A high-aspect ratio, small gap structure that provides a sample surface region without direct ion bombardment has been used to study surface chemistry aspects of fluorocarbon (FC) film deposition and to simulate FC film deposition on trench sidewalls during plasma-based pattern transfer. As on the sidewalls of microscopic trenches being etched, thin FC layers form by arrival of reactive neutrals on the shadowed surface portions of the small gap structure. The deposition rates, composition, and chemical bonding of FC films formed in the small gap structure were determined by ellipsometry and x-ray photoemission spectroscopy as a function of process conditions for C4F8/Ar and CF4/H-2 discharges produced in a dual frequency (40.68/4 MHz) capacitively coupled plasma reactor. Actual trench features were also produced using photoresist patterned organosilicate films for the same plasma processes. Scanning electron microscopy of the trenches shows a characteristic sidewall slope angle for different process conditions. We find that plasma process conditions producing lower FC film deposition rates on the shielded surface of the gap structure yield more vertical trench sidewalls. This relationship confirms the relevance of the small gap structure approach to the examination of trench sidewall chemistry. Since the present approach produces macroscopic samples of gap-deposited FC films, it enables direct surface chemical characterization of a material that is analogous to sidewall deposited films and allows to avoid the difficulties connected with direct measurements of microscopic samples. The lack of ion bombardment for the shielded deposition increases the retention of the chemical structure of the FC film precursors for the deposited films, which promises to be useful for obtaining mechanistic insights on film precursors. (C) 2008 American Vacuum Society.