Embodiments of the invention provide processes for depositing a cobalt layer on a barrier layer and subsequently depositing a conductive material, such as copper or a copper alloy, thereon. In one embodiment, a method for depositing materials on a substrate surface is provided which includes forming a barrier layer on a substrate, exposing the substrate to dicobalt hexacarbonyl butylacetylene (CCTBA) and hydrogen to form a cobalt layer on the barrier layer during a vapor deposition process (e.g., CVD or ALD), and depositing a conductive material over the cobalt layer. In some examples, the barrier layer and/or the cobalt layer may be exposed to a gas or a reagent during a treatment process, such as a thermal process, an in situ plasma process, or a remote plasma process.