Computational Dataset: Precursor design principles for area-selective atomic layer deposition of alumina: quantifying the role of Lewis acidity, steric repulsion and dimerization in surface adsorption

This dataset contains the rawdata and evaluation data of the publication "Effect of substitution, dimerization and Lewis acidity on adsorption energetics: Bonding analysis of Al precursors for (AS-)ALD" In atomic layer deposition (ALD), precursor adsorption behavior plays a critical role in determining growth characteristics. This is particularly important in area-selective ALD (AS-ALD), where adsorption on the non-growth surface (NGS) leads to selectivity loss. In this context, both the ability of a precursor to access reactive surface groups on the NGS and the strength of its binding are key parameters governing the performance of precursors in experiment. Adsorption on the NGS is strongly influenced by the substituents at the central atom, which control the precursor’s Lewis acidity, steric bulk, and propensity for dimerization. We applied energy decomposition analysis (EDA) to a representative set of commonly used aluminum precursors to quantitatively assess how these factors affect adsorption energetics on SiO2 as the NGS, with trimethoxypropylsilane (TMPS) as small-molecule inhibitor (SMI). Using fluoride ion affinity (FIA) as a metric for Lewis acidity, we find that it largely governs the trends in bonding energies to both the surface and the SMIs. Notable exceptions are precursors bearing branched alkyl substituents and a case where proton transfer occurs. For branched alkyl groups, steric repulsion dominates over the Lewis acidity, whereas in case of other substituents they do not determine the trend in bonding. Lewis acidity furthermore determines whether adsorption between the SMI layer remains energetically favorable. In this regime, steric effects—Pauli repulsion and deformation of the SMI layer—substantially weaken the adsorption. Dimerization generally reduces adsorption strength despite the possibility of dimer opening for chlorinated precursors. This weakening effect is less pronounced, however, when adsorption takes place within the inhibitor layer. Based on the insights on bonding energetics and taking other parameters into account, we recommend targeted modifications of existing aluminum precursors and propose systematic strategies for precursor design aimed at minimizing interactions with the NGS.