Redistribution of Activator Tuning of Photoluminescence by Isovalent and Aliovalent Cation Substitutions in Whitlockite Phosphors

Many strategies, including double substitution, addition of charge compensation, cation-size-mismatch and neighboring-cation substitution, have contributed to tuning photoluminescence of phosphors for white light-emitting diodes. These strategies generally involve modification of a certain special site where the activator occupies; tuning strategy based on multiple cation sites is very rare and desirable. Here we report that isovalent (Sr²⁺) and aliovalent (Gd³⁺) substitutions for Ca²⁺ tune the photoluminescence from one band to multiple bands in whitlockite β-Ca_3–<i>x</i>Sr_<i>x</i>(PO₄)₂:Eu²⁺ and β-Ca_{3–3<i>y</i>/7}Gd_2<i>y</i>/7(PO₄)₂:Eu²⁺ phosphors. The saltatory variation of the emission spectra is caused by the removal of Eu²⁺ from the site M(4) to other sites. Moreover, we found the mechanisms of dopant redistribution tuning the luminescence are different. The incorporation of Gd³⁺ makes the site M(4) empty according to the scheme 3Ca²⁺ = 2Gd³⁺ + □, while Sr²⁺ substitution causes the cation sites to be enlarged due to cation size mismatch. Additionally, the influence of the cation substitutions on the photoluminescence thermal stability of phosphors is researched. The strategies, emptying and enlarging sites, developed herein are expected to provide a general route for tuning luminescence of phosphors with multiple sites in the future

Changing Ce³⁺ Content and Codoping Mn²⁺ Induced Tunable Emission and Energy Transfer in Ca_2.5Sr_0.5Al₂O₆:Ce³⁺,Mn²⁺

A series of color-tunable Ce³⁺ single-doped and Ce³⁺, Mn²⁺ codoped Ca_2.5Sr_0.5Al₂O₆ phosphors were synthesized by a high-temperature solid-state reaction. The crystal structure, luminescent properties, and energy transfer were studied. For Ca_2.5Sr_0.5Al₂O₆:Ce³⁺ phosphors obtained with Al­(OH)₃ as the raw material, three emission profiles were observed. The peak of photoluminescence (PL) spectra excited at ∼360 nm shifts from 470 to 420 nm, while that of the PL spectra excited at 305 nm stays unchanged at 470 nm with the increase of Ce³⁺ content. Furthermore, the peak of PL spectra is situated at 500 nm under excitation at ∼400 nm. The relationship between the luminescent properties and crystal structure was studied in detail. Ce³⁺, Mn²⁺ codoped Ca_2.5Sr_0.5Al₂O₆ phosphors also showed interesting luminescent properties when focused on the PL spectra excited at 365 nm. Obvious different decreasing trends of blue and cyan emission components were observed in Ca_2.5Sr_0.5Al₂O₆:0.11Ce³⁺,<i>x</i>Mn²⁺ phosphors with the increase in Mn²⁺ content, suggesting different energy transfer efficiencies from blue- and cyan-emitting Ce³⁺ to Mn²⁺. Phosphors with high color-rendering index (CRI) values are realized by adjusting the doping content of both Ce³⁺ and Mn²⁺. Studies suggest that the Ca_2.5Sr_0.5Al₂O₆:Ce³⁺,Mn²⁺ phosphor is a promising candidate for near UV-excited w-LEDs

Composition Screening in Blue-Emitting Li₄Sr_1+<i>x</i>Ca_{0.97–<i>x</i>}(SiO₄)₂:Ce³⁺ Phosphors for High Quantum Efficiency and Thermally Stable Photoluminescence

Photoluminescence quantum efficiency (QE) and thermal stability are important for phosphors used in phosphor-converted light-emitting diodes (pc-LEDs). Li₄Sr_1+<i>x</i>­Ca_{0.97–<i>x</i>}­(SiO₄)₂:​0.03Ce³⁺ (−0.7 ≤ <i>x</i> ≤ 1.0) phosphors were designed from the initial model of Li₄SrCa­(SiO₄)₂:​Ce³⁺, and their single-phased crystal structures were found to be located in the composition range of −0.4 ≤ <i>x</i> ≤ 0.7. Depending on the substitution of Sr²⁺ for Ca²⁺ ions, the absolute QE value of blue-emitting composition-optimized Li₄Sr_1.4­Ca_0.57­(SiO₄)₂:​0.03Ce³⁺ reaches ∼94%, and the emission intensity at 200 °C remains 95% of that at room temperature. Rietveld refinements and Raman spectral analyses suggest the increase of crystal rigidity, increase of force constant in CeO₆, and decrease of vibrational frequency by increasing Sr²⁺ content, which are responsible for the enhanced quantum efficiency and thermal stability. The present study points to a new strategy for future development of the pc-LEDs phosphors based on local structures correlation via composition screening