This study investigates the structural, luminescent, and photoconversion properties of composite converters based on epitaxial structures containing single-crystalline films of Ce³⁺-doped Ca₂₋ₓY₁₊ₓMg₁₊ₓSc₁₋ₓSi₃O₁₂:Ce (x=0–0.25) (CYMSSG:Ce) garnet, and Y₃Al₅O₁₂ (YAG) or YAG:Ce substrates, grown using the Liquid Phase Epitaxial (LPE) method. The research focuses on a detailed analysis of the properties of film-crystal composite converters to achieve a deeper understanding of their photoconversion performance, providing an innovative approach to designing a new type of film/ substrate converters for white LEDs. This was accomplished by systematically varying the Y/Sc/Mg cation content in the film and adjusting the film thickness within the range of 19–67 µm for CYMSSG:Ce/YAG structures and 10–22 µm for CYMSSG:Ce/YAG:Ce structures. A significant emphasis of this research was placed on mapping the performance of these converters using a color coordinate diagram, a key tool for visualizing the relationship between film composition, thickness, and photoconversion efficiency. The resulting data revealed clear and distinct trends, offering valuable insights into the tunability of the luminescent properties of white LEDs through precise control of content and film thickness.
This work presents a comprehensive study of the structural, luminescent, and photoconversion properties of epitaxial composite phosphor converters based on single crystalline films of Ce3+-activated Ca2−xY1+xMg1+xSc1−xSi3O12:Ce (x = 0–0.25) (CYMSSG:Ce) garnet, grown using the liquid phase epitaxy (LPE) method on single-crystal Y3Al5O12 (YAG) and YAG:Ce substrates. The main goal of this study is to elucidate the structure–composition–property relationships that influence the photoluminescence and photoconversion efficiency of these film–substrate composite converters, aiming to optimize their performance in high-power white light-emitting diode (WLED) applications. Systematic variation in the Y3+/Sc3+/Mg2+ cationic ratios within the garnet structure, combined with the controlled tuning of film thickness (ranging from 19 to 67 µm for CYMSSG:Ce/YAG and 10–22 µm for CYMSSG:Ce/YAG:Ce structures), enabled the precise modulation of their photoconversion properties. Prototypes of phosphor-converted WLEDs (pc-WLEDs) were developed based on these epitaxial structures to assess their performance and investigate how the content and thickness of SCFs affect the colorimetric properties of SCFs and composite converters. Clear trends were observed in the Ce3+ emission peak position, intensity, and color rendering, induced by the Y3+/Sc3+/Mg2+ cation substitution in the film converter, film thickness, and activator concentrations in the substrate and film. These results may be useful for the design of epitaxial phosphor converters with tunable emission spectra based on the epitaxially grown structures of garnet compounds.
The study is dedicated to investigation of the structural, luminescent and photoconversion properties of epitaxial converters based on the single crystalline films of Ce3+ doped Ca3Sc2Si3O12 (CSSG:Ce) garnet. These SCFs with different thicknesses were grown using the liquid phase epitaxy method onto: (i) undoped Gd3Ga2.5Al2.5O12 (GAGG (2.5)) substrates; (ii) Ce3+ doped Gd3Ga2.5Al2.5O12 (GAGG:Ce (2.5) and Gd3Ga3Al2O12 (GAGG:Ce (3) substrates. For the first time, we have examined the phosphor conversion properties of the mentioned film and film-crystal converters under the excitation of a blue LED. We have established a trend line in the color coordinate diagram by systematically varying the film thickness in the 2-30 μm, 17-22 μm and 7-22 μm ranges for CSSG:Ce film/GAGG (2.5) crystal, CSSG:Ce film/GAGG:Ce (2.5) crystal and CSSG:Ce film/GAGG:Ce (3) crystal composite converters, respectively.
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 micropulling-down (mu PD) 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 phosphorconverter (pc) with blue 450 emitting LED as well as investigated the color characteristics of this pc-WLED.
Ce3+ doped Al2O3-YAG eutectics were successfully grown by the horizontal directional crystallization method. The crystallization rate of eutectic growth was changed in the 1–7.5 mm/h range at a growth temperature of 1835 ℃. The microstructure of eutectic samples was investigated using scanning electron microscopy and X-ray microtomography. The intrinsic morphology of eutectic represents the stripe-like channel structure with a random distribution of the garnet Y3Al5O12 (YAG) and Al2O3 (sapphire) phases. The content of these phases in the stripes changes in the 52.9–55.3% and 46.1–47.1% ratios, respectively, depending on the growth rate of the crystallization of the eutectic samples. The luminescent properties of the eutectic demonstrated the dominant Ce3+ luminescence in the garnet phase. The luminescence of the Ce3+ ions in Al2O3 has also been observed and the effective energy transfer processes between Ce3+ ions in the Al2O3 and YAG garnet phases were revealed under high-energy excitation and excitation in the UV Ce3+ absorption bands of sapphire. The phosphor conversion properties and the color characteristics (Al2O3-YAG):Ce eutectic with different thicknesses were investigated under excitation by a blue LED. We have also tested the prototypes of white LEDs, prepared using a blue 450 nm LED chip and (Al2O3-YAG):Ce eutectic photoconverters with 0.15 to 1 mm thicknesses. The results of the tests are promising and can be used for the creation of photoconverters for high-power white LEDs.
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.
This work is dedicated to study the synthesis processes and luminescence properties of micro-crystalline powder phosphors of Ce3+ and Mn2+ doped Ca2YMgScSi3O12 garnets (CYMSSG:Ce and CYMSSG:Ce,Mn) The photoluminescence emission spectra and decay kinetics confirm the formation of Ce3+ multicenters in the CYMSSG:Ce powder phosphor due to local inhomogeneity of the different dodecahedral positions and presence of the energy transfer between high-energy and low energy Ce3+ emission centers in this garnet. The effective Ce3+ to Mn2+ energy transfer process is observed in CYMSSG:Ce, Mn phosphors resulting in the redshift of the emission spectra in comparison with CYMSSG:Ce counterpart. We have shown that CYMSSG:Ce and CYMSSG:Ce, Mn powder phosphors can be used as an efficient photoconverter (PC) for creation of the high-power white LEDs (WLEDs). The prototypes of PC-WLEDs, based on 450 nm emitting blue LED and planar layers of CYMSSG:Ce and CYMSSG:Ce, Mn microcrystalline powder phosphors, embedded in the epoxy resin, were prepared and their photoconversion properties were investigated as well.
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.
This work is devoted to the crystallization and investigation of the optical properties of single crystalline films (SCFs) of Ce3+-doped Y3−xCaxAl5−ySiyO12 garnet, where the content of Ca2+ and Si4+ cations varied in the x = 0.13–0.52 and y = 0.065–0.5 ranges, respectively. The SCF samples were grown using the liquid phase epitaxy technique onto Y3Al5O12 substrates from the melt solution with equimolar Ca and Si content using PbO-B2O3 flux. However, the Ca and Si concentration in Y3−xCax Al5−ySiyO12:Ce SCFs is not equal: the Ca2+ content was systematically larger than that of Si4+, and the Ca2+ excess is compensated for by the Ce4+ ion formation. The absorption, scintillation, and luminescent properties of Y3−xCaxAl5−ySiyO12:Ce SCFs with different Ca/Si concentrations were investigated and compared with the sample of YAG:Ce SCF. Due to the creation of Ce4+ ions, the as-grown Y3−xCaxAl5−ySiyO12:Ce SCFs show relatively low light yield (LY) under α–particle excitation but a fast scintillation response with a decay time in the ns range. After SCF annealing in the reducing (N2 + H2) atmosphere at T > 1000 °C, the recharging of Ce4+→Ce3+ ions occurs. Furthermore, the samples annealed at 1300 °C SCF possess an LY of about 40% in comparison with the reference YAG:Ce SCF and scintillation decay kinetics much closer to that of the SCF counterpart. Due to Ca2+ and Si4+ alloying, the Ce3+ emission spectra in Y3−xCaxAl5−ySiyO12 SCFs are extended to the red range in comparison with the spectra of YAG:Ce SCF. Such an extension is caused by the Ce3+ multicenter formation at the substitutions of both Y3+ and Ca2+ dodecahedral positions in the hosts of these mixed garnets.
A novel synthesis method of Ca3Sc2Si3O12:Ce micropowder with very bright photo-luminescence (PL) has been developed. The conventional solid-state reaction has been modified for Ca3Sc2Si3O12:Ce microparticle crystallization. Pre-synthesis of metal and silicon oxide blends with subsequent high-temperature treatment in reducing (H-2 /N-2) atmosphere enables obtaining Ca3Sc2Si3O12:Ce micropowder with a high PL quantum yield of about 60-70% at Ce3+ content in the 2.5-5 at.% range, which is highly attractive for LED technology. Additionally, the Ca3Sc2Si3O12:Ce phosphors with Ce concentration in the 0.5-2.5% range display higher thermal stability of photoluminescence in comparison with a commercial YAG:Ce phosphor.