A fivefold increase in adhesion energy is observed for poly(acrylic acid) (PAA) modified Cu/TaN interfaces in which the thin copper films are deposited by the hydrogen assisted reduction of bis(2,2,7-trimethyloctane-3,5-dionato) copper in supercritical carbon dioxide. The PAA adhesion layer is sacrificial at the reaction conditions used, and X-ray photoelectron spectroscopy has shown that the Cu/TaN interface is free of contamination following deposition. The resulting average interfacial adhesion energy is just above , which meets adhesion requirements for integration in Cu interconnects. The adhesion measurements are performed with a custom built four-point bend fracture mechanics testing system. Comparison of the copper film thickness to the measured adhesion energy indicated that there is no effect on the adhesion energy as the film thickness changes.