Journal of Vacuum Science & Technology B, Vol.16, No.6, 3015-3020, 1998
Correlation between the early stage of copper metal organic chemical vapor deposition and the material properties of thin film
Cu metal organic chemical vapor deposition has been performed on TiN/Si(100) substrates using Cu(I)(hfac)(vtms) at various substrate (110 less than or equal to T(s)less than or equal to 300 degrees C) and bubbler temperature (0 less than or equal to T-b less than or equal to 30 degrees C) conditions, in which the early stage of film formation characterized by scanning electron microscopy and in situ laser beam (lambda = 6328 Angstrom) reflectance measurement could be well correlated with the surface roughness and the electrical resistivity of the copper films developed in a later stage. All the reflectance versus deposition time curves showed a qualitatively similar shape consisting of three sequential parts: a rapid initial decrease to a minimum, an increase to a maximum, and a gradual decay to almost zero, in which the minimum and maximum roughly correspond to the onset and completion of island coalescence, respectively. As the T-s is raised and/or the Tb is lowered, larger islands were formed in a smaller density at the onset of island coalescence due to a lower nucleation rate. The surface roughness gradually develops with increasing film thickness after forming a continuous film, but it does not saturate at a thickness of similar to 2 mu m and shows a correlation with the average island size in the earlier coalescence stage,i.e., the smaller islands evolves to a smoother surface. Above the threshold temperature (T-s similar to 230 for T-b =30 degrees C) the copper islands begin to show facets and at even higher T-s large truncated polyhedron-shaped copper islands are formed, which upon coalescing leave many interfacial voids to result in a film with a very rough surface and a high electrical resistivity. The copper films deposited at 150 less than or equal to T-s less than or equal to 200 degrees C have a very low value of rho approximate to 2 mu Omega cm, which increases by a factor of similar to 2 when T-s is lowered to 110 degrees C. The latter was accompanied by the formation of smaller islands at the onset of coalescence, and therefore the increase in rho at T-s less than or equal to 150 degrees C was attributed to the electron scattering at the grain boundaries.