Unusual Crystallization Behaviors of Anatase Nanocrystallites from a Molecularly Thin Titania Nanosheet and Its Stacked Forms:  Increase in Nucleation Temperature and Oriented Growth

Crystallization behaviors of anatase nanocrystallites from an ultrathin two-dimensional reactant composed of exfoliated titania nanosheets have been studied by monitoring the heating process of their well-organized films, with which the film thickness can be controlled from a molecularly thin monolayer to a stacked multilayer structure with a stepwise increment of approximately 1 nm. The heated products were identified by means of total reflection fluorescence X-ray absorption near-edge structure analysis and in-plane X-ray diffraction measurements using a synchrotron radiation source. The films composed of five or more layers of stacked nanosheets were transformed into anatase at 400-500 degrees C, which is a normal crystallization temperature of anatase from bulk reactants. As the film became thinner by decreasing the number of nanosheet layers to five or less, the crystallization temperature was found to increase and finally reached 800 degrees C for the monolayer film. Interestingly, preferential growth of anatase along the c-axis was strongly promoted for these ultrathin films. These unusual behaviors may be understood in terms of crystallization from the two-dimensional system of scarcely distributed reactants. The titania nanosheet crystallite is much thinner than the unit cell dimensions of anatase, and therefore, extensive atomic diffusion is required for the transformation particularly for the ultrathin films with a critical number (2-3) of stacked nanosheet layers. There is some structural similarity between anatase and titania nanosheet, which may account for the oriented growth of anatase nanocrystallites.