Temperature dependence of photoluminescence emission characteristics in a natural fluorite

Summary

The temperature dependence of photoluminescence emission of a natural fluorite has been studied in the wavelength region of 380–500 nm and in the temperature range of 17.5–300 K. The emission spectra of the sample show a broad emission band between 380 and 500 nm for temperatures above 100 K. At 100 K and below, vibronic lines appear on the emission band at approximately 413.3, 418.1, 419.3, 420.2, 423.9 and 427.1 nm. This broad emission band and the vibronic lines in fluorite are usually associated with phonon-coupled electronic transitions from 4f⁶5d to 4f⁷ in the Eu²⁺ ion. Temperature dependences of the peak energy, intensity and full-width at half-maximum of the broad emission band are discussed, and the behaviour explained in terms of a configurational coordinate model. The excited state vibrational energy was obtained to be 0.023 ± 0.001 eV and this is lower than the LO phonon energy of 0.062 eV in pure fluorite. The activation energy of thermal quenching of the photoluminescence intensity was found to be 0.022 ± 0.002 eV.