The dependence of early stage of dimethylaluminum hydride (DMAH)-sourced aluminum chemical vapor deposition on underlayer material was investigated. Identical process conditions were used to deposit the aluminum on TiN, TaN and Ti-W surfaces, Surface coverage and particle densities of aluminum deposited on TiN were much greater than those deposited on Ti-W or TaN. Work function measurements performed on the three metal surfaces suggest that the difference in nucleation rate on TiN compared to TaN and Ti-W is due its increased ability to donate electrons to the DMAH decomposition process.