In Situ X‐Ray Photoelectron Spectroscopy Study of Atomic Layer Deposited Cerium Oxide on SiO₂: Substrate Influence on the Reaction Mechanism During the Early Stages of Growth

Abstract Thermal atomic layer deposition (ALD) of cerium oxide using commercial Ce(thd) 4 precursor and O 3 on SiO 2 substrates is studied employing in‐situ X‐ray photoelectron spectroscopy (XPS). The system presents a complex growth behavior determined by the change in the reaction mechanism when the precursor interacts with the substrate or the cerium oxide surface. During the first growth stage, non‐ALD side reactions promoted by the substrate affect the growth per cycle, the amount of carbon residue on the surface, and the oxidation degree of cerium oxide. On the contrary, the second growth stage is characterized by a constant growth per cycle in good agreement with the literature, low carbon residues, and almost fully oxidized cerium oxide films. This distinction between two growth regimes is not unique to the CeO x /SiO 2 system but can be generalized to other metal oxide substrates. Furthermore, the film growth deviates from the ideal layer‐by‐layer mode, forming micrometric inhomogeneous and defective flakes that eventually coalesce for deposit thicknesses above 10 nm. The ALD‐cerium oxide films present less order and a higher density of defects than films grown by physical vapor deposition techniques, likely affecting their reactivity in oxidizing and reducing conditions.