Tolerance Factor and Phase Stability of the Normal Spinel Structure

Cryst. Growth Des., 2020, 20, 3, 2014–2018

Tolerance factor for the normal-spinel structure is introduced as a structural descriptor to predict the phase stability. It is derived following similar principles as those of perovskite and garnet structures, i.e., the geometrical relationship between multitype polyhedra. The calculation of tolerance factor only requires the ionic radii of compositional components involved. A survey of the tolerance factor over 120 AB2X4-type compounds proves the reliability. The numerical values are distributed below 1, which originates from the compressed octahedra which support the framework of spinel. The tolerance factor will be helpful in machine learning and high-throughput screening methods for fast evaluation of phase stability and materials properties of spinel-type compounds.

Structure and luminescence of Ca2Si5N8:Eu2+ phosphor for warm white light-emitting diodes

Chin. Phys. B., 2009,18, 8, 3555.

We have synthesized Ca2Si5N8:Eu2+ phosphor through a solid-state reaction and investigated its structural and luminescent properties. Our Rietveld refinement of the crystal structure of Ca1.9Eu0.1Si5N8 reveals that Eu atoms substituting for Ca atoms occupy two crystallographic positions. Between 10 K and 300 K, Ca2Si5N8:Eu2+ phosphor shows a broad red emission band centred at ~1.97 eV–2.01 eV. The gravity centre of the excitation band is located at 3.0 eV–3.31 eV. The centroid shift of the 5d levels of Eu2+ is determined to be ~1.17 eV, and the red-shift of the lowest absorption band to be ~0.54 eV due to the crystal field splitting. We have analysed the temperature dependence of PL by using a configuration coordinate model. The Huang–Rhys parameter S = 6.0, the phonon energy hv = 52 m eV, and the Stokes shift ΔS = 0.57 eV are obtained. The emission intensity maximum occurring at ~200 K can be explained by a trapping effect. Both photoluminescence (PL) emission intensity and decay time decrease with temperature increasing beyond 200 K due to the non-radiative process.

Double perovskite Cs2AgInCl6:Cr3+: broadband and near-infrared luminescent materials

Inorg. Chem. Front., 2019,6, 3621-3628

Searching for high performance and broader applications of inorganic halide perovskites has drawn extensive attention. In this work, a Cr3+-doped halide perovskite, Cs2AgInCl6:Cr3+, which exhibits broadband near-infrared (NIR) emission is first obtained via the traditional high temperature solid-state reaction. A broad emission band ranging from 850 to 1350 nm centered at 1010 nm with a full-width at half-maximum (FWHM) of 180 nm is assigned to the spin-allowed 4T2 → 4A2 transition of octahedrally coordinated Cr3+ ions in a very weak crystal-field environment. The excitation bands centered at 353, 565 and 800 nm can be attributed to the absorption of the Cs2AgInCl6 host, the Cr3+ d–d transitions of 4A2 → 4T1 and 4A2 → 4T2, respectively. Upon 760 nm excitation, the photoluminescence quantum yield (PLQY) of Cs2AgIn0.9Cl6:0.1Cr3+ is about ∼22.03%. Cs2AgInCl6:Cr3+ phosphors with such broadband NIR emission have potential in phosphor converted light emitting diodes (pc-LEDs) which have applications in bioimaging and biomonitoring.

Sunlight-activated yellow long persistent luminescence from Nb-doped Sr3SiO5:Eu2+ for warm-color mark applications

J. Mater. Chem. C, 2020,8, 1143-1150.

Warm-color persistent luminescent materials are strongly desired for signage markings and medical imaging in comparison with green or blue counterparts. Herein we report a novel yellow long-persistent phosphor, Nb-doped Sr3SiO5:Eu2+, with a peak wavelength of ∼580 nm and persistence time of more than 14 hours at the 0.32 mcd m−2 threshold value after UV radiation. A combination of thermoluminescence (TL), thermoluminescence excitation (TLE), electron paramagnetic resonance (EPR) measurements and density functional theory (DFT) calculations reveals that the persistent luminescence enhancement is attributed to a significant Nb-induced increase of oxygen vacancies that act as electron trapping centers with appropriate trap depths. Groups of time-dependent color-change images are realized with this material, which has potential applications as anti-counterfeit and indicator marks. This investigation also expands the application of transition metal (TM) ions to the field of persistent luminescence and would motivate further exploration of TM substitutions to design and improve silicate or aluminosilicate persistent phosphors with superior performance.

Insight into the Relationship between Crystal Structure and Crystal-Field Splitting of Ce3+ Doped Garnet Compounds

J. Phys. Chem. C., 2018, 122, 6, 3567–3574.

The common understanding of the negative relationship between bond lengths and crystal-field splitting (CFS) is renewed by Ce3+ doped garnets in this work. We represent the contradictory relationship between structure data and spectroscopic crystal-field splitting in detail. A satisfactory explanation is given by expressing crystal-field splitting in terms of crystal-field parameters, on the basis of structural data. The results show that not only the bond length, but also the geometrical configuration have influence on the magnitude of crystal-field splitting. Also it is found that the ligand oxygen behaves differently with regard to multiple site substitution in garnet structure.