The metal–organic Cu(I) complex 1,3-diisopropyl-imidazolin-2-ylidene copper hexamethyl disilazide has been tested as a novel oxygen-free precursor for atomic layer deposition of Cu with molecular hydrogen. Being a strong Lewis base, the carbene stabilizes the metal centre to form a monomeric compound that can be vaporised and transported without visible degradation. A significant substrate dependence of the growth process not only with respect to the film material but also to the structure of the films was observed. On Pd surfaces continuous films are grown and no phase boundary can be observed between the Cu film and the Pd, while island growth is observed on Ru substrates, which as a consequence requires thicker films in order to achieve a fully coalesced layer. Island growth is also observed for ultra-thin (<10 nm) Pd layers on Si substrates. Possible explanations for the different growth modes observed are discussed