Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(II) acetylacetonate: a combined first-principles and reactive molecular dynamics study
X Hu and J Schuster and SE Schulz and T Gessner, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 17, 26892-26902 (2015).
DOI: 10.1039/c5cp03707g
Atomistic mechanisms for the atomic layer deposition using the Cu(acac)(2) (acac = acetylacetonate) precursor are studied using first- principles calculations and reactive molecular dynamics simulations. The results show that Cu(acac)(2) chemisorbs on the hollow site of the Cu(110) surface and decomposes easily into a Cu atom and the acac- ligands. A sequential dissociation and reduction of the Cu precursor Cu(acac)(2) -> Cu(acac) -> Cu are observed. Further decomposition of the acac-ligand is unfavorable on the Cu surface. Thus additional adsorption of the precursors may be blocked by adsorbed ligands. Molecular hydrogen is found to be nonreactive towards Cu(acac)(2) on Cu(110), whereas individual H atoms easily lead to bond breaking in the Cu precursor upon impact, and thus release the surface ligands into the gas-phase. On the other hand, water reacts with Cu(acac)(2) on a Cu2O substrate through a ligand-exchange reaction, which produces gaseous H(acac) and surface OH species. Combustion reactions with the main by- products CO2 and H2O are observed during the reaction between Cu(acac)(2) and ozone on the CuO surface. The reactivity of different co-reactants toward Cu(acac)(2) follows the order H > O-3 > H2O.
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