A technique of metallorganic chemical vapor deposition (MOCVD) of copper thin films on TaN/Si substrates using hexafluoroacetylacetonate-copper(I)-1,5-cyclo-octadine, (hfac)Cu-I(COD), as the precursor was investigated in this study. Due to the lower grain density and larger Cu grain size from Cu-I complex used in the traditional Cu-MOCVD process, we proposed an approach of electroenhanced Cu-MOCVD by supplying a direct current on the TaN/Si substrates. Our experimental results revealed that high-quality Cu films deposited by electroenhanced MOCVD not only reduced the Cu incubation time but also significantly increased the Cu grain density and reduced the Cu grain size. This electroenhanced Cu-MOCVD process was found to be successful in forming smooth and continuous thin copper films as seed layers for electroplating. (c) 2007 The Electrochemical Society.