Highly dispersed Co deposited on Al2O3 particles via CoCp2 + H2 ALD

Nanotechnology. 2020 Apr 24;31(17):175703. doi: 10.1088/1361-6528/ab68e1. Epub 2020 Jan 8.


Highly dispersed cobalt atoms were deposited on porous alumina particles using atomic layer deposition (ALD) with a CoCp2/H2 chemistry at approximately 7 wt%. H2 did not completely reduce the cyclopentadienyl organic ligands bound to deposited Co atoms at ALD reaction conditions. A sharp decline in Co deposited per cycle for two or more ALD cycles indicates that much of the Al2O3 surface is sterically blocked from further CoCp2 deposition after the first CoCp2 exposure. Temperature programmed reduction confirmed that the adsorbed precursor organic ligands persist after H2 exposures during ALD and temperatures as high as 500 °C are required to fully reduce the organic ligands to CH4. High resolution, element sensitive imaging showed that Co atoms were dispersed on the Al2O3 surface and could deposit in previously unobserved multiple growth morphologies, specifically layers that were continuous over several angstroms or discrete nanoparticles. Density functional theory calculations were used to examine Co atom adsorption, show the altered haptic binding of cracked Cp ligands, and to calculate the thermodynamics of Cp ligand decomposition. The lateral steric hindrance between organic ligands bound to deposited Co atoms, Cp ligand decomposition mechanism, and local Al2O3 surface termination all likely determine the observed Co growth morphology during initial ALD cycles.