Nitrogen Self-Diffusion In Magnetron Sputtered Si-C-N Films

Self-diffusion was studied in magnetron sputtered nitrogen-rich amorphous compounds of the system Si-C-N by using nitrogen as a model tracer. As shown by infra-red spectroscopy a transient metastable region exists, where the structure of the material can be visualized as silicon nitride tetrahedra which are connected by carbo-diimide (-N=C=N-) bonds to a three dimensional amorphous network. In this region diffusion studies are carried out by neutron reflectometry and isotope multilayers as a function of annealing time, temperature and chemical composition. Low diffusivities between 10(-20) and 10(-24) m(2)/s were found. In the metastable region, diffusion is faster than diffusion in amorphous silicon nitride by 1 to 2 orders of magnitude, while the activation enthalpies of diffusion between 3.1 and 3.4 eV are the same within error limits. This can be explained by the fact that the diffusion mechanism along SiN4 tetrahedra is identical to that in amorphous silicon nitride, however, the carbo-diimide bonds seem to widen the structure, allowing faster diffusion. A correlation between diffusivities and the number of carbo-diimid bonds present in the material is found, where the highest diffusivities are observed for materials with the highest number of carbo-diimid bonds, close to the composition Si2CN4. (C) 2011 American Institute of Physics. [doi:10.1063/1.3585780]