Controlling The Activator Site To Tune Europium Valence in Oxyfluoride Phosphors

A new Eu3+-activated oxyfluoride phosphor Ca12Al14O32F2:Eu3+ (CAOF:Eu3+) was synthesized by a solid state reaction. Commonly red line emission was detected in the range of 570–700 nm. To achieve the requirement of illumination, this study revealed a crystal chemistry approach to reduce Eu ions from 3+ to 2+ in the lattice. Replacing Al3+–F– by the appreciate dopant Si4+–O2– is adopted to enlarge the activator site that enables Eu3+ to be reduced. The crystallization of samples was examined by powder X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Photoluminescence results indicated that as-synthesized phosphors Ca12Al14-zSizO32+zF2–z:Eu (z = 0–0.5, CASOF:Eu) display an intense blue emission peaking at 440 nm that was produced by 4f–5d transition of Eu2+, along with the intrinsic emission of Eu3+ under UV excitation. Moreover, the effect of Si4+–O2– substitution involved in the coordination environment of the activator site was investigated by further crystallographic ...