Controlling the mechanism of phase transformation of colloidal In2O3 nanocrystals.

Abstract

Controlling the crystal structure of transparent metal oxides is essential for tailoring the properties of these polymorphic materials to specific applications. The structural control is usually done via solid state phase transformation at high temperature or pressure. Here, we report the kinetic study of in situ phase transformation of In2O3 nanocrystals from metastable rhombohedral phase to stable cubic phase during their colloidal synthesis. By examining the phase content as a function of time using the model fitting approach, we identified two distinct coexisting mechanisms, surface and interface nucleation. It is shown that the mechanism of phase transformation can be controlled systematically through modulation of temperature and precursor to solvent ratio. The increase in both of these parameters leads to gradual change from surface to interface nucleation, which is associated with the increased probability of nanocrystal contact formation in the solution phase. The activation energy for surface nucleation is found to be 144 ± 30 kJ/mol, very similar to that for interface nucleation. Despite the comparable activation energy, interface nucleation dominates at higher temperatures due to increased nanocrystal interactions. The results of this work demonstrate enhanced control over polymorphic nanocrystal systems and contribute to further understanding of the kinetic processes at the nanoscale, including nucleation, crystallization, and biomineralization.