Ce Garnet Research Articles

Temperature dependence of photo- and radio-luminescence, scintillation and photoconversion properties of Lu0.6Gd2.4(Al5-xScx)O12:Ce garnet crystals grown by micro-pulling-down method

The luminescence, scintillation and photoconversion properties of Ce3+-doped Lu0.6Gd2.4(Al5-xScx)O12 (x = 1.2, 1.5, 2) garnet crystals grown by micro-pulling-down method were investigated. Increasing Sc3+ concentration induced lattice strain and cracking due to ionic radius mismatch. At low Sc3+ concentration, the strain caused core-concentrated cracks and radial inhomogeneity. At higher Sc3+ concentration, extensive cracking occurred throughout crystals, improving radial homogeneity. With the increase of Sc3+ concentration, the Ce3+ 5d1 → 4f luminescence was slightly blue-shifted due to the decrease in crystal field splitting of the 5d levels. At room temperature (RT), the increase of light yield with increasing Sc3+ concentration was attributed to the decrease in the bandgap value. Above RT, the decrease of photo- and radio-luminescence for all samples was due to the thermal ionization process. The decrease of radioluminescence at low-temperature regions can be caused by the localization of electrons at intrinsic shallow traps. Photoluminescence measurements disclosed that variations in scandium concentration can effectively modulate the correlated color temperature (CCT), color rendering index (CRI), and luminous efficiency (LE) of these luminescent materials. The incorporation of a micro-perovskite phase in the Lu0.6Gd2.4(Al3.8Sc1.2)O12:Ce crystal resulted in a notable enhancement of the luminous efficiency, exhibiting a 38 % increase when compared to the sample devoid of micro-inclusions (e.g. x = 2.0).

Temperature dependence of photoluminescence kinetics and scintillation properties of LuY2(Al5-xScx)O12:Ce (x = 1, 1.5, 2) garnet single-crystalline films

The temperature dependence of photoluminescence (PL) kinetics and scintillation properties were investigated in LuY2(Al5-xScx)O12:Ce (x = 1, 1.5, 2) garnet single-crystalline films grown by the isothermal liquid phase epitaxy method. With the increase of Sc content, the Ce3+ 5d1 level was shifted to higher energy while the Ce3+ 5d2 level was shifted to lower energy due to the decrease in crystal field splitting of the 5d levels. Activation energy of thermal quenching, determined from temperature-dependent PL decay times, decreased with increasing Sc content. At room temperature, the decrease of light yield (LY) value with increasing Sc content is caused by the thermal ionization process. LuY2(Al4Sc)O12:Ce showed a LY value of 510 photons/MeV when excited by 5.5 MeV α-particles, which is ∼21 % larger than that of Lu2Y(Al4Sc)O12:Ce due to a smaller bandgap Eg of the former.

Luminescence and photoconversion properties of Ce-doped Ca3Sc2Si3O12 crystal

This work is dedicated to investigation of the luminescent properties of the prospective photoconversion material based on the crystal of Ce3+ doped Ca3Sc2Si3O12 (CSSG) garnet. The GSSG:Ce crystal was grown using the micro-pulling-down (μPD) method. The CSSG:Ce crystal exhibited an intensive photoluminescence (PL) emission band with two sub-bands peaked at 504 and 545 nm, corresponding to 5d-4f (2F5/2;7/2) transitions. Furthermore, we have investigated also the formation of cerium multicenters in the GSSG:Ce crystal using analyses of the structure of Ce3+ photoluminescence emission and excitation spectra under excitation of the luminescence of this crystal by synchrotron radiation. The formation of Ce3+-multicenters in CSSG:Ce garnet is caused by the local inhomogeneity of the dodecahedral sites of garnet lattice due to localization of the hetero-valent Sc3+ and Si4+ cations in the octahedral and tetrahedral positions of the garnet host. The existence of Ce3+ multicenters resulted in a significant enhancement of the Ce3+ emission band in the red range and improving the performance of conventional YAG:Ce phosphor. The next task of our work was to evaluate the possibility of application of the GSSG:Ce crystal as a light phosphor-converter (pc) for white light-emitting diodes (WLEDs). In the frame of this task, we have successfully developed a prototype of WLED by employing the CSSG:Ce crystal as a phosphor-converter (pc) with blue 450 emitting LED as well as investigated the color characteristics of this pc-WLED.

Luminescent properties of Gd1.4Lu0.1Y1.5Al5O12:Ce and Gd3Ga2.7Al2.3O12:Ce single crystals grown by micro-pulling down technique

The luminescent properties of the single crystals of Ce3+ doped (Gd1−x−yLuxYy)3Al5O12:Ce (x = 0.1; y = 1.5) and Gd3GaxAl5-xO12:Ce (x = 2.7) garnets (GLYAG:Ce and GGAG:Ce) were investigated in this work. Both crystals were grown by the micropulling down method. The conventional absorption and luminescence spectral measurements together with the luminescent spectroscopy under excitation by synchrotron radiation were performed to characterize the optical properties of crystals. It has been found that cumulative effects of reducing the ion radius from Gd3+ to Y3+ and Lu3+ in the dodecahedral sites of the garnets host and alloying of Al3+ ions in octahedral positions instead Ga3+ ions increases the crystal field strength and causes the respective redshift of the Ce3+ emission spectra in GLYAG:Ce crystals in comparison with GAGG:Ce garnet. The energy transfer from Gd3+ cations to Ce3+ has also been registered at the emission spectra and excitation spectra of both crystals. The energies of creation of the excitons bound with the Ce3+ ions in GLYAG:Ce and GAGG:Ce hosts were found to be equal to 6.415 ± 0.15 eV and 6.22 ± 0.15 eV, respectively. Both crystals show well-distinguished thermo- and optically stimulated luminescence (TSL and IR OSL) after α- and β-particle irradiation. Meanwhile, GAGG:Ce crystals show significantly higher TSL and IR OSL intensities (by 3–4 times) and faster OSL decay kinetics in comparison with GLYAG:Ce counterpart.

Luminescence and scintillation properties of Gd3(Al5-xScx)O12:Ce garnet crystals grown by floating zone method

The luminescence and scintillation properties of Ce3+-doped Gd3(Al5-xScx)O12 (x = 1, 1.5, 2, 2.5, 3) garnet crystals grown by the floating zone method were investigated. With increasing Sc content, the Ce3+ 5d1 → 4f luminescence was blue shifted due to a decrease in 5d1-5d2 crystal field splitting (Δ12) of the 5de doublet state. The Sc content showed a strong influence on purity of garnet phase in the Gd3(Al5-xScx)O12:Ce crystals. The presence of secondary phase (perovskite and/or α-Al2O3) results to a poor transparency and a lower light yield (LY) value. The Gd3Al3Sc2O12:Ce crystal exhibited pure garnet phase, highest quantum yield (∼76 %) and transmittance (∼80 %), and highest LY value (6,850 photons/MeV at 662 keV γ rays) among the studied samples. Above RT, a decrease of radioluminescence (RL) yield occurs for all samples due to the thermal ionization process. A decrease of the RL yield at low temperature observed in correlation with the intense thermoluminescence peaks can be explained by the localization of electrons at intrinsic shallow traps.

Single Crystalline Films of Ce3+-Doped Y3MgxSiyAl5-x-yO12 Garnets: Crystallization, Optical, and Photocurrent Properties.

This research focuses on LPE growth, and the examination of the optical and photovoltaic properties of single crystalline film (SCF) phosphors based on Ce3+-doped Y3MgxSiyAl5-x-yO12 garnets with Mg and Si contents in x = 0-0.345 and y = 0-0.31 ranges. The absorbance, luminescence, scintillation, and photocurrent properties of Y3MgxSiyAl5-x-yO12:Ce SCFs were examined in comparison with Y3Al5O12:Ce (YAG:Ce) counterpart. Especially prepared YAG:Ce SCFs with a low (x, y < 0.1) concentration of Mg2+ and Mg2+-Si4+ codopants also showed a photocurrent that increased with rising Mg2+ and Si4+ concentrations. Mg2+ excess was systematically present in as-grown Y3MgxSiyAl5-x-yO12:Ce SCFs. The as-grown SCFs of these garnets under the excitation of α-particles had a low light yield (LY) and a fast scintillation response with a decay time in the ns range due to producing the Ce4+ ions as compensators for the Mg2+ excess. The Ce4+ dopant recharged to the Ce3+ state after SCF annealing at T > 1000 °C in a reducing atmosphere (95%N2 + 5%H2). Annealed SCF samples exhibited an LY of around 42% and similar scintillation decay kinetics to those of the YAG:Ce SCF counterpart. The photoluminescence studies of Y3MgxSiyAl5-x-yO12:Ce SCFs provide evidence for Ce3+ multicenter formation and the presence of an energy transfer between various Ce3+ multicenters. The Ce3+ multicenters possessed variable crystal field strengths in the nonequivalent dodecahedral sites of the garnet host due to the substitution of the octahedral positions by Mg2+ and the tetrahedral positions by Si4+. In comparison with YAG:Ce SCF, the Ce3+ luminescence spectra of Y3MgxSiyAl5-x-yO12:Ce SCFs greatly expanded in the red region. Using these beneficial trends of changes in the optical and photocurrent properties of Y3MgxSiyAl5-x-yO12:Ce garnets as a result of Mg2+ and Si4+ alloying, a new generation of SCF converters for white LEDs, photovoltaics, and scintillators could be developed.

Development of Three-Layered Composite Color Converters for White LEDs Based on the Epitaxial Structures of YAG:Ce, TbAG:Ce and LuAG:Ce Garnets

This work was dedicated to the development of novel types of composite phosphor converters of white LED, based on the epitaxial structures containing Y3Al5O12:Ce (YAG:Ce) and Tb3Al5O12:Ce (TbAG:Ce) single crystalline films, steeply grown, using the liquid-phase epitaxy method, onto LuAG:Ce single crystal substrates. The influence of Ce3+ concentration in the LuAG:Ce substrate, as well as the thickness of the subsequent YAG:Ce and TbAG:Ce films, on the luminescence and photoconversion properties of the three-layered composite converters were investigated. Compared to its traditional YAG:Ce counterpart, the developed composite converter demonstrates broadened emission bands, due to the compensation of the cyan-green dip by the additional LuAG:Ce substrate luminescence, along with yellow-orange luminescence from the YAG:Ce and TbAG:Ce films. Such a combination of emission bands from various crystalline garnet compounds allows the production of a wide emission spectrum of WLEDs. In turn, the variation in the thickness and activator concentration in each part of the composite converter allows the production of almost any shade from green to orange emission on the chromaticity diagram.

New types of composite scintillators based on the single crystalline films and crystals of Gd3Al5-xGaxO12:Ce garnets

This work presents the results on creation of novel types of composite scintillators based on Ce3+ doped Gd3Al5-xGaxO12 single crystalline films grown by the LPE method using PbO–B2O3 flux onto substrate-scintillators prepared from commercial Gd3Al2.3Ga2.7O12:Ce and Gd3Al2Ga3O12:Ce single crystals. The sets of films with different Ga contents x = 1.75–2.25 and various thicknesses in the 13–150 μm range were grown onto the mentioned substrates. The scintillation properties of the respective epitaxial structures (pulse height spectra, light yield and scintillation decay kinetics) were investigated under excitation by α– (239Pu) particles, β- (90Sr+90Y) particles and γ–quanta (137Cs). The best scintillation properties for simultaneous registration of the mentioned particles and quanta in the mixed radiation fluxes are demonstrated with Gd3Al2.75Ga2.25O12 film/Gd3Al2Ga3O12:Ce substrate epitaxial structure.

Li+ incorporation and defect-creation processes imposed by X-ray and UV irradiation in Li-codoped Y3Al5O12:Ce scintillation crystals

This paper reports a detailed study of Li+ incorporation and electron and hole trapping in Li+-codoped Y3Al5O12:Ce garnet scintillation crystals, using the combination of the local probe EPR and NMR methods with optical characterization.

Application of the LPE-Grown LuAG: Ce Film/YAG Crystal Composite Thermoluminescence Detector for Distinguishing the Components of the Mixed Radiation Field.

Single-crystalline films (SCFs) of the LuAG: Ce garnet grown using the liquid-phase epitaxy method onto YAG single-crystal (SC) substrates were investigated for possible applications as composite thermoluminescent (TL) detectors. Such detectors may help to register the different components of ionizing radiation fields with various penetration depths, e.g., heavy charged particles and gamma or beta rays. It was found that the TL signal of LuAG: Ce SCF sufficiently differs from that of the YAG substrate concerning both the temperature and wavelength of emissions. Furthermore, even by analyzing TL glow curves, it was possible to distinguish the difference between weakly and deeply penetrating types of radiation. Within a test involving the exposure of detectors with the mixed alpha/beta radiations, the doses of both components were determined with an accuracy of a few percent.

Basic Characteristics of Dose Distributions of Photons Beam for Radiotherapeutic Applications Using YAG:Ce Crystal Detectors.

Thermostimulated luminescence (TSL) dosimetry is a versatile tool for the assessment of dose from ionizing radiation. In this work, the Ce3+ doped Y3Al5O12 garnet (YAG:Ce) with a density ρ = 4.56 g/cm3 and effective atomic number Zeff = 35 emerged as a prospective TSL material in radiotherapy applications due to its excellent radiation stability, uniformity of structural and optical properties, high yield of TSL, and good position of main glow peak around 290-300 °C. Namely, the set of TSL detectors produced from the YAG:Ce single crystal is used for identification of the uniformity of dose and energy spectra of X-ray radiation generated by the clinical accelerator with 6 MV and 15 MV beams located in Radiotherapy Department at the Oncology Center in Bydgoszcz, Poland. We have found that the YAG:Ce crystal detects shows very promising results for registration of X-ray radiation generated by the accelerator with 6 MV beam. The next step in the research is connected with application of TSL detectors based on the crystals of much heavier garnets than YAG. It is estimated that the LuAG:Ce garnet crystals with high density ρ = 6.0 g/cm3 and Zeff = 62 can be used to evaluate the X-rays produced by the accelerator with the 15 MV beam.

Micropowder Ca2YMgScSi3O12:Ce Silicate Garnet as an Efficient Light Converter for White LEDs.

This work is dedicated to the crystallization and luminescent properties of a prospective Ca2YMgScSi3O12:Ce (CYMSSG:Ce) micropowder (MP) phosphor converter (pc) for a white light–emitting LED (WLED). The set of MP samples was obtained by conventional solid-phase synthesis using different amounts of B2O3 flux in the 1–5 mole percentage range. The luminescent properties of the CYMSSG:Ce MPs were investigated at different Ce3+ concentrations in the 1–5 atomic percentage range. The formation of several Ce3+ multicenters in the CYMSSG:Ce MPs was detected in the emission and excitation spectra as well as the decay kinetics of the Ce3+ luminescence. The creation of the Ce3+ multicenters in CYMSSG:Ce garnet results from: (i) the substitution by the Ce3+ ions of the heterovalent Ca2+ and Y3+ cations in the dodecahedral position of the garnet host; (ii) the inhomogeneous local environment of the Ce3+ ions when the octahedral positions of the garnet are replaced by heterovalent Mg2+ and Sc3+ cations and the tetrahedral positions are replaced by Si4+ cations. The presence of Ce3+ multicenters significantly enhances the Ce3+ emission band in the red range in comparison with conventional YAG:Ce phosphor. Prototypes of the WLEDs were also created in this work by using CYMSSG:Ce MP films as phosphor converters. Furthermore, the dependence of the photoconversion properties on the layer thickness of the CYMSSG:Ce MP was studied as well. The changes in the MP layer thickness enable the tuning of the white light thons from cold white/daylight to neutral white. The obtained results are encouraging and can be useful for the development of a novel generation of pcs for WLEDs.

Remarkable structure and luminescence regulation of a Gd2LuAl5O12:Ce garnet phosphor with a Ca2+/Si4+ pair for high-quality w-WLED lighting.

Doping Gd2LuAl5O12:Ce with a Ca2+/Si4+ pair produced a series of Gd1.97-xLuCaxAl5-xSixO12:0.03Ce (x = 0.0-1.2) garnet new phosphors, and remarkable regulation of the crystal structure and Ce3+ luminescence was achieved. Rietveld refinement and spectral analysis revealed that greater incorporation of Ca2+/Si4+ led to a higher lattice rigidity by cell contraction, a narrower bandgap, a longer average bond length/less distortion of the [CeO8] dodecahedron and decreased centroid shift/crystal field splitting of the Ce3+ 5d energy level. A blue-shifted 4f-5d1 transition, a narrower emission band, improved thermal stability of luminescence and a shorter fluorescence lifetime were observed with increasing Ca2+/Si4+ content. Applying the yellowish-green-emitting Gd0.77LuCa1.2Al3.8Si1.2O12:0.03Ce optimal phosphor (x = 1.2), together with a commercial CaAlSiN3:Eu red phosphor, in 450 nm-excited LED lighting produced a low CCT of ∼3625 K and a high CRI/R9 of ∼95.2/94.8, indicating that the phosphor has application potential in high-performance w-WLED.

Site-selective and cooperative doping of Gd3Al5O12:Ce garnets for structural stabilization and warm WLED lighting of low CCT and high CRI.

Synergistic doping of the metastable Gd3Al5O12:Ce garnet with a Ca2+/Hf4+ pair and Sc3+ to form Gd2.97-xCaxHfxScyAl3O12:0.03Ce (x = 0.5-2.0, y = 0.0-1.5, x + y = 2.0) solid solution was conducted for the structural stabilization and photoluminescence manipulation. The site selection of Ca2+/Hf4+/Sc3+ dopants and the effects of doping on the crystal structure, local coordination, band structure and Ce3+ luminescence were revealed in detail with the results of XRD, Rietveld refinement, TEM, and UV-Vis/photoluminescence spectroscopy. A decrease in Ca2+/Hf4+ and an increase in the Sc3+ content were observed to shrink the lattice, widen the bandgap of the garnet host, red-shift the excitation/emission wavelength, broaden the emission band and shorten the fluorescence lifetime of Ce3+. The spectral changes were rationalized by considering the local coordination and crystal field splitting of the Ce3+ 5d energy level. Application of typical Gd0.97Ca2Hf2Al3O12:0.03Ce (x = 2.0, y = 0) cyan and Gd2.47Ca0.5Hf0.5Sc1.5Al3O12:0.03Ce (x = 0.5, y = 1.5) greenish-yellow phosphors in w-WLED lighting produced low correlated color temperatures of ∼3842 and 3514 K, high color rendering indices of ∼88 and 93 and favorable luminous efficacies of ∼32.9 and 14.7 lm/W under the excitation of 395 nm n-UV and 450 nm blue LED chips, respectively.

Scintillation characteristics and temperature quenching of radio- and photoluminescence of Mg2+-codoped (Lu,Gd)3Al2.4Ga2.6O12:Ce garnet crystals

Luminescence and scintillation characteristics of Mg2+-codoped (LuxGd3-x)Al2.4Ga2.6O12:Ce (x = 0.2–0.8) garnet crystals grown by the micro-pulling down method are investigated. The Ce3+ 5d1 → 4f luminescence is blue-shifted with increasing Lu content due to the decrease in crystal field splitting of the 5 d levels. With increasing Lu content, the shortening of scintillation decay time accompanied with a decrease of LY value as measured at room temperature can be explained by thermal ionization of the Ce3+ 5d1 excited state. Co-doping with Mg2+ results in the shortening of scintillation decay time, the reduction of LY value and afterglow intensity. At low temperature the radioluminescence quenching is observed in correlation with large thermoluminescence peaks, which can be attributed to the localization of electrons at intrinsic shallow traps.

Scintillation yield and temperature dependence of radioluminescence of (Lu,Gd)3Al5O12:Ce garnet crystals

The scintillation characteristics of Lu3-xGdxAl5O12:Ce (x = 1, 1.25, 1.75, 2, and 2.25) garnet crystals were investigated. With increasing Gd content, the Ce3+ 5d1 → 4f luminescence band was red-shifted due to an increase in the crystal field splitting of the 5d levels. In addition, both the light yield value and contribution of fast scintillation component increased. We attribute this effect to the reduced electron trapping effects of shallow traps buried in the bottom of the conduction band, the lower-energy shift of which is due to the increasing Gd content. A decrease of scintillation yield at the lowest temperature region observed for all samples, showing large thermoluminescence peaks in the same temperature range, can be caused by the localization of electrons at shallow traps. Afterglow signals observed at 10 K for all samples after X-rays irradiation can be explained by quantum tunneling of electrons from nearby traps towards the holes captured at the Ce3+ recombination centers.

Composite Color Converters Based on Tb3Al5O12:Ce Single‐Crystalline Films and Y3Al5O12:Ce Crystal Substrates

The development of a novel composite phosphor converter based on single‐crystalline films of Tb3Al5O12:Ce garnet and Y3Al5O12:Ce single‐crystal substrate is reported. The liquid phase epitaxy growth method is chosen for the fabrication of the Tb3Al5O12:Ce/Y3Al5O12:Ce epitaxial structures with excellent photoconversion properties for application in white light‐emitting diodes (LEDs). The influence of Ce3+ concentration and thickness of Y3Al5O12:Ce substrate as well as the thickness of Tb3Al5O12:Ce films on the photoconversion properties is investigated for the construction of warm white LEDs prototypes based on the developed composite phosphor converters.

Optical Properties of YAG:Ce and GGG:Ce Scintillation Crystals Irradiated with a High Fluence Proton Beam

In this paper, we report on the study of the optical properties of YAG:Ce and GGG:Ce garnet crystals after irradiation in a 660~MeV proton beam with a fluence up to 8.9$\times$10$^{14}$ protons/cm$^2$. We found that the transparency of both crystals fell by no more than 7\% in the region of their own luminescence. The light yield of a YAG:Ce sample, measured one year after irradiation, dropped by about 35\%.

LPE Growth of Composite Thermoluminescent Detectors Based on the Lu3−xGdxAl5O12:Ce Single Crystalline Films and YAG:Ce Crystals

This work is dedicated to the development of new types of composite thermoluminescent (TL) detectors for simultaneous registration of the different components of ionization radiation based on the single crystalline films (SCFs) of Ce3+-doped Lu3−xGdxAl5O12:Ce (x = 0–1.5) garnet and Y3Al5O12:Ce (YAG:Ce) substrates using the liquid phase epitaxy (LPE) growth method. For this purpose, the TL properties of the mentioned epitaxial structures were examined in Risø TL/OSL-DA-20 reader under excitation by α- and β-particles from 242Am and 90Sr-90Y sources. We have shown that the cation engineering of SCF content can result in more significant separation of the TL glow curves of SCFs and substrates under α- and β-particle excitations in comparison with the prototype of such composite detectors based on the Lu3Al5O12:Ce (LuAG:Ce)/YAG:Ce epitaxial structure. Specifically, the difference between the TL glow curves of Lu1.5Gd1.5Al5O12:Ce SCFs and YAG:Ce substrates increases up to 120 K in comparison with a respective value of 80 degrees in the prototype based on the LuAG:Ce/YAG:Ce epitaxial structure. Therefore, the LPE-grown epitaxial structures containing Lu1.5Gd1.5Al5O12:Ce SCFs and Ce3+-doped YAG:Ce substrate can be successfully applied for simultaneous registration of α- and β-particles in mixed fluxes of ionization radiation.

Complex Garnets: Microscopic Parameters Characterizing Afterglow

Light yield, time response, afterglow, and thermoluminescence of Ce-doped garnet scintillators and persistent luminescent materials are controlled by a complex interplay between recombination and trapping/detrapping processes. Extensive research has contributed to a good qualitative understanding of how traps, impurities, and the presence of Ce4+ affect the materials properties. In this work we present a quantitative model that can explain the thermoluminescence and afterglow behavior of complex garnets. In particular, the model allows the determination of capture rates and effective capture radii for electrons by traps and recombination centers in Lu1Gd2Ga3Al2O12:Ce garnet ceramics. The model relies on solving a set of coupled rate equations describing charge carrier trapping and recombination in garnet ceramics doped with Ce and also codoped with a known concentration of an intentionally added electron trap, Yb3+. The model is supported by analysis of a complete set of experimental data on afterglow, rise-time kinetics, and X-ray excited luminescence which show that thermoluminescence/afterglow are governed by trapping/detrapping processes following interactive kinetics with dominant recombination channel. The underlying reason for dominant recombination is the presence of a small fraction of Ce4+ (≈2 ppm in the 0.2% Ce-doped sample) which have a very high capture cross section (≈2.7 A effective radius) because of the Coulomb attractive nature of this recombination center. The quantitative insights on capture cross sections and concentrations of Ce4+ help to better understand the optical properties of Ce-doped garnet scintillators and persistent luminescent materials and serve in optimizing synthesis procedures by tuning the Ce3+/Ce4+ ratio by codoping with divalent cations and annealing in an oxygen-containing atmosphere.