Annealing alters the stability, structure, and morphology of fluorocarbon films grown from hot filament chemical vapor deposition (HFCVD) using hexafluoropropylene oxide (HFPO) precursor. The composition of these films is greater than 97% CF2. The as-deposited film in this study contains extraneous hydroxyl (OH) and carbonyl/carboxyl (CO/COO) groups, as revealed by Fourier transform infrared (FTIR) spectroscopy. Such groups al a found to be thermally labile and lead to two Film decomposition regimes, centered at 150 and 300 degreesC. This: is similar to the two decomposition onsets at 150-250 and 300 degreesC observed in irradiated bull; PTFE, which are attributed to the loss of peroxy radicals and COOH groups, respectively. A postdeposition 1 h 400 degreesC in situ vacuum anneal reduced the OH and CO/COO groups in the HFCVD film to below FTIR detection limits. This postanneal film is found to be stable up to 400 degreesC with no evidence of structural changes. The surface morphology of the film quenched from the 1 h 400 degreesC in situ vacuum anneal, as imaged by optical microscopy (OM), resembles that of the as-deposited film, showing no discernible surface features. However, for a film quenched from the 1 h 325 degreesC in situ vacuum anneal, significant crystalline spherulites of up to similar to1 mm in diameter are observed through OM. This is attributed to favorable crystallization in the proximity of the melting temperature of bulk PTFE. Intensity differences in FTIR absorption peaks in this: film, compared to the other films, also support the morphological differences seen.