Deposition of copper by plasma-enhanced atomic layer deposition using a novel N-Heterocyclic carbene precursor

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Coyle, Jason P.
Dey, Gangotri
Sirianni, Eric R.
Kemmell, Marianna L.
Yap, Glenn P. A.
Ritala, Mikko
Leskela, Markku
Elliott, Simon D.
Barry, Seán T.
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American Chemical Society Publications
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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.
Copper amide , Carbene , Atomic layer deposition , Plasma , Metal thin film
Jason P. Coyle, Gangotri Dey, Eric R. Sirianni, Marianna L. Kemell Glenn P. A. Yap, Mikko Ritala, Markku Leskela, Simon D. Elliott Sean T. Barry (2013). Deposition of Copper By Plasma-Enhanced Atomic Layer Deposition Using a Novel N-Heterocyclic Carbene Precursor. Chemistry of Materials, 25 (7), pp 1132–1138. DOI: 10.1021/cm400215q
© 2013, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see