Fabrication of Ce:YAG,Ce,Cr:YAG and Ce:YAG/Ce,Cr:YAG dual-layered composite phosphor ceramics for the application of white LEDs

(Ce_0.001Y_0.999)₃Al₅O₁₂ and (Ce_0.001Y_0.999)₃(Cr_xAl_1−x)₅O₁₂ (x=0.001−0.005) transparent ceramics were synthesized by the solid state reaction and vacuum sintering and their optical properties were measured. High quality white light was obtained when the Ce:YAG/Ce,Cr:YAG dual-layered composite ceramic was directly combined with commercial blue LED chip. A maximum luminous efficacy exceeding 76 lm/W at a low correlated color temperature of 4905 K was obtained. The color temperature can be controlled by variations of Cr³⁺ concentration and the ceramic thickness. Hence, the Ce:YAG/Ce,Cr:YAG dual-layered composite phosphor ceramic may be a promising candidate for white LEDs.     

Ce:YScAG phosphor-converted transparent ceramics with high thermal saturation and weak concentration quenching for LED and LD white lighting

In the high-power white light LEDs/LDs area, obtaining phosphor-converted materials with high thermal stability and high luminous emittance with proper blue/yellow light ratio has been the main challenge in recent years. In this study, a group of (Ce_xY_1-x)₃(Sc_yAl_1-y)₅O₁₂ transparent ceramics with high optical quality were proposed to rise to that challenge. Their spectra were regulated by incorporating Sc³⁺, showing blue shifted emission bands (peak position from 554 nm–538 nm), blue shifted excitation bands (462–445 nm) and narrowed full width at half maxima (120–112 nm). Significantly, the prepared Ce:YScAG transparent ceramics (TC) exhibited decent thermal quenching performance with the photoluminescence intensity at 150 °C maintaining 88.7% of its original value at room temperature. The Sc incorporation impacted the atoms’ occupation and distance, crystal field splitting and energy band structure. Under remote LD excitation mode, the luminous efficiency of the prepared Ce:YScAG TC can achieve 164.8 lm/W. And even if the Ce³⁺ doping reaches 2.0 at%, the LE can still maintain 117.8 lm/W, exhibiting decent concentration quenching characteristic. Consequently, Ce:YScAG TCs have great potential as promising phosphor-converted materials in future high-power LED and LD white lighting.     

Ce/Mn/Cr: Y3Al5O12 phosphor ceramics for white LED and LD lighting with a high color rendering index

Ce/Mn/Cr: Y₃Al₅O₁₂ transparent ceramics with a pure garnet structure and a high color rendering index were prepared by a solid-state reaction method. Mn²⁺ and Cr³⁺ enhance the emission between 500 and 700 nm and expand the conventional Ce: YAG phosphors spectrum. The Ce³⁺ can work both, as activators and sensitizers, and the intense energy transfer from Ce³⁺ to Mn²⁺/Cr³⁺ is realized through the non-radiative and radiative processes. In the sample with the optimized doping concentration the high color rendering index (CRI) value of 75.3 can be achieved under a 450 nm laser diode excitation. The chromaticity coordinates can be tuned from (0.3125, 0.3232) to (0.2917,0.2851) by varying the doping concentration. With the increasing Mn²⁺/Cr³⁺ doping concentration, the lifetime of Ce³⁺, quantum efficiency and luminous efficiency are all gradually decreased. This work effectively offers a scheme for realizing the high color rendering performance of phosphor-converted transparent ceramics in white LEDs/LDs.     

Spectrum regulation of YAG:Ce transparent ceramics with Pr,Cr doping for white light emitting diodes application

YAG:Ce transparent ceramics with high luminous efficiency and color render index were prepared via a solid state reaction-vacuum sintering method. Cr³⁺and Pr³⁺ were applied to expand the spectrum of YAG:Ce transparent ceramics. As prepared ceramics exhibit luminescence spectrum ranging from 500 nm to 750 nm, which almost covers full range of visible light. After the concentration optimization of Ce³⁺, Pr³⁺ and Cr³⁺, high quality white light was obtained by coupling the YAG:Ce,Pr,Cr ceramics with commercial blue LED chips. Color coordinates of the YAG:Ce,Pr,Cr ceramics under 450 nm LED excitation vary from cold white light to warm white light region. The highest luminous efficiency of WLEDs encapsulated by transparent YAG:Ce,Pr,Cr ceramic was 89.3 lm/W, while its color render index can reach nearly 80. Energy transfers between Ce³⁺ → Pr³⁺ and Ce³⁺ → Cr³⁺ were proved in co-doped ceramic system. Transparent luminescence ceramics accomplished in this work can be quite prospective for high power WLEDs application.     

Fabrication and optical properties of divalent Cu2+ ions incorporated Ce:YAG transparent ceramics for white LEDs

Transparent Ce:YAG ceramics via Cu²⁺ incorporating annealed at 1450?°C were successfully fabricated by the solid-state method to probe their potential applications in white light-emitting diodes (LEDs). The influence of Cu²⁺ concentration on the microstructure and optical properties of the Ce:YAG transparent ceramics were systematically investigated. The as-prepared ceramics possessed clean grain boundaries and homogeneous grain size distribution ranging from 3.7 to 6.5?µm. With the addition amount of Cu²⁺ increased, the red component of ceramics gradually increased and then decreased, it reached a maximum of 13.0% at 1.5?at% Cu²⁺ incorporation. By combining with commercially blue LED chips (465?nm) directly, the obtained optimal chromaticity coordinates (CIE) and correlated color temperature (CCT) of ceramics were (x?=?0.3335, y?=?0.3412) and 5450?K, respectively, while its color render index (CRI) was nearly 70 at the thickness of 1.0?mm. Therefore, this study provided an efficient approach to tailor the luminescence property of Ce:YAG ceramic for white LEDs.     

The effect of Lu3+ doping upon YAG:Ce phosphor ceramics for high-power white LEDs

Intense green emission is extremely significant to the color rendering index (CRI) of white LEDs. Various green-emitting YLuAG:Ce phosphor ceramics were successfully prepared by vacuum sintering. The effects of Lu³⁺ doping on structure and luminescence property were investigated in detail. In comparison with YAG:Ce, YLuAG:Ce ceramics own smaller grain size, better luminescence performance and higher thermal stability. The photoluminescence (PL) intensity of YLuAG:Ce ceramics increases by 23.6 % due to the “light scattering enhanced effect”. Furthermore, the Ce³⁺ emission is obviously blue-shifting from 533 nm to 519 nm, and the intensity of YLuAG:Ce ceramics reduces only about 8.9 % at 250 °C, showing better thermal stability (vs 11.1 % of YAG:Ce). The LE of LED packaged by YLuAG:Ce ceramic is up to 148.88 lm/W when the doping Lu³⁺ y is 2.1. The above results show that tailored YLuAG:Ce phosphor ceramic is a potential green-emitting color converter for high-power LEDs (hp-LEDs).     

The influence of air annealing on the microstructure and scintillation properties of Ce,Mg:LuAG ceramics

The microstructures and optical properties of Ce,Mg:Lu₃Al₅O₁₂ scintillator ceramics are investigated with particular focus on the effect of postannealing in air from 1000 to 1450°C. The formation of Al₂O₃ clusters after annealing above 1300°C is evidenced by scanning electron microscopy. The presence of this secondary phase is tentatively explained by the occurrence of Ce and Mg evaporation, proved by inductive coupled plasma optical emission spectrometry measurements, followed by defect diffusion and clustering during high temperature annealing. Meanwhile, optical investigations including absorption, X-ray induced luminescence, light yield, scintillation decay, and thermoluminescence prove the positive role of post-annealing that leads to a brighter and faster scintillation emission. This behavior is associated to the removal of oxygen vacancies occurring during such treatments. In parallel, the partial conversion of Ce³⁺ ions into Ce⁴⁺ is also observed as a consequence of annealings and the role of Ce⁴⁺ ions in the scintillation process is discussed.     

Influence of calcium doping concentration on the performance of Ce,Ca:LuAG scintillation ceramics

Ce,Ca:LuAG scintillation ceramics with different Ca²⁺ co-doping concentrations were prepared by the solid-state reaction method. The concentration of Ce³⁺ was fixed at 0.3 at% and the concentration of Ca²⁺ ranged from 0 to 1.2 at%. We systematically studied how the Ca²⁺ concentration affects the optical quality of Ce,Ca:LuAG ceramics by influencing the microstructure in the vacuum sintering and HIP post-treatment. Good optical transmittance could be obtained with Ca²⁺ concentrations between 0.05 and 0.8 at%, which reached 76.0–81.9 % at 520 nm. The PL and scintillation decay times decrease with increasing Ca²⁺ concentration up to 0.6 at% with no clear trend above this value. The light yield (LY) values at different shaping times decrease with increasing Ca²⁺ concentration but the fast scintillation component (LY_0.5 μs/ LY_3.0 μs) increases significantly from 79 % to 97 %. The co-doping of Ca²⁺ also reduces the afterglow level by more than one order of magnitude.     

Solid-state reaction method to 6Li,Ce:YAG ceramics for thermal neutron detection

ABSTRACT

The crystal structures and optical properties of 5% ⁶Li:Ce_0.09Y_2.91Al₅O₁₂ transparent ceramics prepared by solid-state reaction with different vacuum sintering temperature were investigated in this paper. The results reveal that with the increasing of sintering temperature, the transmittance of ⁶Li,Ce:YAG ceramics increases from 36% (1680°C) to 82% (1780°C) at 1000?nm, and the intensity of absorption peaks at 340 and 460?nm increases. The emission peak wavelengths of ⁶Li:Ce_0.09Y_2.91Al₅O₁₂ ceramics have been measured as 534.5?nm, and there is no red shift. The high transmittance and emission peak (at 534.5?nm) suggested that this material could be a candidate for neutron detection applications.     

Transparent YAG:Ce ceramic with designed low light scattering for high-power blue LED and LD applications

Yellow-emitting YAG:Ce transparent ceramic is recognized as an ideal color converter in high-power blue LEDs and LDs, but the absence of scattering centers in its microstructure leads to a low light extraction efficiency and poor light uniformity. Here, taking advantage of the scattering effect and the transparency of YAG:Ce ceramics, Ce-free YAG phase was used as a second component to form a composite with YAG:Ce phosphor. The sintered YAG:Ce-YAG ceramic possessed a high transparency of ～63 % and a thermal conductivity of 8.9 Wm^?1 K^?1. Due to its beneficial thermal properties and high external quantum efficiency of 70.2 %, the YAG:Ce-YAG ceramic could be excited under a high blue-laser flux density of up to 9.60 W/mm² and showed a luminous emittance of 1220 lm/mm². Due to light scattering arising from the slightly different refractive indices of the two phases, the designed YAG:Ce-YAG ceramic showed better lighting effects than a single-phase transparent YAG:Ce ceramic.     

Fast Ce,Ca:LuAG scintillation ceramics for HEP: Fabrication,characterization, and computation

High-energy physics community is looking for a hard, fast, and low-cost scintillation material, and Ce:Lu₃Al₅O₁₂ (Ce:LuAG) ceramic is one of the competitive candidates. This work presents Ce,Ca:LuAG scintillation ceramics with good optical quality, and the influence of Ce and Ca concentrations on optical and scintillation properties was fully analyzed. At relatively low level of Ce concentration, the less Ca²⁺ content is needed to achieve a significant intensity increase in fast scintillation component while maintaining a relatively high light yield (LY). The introduction of only 0.1 at% Ca²⁺ could increase the LY_{0.5 μs}/LY_{3.0 μs} from 79.9% to 96.1% in Ce,Ca:LuAG ceramics of 0.1 at% Ce. First-principles investigations are further performed to reveal the tuning mechanisms of the scintillation properties of LuAG by Ce and Ca codoping. We show that the Fermi level shifts down with Ca codoping, which increases the Ce⁴⁺ content and decreases the depth of the electron traps (V_O), resulting to a faster decay. Moreover, the formation preference of Ca-V_O complexes over Ce-V_O leads to the suppression of the non-radiative decay of Ce via V_O. In summary, our study demonstrates the realization of the performance tuning of LuAG via Ce and Ca codoping.     

Optimization of Ce3+ concentration and Y4MgSi3O13 phase in Mg2+-Si4+ Co-doped Ce: YAG ceramic phosphors

As a promising replacement for nitride red phosphors, Ce: Y₃(Mg_1.8Al_1.4Si_1.8)O₁₂ (Ce: YMASG) ceramic phosphors have attracted significant attention recently for their advantages in inorganic encapsulation and massive red-shifting of Ce³⁺ emission. In this work, Ce: YMASG with different doping concentrations of Ce³⁺ and Al₂O₃, was fabricated by vacuum sintering to investigate its effects on the elimination of the impurity phase and the enhancement of the luminescent properties of white light-emitting diodes (w-LEDs). It was discovered that the emission wavelength redshifts from 592 to 606 nm as the Ce³⁺ concentration increases, while at 450 K, the emission intensity deteriorates from 0.47 to 0.36 of its initial value. The Rietveld analysis revealed the presence of an impurity phase of Y₄MgSi₃O₁₃ with a concentration of 17.021 wt% in Ce: YMASG. With the introduction of Al₂O₃, the impurity phase was eliminated from the matrix completely, the emission peak shifted to a shorter wavelength, and the thermal stability was greatly improved. When the correlated color temperature was controlled at around 3000 K in the packaged w-LEDs, the commission international de l'éclairage (CIE) chromaticity coordinates shifted toward the bottom left corner of the diagram with increasing concentration of Ce³⁺. Conversely, the luminous efficiency (LE) increased from 36 lm/W to 58.6 lm/W as the concentration of Al₂O₃ increased from 0 to 10 wt%, which demonstrated the application prospect of the fabricated phosphor in warm w-LEDs.     

Ce3+ doped Lu3Al5O12 ceramics prepared by spark plasma sintering technology using micrometre powders: Microstructure,luminescence, and scintillation properties

Ce³⁺ doped Lu₃Al₅O₁₂ (Ce:LuAG) ceramics were fabricated by the solid-state reaction method through spark plasma sintering (SPS) from 1350 °C to 1700 °C for 5 min at a pressure of 50 MPa using micro powders. The average grain size of the SPSed ceramics gradually grew from 0.42 µm (1400 °C) to 1.55 µm (1700 °C), which is nearly one order of magnitude lower than that of vacuum sintered (VSed) Ce:LuAG ceramics (~24.6 µm). Characteristic Ce³⁺ emission peaking at around 510 nm appeared and 92% photoluminescence intensity of room temperature can be reserved at 200 °C revealing excellent thermal stability. The maximum radioluminescence intensity reached around 3 times of VSed Ce:LuAG ceramics and 7.8 times of BGO crystals. The maximum scintillation light yield under γ-ray (¹³⁷Cs) excitation reached 9634 pho/MeV @ 2 μs. It is concluded that SPS technology is a feasible way to develop Ce:LuAG ceramics and further optical enhancement can be expected.     

Influence of cerium doping concentration on the optical properties of Ce,Mg:LuAG scintillation ceramics

Ce,Mg:LuAG scintillation ceramics with Ce dopant content ranging from 0.025?at.% to 0.3?at.% and constant 0.2?at.% Mg codoping were fabricated by solid-state reaction. The effects of Ce concentration and annealing conditions on the microstructure, optical quality and scintillation properties are studied in great details. Lattice parameters as well as the absorption, photoluminescence, radioluminescence and thermoluminescence characteristics are investigated as a function of Ce content. Both the photoluminescence and scintillation decays are measured as well in order to study re-absorption and concentration quenching processes. In addition, an enhanced positive effect of air annealing on radioluminescence intensity and light yield is put in evidence. Moreover, the role of the charge transfer absorption of Ce⁴⁺ is investigated. Thermoluminescence measurements are performed to investigate the influence of both air annealing and Ce concentration on defects acting as traps. Finally, the correlations among steady state scintillation efficiency, light yield, thermoluminescence and Ce³⁺ concentration are found and discussed.     

Characteristics of Y3Al5O12:Ce phosphor powders prepared by spray pyrolysis from ethylenediaminetetraacetic acid solution

Nanometer and submicron-sized YAG:Ce phosphor powders were prepared by spray pyrolysis from the spray solutions with ethylenediaminetetraacetic acid (EDTA). The precursor powders with hollow and thin wall structure turned to the fine-sized YAG:Ce phosphor powders after post-treatment at high temperatures of 1400 and 1500 °C. The mean size of the phosphor powders post-treated at a temperature of 1500 °C was 0.72 μm. The white LEDs formed from the YAG:Ce phosphor powders post-treated at 1400 and 1500 °C showed (0.2781, 0.2871) and (0.2731, 0.2795) on the CIE chromaticity diagram, and about 78.20 and 79.04 of Ra. The luminous efficiency of the white LED formed from the commercial YAG:Ce phosphor powders was 84.36 lm/W. However, the luminous efficiencies of the white LEDs formed from the YAG:Ce phosphor powders post-treated at 1400 and 1500 °C were 47.74 and 76.64 lm/W.     

Preparation and characterization of YAG:Ce thin phosphor films by pulsed laser deposition

We report the use of YAG:Ce phosphor as the raw material to make thin and transparent phosphor films with pulsed laser deposition including the effects of heating temperature, target–substrate distances, annealing times, and annealing atmosphere on the YAG:Ce³⁺ phosphor film crystal types and spectral properties. The results indicated that at a coating temperature of 350°C, the YAG:Ce³⁺ phosphor film had the best crystallinity with an intact film and maximum fluorescence emission. The crystallinity and fluorescence emission intensity of the film gradually decreased as a function of increasing target–substrate distances. As the annealing time increased, the crystallinity and the fluorescence emission intensity of the film first increased and then decreased. The film made with 5 h of annealing had the best crystallinity and the highest fluorescence emission intensity. The crystallinity of the film annealed under air was higher than that made under nitrogen; the fluorescence intensity of the film under air was slightly lower than the film under nitrogen. The emission peak of the prepared film was at 523 nm when excited at 450 nm. This is slightly blue‐shifted versus the emission of commercial phosphor powders. This study offers a theoretical basis for the development of transparent phosphor films.     

One-step combustion synthesis of Tb3Al5O12:Ce phosphor

A simple, one-step, and fast method based on exothermic reactions is described for synthesis of Tb₃Al₅O₁₂:Ce phosphor. Light-emitting diodes (LEDs) were fabricated by depositing this phosphor on a blue chip. Photoluminescence and LED emission are compared with respective results for well-known YAG:Ce phosphor. A significant improvement in color rendering index (CRI) attributed to the red shift of Ce³⁺ emission was observed. Persistent emission is also reported for the first time in the Tb₃Al₅O₁₂:Ce annealed in reducing atmosphere. It well correlates with Ce³⁺ emission and a peak around 80°C in the thermoluminescence glow. The long-lasting emission was associated with host-related electron traps.     

Synthesis, growth mechanism and photoluminescence of monodispersed cubic shape Ce doped YAG nanophosphor

In the present work, a novel method for the synthesis of monodispersed cubic shape Ce-doped yttrium aluminum garnet (YAG:Ce) nanophosphors is reported. Single phase Ce doped YAG nanoparticles are prepared by solvothermal processing, followed by annealing treatment. Morphological investigation by scanning electron microscopy (SEM) showed the formation of monodispersed 500 nm cubic shape Ce-doped YAG phosphor. The crystalline Ce-doped YAG showed broad emission peaks in the range of 480-640 nm with maximum intensity at 524 nm. The emission intensity increased with increase in calcination temperatures while reduced with increase in Ce³⁺ ions concentration. Detailed study was carried out to understand the formation of monodispersed cubic shape Ce doped YAG nanoparticles. It was found that the solvent, surfactant and impurity (counter ions of cerium and aluminum salt) has significant effect on the crystal growth.     

Porous Ce:YAG ceramics with controllable microstructure for high-brightness laser lighting

In order to meet the increasing demand for high-power laser diode lighting and displays, phosphor converters with high-brightness and high-directionality ought to be constructed to enhance the luminance and luminous efficacy. However, the pores formed during the sintering of phosphor ceramics affect the scattering effect and directionality of light. Therefore, porosity optimization and pore size regulation need to be explored. In this work, a series of Ce:YAG ceramics with various porosities and pore sizes were prepared. The influences of porosity and pore size on the microstructure, light confinement ability, and optical properties of Ce:YAG ceramics were studied. The ceramic phosphor with a porosity of 10 vol.% and a pore size of 3 μm exhibits a good spot confinement ability and shows a high luminous flux value of 3430 lm and a central luminance (1669 592 cd/m²) under blue laser excitation. The 10 vol.% Ce:YAG ceramic phosphor with a pore size of 5 μm has the highest emission intensity and gives a maximum luminous efficacy of 268 lm/W and a luminous flux of 4020 lm under 30 W/mm² blue laser excitation. Thus, the porous Ce:YAG ceramics are expected to be a promising candidate for high-brightness laser lighting and projection applications.     

(Ce,Gd):YAG-Al2O3 composite ceramics for high-brightness yellow light-emitting diode applications

(Ce,Gd):YAG-Al₂O₃ composite ceramics were prepared for high-brightness yellow LED (565?590 nm) applications. Phase fraction, microstructure, thermal quenching effect, and luminescent properties of composite ceramics with varying compositions were studied in detail. Collaborating composite ceramics with InGaN blue chips, the relationship between thermal conductivity, temperature rise during LED-driven phosphor conversion, and steady-state luminous efficiency were elucidated. As the proportion of Al₂O₃ increases from 0 to 40 wt%, the steady-state luminous efficiency of yellow LED is enhanced from 100.88–109.49 lm W^?1, benefiting from the increased thermal stability and reduced operating temperature of ceramics (from 141.1–132.2 °C). Additionally, scattering behavior and extraction efficiency of composite ceramics with different thicknesses were investigated.