A new, additive, substrate metallization process, useful for high resolution lithography and microelectronic circuit fabrication has been developed. The process, which involves surface modification with a self-assembled monolayer (SAM) film, selective binding of a catalytic Pd colloid, and electroless (EL) metal deposition, was used to deposit EL Ni on p-type (100) silicon substrates with a native oxide layer. The deposits were characterized by current-potential (I-V) and capacitance-potential (C-V) measurements. and were compared to evaporatively deposited Ni films. Schottky barrier heights for both the EL and evaporated Wi contacts ranged between 0.6 to 0.7 eV; similar to 0.1 to 0.2 eV higher than the typical value for Wi on atomically clean p-type silicon, as expected for contacts separated from the substrate by a thin insulating layer. The similarity of the EL and evaporated Ni barrier heights indicates that the buried organic SAM film and the Pd catalyst did not significantly alter the interfacial electrical characteristics. Heating the EL Ni deposits to over 300 degrees C reduced the Schottky barrier height and increased the leakage current, although less so than on the evaporated contacts.