A new materials system of a single layered Co(W) barrier/liner coupled with a Cu(Mn) alloy seed was investigated. Atom probe tomography visualized the sub-nanoscale structure of Cu(Mn)/Co(W) system, and thereby revealed Cu diffusion behavior of Co(W). Grain boundaries of Co were found to be the diffusion path, and successfully stuffed by W. Mn in Cu(Mn) also segregated to stuff the grain boundaries of Co. Combination of these two additives enabled high barrier property against Cu diffusion of Cu(Mn)/Co(W). Foreseeing tiny and high-aspect-ratio Cu interconnect features, Cu(Mn)/Co(W) was fabricated by ALD/CVD processes. To maximize the performance, minor impurities of the film incorporated from the ligand of the precursors were controlled by precursor selection. Thin, conformal, and smooth films were finally demonstrated onto a trench substrate.