Excitonic recombination in superstoichiometric nanocrystalline TiO2 grown by cluster precursors at room temperature

Abstract

Unprecedented room temperature excitonic emissions are achieved from TiO₂ nanocrystals synthesized at 300 K by supersonic cluster beams. Transmission electron microscopy studies show the crystalline nature of the nanoparticles (NPs) with a diameter ranging from 5 to 30 nm. All the samples show mixed rutile and anatase phases as confirmed by Raman spectroscopy. XPS core level analyses evidence an O/Ti ratio of the as-grown nanoparticles of 2.30 ± 0.04. Two room temperature cathodoluminescence excitonic peaks observed at 3.16 and 3.25 eV are ascribed to the coexistence of rutile and anatase crystallographic phases respectively. Subsequent thermal treatments at 450 °C cause the complete quenching of the UV excitonic emissions and result in a more conventional broad visible band centered at 2.5 eV. HRTEM and XPS studies reveal that, after annealing, the NPs remain single crystals in nature with an O/Ti ratio of 2.20 ± 0.04. These results suggest a correlation between the emission properties and the oxygen concentration of our NPs. The achieved ability to tune the optical properties of TiO₂ nanoparticles is very promising for sensing and energy applications.