Abstract: Disclosed is a SAM forming composition comprising a SAM monomer or precursor having a backbone with a surface reactive group, wherein the backbone contains no Si—C bonds and is selected from the group consisting of a Si—C bond-free polysilane and a trisilylamine. The surface reactive groups are disclosed for the surface to be covered being a dielectric surface and a metal surface, respectively. A process of forming a SAM on a surface and a process of forming a film on the SAM are also disclosed.