The thermal chemistry of tetrakis[Cu(I)-N-sec-butyl-iminopyrrolidinate] and bis[Cu(I)-N,N-dimethyl- N', N''-di-iso-propyl-guanidinate], promising precursor for atomic layer deposition (ALD) applications, was investigated on a Ni(110) single-crystal under ultrahigh vacuum (UHV) conditions by using X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD). Both precursors, which exist as tetramers and dimers in the solid phase, respectively, undergo dissociative adsorption at temperatures below 200 K to produce adsorbed monomers on the surface. A β-hydride elimination step is then operative near 300 K that leads to the release of some of the ligands in dehydrogenated form. The remaining adsorbates obtained from either precursor undergo similar further decomposition between 350 K and 600 K as the Cu atoms are reduced from a Cu(I) oxidation state to metallic Cu(0). Hydrocarbons resulting from the elimination of the terminal moieties include ethene and acetonitrile from the Cu(I)-iminopyrrolidinate and propene from the Cu(I)-guanidinate, which are ejected at ∼420-490 K, and HCN in both cases at ∼570-580 K. These results shows several similarities with the surface chemistry previously reported for bis[Cu(I)-N,N'-di-sec-butyl-acetamidinate], and they suggest a common behavior in the surface reactions of these families of Cu(I)-amidinate, Cu(I)-iminopyrrolidinate, and Cu(I)-guanidinate ALD precursors.

Additional Metadata
Keywords amidinate complexes, atomic layer deposition, copper films, guanidinate complexes, surface chemistry, temperature-programmed desorption, X-ray photoelectron spectroscopy
Persistent URL
Journal Chemistry of Materials
Kim, T. (Taeseung), Yao, Y. (Yunxi), Coyle, J.P, Barry, S.T, & Zaera, F. (Francisco). (2013). Thermal chemistry of Cu(I)-iminopyrrolidinate and Cu(I)-guanidinate atomic layer deposition (ALD) precursors on Ni(110) single-crystal surfaces. Chemistry of Materials, 25(18), 3630–3639. doi:10.1021/cm401707h