Effect of annealing treatments on CeO2 grown on TiN and Si substrates by atomic layer deposition

In this work, we investigate the effect of thermal treatment on CeO2 films fabricated by using atomic layer deposition (ALD) on titanium nitride (TiN) or on silicon (Si) substrates. In particular, we report on the structural, chemical and morphological properties of 25 nm thick ceria oxide with particular attention to the interface with the substrate. The annealing treatments have been performed in situ during the acquisition of X-Ray diffraction patterns to monitor the structural changes in the film. We find that ceria film is thermally stable up to annealing temperatures of 900 °C required for the complete crystallization. When ceria is deposited on TiN, the temperature has to be limited to 600 °C due to the thermal instability of the underlying TiN substrate with a broadening of the interface, while there are no changes detected inside the CeO2 films. As-deposited CeO2 films show a cubic fluorite polycrystalline structure with texturing. Further, after annealing at 900 °C an increase of grain dimensions and an enhanced preferential (200) orientation are evidenced. These findings are a strong indication that the texturing is an intrinsic property of the system more than a metastable condition due to the ALD deposition process. This result is interpreted in the light of the contributions of different energy components (surface energy and elastic modulus) which act dependently on the substrate properties, such as its nature and structure.