Area-Selective Deposition of Ruthenium by Area-Dependent Surface Diffusion

Area-selective deposition (ASD) enables the growth of materials on target regions of patterned substrates for applications in fields ranging from microelectronics to catalysis. Selectivity is often achieved through surface modifications aimed at suppressing or promoting the adsorption of precursor molecules. Here we show, instead, that varying the surface composition can enable ASD by affecting surface diffusion rather than adsorption. Ru deposition from (carbonyl)- (alkylcyclohexadienyl)Ru and H₂ produces smooth films on metal nitrides and nanoparticles on SiO₂. The latter form by surface diffusion and aggregation of Ru adspecies. Kinetic modeling shows that changing the surface termination of SiO₂ from -OH to -CH₃, and thus its surface energy, leads to larger and fewer nanoparticles because of a 1000-fold increase in surface diffusion rates. Kinetic Monte Carlo simulations show that even surface diffusion alone can enable ASD because adspecies tend to migrate from high- to low-diffusivity regions. This is corroborated by deposition experiments on 3D TiN-SiO₂ nanopatterns, which are consistent with Ru migrating from SiO₂ to TiN. Such insights not only have implications for the interpretation of experimental results but may also inform new ASD protocols, based on chemical vapor and atomic layer deposition, that take advantage of surface diffusion.