Structural and bonding patterns arising from the incorporation of fluorine atoms in a graphene-like network relevant to the deposition of carbon fluoride (CFx) films were addressed by first-principles calculations. We find that large N-member (N = 8-12) rings, defects by sheet branching, and defects associated with bond rotation pertain to CFx. The cohesive energy gains associated with these patterns are similar to 0.2-0.4 eV/at., which is similar to those for a wide range of defects in other C-based nanostructured solids. Fullerene-like CFx is predicted for F concentrations below similar to 10 at.%, while CFx compounds with higher F content are predominantly amorphous or polymeric. (C) 2011 Elsevier B. V. All rights reserved.