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.     

Eu3+‐Activated Borogermanate Scintillating Glass with a High Gd2O3 Content

Eu³⁺‐activated borogermanate scintillating glasses with compositions of 25B₂O₃–40GeO₂–25Gd₂O₃–(10?x)La₂O₃–xEu₂O₃ were prepared by melt‐quenching method. Their optical properties were studied by transmittance, photoluminescence, Fourier transform infrared (FTIR), Raman and X‐ray excited luminescence (XEL) spectra in detail. The results suggest that the role of Gd₂O₃ is of significance for designing dense glass. Furthermore, energy‐transfer efficiency from Gd³⁺ to Eu³⁺ ions can be near 100% when the content of Eu₂O₃ exceeds x = 4, the corresponding critical distance for Gd³⁺–Eu³⁺ ion pairs is estimated to be 4.57 Å. The strongest emission intensities of Eu³⁺ ions under both 276 and 394 nm excitation are simultaneously at the content of 8 mol% Eu₂O₃. The degree of Eu–O covalency and the local environment of Eu³⁺ ions are evaluated by the value of Ω_t parameters from Judd–Ofelt analysis. The calculated results imply that the covalency of Eu–O bond increases with the increasing concentration of Eu³⁺ ions in the investigated borogermanate glass. As a potential scintillating application, the strongest XEL intensity under X‐ray excitation is found to be in the case of 6 mol% Eu₂O₃, which is slightly different from the photoluminescence results. The possible reason may be attributed to the discrepancy of the excitation mechanism between the ultraviolet and X‐ray energy.     

Ce3+‐ and Dy3+‐Doped Oxyfluoride Borosilicate Glasses with Near White Luminescence

A series of Ce³⁺/Dy³⁺‐doped oxyfluoride borosilicate glasses prepared by melt‐quenching method are investigated for light‐emitting diodes applications. These glasses are studied via X‐ray diffraction (XRD), optical absorption, photoluminescence (PL), color coordinate, and Fourier transform infrared (FT‐IR) spectra. We find that the absorption and emission bands of Ce³⁺ ions move to the longer wavelengths with increasing Ce³⁺ concentrations and decreasing B₂O₃ and Al₂O₃ contents in the glass compositions. We also discover the emission behavior of Ce³⁺ ions is dependent on the excitation wavelengths. The glass structure variations with changing glass compositions are examined using the FT‐IR spectra. The influence of glass network structure on the luminescence of Ce³⁺/Dy³⁺ codoped glasses is studied. Furthermore, the near‐ideal white light emission (color coordinate x = 0.32, y = 0.32) from the Ce³⁺/Dy³⁺ codoped glasses excited at 350 nm UV light is realized.     

Yellow‐Emitting Y3Si6N11: Ce3+ Phosphors for White Light–Emitting Diodes (LEDs)

A novel Y_3?xSi₆N₁₁: xCe³⁺ yellow phosphor was synthesized using the carbothermal reduction and nitridition method at 1550°C for 16 h in this letter. Photoluminescence spectra indicated that the phosphor showed broad excitation spectrum and had strong absorption in range of 350–450 nm. It also gave a broad emission band (Full width at half maximum = 153 nm) centered at 575 nm under 425‐nm excitation. With increasing Ce³⁺ concentration, the strongest emission intensity was obtained at 5 mol% Ce³⁺ doping amount and a systematic redshift was observed as the Ce³⁺ concentration increased. The results indicate that this novel yellow phosphor is a promising candidate for using in blue‐chip‐excited white light–emitting diodes (LEDs).     

A Simple and Highly Efficient Method for Synthesis of Ce3+‐Activated Borogermanate Scintillating Glasses in Air

Fast Ce³⁺‐activated borogermanate scintillating glasses with the density of 5.58–5.67 g/cm³ were synthesized by melt quenching method in air atmosphere for the first time. The optical transmittance and X‐ray absorption near edge spectroscopy results confirm that Ce⁴⁺ ions can be effectively reduced to Ce³⁺ ions by adding 0.31 mol% Si₃N₄ as a strong reducing agent during glass synthesis. The luminescence behavior under both ultraviolet and X‐ray excitations indicate that the proposed Ce³⁺‐activated borogermanate scintillating glasses have a broad emission band centered at 430 nm and a decay time of less than 25 ns. This will be of great interest in high‐energy physics and nuclear physics engineering.     

Morphology-controlled therapeutic activity of cerium oxide nanoparticles for mild traumatic brain injury

The design and optimization of nanostructures with unique morphologies and properties are at the forefront of biomedical nanotechnology. Cerium oxides are widely used to investigate the effect of morphology on performance. However, elucidating the morphology–activity relationship of cerium oxide nanocrystals in biomedical applications remains challenging. Herein, the therapeutic effects of cerium oxide nanoparticles with different morphologies: cerium oxide nanorods with two different aspect ratios (CeO_x NRs_A and CeO_x NRs_B), cerium oxide nanopolyhedra (CeO_x NPs), and cerium oxide nanocubes (CeO_x NCs) are investigated in in vivo and in vitro mild traumatic brain injury (TBI) models. Cerium oxide nanoparticles inhibit oxidative stress and inflammation after mild TBI, alleviating cognitive impairment; furthermore, the therapeutic effect is significantly affected by their morphology. Owing to the higher Ce³⁺/Ce⁴⁺ ratio, exposure of more active crystal surfaces, and greater number of exposed oxygen vacancies, CeO_x NRs show better activity than CeO_x NPs and CeO_x NCs for mild TBI. Among the two investigated types of cerium oxide nanorods, CeO_x NRs_A, with a higher Ce³⁺/Ce⁴⁺ ratio on the surface, appear to spread better than CeO_x NRs_B in the injured lesions. The factors causing morphology-controlled biomedical performance, such as Ce³⁺/Ce⁴⁺ molar ratio, surface area, and aspect ratio, are discussed.     

Structure and Photoluminescence of A Blue‐Green‐Emitting Phosphor for Near‐UV White LEDs

A series of phosphors Ca_12(0.97?x)Al₁₄O₃₂F₂: 0.03Ce³⁺, xTb³⁺ have been prepared by a hightemperature solid‐state reaction using boric acid as flux. These oxyfluorides crystallize in cubic structure, space group. Under the near ultraviolet excitation within wavelength range 310–390 nm, Ca_12(0.97?x)Al₁₄O₃₂F₂: 0.03Ce³⁺, xTb³⁺ phosphors exhibit an intense emission covering a broad band of 370–500 nm derived from the 5d→4f transitions of Ce³⁺ and a characteristic emission at 544 nm of Tb³⁺. The emission can be tuned from blue to green by altering the relative ratio of Ce³⁺ to Tb³⁺ in the composition. The energy‐transfer mechanism from Ce³⁺ to Tb³⁺ is investigated based on the site occupancy of the luminescence center in the crystal structure of the Ca₁₂Al₁₄O₃₂F₂ host. More importantly, when a certain amount of boric acid is added as flux in the synthesis, the fluorescence intensity of the phosphors increases about 65%. Because of its broad excitation and efficiently tunable blue to green luminescence, the Ca_12(0.97?x)Al₁₄O₃₂F₂: 0.03Ce³⁺, xTb³⁺ phosphors may find promising application as a near UV‐convertible phosphor for white‐light‐emitting diodes.     

Tunable Emission Phosphor Ca4Y6O(SiO4)6:Ce3+, Eu2+: Luminescence and Energy Transfer

A series of Ca_4–yY_6–xO(SiO₄)₆: xCe³⁺, yEu²⁺ samples are synthesized by a high‐temperature solid‐state method. Under 356 nm excitation, Ca₄Y₆O(SiO₄)₆:Ce³⁺ presents a strong blue emission band at 426 nm which are assigned to 4f⁰5d¹→4f¹ transition of Ce³⁺ ion. Ca₄Y₆O(SiO₄)₆:Eu²⁺ shows green emission under 380 nm radiation excitation, and the peak locates at 527 nm which is mainly due to transitions of Eu²⁺ from 4f⁷ ground state to 4f⁶5d¹ excited state. Under 356 nm excitation, a remarkable energy transfer from Ce³⁺ to Eu²⁺ exists in Ca₄Y₆O(SiO₄)₆, and the result reveals that the mechanism of energy transfer is a resonant type via a nonradiative dipole–dipole interaction. The hues of Ca₄Y₆O(SiO₄)₆:Ce³⁺, Eu²⁺ can be adjusted by the energy transfer from Ce³⁺ to Eu²⁺ ions, and a white emission can be achieved by tuning the ratio of Ce³⁺ to Eu²⁺. The results mean that Ce³⁺ may be the effective sensitizer for Eu²⁺‐doped Ca₄Y₆O(SiO₄)₆.     

Role of Al3+ on tuning optical properties of Ce3+‐activated borosilicate scintillating glasses prepared in air

A colorless Ce³⁺‐activated borosilicate scintillating glass enriched with Gd₂O₃ is successfully synthesized in air atmosphere for the first time. The full replacement of 10 mol% BaO by Al₂O₃, and the partial substitution of 3 mol% SiO₂ by Si₃N₄ in the designed glass composition are crucial for this success. The role of Al³⁺ on tuning the optical properties of Ce³⁺‐activated borosilicate scintillating glass synthesized in air are analyzed by optical transmittance, X‐ray absorption near edge spectroscopy (XANES) spectra, photoluminescence (PL) and radioluminescence (RL) spectra. The results suggest that the stable Ce⁴⁺ ions can be effectively reduced to stable Ce³⁺ ions by the full replacement of BaO by Al₂O₃, and both the PL andRL intensity of the designed borosilicate scintillating glass are enhanced by a factor of 6.7 and 5.2, respectively. The integral RL intensity of the synthesized Ce³⁺‐activated borosilicate scintillating glass is ~17.2%BGO, with a light output of about 1180 ph/MeV. The strategy of substituting BaO by Al₂O₃ will trigger more scientific and technological considerations in designing novel fast scintillating glasses.     

Li2SrSiO4:Ce3+, Pr3+ Phosphor with Blue,Red, and Near‐Infrared Emissions Used for Plant Growth LED

Ce³⁺/Pr³⁺ codoped Li₂SrSiO₄ (LSS) phosphors with blue, red, and near‐infrared (NIR) tri‐emission have been prepared via a high‐temperature solid‐state reaction method. Under the excitation of 200 to 400 nm near‐ultraviolet (n‐UV), the photoluminescence (PL) spectra of phosphors are composed of visible and NIR two parts. The former exhibits blue and red emission bands centered at around 428 nm from 5d–4f transition of Ce³⁺ and 611 nm from ¹D₂ → ³H₄ transition of Pr³⁺, those overlap with photosynthesis action spectra of plants and absorption spectra of chlorophylls and carotenoids. While the later presents a broad NIR emission band peaking near 1039 nm caused by the ¹G₄ → ³H₄ of Pr³⁺, matching with the absorption of bacteriochlorophyll. Their emission intensity ratios (B: R: NIR) could be tuned by altering the relative ratios of Ce³⁺ and Pr³⁺ concentration in the phosphors to meet the requirements of multifarious plants and bacteria. The efficient energy transfer from Ce³⁺ to Pr³⁺ takes place in the LSS host, which ascribed to an exchange interaction according to PL spectra and decay curves of phosphors. Results suggest that the present LSS: Ce³⁺, Pr³⁺ phosphors have great potential applications in plant growth n‐UV LED.     

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.     

Enhanced luminescence properties and energy transfer in Ce3+ and Tb3+ co-doped NaCaBO3 phosphor

A series of color-tunable NaCaBO₃: Ce³⁺, Tb³⁺ phosphors have been synthesized on the basis of efficient Ce³⁺→Tb³⁺ energy transfer. The photoluminescence emission and excitation spectra, the lifetime, and the effect of Tb³⁺ concentration are investigated in detail. The enhanced photoluminescence of Tb³⁺ with sharp emission lines could be obtained by the broad excitation band from the allowed 4f–5d absorption of Ce³⁺ ions. The intensity ratio of blue emission from Ce³⁺ and green emission from Tb³⁺ can be tuned by adjusting their concentrations. The energy transfer from Ce³⁺ to Tb³⁺ in NaCaBO₃ was found to be an electric dipole–quadrupole interaction.     

Enhanced photoluminescence quantum yield of Ce3+-doped aluminum–silicate glasses for scintillation application

Ce³⁺-doped 20Gd₂O₃–20Al₂O₃–60SiO₂ (GAS:xCe³⁺) glasses (x = 0.3, 0.7, 1.1, 1.5, 1.9 mol%) with Si₃N₄ as a reducing agent were prepared. The density of the glasses is around 4.2 g/cm³. With the increase in the Ce³⁺ concentration, both the photoluminescence (PL) and PL excitation peaks of GAS:xCe³⁺ glasses show a redshift because the 4f–5d energy levels of Ce³⁺ ions are narrowed. PL quantum yield and PL decay time of GAS:xCe³⁺ glasses are 28.32–50.59% and 43–64 ns, respectively. In addition, they both first increases and then decreases with the Ce³⁺ concentration increasing, reached the maximum when x = 1.1 mol%. The integrated X-ray excited luminescence (XEL) intensity of the GAS:1.1Ce³⁺ glass is 23.86% of that of Bi₄Ge₃O₁₂ (BGO) crystal, and the light yield reaches 1200 ph/MeV with an energy resolution of 22.98% at 662 keV when exposed to γ-rays. The PL and XEL thermal activation energies of GAS:xCe³⁺ glasses are independent of Ce³⁺ ions concentration. Scintillating decay time of the glasses exhibits two components consisting of nanosecond and microsecond levels, and the scintillating decay time gradually decreases with the Ce³⁺ concentration increasing. The difference between PL and scintillating decay time is discussed regarding the different luminescent mechanisms.     

Partial cation substitution of tunable blue-cyan-emitting Ba2B2O5:Ce3+ for near-UV white LEDs

In this study, Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ ions act to tune the emission band to the blue-cyan region in Ba_xSr_yB₂O₅:Ce³⁺ (BSBO), Ba_xCa_zB₂O₅:Ce³⁺ (BCBO), Ba_xZn_uB₂O₅:Ce³⁺ (BZBO), and Ba_xMg_vB₂O₅:Ce³⁺ (BMBO) phosphors. A red shift occurs with the increase of Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ concentration, and a blue shift occurs when the concentrations of Sr²⁺, Ca²⁺, Zn²⁺, and Mg²⁺ exceed the critical value. The emission color can be tuned from deep blue (0.15, 0.12) to cyan (0.16, 0.27) upon 365 nm UV lamp excitation due to the crystal field splitting and centroid shifts. The excitation band shift to long wavelength by introducing ions, so that the synthesized phosphor can be better matched with the n-UV chip. The emission intensity slowly decreases with the temperature increasing. Therefore, the BMBO:Ce³⁺, BZBO:Ce³⁺, BCBO:Ce³⁺, and BSBO:Ce³⁺ phosphors with relatively good thermal stability were synthesized, which could have potential applications in the n-UV white LEDs.     

Effect of CeO2 on the Glass Structure of Sodium Germanate Glasses

Germanate glasses have potential applications as optical fibers. Materials doped with rare earth ions are good candidates for optical, lasing, and magnetic applications. Based on the ternary system, CeO₂–Na₂O–GeO₂ a series of six glasses were fabricated using powder fusion, and varying the Na₂O content from 0 to 45 mol%, and a CeO₂ content constant at 3 mol%. The glasses were analyzed by FT‐IR, Raman and X‐ray photoelectron (XPS) spectroscopies to obtain information about the glass structure, cerium oxidation's state and how it is introduced in the glass network. FT‐IR and Raman spectra revealed the presence of GeO₆ and GeO₄ groups as well as Q² and Q³ units in the glasses with alkali low content. XPS spectra analysis revealed that the cerium ions were reduced from Ce⁴⁺ to Ce³⁺. The nonbonding to total oxygen ratio was estimated from the curve fitting of the O 1s core level spectra. Density and elastic parameters showed a nonlineal tendency in the change of the physical properties as a function of Na₂O content. Finally, photoluminescence spectroscopy confirmed the presence of Ce³⁺ ions. The characteristic 4f → 5d electronic transitions at 360 nm were detected, when a 280 nm excitation line of pulsed laser was used as excitation source.     

Phase formation and spectral evolution of (Sr,Ba)2Si(O,N)4:Eu2+ phosphors

Sr_2‐xBa_xSi(O,N)₄:Eu²⁺ (SB_xSON:Eu²⁺) oxynitridosilicate phosphors were prepared via incorporation of N^3?, Eu²⁺, and Ba²⁺ ions into Sr₂SiO₄ (SSO) lattices. X‐ray diffraction patterns of the prepared powders revealed that SB_xSON:Eu²⁺ was a solid‐solution form of SSO. An increase in x values caused a phase transition and an expansion of the unit cell. The photoluminescence excitation (PLE) spectra of SB_xSON:Eu²⁺ were broad, covering the ultraviolet range to the visible range. Corresponding PL emission spectra strongly depended on the excitation wavelengths and consisted of two emission bands, one in the green‐blue region (A‐band) and the other in the red region (B‐band), which were assigned to Eu(I) and Eu(II), respectively. The B‐band resulted from a dramatic red‐shift of the green emission band assigned to Eu(II) of SSO:Eu²⁺, revealing that the nitridation process preferentially affected the Eu(II) sites. This behavior was explained by crystal field splitting, the fluorescence decay time, and thermal quenching. The Ba²⁺ substitution caused evolution of the PL spectra, and its effects on the spectra were discussed under consideration of ionic size and covalence.     

A New Blue‐Emitting Phosphor of Ce3+‐Activated Fluorosilicate Apatite Ba2Y3[SiO4]3F

Blue‐emitting phosphor of Ce³⁺‐activated fluorosilicate apatite Ba₂Y₃[SiO₄]₃F was prepared via conventional solid‐state reaction method. The X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) excitation and emission spectra, and the decay curves (lifetimes) were applied to characterize the phosphors. The effects of Ce³⁺ activator concentration on the luminescence properties were investigated. Ba₂Y_2.85Ce_0.15[SiO₄]₃F exhibits the brightest blue emission with CIE coordinates of (x = 0.231, y = 0.301). The crystallographic site of Ce³⁺ ions in Ba₂Y₃[SiO₄]₃F lattices was identified. Two kinds of crystallographic Ce³⁺ occupying MI and MII sites in Ba₂Y₃[SiO₄]₃F lattices result in two distinct emission centers. The internal PL quantum efficiency, the temperature‐dependent luminescence, and the activation energy of thermal quenching were investigated to evaluate the potential application. This is a new kind of blue‐emitting phosphor based on apatite structure.     

A Single‐Phased Sr1−y‐3x/2Al2Si2O8: xCe3+, yMn2+ with Efficient Energy Transfer as a Potential Phosphor for White‐Light‐Emitting Diodes

A series of Ce³⁺‐ and Mn²⁺‐(co‐)activated SrAl₂Si₂O₈ phosphors have been prepared at 1350°C under a reducing atmosphere and their photoluminescence properties have been studied as a function of the (co‐)dopant ions concentrations. We have discovered that energy transfer (ET) not only from Ce³⁺ to Mn²⁺ but also from “defects” to Mn²⁺ by the facts that there is existing significant overlap between the emission spectrum of Ce³⁺ (“defects”) and the excitation spectrum of Mn²⁺. The source of the “defects” in the host lattice is originated from the different charge substitution between Ce³⁺ and Sr²⁺. By adopting the principle of ET, the material SrAl₂Si₂O₈: Ce, Mn can act as a phosphor for white‐light ultraviolet light‐emitting diodes (UV‐LEDs) by tuning of the dopants contents.     

Novel Emitting‐Color Tunable Phosphors Ba3Y2(BO3)4:Ce3+,Tb3+ with Efficient Energy Transfer for Near‐UV Light‐Emitting Diodes

This work presents the ultraviolet–visible spectroscopic properties of Ba₃Y₂(BO₃)₄:Ce³⁺,Tb³⁺ phosphors prepared by a high‐temperature solid‐state reaction. Under ultraviolet light excitation, tunable emission from the blue to yellowish‐green region was obtained by changing the doping concentration of Tb³⁺ when the content of Ce³⁺ is fixed. The efficient energy transfer process between Ce³⁺ and Tb³⁺ ions was observed and confirmed in terms of corresponding excitation and emission spectra. In addition, the energy transfer mechanism between Ce³⁺ and Tb³⁺ was proved to be dipole–dipole interaction in Ba₃Y₂(BO₃)₄:Ce³⁺,Tb³⁺ phosphor. By utilizing the principle of energy transfer and appropriate tuning of Ce³⁺/Tb³⁺ contents, Ba₃Y(BO₃)₄:Ce³⁺,Tb³⁺ phosphors can have potential application as an UV‐convertible phosphor for near‐UV excited white light‐emitting diodes.     

Effect of Boron Nitride (BN) on Luminescent Properties of Y3Al5O12:Ce Phosphors and their White Light‐Emitting Diode Characteristics

This article reports a low‐cost yellow‐emitting Y₃Al_5‐xB_xO_12‐xN_x:Ce³⁺ phosphor with an enhanced luminescent intensity and excellent thermal stability for white light‐emitting diodes (LEDs). It was synthesized by a simple gas‐pressure sintering (GPS) process. The effect of B³⁺–N^3? incorporation on the optical properties of Y₃Al₅O₁₂:Ce³⁺ phosphor was investigated. The addition of appropriate amounts of boron nitride (BN) leads to a marked increase in photoluminescent intensity and a slight shift of its emission spectra toward the blue region, which is assigned to the improved crystallinity and increased particle size. Especially, the prepared oxynitride phosphor does not exhibit any thermal quenching under high temperature, and the emission intensity at 250°C even increases up to 175% of that measured at 20°C. Finally, the white LED flat lamp with luminous efficiency as high as 101 lm/W, color rendering index of 72, and correlated color temperature of about 6600 K is successfully realized by using YAG:Ce³⁺ phosphor doped with 0.5 molar ratio BN, which is acceptable and promising for general indoor illuminations to replace fluorescent or incandescent lamps.