Eu3+ Site Distribution and Local Distortion of Photoluminescent Ca3WO6:(Eu3+, K+) Double Perovskites as High‐Color‐Purity Red Phosphors

Abstract In this study, Eu3+ and K+ co‐doped Ca3WO6 double perovskite, a high‐color‐purity red phosphor, is quantitatively investigated using synchrotron X‐ray diffraction Rietveld refinement, energy dispersive X‐ray spectroscopy, and high‐resolution PL spectroscopy. The Eu3+ fluorescence line‐narrowing (FLN) results, used to estimate the Eu3+ occupation at given sites (so‐called A and B sites) in the host crystal (A2BMO6; A, B = Ca; M = W), reveal that the Eu3+ ions have a twin distribution in both the A and B sites with high asymmetry ratios of ΛA = 9.7 and ΛB = 10.7, respectively. More interestingly, at lower Eu3+ doping levels, the ions are predominantly located at the B sites (≈75%), indicating that the high color purity of Ca3WO6:(Eu3+, K+) is mainly caused by the high asymmetry ratios of the Eu3+ sites. Rietveld refinement combined with the FLN technique provides more reliable results for increasing the Eu3+ substitution at the A site with Eu3+ and K+ doping concentrations, which lower the lattice energy of Ca3WO6:(Eu3+, K+). The structural distortions owing to K+ co‐doping in terms of the quadratic elongation and bond‐angle variance exhibit good correlations with the Ca(Eu)O12 A‐site cuboctahedra and Ca(Eu)O6 B‐site octahedra, partially accounting for the higher Λ values.