Thermal quenching of self-trapped exciton luminescence in nanostructured hafnia

The intrinsic optical properties and peculiarities of the energy structure of hafnium dioxide largely determine the prospects for applying the latter in new generation devices of optoelectronics and nanoelectronics. In this work, we have studied the diffuse reflectance spectra at room temperature for a nanostructured powder of nominally pure HfO2 with a monoclinic crystal structure and, as well its photoluminescence in the temperature range of 40-300 K. We have also estimated the bandgap E-g under the assumption made for indirect (5.31 eV) and direct (5.61 eV) allowed transitions. We have detected emission with a 4.2 eV maximum at T < 200 K and conducted an analysis of the experimental dependencies to evaluate the activation energies of thermal quenching (140 meV) and enhancement (3 meV) processes. Accounting for both the temperature behavior of the spectral characteristics and the estimation of the Huang-Rhys factor S >> 1 has shown that radiative decay of self-trapped excitons forms the mechanism of the indicated emission. In this case, the localization is mainly due to the interaction of holes with active vibrational modes of oxygen atoms in non-equivalent (O-3f and O-4f) crystal positions. Thorough study of the discussed excitonic effects can advance development of hafnia-based structures with a controlled optical response.