Inorganic-organic interfaces are playing a key role in a number of emerging technologies. For instance, formation of a robust interface between organic and inorganic materials will play an important role in the successful fabrication of ?molecular electronic? devices. Self-assembly has been successfully used to make the so-called ?bottom contact?. The techniques for ?top contact? formation are still not very well developed. Physical vapor deposition of the top contact metal is the most common approach but it has the disadvantages that it causes penetration and disruption of the organic layer. An alternative strategy has been employed here, where a transition metal coordination complex has been used as the interface initiator. The formation of an interface between tetrakisdimethyl(amido)titanium, Ti[N(CH3)2]4, and conjugated oligo(phenylene-ethynylene) self-assembled monolayers (SAMs) possessing iso-propylamine terminal functional groups on polycrystalline gold was studied. Extent of reaction and stoichiometry at the interface has also been investigated in this study. In the ever evolving field of semiconductor manufacturing, organic materials are becoming increasingly important. Copper is now the choice for metallization, and there is a drive to incorporate carbon-containing, possibly purely organic, and/or porous low dielectric constant (?) interlayer dielectrics to reduce the capacitive cross talk. The deposition of barrier layers between the Cu and the low-? materials is challenging, particularly for carbon-containing, porous dielectrics. Self-assembled monolayers have been utilized to modify dielectric surfaces in order to activate them for the deposition of a smooth and conformal diffusion barrier. More specifically, the atomic layer deposition (ALD) of titanium nitride (TiN) employing molecular beams of Ti[N(CH3)2]4, and ammonia, NH3 has been investigated. Deposition was achieved on silane SAMs on SiO2 possessing different terminations and chain lengths. Nucleation and growth stages were studied by making use of a variety of metrology and surface analysis techniques, namely: ellipsometry, X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, atomic force microscopy, and scanning transmission electron microscopy. The nature of the interactions between the SAM terminal group and Ti[N(CH3)2]4 was pivotal in determining the growth pattern. The growth behavior was also investigated on hyperbranched polymeric films on SiO2 as well as porous low ? substrates modified using these polymeric films.