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.     

The luminescence properties,energy transfer mechanism of the color tunable and high quantum efficiency LaAl2.03B4O10.54: Ce3+, Tb3+ phosphors

Tb³⁺ is a typical green emitting luminescence center in inorganic compounds. However, the absorption of Tb³⁺ is very weak in ultraviolet spectral region (from 240 to 400 nm). Ce³⁺ is often used as a sensitizer to transfer energy to Tb³⁺. In this paper, Ce³⁺ and Tb³⁺ were co-doped into a novel aluminates-borates LaAl_2.03B₄O_10.54. Ce³⁺ can absorb UV light (from 240 to 340 nm) and transfer absorbed energy to co-doped Tb³⁺ effectively and bring bright green emission of Tb³⁺. The crystal structure and fluorescence spectra of phosphors, the efficiency of energy transfer between Ce³⁺ and Tb³⁺, decay dynamics, the thermal stability and internal quantum efficiency of luminescence have been investigated in detail. These results indicate that the color tunable LaAl_2.03B₄O_10.54: Ce³⁺, Tb³⁺ phosphor is a potential green-emitting material. Especially, analysis about the relationship of the doping concentration of luminescence centers and thermal stability of luminescence points out a feasible way to enhance the thermal stability of luminescence in the future.     

High magneto-optical performance of GdFeO3 thin film with high orientation and heavy Ce3+ doping

In this paper, GdFeO₃ thin films with high orientation and heavily Ce³⁺ doping were deposited by radio frequency magnetron sputtering with a matching substrate. The effects of substrates and Ce³⁺ doping on the structure, magnetic and magneto-optical properties of thin films were investigated. As a result, Ce³⁺ doping can not only increase the saturation magnetization but also greatly enhance the magnetic circular dichroism signals of Ce:GdFeO₃ thin films. Based on the density functional theory calculation, it can be found that the probability of electron transition between Ce³⁺ 4f and Fe³⁺ 3d and the difference in the absorption of right and left circularly polarized light increase, which results in the strong magneto-optical effect of Ce:GdFeO₃/STO thin films.     

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.     

Photoluminescence and energy transfer of efficient and thermally stable white-emitting Ca9La(PO4)7:Ce3+, Tb3+, Mn2+ phosphors

The development of novel single-component white-emitting phosphors with high thermal stability is essential for improving the illumination quality of white light-emitting diodes. In this work, we synthesized a series of Ce³⁺, Tb³⁺, Mn²⁺ single- and multiple-doped Ca₉La(PO₄)₇ (CLPO) phosphors with β-Ca₃(PO₄)₂-type structure by the simple high-temperature solid-state reaction. The crystallization behavior, crystal structure, surface morphology, photoluminescence performance, decay lifetime and thermal stability were systematically investigated. The PL spectra and decay curves have evidenced the efficient energy transfer from Ce³⁺ to Tb³⁺ and from Ce³⁺ to Mn²⁺ in the CLPO host, and corresponding energy transfer efficiency reaches 41.8% and 54.1%, respectively. The energy transfer process of Ce³⁺→Tb³⁺ and Ce³⁺→Mn²⁺ can be deduced to the resonant type via dipole-dipole and dipole-quadrupole interaction mechanism, and corresponding critical distance were determined to be 12.23 and 14.4 Å, respectively. Based on the efficient energy transfer, the white light emission can be successfully achieved in the single-component CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ phosphor, which owns CIE chromaticity coordinates of (0.3245, 0.3347), CCT of 5878 K, internal and external quantum efficiency of 84.51% and 69.32%. Especially, compared with the emission intensity at 25 °C, it still remains 98.5% at 150 °C and 92.0% at 300 °C. Based on these results, the single-component white light emission phosphor CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ is a potential candidate for UV-converted white LEDs.     

Oxygen vacancy luminescence and band gap narrowing driven by Ce ion doping with variable valence in SnO2 nanocrystals

Although considerable research works have witnessed the important modulations of oxygen vacancies on the optical, electrical, and magnetic properties of SnO₂ nanostructures, it is not easy to control oxygen vacancy defects in such systems.The difficulty stems from that oxygen vacancy is a kind of atomic defect, and its distribution is sensitive to process conditions and external factors, which makes direct characterization and purposeful control difficult. The purpose of this work on Ce-doped SnO₂ nanocrystals is to investigate the tolerance of the host lattice to Ce ions, the population and evolution of Ce³⁺/Ce⁴⁺ ions, and the possibility to adjust oxygen vacancies by Ce³⁺ ions, and then focus on the influence of oxygen vacancy defects on the band gap and luminescence performance. As Ce doping concentration increases from 0 to 12 at.%, the doped system changes from Ce³⁺ dominated at low doping amount (≤3 at.%) to Ce³⁺/Ce⁴⁺ coexistence at medium doping concentration (3 at.% ∼ 9 at.%), to occurrence of CeO₂ impurity phase at over doping (∼12 at.%). The optimum doping occurs at 6 at.%, which corresponds to the saturated critical point of Ce³⁺ content and the maximum oxygen vacancy concentration. Importantly, the oxygen vacancies in the current Ce-doped SnO₂ nanocrystals is directly regulated by the Ce³⁺ ion concentration on the Sn sites, which plays an important role in the band gap tuning and visible light emission. With Ce concentration increasing from 0 to 12 at.%, the band gap monotonicity decreases from 3.36 eV to 3.12 eV, while the intensity of the oxygen vacancy luminescence band first increases and then decreases, with the turning point at 6 at.%. Both band gap narrowing effect and enhanced emission indicate that Ce-doped SnO₂ should be a promising method to design and manufacture visible light responsive SnO₂ based optoelectronic materials by manipulating oxygen vacancy defects.     

Apatite oxynitride phosphor (Mg,Y)5Si3(O,N)13:Ce3+,Mn2+: A single-phased host with solar-like and efficient emission

During pursuing high color rendering index for full-color-emitting phosphor, low quantum efficiency (QE) is usually accompanying. We intend to elevate the luminescence efficiency when realizing a solar-like spectra distribution, by constructing apatite structure oxynitride, inheriting high covalence and rigidity from oxynitride, and suitable multiple cation sites from oxyapatite compounds. Full-color-emitting apatite structure oxynitride phosphor (Mg,Y)₅Si₃(O,N)₁₃:Ce³⁺,Mn²⁺ has been prepared, and the crystal sites’ occupancies of activators in this host were favorable for white emission. (Mg,Y)₅Si₃(O,N)₁₃:Ce³⁺,Mn²⁺ phosphor shows whole visible light with emission wavelength ranging from 370 to 750 nm, matching the spectra of sunlight quite well. The fabricated white light-emitting diode lamp demonstrated the distinctive overall performance of QE and chromaticity properties (R_a and R₉). Furthermore, correlated color temperature is tunable from cool nature to warm white. The obtained lamp possesses the feature of less blue light hazard and high saturation of red degree, compared with the commercial YAG-based lamp.     

New Magneto‐Optical Film of Ce,Ga:GIG with High Performance

Ce³⁺‐doped Gd₃Fe₅O₁₂ (Ce:GIG) film has a good application prospect in the field of integrated optical device. In this article, Ce:GIG and Ce,Ga:GIG films were deposited onto the quartz glass substrate by using radio‐frequency magnetron sputtering technology. The crystal phase, surface morphology, magnetization, and magnetic circular dichroism properties of films were characterized by using the X‐ray powder diffraction, atomic force microscopy, vibrating sample magnetometer, and circular dichroism spectrometer. The results show that as‐prepared Ce,Ga:GIG films has a good quality and show an excellent magneto‐optical performance, and the doping of Ga³⁺ ion and the annealing process have significant effect on the magnetism and magneto‐optical performances. It is expected that Ce,Ga:GIG film with a moderate Ga³⁺‐doping content is a better candidate than Ce:GIG and Ce:YIG films for the next generation of integrated optical isolator and other magneto‐optical equipment.     

Broadband excited Na3Tb(PO4)2:Ce3+/Eu2+ green/yellow-emitting phosphors with high color purity for LED-based application

To enhance the display quality of light-emitting diodes (LEDs), it is of great significance to exploit green/yellow-emitting phosphors with narrow emission band, high quantum yield, and excellent color purity to satisfy the application. Herein, orthophosphate-based green/yellow-emitting Na₃Tb(PO₄)₂:Ce³⁺/Eu²⁺ (NTPO:Ce³⁺/Eu²⁺) phosphors have been successfully synthesized by a facile solid-state reaction method. The absorption band of NTPO samples was extended to the near-ultraviolet region and the absorption efficiency was significantly improved owing to a highly efficient energy transfer from Ce³⁺/Eu²⁺ ion to Tb³⁺ ion in NTPO host certified by time-resolved PL spectra. Upon 300 nm excitation, the NTPO:Ce³⁺ is characterized by ultra-narrow-band green emission of Tb³⁺ with an absolute quantum yield of 94.5%. Unexpectedly, NTPO:Eu²⁺ emits bright yellow light with a color purity of 73% as a result of the blending of green light emission from Tb³⁺ and red light emission from Eu³⁺. The thermal stability has been improved by controlling the stoichiometric ratio of Na⁺. The prototype white LED used yellow-emitting NTPO:Eu²⁺ phosphor has higher color-rendering index (Ra = 83.5), lower correlated color temperature (CCT = 5206 K), and closer CIE color coordinates (0.338, 0.3187) to the standard white point at (0.333, 0.333) than that used green-emitting NTPO:Ce³⁺ phosphor, indicating the addition of the yellow light component improved the Ra of the trichromatic (RGB) materials.     

Local coordination,electronic structure,and thermal quenching of Ce3+ in isostructural Sr2GdAlO5 and Sr3AlO4F phosphors

Sr₂GdAlO₅:Ce and Sr₃AlO₄F:Ce are isostructural phosphors in which the Ce³⁺ 4f-5d₁ transition can be efficiently excited by a photon with energy lower than 3.1 eV. Herein, we analyze the crystal chemistry of the Ce³⁺ local coordination, compare the thermal quenching behavior and construct the electronic structure of Ce³⁺ in them. The Rietveld refinement on two occupancy models suggests that Gd³⁺ only occupies the 8h site in Sr₂GdAlO₅; this provides a hint on the preferred occupancy of dopant Ce³⁺ in this site. The large crystal filed splitting of Ce_8h is mainly due to the fact that the 8h site is bonded to two oxygen with relatively short d_Sr/Gd-O and forms a quasi-square antiprism which experiences a large distortion. The Ce³⁺ 5d-4f luminescence in Sr₃AlO₄F is much more stable against thermal quenching than that in Sr₂GdAlO₅, as evidenced by the temperature-dependent luminescence intensity and luminescence decay studies. The energy of the O²⁻-Eu^3+/2+ and O²⁻-Ce^4+/3+ charge transfer as well as bandgap were estimated and the electronic structure of Ce³⁺ were constructed. A larger energy barrier ΔE_dC between the Ce³⁺ 5d₁ level and the conduction band bottom in Sr₃AlO₄F is seen from the Vacuum Referred Binding Energy (VRBE) diagrams which explains the higher thermal quenching temperature by thermal ionization model.     

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.     

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.     

Insight into luminescent properties,energy transfer and thermal stability of NaBa4(AlB4O9)2Cl3:Ce3+, Tb3+ phosphors

A series of Ce³⁺ and Tb³⁺ singly- and co-doped NaBa₄(AlB₄O₉)₂Cl₃ (NBAC) phosphors have been synthesized via high-temperature solid state route. The crystal structure, morphology, photoluminescent properties, thermal properties and energy transfer process between Ce³⁺ and Tb³⁺ were systematically investigated. The structure refinements indicated that the phosphors based on NBAC crystallized in P42nm polar space group in monoclinic phase. The emission color could be tuned from blue (0.1595, 0.0955) to green (0.2689, 0.4334) via changing the ratio of Ce³⁺/Tb³⁺. The energy transfer mechanism of Ce³⁺/Tb³⁺ was verified to be dipole–quadrupole interaction via the examination of decay times of Ce³⁺ based on Dexter's theory. The good thermal stability showed the intensities of Ce³⁺ at 150°C were about 66.9% and 64.88% in NBAC:0.09Ce³⁺ and NBAC:0.09Ce³⁺, 0.07Tb³⁺ of that at room temperature, and the emission intensities of Tb³⁺ remained 102.41% in NBAC:0.11Tb³⁺ and 95.22% in NBAC:0.09Ce³⁺, 0.07Tb³⁺ due to the nephelauxetic shielding effect and the highly asymmetric rigid framework structure of NBAC. The maximum external quantum efficiency (EQE) of Ce³⁺ in NBAC:0.09Ce³⁺, yTb³⁺ phosphors could reach 43.38% at y = 0.13. Overall, all the results obtained suggested that NBAC:Ce³⁺, Tb³⁺ could be a promising option for n-UV pumped phosphors.     

Structural analysis and electrode performance of Ce doped SrMnO3 synthesised by EDTA citrate complexing process

Abstract

Sr_1?xCe_xMnO₃ (SCM, 0·1≤x≤0·4) powders were synthesised by an ethylenediaminetetraacetic acid citrate complexing process, and their properties were investigated. The synthesised Sr_1?xCe_xMnO₃ powders showed a pure perovskite phase, whereas the composition with x?=?0·4 had second phases. The unit cell volumes increased with increasing Ce content because substituted Ce ions formed some Mn³⁺ ions, which have a larger ionic radius than Mn⁴⁺. The electrical conductivity improved with increasing Ce content up to x?=?0·3 (291 S cm^?1 at 750°C), revealing a double exchange interaction. Although the electrical conductivity was increased by doping Ce ions, the polarisation resistance increased due to the increase in lattice distortion with doping Ce content. The substitution of Ce ions for Sr in SrMnO₃ led to the formation of larger Mn³⁺ ions than Mn⁴⁺ ions and lattice distortion, which would affect the electrical and oxygen ion conductivity.     

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.     

Inorganic remote glass film based on yellowish-green (Y,Ba)3(Al,Si)5O12:Ce garnet phosphor for warm white LEDs

Compared with other fluorescent crystal phases, garnet has better structural stability in a glass matrix and renders precisely controllable emissions due to the abundant lattice control positions. In this work, we regulate the coordination field of Ce³⁺ ion based on the co-substitution method and achieve the spectra regulation in the yellow–green range. We used Ba²⁺–Si⁴⁺ cations to replace Y³⁺–Al³⁺ cations in Y₃Al₅O₁₂ (YAG) matrix to obtain blue-shift of the emission peak from 552 to 539 nm. The centroid shift and crystal field splitting decrease with the decreasing covalency of the bond between the Ce³⁺ ion and the surrounding anions owing to the higher electronegativity of Si⁴⁺ ions than Al³⁺ ions. The corresponding fluorescent films were prepared by a low-temperature co-sintering process based on the as-made Ba²⁺–Si⁴⁺ co-substituted phosphor. X-ray powder diffractometer and scanning electron microscopy images showed that the fluorescence crystals were less eroded and evenly dispersed in the glass matrix. Spectral analysis showed that the garnet phase was protected by using lead-free borosilicate glass with a low melting point, and the quantum efficiency of phosphor-in-glass (PiG) retains 98% of the corresponding phosphor. By adjusting the ratio of garnet phosphor to commercial red nitride phosphors, a warm white fluorescence with a color rendering index of 80.3 and color temperature of 3899 K was obtained. The prepared warm white film has potential application value in the whole spectra field.     

Dual effect synergistically triggered Ce:(Y,Tb)3(Al,Mn)5O12 transparent ceramics enabling a high color-rendering index and excellent thermal stability for white LEDs

Ce:Y₃Al₅O₁₂ transparent ceramics (TCs) with appropriate emission light proportion and high thermal stability are significant to construct white light emitting diode devices with excellent chromaticity parameters. In this work, strategies of controlling crystal-field splitting around Ce³⁺ ion and doping orange-red emitting ion, were adopted to fabricate Ce:(Y,Tb)₃(Al,Mn)₅O₁₂ TCs via vacuum sintering technique. Notably, 85.4 % of the room-temperature luminescence intensity of the TC was retained at 150 °C, and the color rendering index was as high as 79.8. Furthermore, a 12 nm red shift and a 16.2 % increase of full width at half maximum were achieved owing to the synergistic effects of Tb³⁺ and Mn²⁺ ions. By combining TCs with a 460 nm blue chip, a warm white light with a low correlated color temperature of 4155 K was acquired. Meanwhile, the action mechanism of Tb³⁺ ion and the energy transfer between Ce³⁺ and Mn²⁺ ions were verified in prepared TCs.     

Processing of Transparent Polycrystalline AlON:Ce3+ Scintillators

A new polycrystalline ceramic scintillator is reported for potential use in radiation detection and medical imaging applications. The goal was to develop cerium‐activated aluminum oxynitride (AlON:Ce³⁺) ceramics, which can be produced using ceramic processes in comparison to the high‐cost, low‐yield single‐crystal growth technique. A phase pure AlON:Ce³⁺ powder with cubic symmetry was successfully synthesized at high temperature under a reducing atmosphere to convert Ce⁴⁺ to Ce³⁺ in the solid solution. Two different activator concentrations (0.5 and 1.0 mol%) were explored. Fully dense and transparent AlON:Ce³⁺ ceramics were produced by a liquid‐phase‐assisted pressureless sintering. The crystal field splitting around the Ce³⁺ activator in the AlON was comparable to the splitting induced by Br^? and the Cl^? ligands, which produced an emission spectrum perfectly matching the maximum quantum efficiency range of the photomultiplier tube for radiation detection. Both optical excitation and radiation ionizations in AlON:Ce³⁺ were demonstrated. Challenges and mechanisms related to the radioluminescence efficiency are discussed.     

The electrical properties of (Ba,Ca, Ce,Ti, Zr)O3 thermistor for wide-temperature sensor architecture

A series of new negative temperature coefficient (NTC) thermal materials based on (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ (0.00 ≤ x ≤ 0.20) ceramics were synthesized by a solid-state method. X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy were used to demonstrate the crystal structure, morphology, and composition of the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics, which were composed of solid solution based on the BaTiO₃ phase. The average grain size of doped ceramic samples experienced the process of first decreasing and then increasing. The doping of Ce has reduced the sintering temperature. The temperature-dependent resistance analysis revealed that with the change of doping amount x, the thermal constant B_300/1200 (1.21 × 10⁴–1.13 × 10⁴ K) and the activation energy E_a300/1200 (0.9777–1.0471eV) was initially increased to maximum values at x = 0.05, followed by the decreasing when x > 0.05. It has been established that the concentration of oxygen vacancies is affected by the transition between Ce⁴⁺ and Ce³⁺ provided by high levels of Ce doping. (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics exhibited excellent negative temperature characteristics in the range of 300–1200 °C. Moreover, the temperature resistance linearity was improved after samples were aged. Hence, the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics were regarded as a promising material for high-temperature NTC thermistors in a wide temperature range.     

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.