A method for selective deposition of self-assembled monolayers to the surface of a substrate for use as a diffusion barrier layer in interconnect structures is provided comprising the steps of depositing a first self-assembled monolayer to said surface, depositing a second self-assembled monolayer to the non-covered parts of said surface and subsequently heating said substrate to remove the first self-assembled monolayer. The method of selective deposition of self-assembled monolayers is applied for the use as diffusion barrier layers in a (dual) damascene structure for integrated circuits.