The molecular etcher carbonyl fluoride (COF2) or any of its variants, are provided for, according to the present invention, to increase the efficiency of etching and/or cleaning and/or removal of materials such as the unwanted film and/or deposits on the chamber walls and other components in a process chamber or substrate (collectively referred to herein as “materials”). The methods of the present invention involve igniting and sustaining a plasma, whether it is a remote or in-situ plasma, by stepwise addition of additives, such as but not limited to, a saturated, unsaturated or partially unsaturated perfluorocarbon compound (PFC) having the general formula (CyFz) and/or an oxide of carbon (COx) to a nitrogen trifluoride (NF3) plasma into a chemical deposition chamber (CVD) chamber, thereby generating COF2. The NF3 may be excited in a plasma inside the CVD chamber or in a remote plasma region upstream from the CVD chamber. The additive(s) may be introduced upstream or downstream of the remote plasma such that both NF3 and the additive(s) (and any plasma-generated effluents) are present in the CVD chamber during cleaning.