Controlling The Activator Site To Tune Europium Valence in Oxyfluoride Phosphors

A new Eu 3+ -activated oxyfluoride phosphor Ca 12 Al 14 O 32 F 2:Eu 3+ (CAOF:Eu 3+ ) 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 Al 3+ –F – by the appreciate dopant Si 4+ –O 2– is adopted to enlarge the activator site that enables Eu 3+ 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 Ca 12 Al 14- z Si z O 32+ z F 2– 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 Eu 2+, along with the intrinsic emission of Eu 3+ under UV excitation. Moreover, the effect of Si 4+ –O 2– substitution involved in the coordination environment of the activator site was investigated by further crystallographic data from Rietveld refinements. The 19 F solid-state nuclear magnetic resonance (NMR) data were in agreement with refinement and photoluminescence results. Furthermore, the valence states of Eu in the samples were analyzed with the X-ray absorption near edge structure (XANES). The quantity of substituted Si 4+ –O 2– tunes chromaticity coordinates of Ca 12 Al 14– z Si z O 32+ z F 2– z:Eu phosphors from (0.6101, 0.3513) for z = 0 to (0.1629, 0.0649) for z = 0.5, suggesting the potential for developing phosphors for white light emitting diodes (WLEDs). Using an activator that is valence tunable by controlling the size of the activator site represents a hitherto unreported structural motif for designing phosphors in phosphor converted light emitting diodes (pc-LEDs).