Cation and polyhedron substitution strategies: Effects on local crystal structure and on Bi3+ and Eu3+ co-doped inverse garnet phosphors’ luminescence property

Following the rapid growth of lightning technology, the development of red-emitting phosphors is effective for improving color temperature and color rendering index for w-LEDs devices. Herein, a single phased garnet phosphor with cation and polyhedron substitution modification was firstly prepared. For Mg₃Gd₂Ge₃O₁₂: Bi³⁺, Eu³⁺, the intensity has been remarkably improved by about 16% compared to the one without Bi³⁺ sensitization. The energy transfer mechanism is identified in this work. Based on cation and polyhedron substitution strategies, novel phosphors with different compositions were obtained and further modified the PL properties. With Lu³⁺ substitution, the bond lengths between Bi³⁺ ion and anion ligands are decreased and the site symmetry has been strengthened, which leads to a 21 nm blue shift when Lu³⁺ totally replaced Gd³⁺ ions. In addition, Lu³⁺ and [SiO₄] substitution strategies both effectively increased symmetric rigid structure, which leads to a significant improvement in thermal stability, indicating the samples own great potential in optical applications This work provides a new insight to synthesis red-emitting phosphors for warm white-LEDs.     

Red-shift and improved afterglow of Sr3Al2-xBxO5Cl2:Eu2+, Dy3+ phosphors via a cation substitution strategy

Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ (x = 0, 0.2, 0.4) long persistent phosphors were prepared via solid-state process. The pristine Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺ phosphor exhibits orange/red broad band emission around 609 nm, which can be attributed to the electric radiation transitions 4f⁶5 d¹→4f⁷ of Eu²⁺. Upon the same excitation, the B³⁺-doped Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphors display red-shift from 609 nm to 625 nm with increasing B³⁺ concentrations. The XRD patterns show that Al³⁺ can be replaced by B³⁺ in the host lattice at the tetrahedral site, which causes lattice contraction and crystal field enhancement, and thereafter achieves the red-shift on the emission spectrum. The XPS investigation provides direct evidence of the dominant 2-valent europium in the phosphor, which can be ascribed for the broad band emission of the prepared phosphors. The afterglow of all phosphors show standard double exponential decay behavior, and the afterglow of Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺is rather weak, while the sample co-doped with B³⁺shows longer and stronger afterglow, as confirmed after the curve simulation. The analysis of thermally stimulated luminescence showed that, when B³⁺ is introduced, a much deeper trap is created, and the density of the electron trap is also significantly increased. As a result, B³⁺ ions caused redshift and enhanced afterglow for the Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphor.     

A new mechanoluminescence phosphor Na3Sc2(PO4)3:Eu2+: Phase transition-assisted defect formation in a polymorphic composition

A new mechanoluminescent phosphor was developed from a sodium (Na) superionic conductor (NASICON)-structured Na₃Sc₂(PO₄)₃:Eu²⁺ phosphor that is known for its self-healing properties. The compound that crystalized assuming monoclinic C2/c symmetry was found to be blue-emitting, with no noticeable persistent luminescence. Thermoluminescence analysis showed that the phosphor had two prominent distinct thermal emission bands corresponding to the high-temperature β- and γ-phases of the composition. The mechanoluminescence properties of the material that does not have any persistent luminescence at room temperature were investigated by imparting impulsive strain. The compound on charging with 365 nm radiation was found to have significant mechanoluminescent emission originating from shallow defects present in the β-phase of composition that formed by the stress-induced phase transition process. Its emission characteristics and temporal behavior were investigated by varying the impact velocity.     

Narrow-band emitters in LED backlights for liquid-crystal displays

Over the last decade, narrow-band emitters have been recognized as key enablers for light emitting diodes (LEDs) backlights in liquid-crystal displays (LCDs) by competing with other display technologies. Today, efforts have been devoted to the exploration of narrow-band green/red luminescent materials with high quantum efficiency and excellent stability to optimize the performance of LED backlights. This review first presents an overview of the significant progress made in the development of narrow-band emitters used in LED backlights for LCDs with the emphasis on the versatile materials databases from doped phosphors to luminescent II–VI, III-V semiconductor quantum dots, and the recent halide perovskites nanocrystals and bulk metal halides. Subsequently, the correlation of structure-luminescence properties, and the device performance optimization of these emitters have been analyzed. The focus is placed on summarizing and comparing the remarkable examples of outdated and new narrow-band luminescent materials as potential candidates in LED backlights. Finally, the outlooks and challenges in discovering new narrow-band emitters have been proposed.     

Oxidation of doped europium in BaMgAl10O17 by annealing studied by x‐ray‐absorption fine‐structure measurements

Abstract— We studied the influence of annealing in air on doped europium in BaMgAl₁₀O₁₇ by performing x‐ray absorption fine‐structure measurements. We determined the oxidation of doped divalent europium by annealing in air at over 500°C. The interatomic distance between the europium and the surrounding oxygen atoms was compressed by oxidation. It also appears that the oxidation process of europium is determined by the diffusion of oxygen into BaMgAl₁₀O₁₇.     

Luminescent properties of Sr2MgSi2O7 and Ca2MgSi2O7 long lasting phosphors activated by Eu, Dy

Long lasting afterglow phosphors Sr₂MgSi₂O₇:Eu,Dy and Ca₂MgSi₂O₇:Eu,Dy were prepared by solid-state reaction method. It is revealed by the results that both phosphors show two emission peaks that are caused by the different emitting centers Eu²⁺ held in the host lattice. Wavelength shift was observed due to the slight differences in the structure parameters of the two hosts. Investigation on afterglow property shows that Sr₂MgSi₂O₇:Eu,Dy phosphor held a better afterglow property than Ca₂MgSi₂O₇:Eu,Dy phosphor. Thermal simulated luminescence study indicates that the long afterglow is generated by a higher trap concentration formed by the co-doped rare earth ions within the host.     

Influence of ZrO2 particles on the optical properties of pc-LEDs

Experimental and modeling progress and results aiming to increase the color uniformity of hemisphere-type pcW-LEDs are proposed. By adding micrometric zirconia particles, the light scattering is enhanced, that induces a decrease of phosphor necessary to obtain a specific CCT. The optical model is able to determine the optical properties (CCT, angular CCT distribution, chromaticity and packaging efficiency) in a hemisphere LED for various amount of YAG-phosphor and ZrO₂-zirconia particles. Based on previous process, the work is in the first step to fit the effective radius and refractive index that will be implemented in the optical model. In the second step, the optical model is compared with the experimental measurement to determine the absorption coefficient and conversion efficiency of a package of silicone resin containing phosphor and zirconia. Finally, the model, confirmed by selected experimental results, allows determining the optical properties of any king of package that lead to a CCT emission ranging from 4500 K to 6500 K. The analysis of these data is interpreted by comparing, for a specific CCT, the phosphor loss, the packaging efficiency and the angular distribution of CCT. The results show that if the effort is targeted on one of the previous parameters, there is always a counterpart on the other ones. Increasing the color uniformity will induce to decrease the packaging efficiency.     

Low-temperature synthesis of nanocrystalline ZnGa2O4:Tb phosphors via the Pechini method

The synthesis of trivalent terbium doped ZnGa₂O₄ nanosized new phosphors by the Pechini method was reported. Well-crystallized ZnGa₂O₄:Tb³⁺ phosphors were obtained at low-temperature about 550 °C. The phosphors formed porous agglomerates which consist of spherical nanocrystallites with a uniform size at about 30 nm. The photoluminescence of the phosphors included both the luminescence of ZnGa₂O₄ host and characteristic emission of Tb³⁺, and the excitation spectra showed an energy transfer from the host lattice to the activator. The Tb³⁺ emission from the phosphors prepared by the Pechini process was more intensive than that of phosphors by solid-state reaction process.     

Effect of NaCl on the properties of Eu-doped Ca-α-SiAlON phosphors prepared by combustion synthesis

Eu-doped Ca-α-SiAlON phosphors, featuring high phase purity, uniform particle size of 3–5 μm and good luminescent properties with a yellow emission spectrum under blue light excitation, were prepared by a highly efficient combustion synthesis (CS) method. A certain amount of NaCl was applied as an innovative additive to regulate and control the properties of synthesized phosphors. Further, the effects of NaCl additive in the CS system were systematically investigated and rational proposed. It was found that the effect on accelerating nitridation and crystallization played a dominant role in the reaction as the content of NaCl was less than 6 wt%, while the effect of absorbing reaction heat through vaporization was dominant with the further-increased content of NaCl. The intensity of the emission spectrum for the sample doped with 6 wt% of NaCl was remarkably enhanced, nearly 40% more than the sample which was not NaCl-doped. Moreover, a continuous blue-shift phenomenon in emission spectra was observed with the increased content of NaCl.     

Spectroscopic characterizations of Er doped LaPO4 submicron phosphors prepared by homogeneous precipitation method

Hexagonal shaped LaPO₄ submicron particles doped with various concentrations of Er were successfully prepared by homogenous precipitation method using metal nitrates and ammonium phosphate. Particles of approximate particle size 125 nm and size distribution of 85 nm are obtained with good crystallinity. After heat treatment at 1200 °C for 2 h, the particles are characterized for their various optical properties such as absorption, emission, fluorescence decay and optical band gap. Optical absorption and emission data are numerically analyzed with the help of Judd–Ofelt model to evaluate various radiative spectral properties such as radiative decay rates, radiative quantum yield, emission cross-section and fluorescence branching ratios of various emission transitions. Though the radiative quantum yield of 1554 nm emission approaches the theoretical limit of 100%, the experimentally measured quantum yield is only 11% at 12 W/cm² at 980 nm excitation power density in 2% Er doped LaPO₄.