The vast biomedical potential of cold atmospheric pressure plasmas (CAPs) is governed by the formation of reactive species. These biologically active species are formed upon the interaction of CAPs with the surroundings. In biological milieu, water plays an essential role. The development of biomedical CAPs thus requires understanding of the sources of the reactive species in aqueous media exposed to the plasma. This is especially important in case of the COST RF plasma jet, which is developed as a reference microplasma system. In this work, we investigated the formation of the OH radicals, H atoms and HO in aqueous solutions exposed to the COST plasma jet. This was done by combining experimental and modelling approaches. The liquid phase species were analysed using UV-Vis spectroscopy and spin trapping with hydrogen isotopes and electron paramagnetic resonance (EPR) spectroscopy. The discrimination between the species formed from the liquid phase and the gas phase molecules was performed by EPR and H-NMR analyses of the liquid samples. The concentrations of the reactive species in the gas phase plasma were obtained using a zero-dimensional (0D) chemical kinetics computational model. A three-dimensional (3D) fluid dynamics model was developed to provide information on the induced humidity in the plasma effluent. The comparison of the experimentally obtained trends for the formation of the species as a function of the feed gas and effluent humidity with the modelling results suggest that all reactive species detected in our system are mostly formed in the gas phase plasma inside the COST jet, with minor amounts arising from the plasma effluent humidity.
A hybrid model, called the hybrid plasma equipment model, was used to study Ar/Cl2 inductively coupled plasmas used for the etching of Si. The effects of substrate bias, source power and gas pressure on the plasma characteristics and on the fluxes and energies of plasma species bombarding the substrate were observed. A comparison with experimentally measured etch rates was made to investigate how the etch process is influenced and which plasma species mainly account for the etch process. First, the general plasma characteristics are investigated at the following operating conditions: 10% Ar 90% Cl2 gas mixture, 5 mTorr total gas pressure, 100 sccm gas flow rate, 250 W source power, −200 V dc bias at the substrate electrode and an operating frequency of 13.56 MHz applied to the coil and to the substrate electrode. Subsequently, the pressure is varied from 5 to 80 mTorr, the substrate bias from −100 to −300 V and the source power from 250 to 1000 W. Increasing the total gas pressure results in a decrease of the etch rate and a less anisotropic flux to the substrate due to more collisions of the ions in the sheath. Increasing the substrate bias has an effect on the energy of the ions bombarding the substrate and to a lesser extent on the magnitude of the ion flux. When source power is increased, it was found that, not the energy, but the magnitude of the ion flux is increased. The etch rate was more influenced by a variation of the substrate bias than by a variation of the source power, at these operating conditions. These results suggest that the etch process is mainly affected by the energy of the ions bombarding the substrate and the magnitude of the ion flux, and to a lesser extent by the magnitude of the radical flux.
Cyrogenic etching of silicon is envisaged to enable better control over plasma processing in the microelectronics industry, albeit little is known about the fundamental differences compared to room temperature. We here present molecular dynamics simulations carried out to obtain sticking probabilities, thermal desorption rates, surface diffusion speeds and sputter yields of F, F 2 , Si, SiF, SiF 2 , SiF 3 , SiF 4 and the corresponding ions on Si(100) and on SiF 1-3 surfaces, both at cryogenic and near-room temperature. The different surface behavior during conventional etching and cryoetching is discussed. F 2 is found to be relatively reactive compared to other species like SiF 0-3 . Thermal desorption occurs at a significantly lower rate at cryogenic conditions, which results in an accumulation of physisorbed species. Moreover, ion incorporation is often observed for ions with energies of 30-400 eV, which results in a relatively low net sputter yield. The obtained results suggest that the actual etching of Si, under both cryogenic and near-room temperature conditions, is based on the complete conversion of the Si surface to physisorbed SiF 4 , followed by subsequent sputtering of these molecules, instead of direct sputtering of the SiF 0-3 surface.
In this paper, a simulation method is described to predict the etching behaviour of Cl2/O2/Ar inductively coupled plasmas on a Si substrate, as used in shallow trench isolation for the production of electronic devices. The hybrid plasma equipment model (HPEM) developed by Kushner et al is applied to calculate the plasma characteristics in the reactor chamber and two additional Monte Carlo simulations are performed to predict the fluxes, angles and energy of the plasma species bombarding the Si substrate, as well as the resulting surface processes such as etching and deposition. The simulations are performed for a wide variety of operating conditions such as gas composition, chamber pressure, power deposition and substrate bias. It is predicted by the simulations that when the fraction of oxygen in the gas mixture is too high, the oxidation of the Si substrate is superior to the etching of Si by chlorine species, resulting in an etch rate close to zero as is also observed in the experiments.
In this review, we discuss the progress of emerging dry processes for nanoscale fabrication. Experts in the fields of plasma processing have contributed to addressing the increasingly challenging demands in achieving atomic-level control of material selectivity and physicochemical reactions involving ion bombardment. The discussion encompasses major challenges shared across the plasma science and technology community. Focus is placed on advances in the development of fabrication technologies for emerging materials, especially metallic and intermetallic compounds and multiferroic, and two-dimensional (2D) materials, as well as state-of-the-art techniques used in nanoscale semiconductor manufacturing with a brief summary of future challenges.
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