ISBN 9783868534672

978-3-86853-467-2, Reihe Physik

Jakob Philipp Barz
Particle dynamics simulation and diagnostics of the PECVD processes in fluorocarbon rf discharges

203 Seiten, Dissertation Universität Stuttgart (2010), Softcover, A5

Zusammenfassung / Abstract

The present work deals with the investigation of fluorocarbon plasmas by different experimental methods and supporting numerical analysis of the plasma with an emphasis on plasma-chemical interactions. Several insights could be gained from the combined experimental and numerical approaches, especially concerning the conclusiveness of the results and previous observations from the literature. Plasma diagnostics were performed with non-invasive methods, such as UI probe measurements, microwave interferometry, laser-induced fluorescence, UV absorption measurements, and mass spectrometry.

The complementary numerical simulations accounted for the electron-neutral interactions, discharge dynamics, and chemical reactions. From the excitation and ionization cross sections of argon as well as the dissociation, ionization, and attachment cross sections of trifluoromethane, the field-dependence of transport parameters were obtained. These transport parameters were used as input data for fluid-modeling of the discharge. For the plasma dynamics simulation, the Boltzmann-equation was solved numerically for transport of mass, momentum, and energy in a time-dependent two-term approach. The so-obtained electron density and the power-voltage characteristics were compared to measurements with microwave interferometry and the UI probe, respectively.

An overall good agreement of the numerical and measured electron densities was obtained over a large variation range of plasma power, gas composition, and pressure. The power-voltage characteristics showed a good agreement between numerical results and data obtained right after ignition of plasma. It was further found that the measured data showed time-dependent developments from which strong deviations resulted. The time scales of changes were typically in the range of milliseconds to seconds after ignition. It was concluded that compositional changes in the gas phase were the reason. The high abundance of oligomers as well as small molecules like HF in the gas phase on one hand, and the loss of molecules by polymer deposition on the other hand affect the charge carrier mobilities and the ionic composition, such result in the changes observed. Furthermore, from this investigation, the major fragmentation processes were identified.

For the investigation of the reaction-diffusion processes, investigations by laser-induced fluorescence were carried out. In order to obtain best resolution along the axial direction of the plasma reactor, the conventional crossed-beam technique was modified. Such, a resolution of up to 60 micrometers became possible. Thus, highly-resolved axial densities of two plasma abundant intermediates, fluoromethylidine and difluorocarbene, were obtained. For the analysis of the gas phase kinetics, a numerical chemical-diffusion model was set up. To complete the analysis of the plasma dynamics, the deposition of plasma polymer onto substrates was examined. The deposition rate was determined, and changes in the surface chemistry at the transition form uncovered substrates to closed films were revealed. For the identification of the deposition precursors, results from the chemical-diffusion model were adopted for the analysis.

The oligomer molecules, which are produced at high results according to the simulation, were shown to correlate well with the polymer deposition rate. It was found by electron spin resonance (ESR) that chemical reactions took place within the deposited polymer films. The restructuring of the polymer by these reactions resulted in highly cross-linked films according to x-ray photoelectron spectroscopy (XPS). Further, it was found that the amount of fluorine in the polymer was lower than could be expected from the oligomers formed according to the chemical model. Such, it was suggested that ejection of fluorine containing species was taking place especially during the plasma glow, promoted by electron and ion bombardment, and radiation. Moreover, the ejection of fluorine containing species was tentatively ascribed to the production of difluorocarbene at the surface of the plasma chamber as observed by LIF.

Concluding, radical and metastable fluxes from the electrodes, combined with isotropic gas phase reactions, determine the density profiles of several species from trifluoromethane plasmas. They strongly feed back the plasma chemistry, which itself feeds back the plasma particle dynamics. According to models, the deposition occurs via formation of oligomers in the gas phase, which deposit on the surface either as neutrals or ions, and become crosslinked by subsequent reactions. The origin of the particle fluxes at the electrodes is not yet identified, but indications were found for the chemical cross-linking processes being the cause.