Ellipsometric Porosimetry for the Microstructure Characterization of Plasma-Deposited SiO2-Like Films

SiO2 layers have been deposited from Ar/O2/hexamethyldisiloxane mixtures in a remote expanding thermal plasma setup enabling a good control of both the ion flux (by changing the deposition chemistry and the arc plasma parameters) as well as the ion energy. This latter is achieved by an additional rf substrate biasing or a tailored ion biasing technique, i.e. a low frequency pulse-shaped bias. The role of the ion energy and ion-to-growth flux ratio on the film microstructure and densification at low substrate temperature (100ºC) has been investigated by means of ellipsometric porosimetry. This technique monitors the refractive index change due to the adsorption (and desorption) of ethanol vapors in the volume of macro-meso-micro pores in the SiO2 layer. From the analysis of the adsorption isotherm and the presence of hysteresis during the desorption step as a function of the equilibrium partial pressure, the open porosity in the layer can be determined. It is found that both biasing techniques lead to densification of the deposited layer, which experiences a transition from micro-/ mesoporosity to microporosity and eventually non-porosity, as function of the increasing ion energy. Although both biasing techniques lead to a comparable critical ion energy value per deposited SiO2 unit (about 100 eV), the ion-to-growth flux ratio and ion energy are not found to be interchangeable parameters. In fact, in the case of the rf bias, the meso- and large micropores are first affected leading to a quantitative decrease of porosity, i.e. from 11% to 3% at an ion energy less than 20 eV. A further increase in ion energy eventually reduces the presence of smaller micropores leading to non porous films at energy of 45 eV. When the pulse-shaped biasing technique is adopted, the micro- and mesopores are simultaneously affected over the whole range of available ion energy, leading to a non porous layer only at very high energy values, i.e. 240 eV. This difference is attributed to the increasing ion-to-growth flux ratio accompanying the rf biasing, as a consequence of the rf plasma generation in front of the substrate.