Cathodo-luminescence of color centers induced in sapphire and yttria-stabilized zirconia by high-energy electrons

We have studied the color-center production in sapphire and yttria-stabilized zirconia (YSZ) single crystals by cathodo-luminescence (CL) spectroscopy for electron energies ranging between 400 and 1250 keV in a high-voltage electron microscope. Emission spectra were collected for in-beam conditions near room temperature and at 200 K. Comparison was made with CL spectra recorded for 3-keV-20-keV electrons in a scanning electron microscope. For high-energy electrons, CL spectra for sapphire revealed broad emission bands centered at photon energies about 3.0 eV and 3.8 eV that were, respectively, assigned to oxygen vacancies (F⁰ and F⁺ centers) induced by elastic collisions, on the basis of photoluminescence (PL) data. No such bands were recorded for 3-keV and 5-keV electrons. Two similar bands were also recorded for YSZ (with 9.5 and 18 mol. % yttria) at about 2.8 eV and 4.1 eV that can be, respectively, attributed to the native oxygen vacancies (F²⁺ centers) and F⁺ centers. The 4.1-eV band was not seen for 20-keV electrons: it was only produced for high electron energies by elastic collision processes. Instead, the small side band was also found at 2.85 eV for 20-keV electrons. PL excitation contour plots of virgin and irradiated YSZ were also recorded to support our discussion on point-defect identification. CL band intensities show a maximum versus electron energy, whereas point-defect concentrations should increase due to the increase of oxygen atom displacement cross section. The effect of electron energy on the different steps of the CL process is discussed to account for such a behavior.