The Charge Transfer Band as a Key to Study the Site Selection Preference of Eu3+ in Inorganic Crystals.

Abstract

On account of the strong oxidizing property of the europium(III) ion, its charge transfer band (CTB) can be easily formed in many inorganic compounds. In this work, the Eu3+ ions were singly doped into the K3LuSi2O7 compound with a hexagonal structure, and two kinds of Eu3+-O2- CTBs were detected by monitoring at specific wavelengths. The qualitative analysis of Eu3+ ion site occupation was illuminated by combining Eu3+-O2- CTBs with the corresponding cell volume. Furthermore, the two kinds of Eu3+ sites are eventually assigned to the K(2) and Lu sites, which means that Eu3+ ions selectively occupy the site with a low coordination number, according to the calculated CT energy by the dielectric theory of complex crystals and the magnitude of CT energy in the excitation spectra. Meanwhile, at high temperatures, the CTB does not show the traditional thermal quenching like f-f transitions but demonstrates thermal enhancement; thus, by using this opposite variation in excitation spectra, a noninvasive optical thermometer is presented, and this opposite variation tendency is thought to be the difference of thermal stability of disparate excited energy states. When new luminescent phosphors are designed with interesting spectral properties, this work will give us an alternative approach to determine the site occupation preference of Eu3+, especially when there are more than two different sites in the compound.