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Strongly bound excitons in anatase TiO2 single crystals and nanoparticles

Baldini, E.; Chiodo, L.; Dominguez, A.; Palummo, M.; Moser, S.; Yazdi-Rizi, M.; Aubock, G.; Mallett, B. P. P.; Berger, H.; Magrez, A.; Bernhard, C.; Grioni, M.; Rubio, A.; Chergui, M.

NATURE COMMUNICATIONS
2017
VL / 8 - BP / - EP /
abstract
Anatase TiO2 is among the most studied materials for light-energy conversion applications, but the nature of its fundamental charge excitations is still unknown. Yet it is crucial to establish whether light absorption creates uncorrelated electron-hole pairs or bound excitons and, in the latter case, to determine their character. Here, by combining steady-state angle-resolved photoemission spectroscopy and spectroscopic ellipsometry with state-of-the-art ab initio calculations, we demonstrate that the direct optical gap of single crystals is dominated by a strongly bound exciton rising over the continuum of indirect interband transitions. This exciton possesses an intermediate character between the Wannier-Mott and Frenkel regimes and displays a peculiar two-dimensional wavefunction in the three-dimensional lattice. The nature of the higher-energy excitations is also identified. The universal validity of our results is confirmed up to room temperature by observing the same elementary excitations in defect-rich samples (doped single crystals and nanoparticles) via ultrafast two-dimensional deep-ultraviolet spectroscopy.

AccesS level

Green submitted, Green published, Gold

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