Role of Rare Earth Elements and Entropy on the Anatase-To-Rutile Phase Transformation of TiO Thin Films Deposited by Ion Beam Sputtering.

The role played by oxygen vacancies and rare earth (RE) elements in the anatase-to-rutile (A-R) phase transformation of titanium dioxide (TiO) is still a matter of controversy. Here, we report the A-R transformation of TiO thin solid films as obtained by ion beam sputtering a RE-decorated titanium target in an oxygen-rich atmosphere. The samples correspond to undoped, single-doped (Sm, Tm, and Tb), and codoped (Sm:Tb, Sm:Tm, and Sm:Tb:Tm) TiO films. In the as-prepared form, the films are amorphous and contain ∼0.5 at. % of each RE. The structural modifications of the TiO films due to the RE elements and the annealing treatments in an oxygen atmosphere are described according to the experimental results provided by Raman scattering, X-ray photoelectron spectroscopy, and optical measurements. The A-R transformation depends on both the annealing temperature and the characteristics of the undoped, single-doped, and codoped TiO films. As reported in the literature, the A-R transformation can be inhibited or enhanced by the presence of impurities and is mostly related to energetic contributions. The experimental results were analyzed, considering the essential and stabilizing role of the entropy of mixing in the A-R transformation due to the introduction of more and multiple quantum states originated in vacancies and impurities in the anatase phase.