Nucleation kinetics during homoepitaxial growth of TiN(001) by reactive magnetron sputtering

We use scanning tunneling microscopy to study the nucleation of homoepitaxial TiN layers grown on TiN(001) by ultrahigh vacuum reactive magnetron sputtering in pure N₂. Nucleation lengths are measured using in situ scanning tunneling microscopy as a function of temperature on two-dimensional islands as well as on large open terraces. At low growth temperatures, 500Tₛ8650.2em0ex^∘C, nucleation is diffusion limited and we extract a surface diffusion energy of 1.4±0.10.3em0exeV. At higher temperatures, 865Tₛ10100.2em0ex^∘C, nucleation is limited by the formation rate of stable clusters for which we obtain an activation energy of 2.6±0.20.3em0exeV. Ab initio calculations combined with our experimental results suggest that the primary diffusing adspecies are TiNₓ molecules with $x=2$ and/or 3.