Synthesis of Zirconium Guanidinate Complexes and the Formation of Zirconium Carbonitride via Low Pressure CVD

Thin films of zirconium carbonitride have been deposited on glass at 600 degrees C from two novel guanidinate precursors: [ZrCp'{eta(2)-((PrN)-Pr-i)(2)CNMe2}(2)Cl] and [ZrCp'(2){eta(2)-((PrN)-Pr-i)(2)CNMe2}Cl] (2) (Cp' = monomethylcyclopentadienyl). Both compounds 1 and 2 were structurally characterized by X-ray crystallography. The films grown via low pressure chemical vapor deposition (LPCVD) from compound 1 were mirror-like with a red-brown sheen whereas those from 2 were gray. Chlorine was present in the films although the levels were no higher than 3 at.%. These two compounds clearly show how the coordination environment around the metal center affects the composition of the film, as films from 1 were nitrogen rich and those from 2 were carbon rich. The films were uniform, adhesive, abrasion resistant, conformal, and hard, being resistant to scratching with steel and brass scalpels.