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The Consequences of Random Sequential Adsorption for the Precursor Packing and Growth-Per-Cycle of Atomic Layer Deposition Processes.

Ilker TezsevinJ H DeijkersMarc J M MerkxWilhelmus Erwin M M KesselsTania E SandovalAdriaan J M Mackus
Published in: The journal of physical chemistry letters (2024)
Atomic layer deposition (ALD) processes are known to deposit submonolayers of material per cycle, primarily attributed to steric hindrance and a limited number of surface sites. However, an often-overlooked factor is the random sequential adsorption (RSA) mechanism, where precursor molecules arrive one-by-one and adsorb at random surface sites. Consequently, the saturation coverage of precursors significantly deviates from ideal closed packing. In this study, we investigated the influence of RSA on precursor adsorption saturation and, consequently, on the growth per cycle (GPC) of the ALD processes. Our simulations revealed that the RSA model leads to a 22% to 40% lower surface density compared to the reference case of ordered packing. Furthermore, based on the precursor shape and size, we estimated GPC values with an average accuracy of 0.05 Å relative to experimental literature data. This work shows the critical role of RSA in ALD, emphasizing the need to consider this mechanism for a more accurate process design and optimization.
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