Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Abstract

The kinetics of the thermal chemistry of methylcyclopentadienyl manganese tricarbonyl on copper surfaces was followed by infrared absorption spectroscopy analysis of the gas surrounding the substrate. Dissociative adsorption of the MeCpMn(CO)3 precursor was seen at low temperatures, below 400 K, and was determined to occur via the initial loss of a single carbon monoxide ligand. Full decarbonylation was observed starting at a surface temperature of approximately 510 K, and full decomposition of the Mn precursor was seen to be complete by 540 K. All these transitions were determined to occur at temperatures at least 100 K lower than those reported on silicon oxide surfaces. Comparison with reference spectra afforded the identification of the main hydrocarbon product as a mixture of methylcyclopentadiene isomers. Isothermal measurements of MeCpMn(CO)3 partial pressure versus reaction time highlighted a deviation from first-order kinetics, an effect associated with changes in surface reactivity. A self-limit...