Chemical Unit Cosubstitution and Tuning of Photoluminescence in the Ca2(Al1–xMgx)(Al1–xSi1+x)O7:Eu2+ Phosphor

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

The union of structural and spectroscopic modeling can accelerate the discovery and improvement of phosphor materials if guided by an appropriate principle. Herein, we describe the concept of “chemical unit cosubstitution” as one such potential design scheme. We corroborate this strategy experimentally and computationally by applying it to the Ca2(Al1–xMgx)(Al1–xSi1+x)O7:Eu2+ solid solution phosphor. The cosubstitution is shown to be restricted to tetrahedral sites, which enables the tuning of luminescent properties. The emission peaks shift from 513 to 538 nm with a decreasing Stokes shift, which has been simulated by a crystal-field model. The correlation between the 5d crystal-field splitting of Eu2+ ions and the local geometry structure of the substituted sites is also revealed. Moreover, an energy decrease of the electron–phonon coupling effect is explained on the basis of the configurational coordinate model.
 

Synthesis, structure and tunable red emissions of Ca(Al/Si)2N2(N1−xOx):Eu2+prepared by alloy-nitridation method

J. Lumin., 2013, 137, 173. https://doi.org/10.1016/j.jlumin.2012.12.053

 A series of phosphors, Eu-doped Ca(Al/Si)2N2(N1−xOx), derivatives of CaAlSiN3, were synthesized by alloy-nitridation method. We demonstrated that their emission peaks can be tuned from 650 nm to 610 nm by oxygen preferential substitutions of nitrogen located at one of two crystallographic sites. Two luminescent centers corresponding to two types of Eu2+-coordination modes, i.e. EuNI2NII3 and EuNI2NII2O, were identified and accounted for the emission band structures, emission band shifts with oxygen/nitrogen substitutions, and the dependence of peak position and integrated emission intensity on temperature. As a typical example, Ca(Al/Si)2N2(N0.80O0.20):0.02Eu showed intense orange–red emission peaking at 622 nm and kept the feature of excellent chemical stabilities, which would have potential applications in fabricating the white light-emitting diode. The excellent luminescent properties of these materials, such as wavelength-tunable red emission and excellent chemical stabilities, make them practical for use in typical LED package.

Synthesis of YAG phosphor particles with excellent morphology by solid state reaction

J. Cryst. Growth., 2013, 365, 24. https://doi.org/10.1016/j.jcrysgro.2012.12.022

Cerium doped yttrium aluminum garnet (YAG:Ce) has been chosen as WLED phosphors for its appropriate spectral property. However, YAG powders synthesized by several methods do not satisfy commercial requirements in mobility, size distribution, luminescent intensity, etc. With flux added in the synthesis, well-shaped crystallites can nucleate and grow in the wetted micro domains. High temperature compensates the adverse effect of intermediate product on particle size. The final products are phosphor powders composed of uniformly distributed large particles. Preferred orientation in the XRD patterns confirms that the isolated particles are single crystals other than agglomeration of fine grains. This kind of phosphors has a better performance in WLED devices. This work will improve the commercial production of WLED phosphors.

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

J. Lumin., 2011, 131, 2, 336. https://doi.org/10.1016/j.jlumin.2010.10.032

Oxonitridosilicate phosphors with compositions of (Y1−xCex)2Si3O3N4 (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce3+ ions have substituted for Y3+ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce3+ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce3+ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.

Crystal structure and photoluminescence of (La1-xCex)5Si3O12N

J. Alloys Compd., 2011, 509, 5, 2099. https://doi.org/10.1016/j.jallcom.2010.10.148

Oxonitridosilicate phosphors with compositions of (La1−xCex)5Si3O12N (x = 0–0.1) have been synthesized. The XRD analyses show that all the compounds are single polycrystalline La5Si3O12N phase. La atoms occupy two crystallographic sites in the structure. Two groups of photoluminescence spectra have been observed and can be ascribed to the excitation and emission of the two types of Ce3+ photoluminescence centers (Ce(1)3+ and Ce(2)3+) in the crystallographic sites of La(1) and La(2). The energy transfer between the two types of photoluminescence centers has been discussed. Schematic energy levels of Ce3+ ions at the two crystallographic sites are given. Luminescence concentration quenching occurs when Ce content is more than 3 mol%. The quenching temperature is evaluated to be about 406 K for the 3 mol% Ce content sample. This study shows these phosphors potential candidates for application in three-phosphor-converted white LEDs.

Synthesis, structure and luminescence of LaSi3N5:Ce3+ phosphor

J. Lumin., 2009, 129, 3,165. https://doi.org/10.1016/j.jlumin.2008.08.005

In this work, new LaSi3N5:Ce3+ phosphors have been synthesized by solid-state reaction. Rietveld refinement of the crystal structure of La1−xCexSi3N5 reveals that Ce atoms substituted for La atoms occupy 4a crystallographic positions. Broad emission and excitation bands observed were attributed to the transitions between the doublet ground state of the 4f1 configuration and the crystal field components of the 5d1 excited state. At 77 K, the centroid and crystal field splitting εcfs of the 5d levels of Ce3+ in LaSi3N5:Ce3+ compounds were valuated at 33.4×103 and 11.3×103 cm−1, respectively. The zero-phonon line and the Stokes shift were measured to be 26.0×103 and 5.0×103 cm−1, respectively.

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

Chin. Phys. B., 2009,18, 8, 3555. https://iopscience.iop.org/article/10.1088/1674-1056/18/8/070

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.