Embodiments of the present invention provide systems and methods for depositing materials on either side of a freestanding film using selectively thermally-assisted chemical vapor deposition (STA-CVD), and structures formed using same. A freestanding film, which is suspended over a cavity defined in a substrate, is exposed to a fluidic CVD precursor that reacts to form a solid material when exposed to heat. The freestanding film is then selectively heated in the presence of the precursor. The CVD precursor preferentially deposits on the surface(s) of the freestanding film.