An insight into the preferential substitution and structural repair in Eu2+-doped whitlockite-type phosphors-combining experiment and theoretical calculation

Due to the wide compositional variability and structural tolerance, Eu2+-doped whitlockite β-Ca3(PO4)2 (TCP)-type phosphors with different visible emissions have been realized by manipulating the chemical compositions. However, the site preference of the dopant Eu2+ at the multi-cation sites has been a dispute recently. In this study, a combination of experimental and theoretical calculations was applied to identify the preferential occupancy and variable optical behavior of Eu2+ through the evolution of Ca10.5−0.5xKx(PO4)7 (0 ≤ x ≤ 1) isostructures. Both spectral analysis and theoretical calculations reveal that Eu2+ prefers to occupy the loose Ca(4) sites and produce a narrow band emission around 420 nm. Moreover, a continuous increase in the K content compels the redistribution of dopants from the Ca(4) into the Ca(3) site, resulting in an abrupt spectral shift to 470 nm. Moreover, a vacancy defect repair effect was proposed for the enhancement in the luminescence of Ca10.5−0.5xKx(PO4)7:Eu2+, in which the incorporation of K+ repaired the half-unoccupied Ca(4) sites and benefitted the reduction of Eu3+ to Eu2+. Moreover, to further prove the significant vacancy repair and dopant redistribution effects, Na+- and Li+-doped systems were investigated. In addition, together with the reported Sr2+- or Gd3+-doped systems, the preferential occupancy and saltatory spectral variations of Eu2+ in whitlockite-type phosphors were uniformly clarified by cationic modification events.