The early transition metals Ruthenium (Ru) and Cobalt (Co) are of high interest as alternative materials for replacing Cu in next generation interconnects. Plasma-enhanced atomic layer deposition (PE-ALD) is used to deposit metal thin films in high-aspect ratio structures of vias and trenches in nanoelectronic devices. At the initial stages, the surface reactions between metal precursors and substrate and corresponding chemistries are vital to understand the reaction mechanism and deposition process. But, the reaction mechanism in atomic scale is not yet understood. The reported incubation period and steady growth-per-cycle vary from report to report in the literature. In this study, we investigated the reactions between the precursors RuCp2/CoCp2 and substrate H:Si(100) to reveal the reaction mechanism in atomic scale at the initial stages of metal deposition. We investigated the chemistry and plausible Cp ligand elimination mechanism on various substrates. These include (1) bare Si(100), (2) H:Si(100), and (3) NHx-terminated Si(100) substrates. For the elimination of Cp ligands, two plausible mechanisms are proposed: (1) CpH formation and desorption via H transfer mechanism on H:Si(100) and NHx-terminated Si(100) surfaces, and (2) mechanism of metal-carbon bond breaking into metal atom and two Cp rings on bare Si(100) surface. Our results show that for CoCp2, NHx termination can promote the 1st Cp ligand elimination via CpH formation and desorption compared to H termination, where the reactions are endothermic for eliminating two Cp ligands for both RuCp2 and CoCp2. On bare Si(100) substrate, metal precursors RuCp2 and CoCp2 can undergo metal-carbon bond breaking into metal atom and two Cp rings and the overall reactions are much more exothermic than on H or NHx passivated Si(100) substrates. Our studies show that the experimentally observed incubation period at the initial stages is attributed to the surface H terminations that the surface reactivity is hindered on these H passivated Si(100) substrates. N2/H2 plasma pre-treatment on Si substrate could help to shorten the incubation period for CoCp2. The surface reactivity is highly dependent on substrate terminations, which explains why the reported incubation period and GPC vary from report to report.
Supporting Information for: Chemistries and Surface Reaction Mechanisms at the Initial Stages of Plasma-Enhanced Atomic Layer Deposition of Ru and Co on Silicon Substrate