Journal of Physical Chemistry C vol:119 issue:12 pages:6592-6603
Atomic layer deposition (ALD) of ruthenium using two ruthenium precursors, i.e. Ru(C5H5)2 (RuCp2) and Ru(C5H5(C4H4N) (RuCpPy), is studied using density functional theory. By investigating the reaction mechanisms on bare ruthenium surfaces, i.e. (001), (101) and (100) and H-terminated surfaces, an atomistic insight in the Ru ALD is provided. The calculated results show that on the Ru surfaces, both RuCp2 and RuCpPy can undergo dehydrogenation and ligand dissociation reactions. RuCpPy is more reactive than RuCp2. By forming a strong bond between N of Py and Ru of the surface, RuCpPy can easily chemisorb on the surfaces. The reactions of RuCp2 on the surfaces are less favorable as the adsorption is not strong enough. This could be a factor contributing to the higher growth-per-cycle of Ru using RuCpPy, as observed experimentally. By studying the adsorption on H-terminated Ru surfaces, we showed that H can prevent the adsorption of the precursors, thus inhibiting the growth of Ru. Our calculations indicate that the H content on the surface can have an impact on the growth-per-cycle. Finally, our simulations also demonstrate large impacts of the surface structure on the reaction mechanisms. Of the three surfaces, the (100) surface, which is the less stable and has a zigzag surface structure, is also the most reactive one.