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

• Published in: Chemistry of materials Vol. 25; no. 7; pp. 1132 - 1138
• Main Authors: Coyle, Jason P, Dey, Gangotri, Sirianni, Eric R, Kemell, Marianna L, Yap, Glenn P. A, Ritala, Mikko, Leskelä, Markku, Elliott, Simon D, Barry, Sean T
• Format: Journal Article
• Language: English
• Published: American Chemical Society 09.04.2013
• Subjects: atomic layer deposition; plasma; metal thin film; carbene; copper amide
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm400215q

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.