Thermal atomic layer etching is rapidly becoming an important complementary processing technology in manufacturing 5 and 3 nm devices in the semiconductor industry. Critically, stacked chip architectures such as 3D NAND and 3D DRAM require conformal isotropic etching to remove material such as HfO₂ in hard-to-reach locations with aspect ratios that can be >50. To achieve repeatable device performance throughout a 3D stack, the removal rate (etch per cycle) of the etched material during an etch process need to be controlled such that the overall etch is the same from top to bottom of the device stack. In this work, we have modelled the reaction kinetics and transport processes of reactants and by-products during a cyclical ligand exchange-based ALE process. This ALE process consists of two steps: a fluorination step, followed by a fluorine-to-chlorine ligand exchange-based removal step. Experimental data revealed that the fluorine dosing during the fluorination step was predominantly responsible for controlling the etch rate of the ALE process but had only a minimal impact on the etch profile inside these holes. The ligand exchange dosing, on the other hand, predominantly controlled the etch profile (depth loading) with equal etch rates top-to-bottom obtained when the step was operated close to saturation. Our model predicts, in agreement with the experiment, that adsorption and reaction rates during fluorination on HfO₂ surfaces are significantly slower than transport times inside these deep holes leading to essentially flat fluorination profiles even if the fluorination step is not operated in saturation mode. In contrast, transport rates with the ligand exchange molecule are slow in comparison but adsorption and ligand exchange rates with the fluorinated hafnium appear to be significantly higher than for fluorine during the fluorination step. Slow transport in combination with high surface reaction rates for the ligand exchange step led to an etch rate that was dependent on aspect ratio (feature depth) in processes that used sub‑saturation exposures.