Role of the Deposition Precursor Molecules in Defining Oxidation State of Deposited Copper in Surface Reduction Reactions on H-Terminated Si(111) Surface.

Surface-limited deposition reactions leading to the formation of copper nanoparticles on H-terminated Si(111) surface can serve as a model for understanding the role of structure of the deposition precursor molecules in determining the oxidation state of the metal deposited. This study compares three different precursor molecules: Cu(acac) (Cu(II) acetylacetonate), Cu(hfac), and Cu(hfac)VTMS (Cu(I)-(hexafluoroacetylacetonato)-vinyltrimethylsilane) as copper deposition sources in a process with a controlled oxidation state of copper. X-ray photoelectron spectroscopy suggests that single-electron reduction governs the deposition of Cu(I) from the first two precursor molecules and that the last of the precursors studied yields predominantly metallic copper. Time-of-fight secondary ion mass spectrometry (ToF-SIMS) and infrared spectroscopy are utilized to interrogate surface species produced. Atomic force microscopy is used to quantify the deposition process and to follow the size distribution of the deposited copper containing nanoparticles. A plausible explanation supported by density functional theory calculations is offered on the basis of the difference in the reaction pathways for Cu(I) and Cu(II) precursors.