Finite-size and pressure effects on the Raman spectrum nanocrystalline anatse TiO2 -: art. no. 184302

The Raman scattering behavior of anatase nanocrystals with average diameters of 4, 8, 20, and 34 nm has been compared with bulk crystal data in order to establish size-dependent changes to the phonon spectrum at ambient conditions. Further, the high-pressure behavior of the anatase nanocrystals was examined at room-temperature using in situ Raman scattering data obtained in diamond-anvil cells to a maximum pressure of 41 GPa. The size-dependent changes to the Raman spectrum are best explained in terms of three-dimensional confinement of phonons in finite-sized nanocrystalline anatase. The difference in slopes obtained for the pressure shifts of Raman modes between nanocrystalline and single crystal anatase is in conformity with the observed size-dependent bulk modulus values. The metastability of anatase as a function of pressure is demonstrated to be size dependent, with smaller crystallites preserving the structure to higher pressures. Three size regimes have been recognized for the pressure-induced phase transition of anatase at room temperature: an anatase-amorphous transition regime,at the smallest crystallite sizes, an anatase-baddeleyite transition regime at intermediate crystallite sizes, and an anatase-alpha-PbO2 transition regime comprising large nanocrystals to macroscopic single crystals. This size-dependent phase selectivity of anatase at high pressures explains the recent contradictory experimental data. A semiquantitative phase diagram for anatase metastability as a function of size and pressure at room temperature is proposed.