Impact of Eu3+ Dopants on Optical Spectroscopy of Ce3+: Y3Al5O12‐Embedded Transparent Glass‐Ceramics

Transparent glass‐ceramics containing Ce³⁺: Y₃Al₅O₁₂ phosphors and Eu³⁺ ions were successfully fabricated by a low‐temperature co‐sintering technique to explore their potential application in white light‐emitting diodes (WLEDs). Microstructure of the sample was studied using a scanning electron microscope equipped with an energy dispersive X‐ray spectroscopy. The impact of co‐sintering temperature, Ce³⁺: Y₃Al₅O₁₂ crystal content and Eu³⁺ doping content on optical properties of glass‐ceramics were systematically studied by emission, excitation spectra, and decay curves. Notably, the spatial separation of these two different activators in the present glass‐ceramics, where Ce³⁺ ions located in YAG crystalline phase while the Eu³⁺ ones stayed in glass matrix, is advantageous to the realization of both intense yellow emission assigned to Ce³⁺: 5d→4f transition and red luminescence originating from Eu³⁺: 4f→4f transitions. As a result, the quantum yield of the glass‐ceramic reached as high as 93%, and the constructed WLEDs exhibited an optimal luminous efficacy of 122 lm/W, correlated color temperature of 6532 K and color rendering index of 75.     

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.     

Crystal Structure and Optical Performance of Al3+ and Ce3+ Codoped Ca3Sc2Si3O12 Green Phosphors for White LEDs

Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSS:Ce) green phosphors used for white light‐emitting diodes (LEDs) are synthesized and codoped with Al³⁺ via a solid‐state reaction method. The crystal structure and vibrational modes are analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, and Raman scattering spectroscopy. The energy transfer behavior and optical performance are characterized by photoluminescence and excitation spectra, quantum efficiency, and time‐resolved photoluminescence. The incorporation of Al³⁺ into CSS:Ce can inhibit the formation of the impurity phases Sc₂O₃ and CeO₂, improve crystallinity, and enhance the photoluminescence intensity as well as quantum efficiency. The substitution of Sc³⁺ with Al³⁺ increased the crystal field splitting of Ce³⁺ and resulted in the red shift of photoluminescence. The results show that Ca₃Sc_2?xAl_xSi₃O₁₂:Ce³⁺ has high quantum efficiency, making it a promising green phosphor that can be collocated with a commercial 450 nm blue LED and a red phosphor for solid‐state lighting applications.     

Improvement of Luminescence Properties of Blue‐to‐Red Emitting NaCaBO3: Ce3+, Mn2+ Phosphor Prepared by Sol–Gel Method

Color‐tunable phosphors NaCaBO₃: Ce³⁺, Mn²⁺ were synthesized by sol–gel (SG) and solid state (SS) method. SEM observation indicated that the microstructure of phosphor (SG) consisted of regular fine grains with an average size of about 5 μm. NaCaBO₃: Ce³⁺, Mn²⁺ showed two emission bands: one at 425 nm for Ce³⁺ and another at 610 nm for Mn²⁺. NaCaBO₃: Ce³⁺, Mn²⁺ (SG) exhibit higher energy‐transfer efficiency (90%) and higher Mn²⁺ quantum efficiency (80%) than SS samples, due to smooth surface, narrow size distribution, and improved homogeneity of sensitizer/activator ions. NaCaBO₃: Ce³⁺, Mn²⁺ exhibits blue‐to‐red tunable color by changing Ce³⁺/Mn²⁺ ratio.     

Highly thermal stable and color tunable composite fluorescent ceramics for high-power white LEDs

All-inorganic fluorescent materials with high luminescence efficiency, high thermal stability and adjustable spectrum are urgently needed, especially for high-power white LEDs. In this work, Y_2.84Lu_0.1Al₅O₁₂: 0.06Ce³⁺ fluorescent ceramics were prepared firstly by vacuum sintering technology, and then Y_2.84Lu_0.1Al₅O₁₂: 0.06Ce³⁺/SrAlSiN₃: Eu²⁺ composite fluorescent ceramics were synthesized by technology screen-printing and laser ablation. Under 460 nm excitation, the composite fluorescent ceramic exhibits a broad emission band from 500 nm to 675 nm, which is attributed to the 5d → 4f transitions of Ce³⁺ and Eu²⁺ ions, respectively. By controlling the screen-printed times, the color coordinates of the composite fluorescent ceramics could be tuned from (0.3125, 0.2437) to (0.4106, 0.3824), and the correlated color temperature can vary from 3296 to 9689 K. In particular, the thermal stability of composite fluorescent ceramics is improved obviously after laser ablation. At 423 K, the luminescence intensity at 535 nm and 620 remains 91% and 94% of that at room temperature, respectively. Combining a 460 nm blue chip and the composite fluorescent ceramic, a white LED with CRI = 90, and the maximum luminous efficiency can be up to 148 lm/W. Our results indicate that Y_2.84Lu_0.1Al₅O₁₂: 0.06Ce³⁺/SrAlSiN₃: Eu²⁺ composite fluorescent ceramics could be used in high-power white LEDs.     

Enhanced Sunlight Excited 1‐μm Emission in Cr3+–Yb3+ Codoped Transparent Glass‐Ceramics Containing Y3Al5O12 Nanocrystals

Cr³⁺–Yb³⁺ codoped transparent glass‐ceramics containing Y₃Al₅O₁₂ nanocrystals were prepared by heat treatment of as‐prepared glass sample and characterized by X‐ray diffraction and transmission electron microscopy. The efficient energy transfer from Cr³⁺ to Yb³⁺ ions through multi‐phonon‐assisted process was confirmed by the luminescence spectrum and fluorescent lifetime measurements. When excited by the lights from a solar simulator in the wavelength region of 400–800 nm, greatly enhanced near‐infrared emission around 1 μm was achieved from Cr³⁺–Yb³⁺ codoped glass ceramic compared with that from as‐prepared glass and Ce³⁺–Yb³⁺ codoped glass ceramic. These results demonstrate that the Cr³⁺–Yb³⁺ codoped glass ceramic is a promising material for enhancement of the efficiency of solar energy utilization.     

Preparation of γ‐aluminum oxynitride phosphor with Eu doping by direct nitridation in ammonia and postannealing

γ‐aluminum oxynitride (γ‐AlON) with spinel structure has attracted much attention for structural and functional application. γ‐AlON powders were successfully prepared by direct nitridation method of Al/Al(OH)₃ starting mixture in ammonia and then calcined at high temperature. XRD, SEM, TEM, EDX, and photoluminescence were conducted to investigate the detail procedure and the optical properties of AlON: xEu phosphors. Nitrogen was introduced by the nitridation of metallic aluminum, appropriate Al amount and nitridation condition was necessary to obtain phase pure γ‐AlON. The as‐prepared AlON powders exhibited multifaceted grain morphology with fine particle size (1‐5 μm). Eu₂O₃ activator was reduced and transformed to EuAl₁₂O₁₉ by reaction with alumina, which remained in the product when x > 0.25%. Under 331 nm excitation, AlON: xEu phosphors exhibited emission bands of 475 and 410 nm. 475 nm band reached a plateau at x = 0.25% due to the solubility of Eu²⁺ ion in AlON, whereas 410 nm band showed a linear increase in intensity with Eu²⁺ doping amount, which was believed to be the contribution of EuAl₁₂O₁₉. The present approach combination of direct nitridation in ammonia and postcalcination process showed potential application for AlON ceramic and AlON phosphors.     

Effects of sintering aids on microstructure,mechanical, and optical properties of AlON ceramics synthesized by SPS

Aluminum oxynitride (AlON) ceramics doped with different sintering aids were synthesized by spark plasma sintering process. The microstructures, mechanical, and optical properties of the ceramics were investigated. The results indicate that the optimal amount of sintering aids is 0.06 wt% La₂O₃ + 0.16 wt% Y₂O₃ + 0.30 wt% MgO. The addition of La³⁺ and Mg²⁺ decreases the rate of grain boundary migration in ceramics, promotes pore elimination, and inhibits grain growth. The addition of Y³⁺ facilitates liquid-phase sintering of AlON ceramics. Moreover, the addition of Mg²⁺ effectively promotes twin formation in the ceramics, which hinders crack propagation and dislocation motion when the ceramics are loaded. Hence, the AlON ceramic doped with 0.06 wt% La₂O₃ + 0.16 wt% Y₂O₃ + 0.30 wt% MgO exhibits a relative density of 99.95%, an average grain size of 9.42 μm, and a twin boundary content of 10.3%, which contributes to its excellent mechanical and optical properties.     

Fabrication and Scintillation Performance of Nonstoichiometric LuAG:Ce Ceramics

Nonstoichiometric LuAG:Ce Ceramics ([Lu_(1–x)Ce_x]₃Al₅O₁₂, x = 0.005) with different excess of Lu³⁺ were designed on the basis of Lu₂O₃‐Al₂O₃ phase diagram and fabricated by a solid‐state reaction method. Without using any traditional sintering aids, pure phase and good optical performance were obtained in such a Lu‐rich LuAG:Ce ceramics. In addition, scintillation efficiency and light yield of 1% excess of Lu³⁺ ceramic sample were found 16 times and 1.82 times higher than that of commercial Bi₄Ge₃O₁₂ (BGO) single crystals, respectively. Such values are comparable or even better than those in most of LuAG:Ce single crystals. However, antisite defects were also induced by excess of Lu doping, whose luminescence was found at 350–410 nm in Lu‐rich LuAG:Ce ceramics. The relationship of excess content of Lu and the microstructure, optical quality, and scintillation performance were clarified and discussed. Furthermore, by utilizing X‐ray absorption near edge spectroscopy technique, the charge state stability of cerium in Lu‐rich LuAG:Ce ceramics was examined. It appears that the excess of isovalence Lu³⁺ doping has a negligible effect on the cerium valence instability and creation of stable Ce⁴⁺ center.     

Spectral and Laser Properties of Yb:LuAG Transparent Ceramics Fabricated by Tape Casting Method

Yb³⁺‐doped LuAG laser ceramics with different Yb³⁺‐doping concentrations were successfully fabricated by nonaqueous tape casting method and vacuum sintering technology. XRD patterns and SEM morphologies of the ceramics were presented. The optical in‐line transmittance of the Yb‐doped LuAG ceramics was about 83% at 1030 nm. The fluorescence lifetime of annealed and unannealed ceramic samples was compared. From the spectroscopic properties, it can be seen that the ceramics had a large emission cross section of 2.9 × 10^?20 cm² with a FWHM of about 7.2 nm at 1030 nm. Under 100% population inversion, the maximum gain coefficient was estimated to be 12.4 cm^?1 at 1030 nm. With a fiber‐coupled diode laser as pump source, CW laser at 1030 nm was demonstrated and the maximum output power of 338.9 mW was achieved with a slop efficiency of 19%. A tuning range from 1028 to 1036 nm was obtained.     

3D printed ceramic phosphor and the photoluminescence property under blue laser excitation

An Al₂O₃/YAG: Ce³⁺ ceramic phosphor was fabricated for high-flux laser lighting using the digital lighting process (DLP)-based 3D printing method for the first time. The photocurable ceramic suspension for 3D printing was prepared by blending well-treated Al₂O₃/YAG: Ce³⁺ composite powders with photosensitive resin monomers and photo-initiators. The printing parameters, debinding and sintering processes were designed delicately to fabricated the dense sub-millimeter-sized cylinder ceramic with high dimensional accuracy. The ceramic showed excellent luminescence property under blue laser excitation with a threshold of 20.7 W/mm², higher than that prepared via dry-pressing followed by vacuum sintering. The luminescence properties and the microstructures of both ceramics were further comparatively investigated to find the possible interpretations for improvement of laser flux for the 3D-printed ceramic. The present work indicated that the new developed 3D printing method was promising for preparing luminescent ceramics for high-flux laser lighting in a rapid, effective, low-cost and precision-controlled manner.     

Efficient energy transfer of Ce to Nd in SrF2 transparent ceramics for enhancing NIR emission

High optical quality Nd³⁺ and Ce³⁺ co-doped SrF₂ (Nd³⁺, Ce³⁺: SrF₂) transparent ceramics were fabricated successfully by a simple hot-pressing (HP) method. The phase composition, in-line transmittance, absorption and emission spectra, as well as the detailed energy transfer of Nd³⁺ and Ce³⁺ were investigated. In addition, the Judd- Ofelt (J-O) theory was adopted to evaluate the luminescence property. The SrF₂ transparent ceramic samples exhibited excellent optical properties, up to 82 % at 400 nm and 92.5 % at 1054 nm. The fracture surface of SrF₂ transparent ceramic proved nearly dense microstructure and EDS results demonstrated uniform doping. The addition of cerium ions changed the crystal field environment of neodymium ions and shifted the emission peak to higher wavelengths at 796 nm excitation. Moreover, through the energy transfer process of Ce³⁺ to Nd³⁺, the occurrence of concentration quenching phenomenon was avoided under 298 nm excitation, and the emission cross-section of ⁴F_3/2→⁴I_11/2 increased to 3.1 × 10⁻²⁰ cm².     

The effects of Mg2+/Si4+ co-substitution for Al3+ on sintering and photoluminescence of (Gd,Lu)3Al5O12:Ce garnet ceramics

A series of phase-pure [(Gd_0.6Lu_0.4)_0.99Ce_0.01]₃[Al_1-z(Mg/Si)_z]₅O₁₂ (z = 0-0.10) garnet phosphor powders were prepared via gel-combustion, which were then sintered into ceramics (up to 1550 °C) under atmospheric pressure. Dilatometry revealed that equimole of Mg²⁺/Si⁴⁺ substitution for Al³⁺ accelerates densification and lowers the activation energy for grain boundary diffusion in the intermediate stage of sintering (∼1150–1370 °C), which was assayed to be ∼353 kJ/mol for z = 0 and ∼289 kJ/mol for z = 0.10. The acceleration effects of Mg²⁺/Si⁴⁺ on sintering and grain growth were further demonstrated by the results of ramp and holding sintering. Firing at 1550 °C for 4 h also produced ∼99 % dense ceramics for the Mg²⁺/Si⁴⁺ codoped garnet powders. Through considering crystal splitting of the Ce³⁺ 5d energy level, photon-phonon coupling, and crystal structure/microstructure, the influences of Mg²⁺/Si⁴⁺ content and material form on Ce³⁺ luminescence, including intensity, external/internal quantum efficiencies, emission wavelength, CIE color coordinates and decay time, were clarified in detail.     

Phase evolution and chemical durability of Zr1‐xCexO2 (0 ≤ x ≤ 1) ceramics

Ce‐doped zirconia ceramics with general stoichiometry of Zr_1‐xCe_xO₂ (0 ≤ x ≤ 1) have been obtained by substitution of Ce⁴⁺ for Zr⁴⁺ in ZrO₂. The phase and microstructure evolutions of the ceramics were investigated, and the effects of composition, temperature, and pH value on the chemical durability of the ceramics were also studied. The results show that the phase transformation from monoclinic to tetragonal takes place at about x = 0.2, and from tetragonal to cubic at about x = 0.6. It is found that the increase in Ce content and/or sinter temperature promote the phase transformation. The leaching studies show that the normalized leaching rates of Ce (LR_Ce) increase with increasing Ce content. Moreover, LR_Ce in acid solution are higher than those in neutral and alkaline solution. After 42 days, LR_Ce is 10^?5 ~ 10^?7 g m^?2 d^?1 under all different leaching conditions, exhibiting their excellent chemical durability.     

Transparent ultrafine Yb3+:Y2O3 laser ceramics fabricated by spark plasma sintering

Conventional ceramic processing techniques do not produce ultrafine‐grained materials. However, since the mechanical and optical properties are highly dependent on the grain size, advanced processing techniques are needed to obtain ceramics with a grain size smaller than the wavelength of visible light for new laser sources. As an empirical study for lasing from an ultrafine‐grained ceramics, transparent Yb³⁺:Y₂O₃ ceramics with several doping concentrations were fabricated by spark plasma sintering (SPS) and their microstructures were analyzed, along with optical and spectroscopic properties. Laser oscillation was verified for 10 at.% Yb³⁺:Y₂O₃ ceramics. The laser ceramics in our study were sintered without sintering additives, and the SPS produced an ultrafine microstructure with an average grain size of 261 nm, which is about one order of magnitude smaller than that of ceramics sintered by conventional techniques. A load was applied during heating to enhance densification, and an in‐line transmittance near the theoretical value was obtained. An analysis of the crystal structure confirmed that the Yb³⁺:Y₂O₃ ceramics were in a solid solution. To the best of our knowledge, this study is the first report verifying the lasing properties of not only ultrafine‐grained but also Yb‐doped ceramics obtained by SPS.     

Dy3+/Ce3+ Codoped YAG Transparent Ceramics for Single‐Composition Tunable White‐Light Phosphor

Superior optical, thermal, and mechanical properties of transparent ceramics are very important in the applications of solid lasers, solid‐state lighting, and transparent armors. Herein, a series of (Dy_0.03Ce_xY_0.97?x)₃Al₅O₁₂ transparent ceramics were fabricated using vacuum reactive sintering method. Importantly, these Dy³⁺/Ce³⁺ codoped yttrium aluminum garnet (YAG) transparent ceramics served as single‐composition tunable white‐light phosphors for UV‐LEDs is developed for the first time. By combining with commercially available UV‐LEDs directly, the optimal chromaticity coordinates and correlated color temperature (CCT) are (x = 0.33, y = 0.35) and 5609 K, respectively. Notably, the codoping of Ce³⁺ enhances the luminescent intensity of Dy³⁺ ions while excited at 327 nm. The emission color of YAG transparent ceramics can be tuned from white to yellow through energy transfer between Dy³⁺ and Ce³⁺. These new phosphors, possessing of pure CIE chromaticity and environmentally friendly nature, are promising for applications in white UV‐LEDs.     

Effects of Sintering Aids on the Transparency and Conversion Efficiency of Cr4+ Ions in Cr: YAG Transparent Ceramics

Tetravalent chromium‐doped Y₃Al₅O₁₂ ceramics were fabricated by solid‐state reactive sintering method using high‐purity Y₂O₃, α‐ Al₂O₃, and Cr₂O₃ powders as the starting materials. CaO and MgO were co‐doped as the sintering aids. The effects of TEOS and divalent dopants (CaO and MgO) on the optical qualities, the conversion efficiency of Cr⁴⁺ ions, and the microstructure evolutions of 0.1 at.% Cr⁴⁺: YAG ceramics were investigated. Fully dense, dark brown colored Cr⁴⁺: YAG ceramics with an average grain size of 3.1 μm were achieved. The in‐line transmittance of the as‐prepared ceramic at 2000 nm was 85.3% (4 mm thick), and the absorption coefficient at 1030 nm (the characteristic absorption peak of Cr⁴⁺ ions) was as high as 3.7 cm^?1, which was higher than that of corresponding single crystals fabricated by Czochralski method.     

The Cr‐doping effect on white light emitting properties of Ce:YAG phosphor ceramics

The Cr/Ce‐doped YAG transparent ceramic was fabricated by the solid‐state reaction in vacuum. The Cr/Ce‐doped YAG ceramic phosphor effectively complement the red spectral component and improve the color rendering performance when excited by blue light that is due to the effective energy transfer between Cr³⁺ ion and Ce³⁺ ion. However, the energy transfer from Ce³⁺ to Cr³⁺ ion leads to energy loss and therefore the luminous efficacy of the WLED which is composed of blue LED chip and the Cr/Ce‐doped YAG ceramic phosphor decreases. The composite phase structure of ceramic phosphor is designed for improving the extraction efficacy and increasing the luminous efficacy by breaking the total internal reflection (TIR) at the interface between air and ceramic.     

Preparation and Application of Strong Near‐Infrared Emission Phosphor Sr3SiO5:Ce3+,Al3+,Nd3+

This work investigated the near‐infrared (NIR) emission properties of mCe³⁺, xNd³⁺ codoped Sr_3?m?x(Si_1?m?xAl_m+x)O₅ phosphors. Samples with various doping concentrations were synthesized by the high‐temperature solid‐state reaction. Al³⁺ ions have the ability to promote Ce³⁺ ions to enter into the Sr²⁺ sites and to improve the visible emission of Ce³⁺. Thus the NIR emission of Nd³⁺ is enhanced by the energy‐transfer process, which occurred from Ce³⁺ to Nd³⁺. The device based on these NIR emission phosphors is fabricated and combined with a commercial c‐Si solar cell for performance testing. Short‐circuit current density of the solar cell is increased by 7.7%. Results of this work suggest that the Sr_2.95Si_0.95Al_0.05O₅:0.025Ce³⁺, 0.025Nd³⁺ phosphors can be used as spectral convertors to improve the efficiency of c‐Si solar cell.     

Production and optical properties of Ce3+-activated and Lu3+-stabilized transparent gadolinium aluminate garnet ceramics

We first report the novel Ce³⁺-activated and Lu³⁺-stabilized gadolinium aluminate garnet (GAG) transparent ceramics derived from their precipitation precursors via a facile co-precipitation strategy using ammonium hydrogen carbonate (AHC) as the precipitant. The resulting precursors in liquid phase were substantially homogeneous solid solutions and could directly convert into sinterable garnet powders via pyrolysis. Substituting 35 at.% of Lu³⁺ for Gd³⁺ was effective to stabilize the cubic GAG garnet structure and transparent (Gd,Lu)₃Al₅O₁₂:Ce ceramics were successfully fabricated by vacuum sintering at 1715°C. The ceramic transparency was improved by optimizing the particle processing conditions and the best sample had an in-line transmittance of ~70% at 580 nm (Ce³⁺ emission center) and over 80% in partial infrared region with a fine average grain size of ~4.5 μm. Transparent (Gd,Lu)₃Al₅O₁₂:Ce ceramics have a short critical wavelength (<200 nm) and a maximal infrared cut-off at ~6.6 μm. Both the (Gd,Lu)₃Al₅O₁₂:Ce phosphor powder and the transparent ceramic exhibited characteristic yellow emission of Ce³⁺ with strong broad emission bands from 490 to 750 nm upon UV excitation into two groups of broad bands around 340 and 470 nm. The photoluminescence and photoluminescence excitation intensities as well as the quantum yield were greatly enhanced via high-temperature densification. Both the phosphor powder and ceramic bulk had short effective fluorescence lifetimes.