First-principles calculations reveal precursor-dependent reaction mechanisms in ZrO2 atomic layer deposition (opens in new tab)

While atomic layer deposition (ALD) of ZrO2 enables conformal, high–κ dielectric films with sub-nanometer thickness control, the atomistic origins of precursor-dependent reactivity remain unresolved. Here, density functional theory (DFT) is used to dissect the ligand-controlled half-reactions of ZrO2 ALD using TDMAZr and TEMAZr with O3 as the oxidant. During the first half-cycle, TDMAZr adsorption and dissociation proceed with a lower maximum activation barrier and a more exothermic profile t...