Characterization of low pressure chemical vapor deposited polymeric fluorinated carbon m (C:FX)n thin films with low dielectric constant

Thermal chemical vapor deposition of fluorinated carbon thin films in the polymeric form is described by hot filament decomposition of the gaseous C₃F₆O precursor. Decomposition at filament temperatures, ≤450 °C produces films in the ordered (CF₂)_2n polymeric chain structure as in a tetrafluoroethylene polymer. A composite of (CF₂)_2n chains structure and crosslinked m(C:F_x)_n phases are formed in films deposited at filament temperature ≥600 °C. Polymerization of :CF₂ radicals results in (CF₂)_2n chain structure and the crosslinked phase emerges from a separate process involving reaction among the CF₃, CFO and CF₃CO radicals and including CF₂. Substrate temperature affects both the C-to-F bonding configuration and the relative ratio of the composite phases. Dominant C–CF bonding structure in the low (<-5 °C) substrate temperature films is thermally less stable compared to the C–F structure, which dominates the crosslinked structure in films deposited at high (∼70 °C) substrate temperatures. Dielectric properties of the composite films are studied using the electrical equivalent model and a correlation with the C-to-F bond structure is established. High polymeric (CF₂)_2n phase determines the electrical impedance and the dielectric constant of the film, and the crosslinked phase imparts structural stability. PACS 81.15.Gh; 73.61.Ph; 77.84.Jd; 79.60.Fr