Film stacks of a-SiC:H and molecularly templated nanoporous silica thin films have been prepared, and alkylation of pore surfaces of the nanoporous silica layer by the a-SiC:H layer was studied. The a-SiC:H thin films were deposited by high-density plasma chemical vapor deposition (HDP-CVD) using trimethylsilane (3MS) as the precursor. Carbon is found to uniformly distribute in the thin nanoporous silica film, and the carbon content in the nanoporous film decreases with increasing the a-SiC:H deposition temperature. We used the modified Sanderson formalism to estimate the corresponding Si(2p) and C(1s) electron energies in x-ray photoelectron spectra (XPS) for possible terminal species on pore surfaces in the nanoporous silica layer. According to the XPS analysis and thermal desorption mass spectroscopy, the terminal species are probably in the chemical form of alkoxyl structures. The alkoxyl terminal groups introduced into the nanoporous silica thin film are believed to stem from hydrocarbons trapped in microvoids in the a-SiC:H film, which are formed during the HDP-CVD deposition. The terminal alkoxyl groups in the nanoporous silica layer can greatly enhance the hydrophobicity of the nanoporous silica dielectric, and hence improve the dielectric property of the film stack of a-SiC:H/nanoporous silica. An effective dielectric constant smaller than 1.7 can be obtained for the film stacks. © 2004 American Vacuum Society.