Alkoxysilane having various functional headgroups (amino and mercapto) and morphologies was deposited by supercritical CO(2) onto a porous dielectric material to replace the metallic barrier used in semiconductor devices. These organic layers were successfully coated with Cu. The morphologies of the stacks were investigated by X-ray and neutron reflectometry and atomic force microscopy. Whereas PVD Cu deposition is not adapted to silanized dielectric material with mercapto and aminopropyltrimethoxysilane but acceptable with aminoethylaminopropyltrimethoxysilane, the MOCVD process is more interesting. XRR and NR data clearly indicate that silane layers remain intact after copper deposition and, depending on the Cu immobilization capability of the chemical function of the silane and its orientation into the layer, the Cu film morphologies are different. Dense, thin films having small Cu grains were obtained with an aminoethylaminopropyltrimethoxysilane layer, and thick films having a low density and large Cu grains were obtained with an aminopropyltrimethoxysilane layer. Nucleation and growth mechanisms are discussed.