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.     

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.     

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.     

A single-structured LuAG:Ce,Mn phosphor ceramics with high CRI for high-power white LEDs

The realization of high color rendering index (CRI) is still a great challenge for high-power LEDs (hp-LEDs), which is hindered by the phosphor converter. In this work, based on the strategy of Ce³⁺ and Mn²⁺ multi-ion substitution, the single-structured LuAG:Ce,Mn ceramics with high CRI were prepared via regulating the ratio of tri-color (red, green, and blue) components. The effects of Mn²⁺-Si⁴⁺ pairs doping content on the crystal structure, morphologies, and luminescence properties were investigated in detail. The red emission centered at 590  and 750 nm were effectively compensated by regulating Mn²⁺ occupancy sites, resulting in a significant improvement of CRI. Pure white light with general CRI R_a up to 91.0, special CRI R₉ reaching 37.9 and LE as high as 85.07 lm/W was achieved, when the hp-LEDs were constructed from related phosphor ceramic Ce02Mn7. These results suggest that the LuAG:Ce,Mn phosphor ceramics are highly promising color converters for hp-LEDs application.     

The influences of stoichiometry on the sintering behavior,optical and scintillation properties of Pr:LuAG ceramics

Sintering aids may enter the host lattice, create defects, and seriously deteriorate the scintillation properties of ceramic scintillators. In this study, the 0.3at%Pr:LuAG ceramics with different excess of Lu were fabricated by the solid-state reactive sintering without aids. The influences of stoichiometry on the sintering behaviors, optical and scintillation properties of the ceramics are systematically studied. The results show that the stoichiometric ceramics experience an abnormal grain growth during sintering. The Lu excess can restrain the abnormal grain growth of the ceramics because of the impurity drag effect. The excess Al₂O₃ as optical scattering centers, can also pin in the grain boundary to limit the fast migration of the grain boundaries. The light yield value of the as-sintered ceramics decreases with the increase of Lu content. After air-annealing, the ceramics with appropriate excess of Lu can achieve better optical quality and higher light yield compared to the stoichiometric Pr:LuAG ceramics.     

Microstructure,luminescence, and dielectric properties of microwave-sintered Ce:LuAG nano-ceramics

Herein, phase pure and highly crystalline Ce:LuAG nano-ceramics were fabricated using a novel, ultra-fast microwave sintering approach. The influence of microwave sintering on the microstructural, photoluminescence, and dielectric characteristics of Ce:LuAG nano-ceramic powders was examined. Microwave-assisted sintering of Ce:LuAG nano-ceramic powders yielded high crystallinity, low lattice strain, and reduced grain size. The process also improved the sintering kinetics and enhanced the surface diffusion between the grains, resulting in enhanced luminescence and dielectric properties. The Cole-Cole impedance plots showed single semicircular arcs, indicating non-Debye relaxation and a high dielectric constant in the microwave-sintered Ce:LuAG nano-ceramic and highlighting its potential for use in optoelectronics.     

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.     

Effects of non-stoichiometric defects on the dielectric properties of (Ba0.5Sr0.5)xTiO3-ZnGa2O4 composite ceramics

In order to explore the effects of non-stoichiometric defects on the dielectric properties of composite ceramics, 70 wt% (Ba_0.5Sr_0.5)_xTiO₃-30 wt%ZnGa₂O₄ ((BS)_xT50-ZG, x = (Ba + Sr)/Ti = 0.99, 1.00, 1.01 and 1.05) composite ceramics were fabricated by the traditional sintering technique. The association between structure and dielectric properties has been studied. The results show that the distortion of the crystal lattice brought by the partial Schottky defects, namely [V″_Ba,Sr–V^˙˙_O]^× and [V′′′′_Ti–2V^˙˙_O]^×, induces a decrease in the Curie temperature of (BS)_xT50-ZG composite ceramics. The orientation of the elastic dipoles brought by oxygen vacancies causes the pinning of the domain walls, which reduces the dielectric loss at low frequencies. Tunability is related to the dipole polarization caused by [V″_Ba,Sr–V^˙˙_O]^× and [V′′′′_Ti–2V^˙˙_O]^× defect complexes. In addition, compared with the composite ceramic with x = 1, the Q values of the composite ceramics with x < 1 and x > 1 decreases due to the deterioration of the microstructure homogeneity and the enhancement of the disorder of the B-site cations in (BS)_xT50.     

On fast LuAG:Ce scintillation ceramics with Ca2+ co-dopants

“Defect engineering” was a valid strategy to modify the performance of LuAG:Ce scintillator, usually realized by Me²⁺/Me⁺ co-doping. To investigate the effects of Ca²⁺ co-doping on the scintillation properties of LuAG:Ce, a set of LuAG:Ce ceramics with Ca²⁺ concentrations ranging from 0 to 0.5 at.% were manufactured. The absorption spectra, radioluminescence spectra (RL spectra), light yield, RL spectra as a function of temperature, decay time, and TSL curves of the ceramic products were carefully measured. With Ca²⁺ co-doping, the scintillation performance of LuAG:Ce ceramics was greatly improved. Especially for the 0.2 at.% Ca²⁺ co-doped one, it has a high light yield value of 24, 400 ph/MeV, a fast scintillation decay time of 48 ns, and a small slow component contamination. And the role of Ca²⁺ in the scintillation mechanism of LuAG:Ce ceramics was also discussed in this paper.     

High transparency Cr,Nd:LuAG ceramics prepared with MgO additive

Cr (0.2 at.%) and Nd (0.8 at.%) co-doped Lu₃Al₅O₁₂ ceramics were fabricated with MgO as the sintering additive. The addition of a small amount of MgO can affect the grain boundary mobility and influence the number and location of micropores in ceramics during the sintering process. The results show that when the MgO content is 0.02 wt.%, high-transparency Cr,Nd:LuAG ceramics can be obtained by vacuum sintering at 1670 °C for 5 h followed by hot isostatic pressing (HIP) post-sintering at 1750 °C in an argon atmosphere (P = 200 MPa) for 5 h. The optimum in-line transmittance of the HIPed Cr,Nd:LuAG ceramics (3 mm thick) is 83.5% at a wavelength of 840 nm and 84.0% at 710 nm.     

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.     

Investigation of an LuAG:Ce translucent ceramic synthesized via spark plasma sintering: Towards a facile synthetic route,robust thermal performance,and high-power solid state laser lighting

The aim of this study is to investigate a thermally robust green-yellow color converter for high-power solid state laser lighting applications. LuAG:Ce translucent ceramics (TCs) were synthesized via the spark plasma sintering (SPS) technique and LiF was used as additive. The as-prepared ceramics show remarkably superior thermal and luminescent properties: a high external quantum efficiency (77%), a low thermal quenching (4.1% drop at 200 °C), a good thermal conductivity (6.3 W m^?1K^?1), and a high reliability (only a 1.9% drop after 1000 h, at 85 °C and 85% humidity). A prototype lamp using the TC (and a 450 nm laser diode), with the increasing driving power (up to 8.7 W), shows increasing luminous flux (238–472 lm) with stable luminous efficiency (54.3-56.6 lm/W). This indicates that the translucent ceramic can be used for high-power laser-lighting.     

Optical properties of YMASG:Ce fluorescent ceramics prepared by hot-pressure sintering

Cerium-doped yttrium aluminum garnet (YAG:Ce) based transparent ceramics have been widely used in fluorescent lighting as high-quality inorganic fluorescent conversion materials. This paper further explores the Mg²⁺-Si⁴⁺ ions doped YAG:Ce transparent ceramics by combining the solid-phase reaction method with vacuum hot-pressure sintering and implementing protection measures against hot-pressure mold contamination, and also investigates the effect of different Mg²⁺-Si⁴⁺ doping contents on the structure, transmittance and luminescence properties of the ceramics under hot-pressure sintering. In this work, pure-phase YMASG:Ce transparent fluorescent ceramics with a grain size of about 3-6 μm and clear and clean grain boundaries were obtained with an In-line transmittance of 67% at 800 nm. Under the excitation at 460 nm, the emission peak was red-shifted by 26 nm and the full width at half maxima (FWHM) was broadened with the increase of Mg²⁺-Si⁴⁺ content, which shows that the Mg²⁺-Si⁴⁺ ion pair effectively complements the absence of the red light component in the YAG:Ce emission spectrum. The optimized YMASG:Ce ceramics obtained high-quality warm white light with a low correlated color temperature (CCT) and a high color rendering index (CRI) under the excitation of the blue LED chip. This work proved the feasibility of vacuum hot-pressure sintering to prepare YMASG:Ce transparent fluorescent ceramics, and provided a new approach for studying YMASG:Ce-based ceramics, which was significant for the application of high-power visible laser illumination.     

Cation-substitution induced stable GGAG:Ce3+ ceramics with improved optical and scintillation properties

Among the aluminate garnet materials, cerium doped gadolinium gallium aluminum garnet ceramics (GGAG:Ce) have shown great performance advantages, which suggests their promising applications in medical imaging, high energy rays detection and high power LED lighting. The goal of this work is to raise the thermostability of GGAG:Ce by means of partial Y³⁺ substitution, and to find out the relationship between the crystal structure and the optical properties. GGAG:Ce³⁺,xY³⁺ ceramics were prepared via chemical precipitation, and a combination of sintering in oxygen atmosphere and hot isostatic pressing. In order to identify the detailed crystal structure information, Rietveld refinements were first taken on the XRD patterns. Crystal structure refinements verify the ability of mutual substitution of Y and Ga atoms between the dodecahedron and octahedral sites. The optical, luminescent and scintillation properties have been investigated. Results show that the transmittance of the sample can reach 77% at the emission peak wavelength, while the spectrally corrected light yield value reaches 61,000 ± 1200 photons/MeV.     

Effect of air annealing on the optical properties and luminescence performance of Ce:YAG ceramics for light-emitting diodes at different Ce concentrations

(Y_1-x%Ce_x%)₃Al₅O₁₂ (x = 0.2,0.4,0.6,0.8,1.0) transparent ceramics were fabricated by vacuum sintering technology, followed by air annealing at different temperatures. Transmittance of ceramics, valence of cerium, and luminescent properties with varying annealing temperatures are studied in detail. The negative effect of Ce³⁺ oxidation induced by annealing gets increasingly evident when Ce concentration increases. Collaborating Ce:YAG ceramics with InGaN blue chips, light-emitting diodes (LEDs) with superior performance were constructed. The relationships between Ce concentration, annealing temperature, and luminous flux of LEDs are elucidated, showing that the optimized annealing temperature of Ce:YAG ceramics decreases from 1200 °C to 900 °C as Ce concentration increases from 0.2 at% to 1.0 at%. The luminous fluxes of optimized LEDs increase by ～10 % compared with that of unannealed LEDs.     

The phase,microstructure evolution and the Nd3+ function in the fabrication process of LuAG transparent ceramics

Nd:LuAG transparent ceramics were fabricated by the solid-state reaction under vacuum sintering using SiO₂ and MgO as sintering aids, commercial Lu₂O₃, Al₂O₃ and Nd₂O₃ as raw materials. The Nd doping concentration was adopted from 0 at. % to 1.3 at. %. The phase transformation and microstructure evolution of 1.3 at. % Nd:LuAG ceramics under different sintering temperature was investigated in detail. Meanwhile, the effects of Nd₂O₃ on the grain growth were surveyed. The results shown that when the samples were sintered at 1780?°C, the 1.3 at. % Nd:LuAG ceramic had clean gain boundary, and the transmittance of it reached 83.8% at 1064?nm.     

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.     

Effect of Ca2+ and Mg2+ ions on the sintering and spectroscopic properties of cr-doped yttrium aluminum garnet ceramics

In this work, we investigated the effects of Ca²⁺ and Mg²⁺ ions and annealing temperature on the spectroscopic parameters of chromium-doped yttrium aluminum garnet ceramics (Cr:YAG). Samples were obtained with either a separate or a simultaneous addition of calcium and magnesium oxides. To achieve this, aqueous suspensions were prepared using Y₂O₃, Al₂O₃, Cr₂O₃, MgO, and CaO high-purity powders as raw materials. The obtained suspensions were freeze-granulated, pressed into pellets, debinded, and subjected to reactive sintering in vacuum at 1715°C for 6 h. Each material was annealed in air with temperatures between 1300 and 1700°C. Samples were also compared to Cr:YAG ceramics with the addition of silica as a sintering aid. All the materials obtained were then exposed to 445 nm excitation, and emission spectra in the visible and infrared wavelengths were recorded. The results showed that the emission spectra of Cr:YAG ceramics varied according to the annealing conditions: as-sintered samples exhibited strong emissions of around 680 nm and, after air annealing, of around 1400 nm. This phenomenon is attributed to the Cr³⁺→Cr⁴⁺ transition. Samples doped solely with MgO exhibited the highest emission intensity in the infrared region. Thus, Mg²⁺ ions provided the best conversion efficiency of chromium ions.     

Improving the luminescence and afterglow properties of Mg3Y2Ge3O12:Cr3+ by co-doping Bi3+

Generally, the emission intensity and afterglow of the near infrared phosphors can be improved by co-doping the sensitizer. In this work, Bi³⁺ ions as sensitizer are introduced into the near infrared phosphor Mg₃Y₂Ge₃O₁₂:Cr³⁺, and the luminescence properties are investigated. According to the principle of radius adaptation, Bi³⁺ ions would occupy eight coordinates in the host instead of Y³⁺ and Mg²⁺. Through structural refinement, theoretical calculation and experimental phenomena, there are two kinds of luminescent sources for Bi³⁺ ions, which come from ³P₁ → ¹S₀ (441 nm) and MMCT (330 nm), respectively. In addition, the substitution of Bi³⁺ for Mg²⁺ will result in inequivalent substitution forming defects (Bi_Mg·), and the trap depth is 0.55 eV. For Bi³⁺ and Cr³⁺ co-doped Mg₃Y₂Ge₃O₁₂, there are two factors can that can affect the luminescent properties of Cr, which are energy transfer and defects. The samples are obtained with three times the original emission intensity with the introduction of defects. At the same time, Bi³⁺ ions capture electrons to form new electron traps Bi²⁺ (Bi³⁺ + e^-) and the trap depth is 0.81 eV. Therefore, under the action of two traps Bi_Mg· and Bi²⁺ (Bi³⁺ + e^-), the afterglow characteristics of the samples are improved and the time can reach 1.5 h.