Cap layers for Cu interconnects in ultra-large-scale integrated devices (ULSIs), with a low dielectric constant (k-value) and strong barrier properties against Cu and moisture diffusion, are required for the future further scaling of ULSIs. There is a trade-off, however, between reducing the k-value and maintaining strong barrier properties. Using quantum mechanical simulations and other theoretical computations, we have designed ideal dielectrics: SiCH films with Si–C2H4–Si networks. Such films were estimated to have low porosity and low k; thus they are the key to realizing a cap layer with a low k and strong barrier properties against diffusion. For fabricating these ideal SiCH films, we designed four novel precursors: isobutyl trimethylsilane, diisobutyl dimethylsilane, 1, 1-divinylsilacyclopentane and 5-silaspiro [4,4] noname, based on quantum chemical calculations, because such fabrication is difficult by controlling only the process conditions in plasma-enhanced chemical vapor deposition (PECVD) using conventional precursors. We demonstrated that SiCH films prepared using these newly designed precursors had large amounts of Si–C2H4–Si networks and strong barrier properties. The pore structure of these films was then analyzed by positron annihilation spectroscopy, revealing that these SiCH films actually had low porosity, as we designed. These results validate our material and precursor design concepts for developing a PECVD process capable of fabricating a low-k cap layer.