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Phase Equilibrium of TiO2 Nanocrystals in Flame-Assisted Chemical Vapor Deposition.

Nano-scale titanium oxide (TiO2 ) is a material useful for a wide range of applications. In a previous study, we showed that TiO2 nanoparticles of both rutile and anatase crystal phases could be synthesized over the size range of 5 to 20 nm in flame-assisted chemical vapor deposition. Rutile was unexpectedly dominant in oxygen-lean synthesis conditions, whereas anatase is the preferred phase in oxygen-rich gases. The observation is in contrast to the 14 nm rutile-anatase crossover size derived from the existing crystal-phase equilibrium model. In the present work, we made additional measurements over a wider range of synthesis conditions; the results confirm the earlier observations. We propose an improved model for the surface energy that considers the role of oxygen desorption at high temperatures. The model successfully explains the observations made in the current and previous work. The current results provide a useful path to designing flame-assisted chemical vapor deposition of TiO2 nanocrystals with controllable crystal phases.