Deposition of Copper by Plasma-Enhanced Atomic Layer Deposition Using a Novel N-Heterocyclic Carbene Precursor

Two novel N-heterocyclic carbene (NHC)-containing copper(I) amides are reported as atomic layer deposition (ALD) precursors. 1,3-Diisopropyl-imidazolin-2-ylidene copper hexamethyldisilazide ( 1 ) and 4,5-dimethyl-1,3-diisopropyl-imidazol-2-ylidene copper hexamethyldisilazide ( 2 ) were synthesized and structurally characterized. The thermal behavior of both compounds was studied by thermogravimetric analysis (TGA), and they were both found to be reasonably volatile compounds. Compound 1 had no residual mass in the TGA and showed long-term stability at temperatures as high as 130 °C, while 2 had a residual mass of 7.4%. Copper metal with good resistivity was deposited using 1 by plasma-enhanced atomic layer deposition. The precursor demonstrated self-limiting behavior indicative of ALD, and gave a growth rate of 0.2 Å/cycle. Compound 2 was unsuccessful as an ALD precursor under similar conditions. Density functional theory calculations showed that both compounds adsorb dissociatively onto a growing copper film as long as there is some atomic roughness, via cleavage of the Cu-carbene bond.