Hydrogenated and fluorinated amorphous silicon films (a‐Si:H,F) have been deposited in a parallel‐plate rf plasma reactor fed with SiF₄‐H₂ mixtures. The plasma phase characterization has been performed by optical emission spectroscopy for the analysis of the emitting species (SiF^*₃,SiF^*₂,SiF^*,H^*, and H^*₂), mass spectrometry for the analysis of stable species, and Langmuir electrical probes for the evaluation of electron density (n_e) and temperature (kT_e). The deposition rate (r_D) has been monitored by laser interferometer. The effect of the rf power, gas composition, total pressure, and dopant (B₂H₆, PH₃) addition on the plasma phase composition and on the film growth rate has been studied. The data have been discussed on the basis of a chemical model where the chemisorption of SiF₄ and SiF₂ and the subsequent interaction with H atoms are the determinant steps also from the kinetic point of view. It has been found that the rate equation r_D ∝ [H][SiF₂] is able to fit the experimental results.

Nanostructured polytetrafluoroethylene (PTFE)-like thin films can be deposited, in certain experimental conditions, by modulated discharges fed with tetrafluoroethylene (TFE). These coatings are characterized by a unique morphology consisting of highly twisted micron-long ribbons, which leads to an extremely high water repellency of the surface. In the present work, the diagnostics of the plasma phase is presented, coupled with that of the coating, in order to understand the film growth mechanism in different discharge regimes. When the duty cycle (DC) is increased in modulated C₂F₄ plasmas, the monomer depletion increases, too, and many recombination reactions take place at progressively higher rates, resulting in the formation of CF₄, C₂F₆, C₃F₆, C₃F₈, and C₄F₁₀; the formation of powders in the homogeneous phase, however, was never evidenced. The modulation of C₂F₄ plasmas strongly affects the morphology of the resulting coating, as revealed by atomic force microscopy (AFM), ranging from bumpy to ribbon-like structures. The latter, moreover, are found to be more PTFE-like with respect to the remaining part of the film. In the last part of the paper, a deposition mechanism is proposed, where low radical densities in the plasma and surface migration of the precursors are the keys for the growth of ribbon-like structures.