Ab initio analysis of nucleation reactions during tungsten atomic layer deposition on Si(100) and W(110) substrates

Abstract

Novel insight into the mechanisms that govern nucleation during tungsten atomic layer deposition is presented through a detailed analysis using density functional theory. Using the calculated energetics, the authors suggest the most probable series of reactions that lead to monolayer formation on desired growth surfaces, Si(100) and W(110), during sequential doses of WF6 and SiH4. From this analysis, they conclude that a relatively high-energy barrier exists for initial nucleation of WF6 on a silicon substrate; therefore, the system is limited to physical adsorption and is only capable of accessing nucleation pathways once the reaction barrier is energetically accessible. During early doses of WF6, the initial silicon surface acts as the reductant. Results from this half-reaction provide support for the noncoalesced growth of initial W layers since nucleation is shown to require a 2:1 ratio of silicon to WF6. In addition, the release of H2 is significantly favored over HF production leading to the formation of fluorine-contaminated silicon sites; etching of these sites is heavily supported by the absence of fluorine observed in experimentally deposited films as well as the high volatility of silicon-subfluorides. In the second half-reaction, SiH4 plays the multipurpose role of stripping fluorine atoms from W, displacing any adsorbed hydrogen atoms, and depositing a silicon-hydride layer. Saturation of the previously formed W layer with silicon-hydrides is a crucial step in depositing the consecutive layer since these surface species act as the reductants in the succeeding dose of WF6. The SiH4 half-reaction reaches a limit when all fluorine atoms are removed as silicon-subfluorides (SiFxHy) and tungsten sites are terminated with silicon-hydrides. The WF6 dose reaches a limit in early doses when the reductant, i.e., the surface, becomes blocked due to the formation of a planar network of fluorine-containing tungsten intermediates and in later cycles when the reductant, i.e., adsorbed silicon-hydrides, is etched entirely from the surface. Overall, the calculated energetics indicate that WFxHy, SiFx, and H2 molecules are the most probable by-products released during the ALD process. Results from this work contribute significantly to the fundamental understanding of atomic layer growth of tungsten using silicon species as reducing agents and may be used as a template for analyzing novel ALD processes.