The impact of the density and type of reactive sites on the characteristics of the atomic layer deposited WNxCy films.

The growth of tungsten nitride carbide (WNxCy) films obtained by atomic layer deposition using triethylboron, tungsten hexafluoride, and ammonia precursors is determined by the density and type of reactive sites. The film properties change as a function of thickness. On silicon dioxide and silicon carbide, growth is initially nonlinear such that the transient regimes are characterized by island formation, as evidenced by a parabolic tungsten growth curve extending to film thicknesses of up to 5 nm. Such films have low densities of ∼4–6 g cm-3 corresponding to only ∼30%–45% of the bulk density of ∼13.1 g cm-3 determined for a WN0.45C0.55 composition. X-ray reflectivity, thermal desorption, and elastic recoil detection spectroscopies reveal surface roughening and compositional and density differences close to the substrate surface. The offset from linear growth in the case of WNxCy films deposited on silicon dioxide is induced by the initial reaction of silanol and siloxane groups with triethylborane resulting in passivating ethylsilyl groups on the surface. A transient regime is not observed for WNxCy growth on hydrogen-terminated silicon with the initial growth being dominated by the reduction of tungsten hexafluoride to tungsten. On silicon nitride a short transient regime is observed relative to the carbide and oxide surfaces attributed to the enhanced binding of the triethylboron precursor. [ABSTRACT FROM AUTHOR]