Kinetic and mechanistic studies of the chemical vapor deposition of tungsten nitride from bis(tertbutylimido)bis(tertbutylamido)tungsten

The chemical vapor deposition (CVD) of tungsten nitride from a single sourc e reagent, bis(tertbutylimido)-bis(tertbutylamido)tungsten ((t-BuN)(2)W(NKB ut)(2)), is examined with particular focus placed on the mechanisms and ene rgetics involved in the activation and thermal decomposition of this CVD pr ecursor. The main reactions that take place are (1) activated adsorption of the precursor, (2) hydrogen addition/exchange, leading to the evolution of tert-butylamine, (3) ligand activation via both gamma -hydride activation and B-methyl elimination processes, and (4) Ligand decomposition via C-N bo nd rupture. The activation energies fbr each of these processes were examin ed and found to be similar to 30 kcal/mol for the process(es) leading to th e evolution of tert-butylamine and similar to 40 kcal/mol for the various r eactions which lead to the fragmentation of the precursor ligands (pathways which appear to involve both C-H and C-C bond activation as well as the ru pture of the ligand C-N bonds). The growth surface of the deposited film co ntained extensive quantities of carbon in addition to tungsten and nitrogen . The data also suggest that the growth in UHV does not yield a stable bulk nitride phase. Rather, it was found that the nitrogen appears to be presen t at levels consistent with the formation of a solid solution and that anne aling to 700 K results in the loss of the nitrogen from the bulk film (as N -2).