Methods are provided for depositing an oxygen-doped dielectric layer. The oxygen-doped dielectric layer may be used for a barrier layer or a hardmask. In one aspect, a method is provided for processing a substrate including positioning the substrate in a processing chamber, introducing a processing gas comprising an oxygen-containing organosilicon compound, carbon dioxide, or combinations thereof, and an oxygen-free organosilicon compound to the processing chamber, and reacting the processing gas to deposit an oxygen-doped dielectric material on the substrate, wherein the dielectric material has an oxygen content of about 15 atomic percent or less. The oxygen-doped dielectric material may be used as a barrier layer in damascene or dual damascene applications.