Role of the Plasma Activation Degree on Densification of Organosilicon Films

The possibility of controlling the density of organosilicon films was investigated by tuning the plasma activation degree without providing extra energy to the structure, as usually reported in the literature. For this purpose, thin films were deposited in plasmas fed with hexamethyldisiloxane/Ar mixtures at a total pressure of 9.5 Pa. The power of the radiofrequency excitation signal, P, ranged from 50 to 300 W to alter the average energy of the plasma species while the electrical configuration was chosen to avoid direct ion bombardment of the growing films. In this way, it was possible to evaluate the effect of P on the film properties. Thickness and deposition rate were derived from profilometry data. X-ray energy dispersive and infrared spectroscopies were, respectively, applied to analyze the chemical composition and molecular structure of the layers. Surface topography and roughness were determined by atomic force microscopy while nanoindentation was used to evaluate the mechanical properties of the films. From electrochemical impedance spectroscopy the total resistance to the flow of electrolyte species was derived. The main alteration observed in the structure with changing P is related to the proportion of the methyl functional which remains connected to the Si backbone. Chain crosslinking and film density are affected by this structural modification induced by homogeneous and heterogeneous plasma reactions. The density increase resulted in a film with hardness comparable to that of the silica and more resistant to the permeation of oxidative species, but preserving the organosilicon nature of the structure.