass spectrometry of reactive plasmas

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.

Unexpected O and O3 production in the effluent of He/O2 microplasma jets emanating into ambient air

Microplasma jets are commonly used to treat samples in ambient air. The effect of admixing air into the effluent may severely affect the composition of the emerging species. Here, the effluent of a He/O2 microplasma jet has been analyzed in a helium and in an air atmosphere by molecular beam mass spectrometry. First, the composition of the effluent in air was recorded as a function of the distance to determine how fast air admixes into the effluent. Then, the spatial distribution of atomic oxygen and ozone in the effluent was recorded in ambient air and compared with measurements in a helium atmosphere. Additionally, a fluid model of the gas flow with reaction kinetics of reactive oxygen species in the effluent was constructed. In ambient air, the O density declines only slightly faster with distance compared with a helium atmosphere. In contrast, the O3 density in ambient air increases significantly faster with distance compared with a helium atmosphere. This unexpected behavior cannot be explained by simple recombination reactions of O atoms with O2 molecules. A reaction scheme involving the reaction of plasma-produced excited species of unknown identity with ground state O2 molecules is proposed as a possible explanation for these observations.

Surface reactions as carbon removal mechanism in deposition of silicon dioxide films at atmospheric pressure

The deposition of thin SiOxCyHz or SiOxHy films by means of an atmospheric pressure microplasma jet with helium/hexamethyldisiloxane (HMDSO)/O2 mixtures and the surface reactions involving oxygen have been studied. It is shown, that the carbon content in the film can be controlled by choosing the right O2/HMDSO ratio in the gas mixture. The microplasma jet geometry and localization of the deposition at a spot of few square millimeters allows studying the role of oxygen in the deposition process. This is done by alternating application of He/HMDSO plasma and He/O2 plasma to the same deposition area, here achieved by a treatment of a rotating substrate by two jets with above mentioned gas mixtures. It is shown that carbon-free SiOxHy film can be deposited in this way and that surface reaction with oxygen is the main loss mechanism of carbon from the film.

Molecular beam sampling system with very high beam-to-background ratio: The rotating skimmer concept

A novel method of reducing the background pressure in a vacuum system used for sampling a molecular beam from a high pressure region is presented. A triple differential pumping stage is constructed with a chopper with rotating skimmer within the first pumping stage, which serves effectively as a valve separating periodically the vacuum system from the ambient environment. The mass spectrometry measurement of the species in the molecular beam show an excellent beam-to-background ratio of 14 and a detection limit below 1 ppm. The potential of this method for detection of low density reactive species in atmospheric pressure plasmas is demonstrated for the detection of oxygen atoms generated in an atmospheric pressure microplasma source.

Mass spectrometry of atmospheric pressure plasmas

Atmospheric pressure non-equilibrium plasmas (APPs) are effective source of radicals, metastables and a variety of ions and photons, ranging into the vacuum UV spectral region. A detailed study of these species is important to understand and tune desired effects during the interaction of APPs with solid or liquid materials in industrial or medical applications. In this contribution, the opportunities and challenges of mass spectrometry for detection of neutrals and ions from APPs, fundamental physical phenomena related to the sampling process and their impact on the measured densities of neutrals and fluxes of ions, will be discussed. It is shown that the measurement of stable neutrals and radicals requires a proper experimental design to reduce the beam-to-background ratio, to have little beam distortion during expansion into vacuum and to carefully set the electron energy in the ionizer to avoid radical formation through dissociative ionization. The measured ion composition depends sensitively on the degree of impurities present in the feed gas as well as on the setting of the ion optics used for extraction of ions from the expanding neutral-ion mixture. The determination of the ion energy is presented as a method to show that the analyzed ions are originating from the atmospheric pressure plasma.

Mass spectrometry of positive ions and neutral species in the effluent of an atmospheric pressure plasma with hexamethyldisiloxane and oxygen

The effluent of a non-equilibrium atmospheric pressure plasma jet in He with admixture of hexamethyldisiloxane (HMDSO) and O2 has been investigated by means of molecular beam mass spectrometry. Positive ions and neutral plasma chemistry products have been detected and their possible role in the deposition of good-quality SiO2 films is discussed. Positive ion spectra reveal the presence of protonated water clusters and H+ : HMDSO and H3O+ : HMDSO ions. These ions are most probably produced by photoionization. This is corroborated by optical emission spectroscopy data obtained in the wavelength range of 50–300 nm, where helium excimer continuum emission centred around 84 nm has been observed. No ion driven polymerization products of HMDSO have been detected. Measurements of neutral species have allowed the quantification of the HMDSO depletion and absolute densities of trimethylsilanol and pentamethyldisiloxane. Two neutral polymerization products have been observed as well. The results indicate that the Si–O bond of HMDSO is preferentially broken. Additionally, the mass balance of plasma chemistry products is discussed.

The influence of the ionizer geometry on the absolute density calibration of reactive neutral species in a molecular beam mass spectrometry

Molecular beam mass spectrometry is a powerful diagnostic technique, which can be used for the measurement of absolute number densities of reactive species in non-equilibrium reactive plasmas. However, the calibration of absolute number densities is susceptible to systematic errors. Critical issues are the proper design of the sampling system and the correction of the background signal. Here we discuss the effect of reflections of particles from the molecular beam in an ionizer, formation of additional background particle density in the ionizer, and its effect on the density calibration of reactive particle densities. A Monte Carlo simulation of particle trajectories in the ionizer is used to estimate the detection probability of a beam particle after the collision with the ionizer wall. The simulation shows that as much as two-third of the signal can be due to scattered particles in the commercially available mass spectrometers. This effect leads to systematic underestimation of densities of reactive particles, which are reactive at the surface and, therefore, do not have any background density. A simple change in the ionizer geometry is suggested, which can significantly reduce this problem.