Spectroscopic characterization of ZrO2 thin films grown by atomic layer deposition

Zirconium dioxide films grown by atomic layer deposition from ZrCl4 and H2O at substrate temperatures of 500-870 K were characterized using spectroscopic methods. A significant influence of the phase composition on absorption and photoluminescence spectra was observed. The band-gap energies determined from absorption spectra of films with monoclinic structure grown at 670-870 K ranged from 5.25 to 5.28 eV. Low-temperature (10 K) photoexcitation of these films resulted in a non-elementary emission band with the maximum at 4.25-4.35 eV, tentatively assigned to the radiative decay of self-trapped excitons. The low-energy edges of the excitation spectra coincided with the edges of intrinsic absorption. A film that was grown at 500 K and contained tetragonal ZrO2 with large amounts of impurities had an absorption edge at 5.26 eV and wide emission band at 3.0 eV, which could be excited at as low photon energy as 4.9 eV. (author)