Exciton Bleaching and Ultrafast Electron Cooling in Anatase TiO2 Nanoparticles Revealed by Two-Dimensional Deep-Ultraviolet Spectroscopy
The recent unravelling of strongly bound excitons in anatase TiO$_2$ nanoparticles at room temperature has shed light on the importance of many-body effects in samples used for applications. Here, we demonstrate the interplay between many-body interactions and correlations in highly-excited anatase TiO$_2$ nanoparticles by means of ultrafast two-dimensional deep-ultraviolet spectroscopy. We observe that the exciton optical nonlinearities upon non-resonant excitation are dominated by phase-space filling and long-range Coulomb screening, reflecting the dynamics of the photoexcited electron density. By tracking the renormalization of the exciton feature over time, we unveil the timescales involved in the intraband hot electron thermalization. We observe that the strong electron-phonon coupling results in an ultrafast dissipation of the electronic excess energy within 50 fs. Our findings open new perspectives in the design of alternative resonant excitation schemes to be tested in photocatalysis and nanotechnology.