Disclosed are methods of depositing films of material on semiconductor substrates employing the use of a secondary purge. The methods may include flowing a film precursor into a processing chamber and adsorbing the film precursor onto a substrate in the processing chamber such that the precursor forms an adsorption-limited layer on the substrate. The methods may further include removing at least some unadsorbed film precursor from the volume surrounding the adsorbed precursor by purging the processing chamber with a primary purge gas, and thereafter reacting adsorbed film precursor while a secondary purge gas is flowed into the processing chamber, resulting in the formation of a film layer on the substrate. The secondary purge gas may include a chemical species having an ionization energy and/or a disassociation energy equal to or greater than that of O2. Also disclosed are apparatuses which implement the foregoing processes.