Chem. Mater., 2017, 29, 17, 7563–7570. https://doi.org/10.1021/acs.chemmater.7b02724

Eu²⁺ local environments in various crystallographic sites enable the different distributions of the emission and excitation energies and then realize the photoluminescence tuning of the Eu²⁺ doped solid state phosphors. Herein we report the Eu²⁺-doped Ca₁₀M(PO₄)₇ (M = Li, Na, and K) phosphors with β-Ca₃(PO₄)₂-type structure, in which there are five cation crystallographic sites, and the phosphors show a color tuning from bluish-violet to blue and yellow with the variation of M ions. The difference in decay rate monitored at selected wavelengths is related to multiple luminescent centers in Ca₁₀M(PO₄)₇:Eu²⁺, and the occupied rates of Eu²⁺ in Ca(1), Ca(2), Ca(3), Na(4), and Ca(5) sites from Rietveld refinements using synchrotron power diffraction data confirm that Eu²⁺ enters into four cation sites except for Ca(5). Since the average bond lengths d(Ca–O) remain invariable in the Ca₁₀M(PO₄)₇:Eu²⁺, the drastic changes of bond lengths d(M–O) and Eu²⁺ emission depending on the variation from Li to Na and K can provide insight into the distribution of Eu²⁺ ions. It is found that the emission band at 410 nm is ascribed to the occupation of Eu²⁺ in the Ca(1), Ca(2), and Ca(3) sites with similar local environments, while the long-wavelength band (466 or 511 nm) is attributed to Eu²⁺ at the M(4) site (M = Na and K). We show that the crystal-site engineering approach discussed herein can be applied to probe the luminescence of the dopants and provide a new method for photoluminescence tuning.

Inorg. Chem., 2017, 56, 19, 11837–11844. https://doi.org/10.1021/acs.inorgchem.7b01816

Exploring high-performance narrow-band red-emitting phosphor is an important challenge for improving white light LEDs. Here, on the basis of three interesting nitride phosphors with similar vierer rings framework structure, two phosphor series, Eu2+-doped Sr(LiAl)1–xMg2xAl2N4 and Sr(LiAl3)1–y(Mg3Si)yN4 (x, y = 0–1), are successfully synthesized by a solid state reaction. They show narrow-band red emission with tunable emission peaks from 614 to 658 nm and 607 to 663 nm. The varying luminescence behaviors with composition and structure are discussed based on centroid shift, crystal field splitting and Stokes shift. On the basis of experimental data, we construct the host referred binding energy (HRBE) and vacuum referred binding energy (VRBE) schemes of divalent/trivalent lanthanide-doped end-member compounds, and further give thermal quenching mechanism of these series phosphors.

Inorg. Chem. 2018, 57, 2, 609–616. https://doi.org/10.1021/acs.inorgchem.7b02431

A series of Eu2+-doped orthosilicate-orthophosphate solid-solution phosphors, KxBa1.97–x(Si1–xPx)O4:0.03Eu2+, have been synthesized via the conventional solid-state reaction. Using varying compositions, the lowest-energy excitation can be tuned from 470 to 405 nm, with an emission from 515 to 423 nm. We determined how chainlike cation polyhedra controlled excitation- and emission-band features by introducing in-chain characteristic length d22 and outside-chain characteristic length d12 and that there was a nearly linear relationship between the lowest-energy-excitation position and the ratio of d22 to d12. This influence of chainlike polyhedra on luminescence can be understood through the inductive effect. Luminescent thermal properties are improved remarkably by the cosubstitution of K+ and P5+ ions for Ba2+ and Si4+ ions with a T1/2 over 200 °C. We have established the host-referred-binding-energy (HRBE) and vacuum-referred-binding-energy (VRBE) schemes for the electronic structure of the series of lanthanide-doped phosphors according to the Dorenbos model and given a thermal-quenching mechanism for this series of phosphors.

J. Am. Chem. Soc., 2015, 137, 39, 12494. https://pubs.acs.org/doi/10.1021/jacs.5b08315.