Synthesis and luminescent properties of BaGd2O4:Dy3+, an novel scintillating phosphor

The BaGd_2?x O₄:xDy³⁺ (0 ≤ x ≤ 0.08) phosphors were synthesized at 1,300 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction, photoluminescence excitation spectra, photoluminescence (PL) spectra, X-ray excited luminescence (XEL) spectra, and thermoluminescence (TL) spectra. It is found that the quenching concentration of Dy³⁺ ions in BaGd₂O₄ host is dependent on the selected excitation wavelength. The optimal PL intensity for the investigated BaGd_2?x O₄:xDy³⁺ phosphors is found to be x = 0.01, 0.02, and 0.04, upon excitation by 234, 277, and 350 nm ultraviolet light, respectively. The energy transfer among Dy³⁺ ions upon excitation by 350 nm is confirmed to be an electric dipole–dipole interaction mechanism based on the fitting of Huang’s rule. In addition, the intensive XEL from BaGd₂O₄:Dy³⁺ phosphor is observed by the naked eyes at room temperature, and TL properties of the investigated phosphors are analyzed and discussed. All the results imply that the investigated phosphors could be a promising scintillating phosphor.     

Photoluminescence spectra of thenardite Na2SO4 activated with rare-earth ions, Ce, Sm, Tb, Dy and Tm

Five Na₂SO₄:RE³⁺ phosphors activated with rare-earth (RE) ions (RE³⁺=Ce³⁺, Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) were synthesized by heating natural thenardite Na₂SO₄ from Ai-Ding Salt Lake, Xinjiang, China with small amounts of rare-earth fluorides, CeF₃, SmF₃, TbF₃, DyF₃ and TmF₃, at 920 °C in air. The photoluminescence (PL) and optical excitation spectra of the obtained phosphors were measured at 300 and 10 K. In the PL spectrum of Na₂SO₄:Ce³⁺ at 300 K, two overlapping bands with peaks at 335 and 356 nm due to Ce³⁺ were first observed. Narrow bands observed in PL and excitation spectra of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors were well identified with the electronic transitions within the 4fⁿ (n=5, 8, 9 and 12) configurations of RE³⁺. The existence of excitation bands with high luminescence efficiency at wavelengths shorter than 230 nm is characteristic of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors. The obtained results suggest that these phosphors are unfavorable as the phosphor for usual fluorescence tubes, i.e., mercury discharge tubes, but may be favorable as the phosphor for UV-LED fluorescent tubes and as cathodoluminescence, X-ray luminescence and thermoluminescence phosphors.     

Thermodynamics stability,electronic structures and spectroscopic properties of defects and Ce3+ ions in Y2O3

Thermodynamic properties, electronic structures and spectroscopic properties of defects and Ce³⁺ in Y₂O₃ are studied by using the hybrid density functional theory associated with multi-reference configuration interaction ab-initio calculations. Thermodynamic transition energy levels of the easily generated oxygen vacancies in the host are analyzed according to HSE06-calculated formation energies, which may be conducive to interpretations of the persistent luminescence (PersL) of Y₂O₃-based phosphors. Besides, the locations of impurity states (caused by V_O and Ce³⁺) in energy bands are obtained from derived density of states. Moreover, energies and oscillator strengths of 4f₁ → 5d₁₋₅ transitions of Ce³⁺ ions (at Y1 and Y2 sites) calculated from the CASSCF/CASPT2/RASSI−SO method agree reasonably well with experimental excitation spectra of Y₂O₃: Ce³⁺ phosphors, achieving the assignment of excitation spectra. The presented calculations can be applied to identify luminescent centers in Ce³⁺-doped phosphors and reveals possible native defects and their roles in the PersL of phosphors.     

Luminescence spectroscopy and energy transfer in Eu2+/Mn2+-doped KCaPO4 phosphors

Eu²⁺/Mn²⁺-doped KCaPO₄ phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), SEM, photoluminescence excitation, and emission spectra, and the luminescence decay curves were measured. Mn²⁺ singly doped KCaPO₄ shows the weak origin-red luminescence band peaked at about 590 nm. The Eu²⁺/Mn²⁺ co-doped phosphors emit two distinctive luminescence bands: a blue one centered at 480 nm originating from Eu²⁺ ions and a broad red-emitting one peaked at 590 nm from Mn²⁺ ions. The luminescence intensity from Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ ions. The efficient energy transfer from Eu²⁺ to Mn²⁺ was verified by the photoluminescence spectra together with the luminescence decay curves. The resonance-type energy transfer via a dipole–quadrupole interaction mechanism was supported by the decay lifetimes. The emission colors could be tuned by changing the Mn²⁺-doping concentration.     

Effect of γ-irradiation on structural,morphological and luminescence properties of cerium-doped Y3Al5O12 nano-material

ABSTRACT

Cerium-doped yttrium aluminum garnet (YAG: Ce³⁺) nanopowder phosphors have been elaborated by sol–gel process and annealed at 900°C for 2?h. The prepared phosphors were exposed to gamma radiation, using ⁶⁰Co source, at different doses ranging from 5 to 100?kGy. The influence of γ-irradiation on the structural, morphological and luminescence properties of YAG: Ce³⁺ phosphors were investigated in detail by X-ray diffraction, ?eld emission scanning electron microscopy (FESEM), Fourier transforms infrared spectroscopy (FTIR) and photoluminescence measurements. The XRD analysis confirmed the presence of single cubic phase for all samples of YAG: Ce³⁺ nanophosphors independent of γ-rays dose. FESEM micrograph results revealed that the particles present flate-like shapes and high density of dislocation for sample irradiated at 100?kGy of γ-ray. The YAG: Ce³⁺ nanophosphors showed broad green–yellow emission band in the range of 450–700?nm with maximum intensity at 538?nm assigned to the 5d → 4f transitions of Ce³⁺ ion. The emission intensity of YAG: Ce³⁺ phosphors vary with the γ-ray irradiation and reach the maximum for sample irradiated to a dose of 25?kGy. The variation of luminescence intensity is related to the crystallite size and Ce⁴⁺ ions content in YAG host nanomaterial.     

Luminescence of excitons and antisite defects in Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

The luminescence of excitons and antisite defects (ADs) was investigated, as well as the specific features of the excitation energy transfer from excitons and ADs to the activator (Ce³⁺ ion) in phosphors based on Lu₃Al₅O₁₂:Ce (LuAG:Ce) single crystals and single-crystalline films, which are characterized by significantly different concentrations of ADs of the Lu _Al ³⁺ type and vacancy-type defects. The luminescence band with λ_max = 249 nm in LuAG:Ce single-crystal films is due to the luminescence of self-trapped excitons (STEs) at regular sites of the garnet lattice. The excited state of STEs is characterized by the presence of two radiative levels with significantly different transition probabilities, which is responsible for the presence of two excitation bands with λ_max = 160 and 167 nm and two components (fast and slow) in the decay kinetics of the STE luminescence. In LuAG:Ce single crystals, in contrast to single-crystal films, the radiative relaxation of STEs in the band with λ_max = 253.5 nm occurs predominantly near Lu _Al ³⁺ ADs. The intrinsic luminescence of LuAG:Ce single crystals at 300 K in the band with λ_max = 325 nm (τ = 540 ns), which is excited in the band with λ_max = 175 nm, is due to the radiative recombination of electrons with holes localized near Lu _Al ³⁺ ADs. In LuAG:Ce single crystals, the excitation of the luminescence of Ce³⁺ ions occurs to a large extent with the participation of ADs. As a result, slow components are present in the luminescence decay of Ce³⁺ ions in LuAG:Ce single crystals due to both the reabsorption of the UV AD luminescence in the 4f-5d absorption band of Ce³⁺ ions with λ_max = 340 nm and the intermediate localization of charge carriers at ADs and vacancy-type defects. In contrast to single crystals, in phosphors based on LuAG:Ce single-crystal films, the contribution of slow components to the luminescence of Ce³⁺ ions is significantly smaller due to a low concentration of these types of defects.     

Nanomechanical properties inside the scratch grooves of soda–lime–silica glass

Zn_2?2x Mn_2x GeO₄ (x=0, 0.001, 0.01) phosphors were prepared by conventional solid state reaction technique. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflection spectra, photoluminescence (PL), and cathodoluminescence (CL) spectroscopy were utilized to characterize the synthesized phosphors. The Mn²⁺-activated Zn₂GeO₄ phosphors exhibit narrow emission band at 532 nm under the excitation of ultraviolet light, which due to the ⁴T₁(⁴G)–⁶A₁(⁶S) transition of Mn²⁺ ions. Also it is observed that there exists energy transfer between the Zn₂GeO₄ host lattice and the activator (Mn²⁺). Under excitation of low-voltage electron beams, Zn₂GeO₄:Mn²⁺ shows strong green emission band dominating at 535 nm, corresponding to the ⁴T₁(⁴G)–⁶A₁(⁶S) emission of Mn²⁺ ions. The emission intensity and chromaticity coordinates of Zn₂GeO₄:Mn²⁺ as a function of accelerating voltage and the filament current were also investigated.     

SrAl4O7:Tm3+/Yb3+ nanocrystalline blue phosphor: structural, thermal and optical properties

Strontium aluminate (SrAl₄O₇) nanophosphor codoped with Tm³⁺–Yb³⁺ has been synthesized through the combustion route using urea as the reducing agent. Structural, thermal and optical characterizations have been carried out. Heat treatment of the samples shows a change in the crystallite phases and the relative luminescence intensities for the different bands. The nanocrystalline particles in the as-synthesized sample seem to arrange in rod like shapes of submicrometer length on annealing. A broad (350–550 nm) emission in the UV–green region is observed when 266 nm radiation is used for excitation. Intense upconversion (UC) emissions in blue, red and infrared are seen with excitation by 976 nm radiation. An emission at 364 nm not observed earlier and attributed to ¹D₂→³H₆ transition in Tm³⁺ is also seen. The blue emission from SrAl₄O₇:Tm³⁺/Yb³⁺ codoped nanophosphor (annealed at 1200°C) exhibits high color purity (89%) and is comparable to phosphors used commercially. The energy transfer mechanisms, responsible for these UC emissions, are proposed and discussed.     

Luminescence properties of LiPrxCe1−xP4O12

LiPr_1−xCe_xP₄O₁₂ (x=0, 0.002, 0.02; 0.1) powder samples were prepared using the melt solution technique. Luminescent parameters of LiPr_1−xCe_xP₄O₁₂ phosphors have been investigated under ultraviolet-vacuum ultraviolet (3-12 eV) synchrotron radiation and X-rays excitation at room and near liquid He temperatures. Excitation luminescence spectra of Ce³⁺ emission, luminescent spectra and decay curves from the lower excited state levels of the 4f¹5d¹ and 5d¹ electronic configuration of the Pr³⁺ and Ce³⁺, respectively, clearly indicate energy transfer from Pr³⁺ to Ce³⁺. Energy migration proceeds via the Pr-sublattice followed by nonradiation transfer from Pr³⁺ to Ce³⁺ ions.     

Photoluminescence study in Ce activated M6B5AlO15 (M = Sr,Ca, Ba) and mixed host aluminoborate phosphors

In this paper we report the modified solid state synthesis of Ce³⁺ activated Sr₆B₅AlO₁₅, Ca₆B₅AlO₁₅ Ba₆B₅AlO₁₅ and mixed host aluminoborate phosphors. The prepared phosphors were characterized by photoluminescence technique. The PL excitation spectra showed the excitation peaks ranging from 300 to 400 nm and emission spectra are observed in UV-blue region of spectrum and it varied for different hosts. This kind of emission is due to 4f⁶5d → 4f⁷ transition of Ce³⁺ ion. Further PLE and PL emission spectra for various compositions Ca₅Sr₁B₅AlO₁₅, Ca₄Sr₂B₅AlO₁₅, Ca₃Sr₃B₅AlO₁₅, Ca₂Sr₄B₅AlO₁₅, CaSr₅B₅AlO₁₅ are also taken which shows Ce³⁺ emission at 428 nm, 425 nm, 432 nm, 427 nm, 438 nm respectively. The calculated ²F_J (J = 7/2, 5/2) energy gap of Ce³⁺ in all hosts have been calculated and obtained values for Sr₆B₅AlO₁₅, Ba₆B₅AlO₁₅ phosphors are 1888 cm⁻¹ and 1330 cm⁻¹ respectively. PL emission spectra of mixed host aluminoborates have shown slight variations in positions of emission peaks.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

Effect of sintering temperature of Ce<Superscript>3+</Superscript>-doped Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> phosphors on light emission and properties of crystal structure for white-light-emitting diodes

The effect of the sintering temperature of Ce³⁺-doped Lu₃Al₅O₁₂ (Ce-LuAG) phosphors on the emission and properties of the crystal structure was studied. A cathodoluminescence peak at 317 nm, which was assigned to lattice defects, was exhibited in addition to emission peaks at 508 and 540 nm for the Ce-LuAG phosphors. The intensities of the 317 nm emission peak for the phosphors with mean particle diameters of 5.0 and 10.0 µm formed at a low sintering temperature of 1430 °C were higher than those for the phosphors with mean particle diameters of 18.0 and 20.5 µm formed at a high sintering temperature of 1550 °C. In contrast, the electroluminescence spectra for fabricated white-light-emitting diodes (LEDs) using the phosphors revealed that the intensity of the peak at 540 nm was strong for the mean particle diameters of 18.0 and 20.5 µm. The intensity of the 540 nm peak, which is attributed to the 4f→5d transition of the Ce³⁺ activator, showed a dependence on the sintering temperature. The relationship between the optical properties and the lattice defects is discussed.     

Luminescence of Ce3+ ion in aluminate based phosphors for scintillator

Ce³⁺ activated aluminate based phosphors prepared by combustion synthesis are reported here. The emission of Ce³⁺ ion is observed around 321–354 nm in the ultraviolet region of the spectrum. The intensity of strong photoluminescence emission peak of Ce³⁺ ion increases when Mg is added to CaAl₁₂O₁₉ phosphor. The Ce³⁺ emission in CaAl₁₂O₁₉:Ce,Mg phosphor may be useful for scintillation application.     

红色LiMBO3 : Re3+(Re=Eu,Sm) 发光材料的特性

采用固相法制备了红色LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)发光材料,研究了材料的发光性能。研究发现LiM(M=Ca, Sr, Ba)BO₃ : Eu³⁺材料呈现多峰发射,最强发射分别位于610,615,613 nm处,分别监测这三个最强峰,所得激发光谱峰值位于369,400,470 nm。LiM(M=Ca, Sr, Ba)BO₃ : Sm³⁺材料也呈多峰发射,分别对应Sm³⁺的⁴G_5/2→⁶H_5/2、⁴G_5/2→⁶H_7/2和⁴G_5/2→⁶H_9/2跃迁发射;分别监测602,599,597 nm三个最强发射峰,所得激发光谱峰值位于374,405 nm。研究了激活剂浓度对材料发射强度的影响,结果随激活剂浓度的增大,发射强度先增强后减弱,即,存在浓度猝灭效应。实验表明,加入电荷补偿剂Li⁺、Na⁺或K⁺均可提高LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)材料的发射强度。     

Enhanced Up-Conversion Emission in Al<Superscript>3+</Superscript> Co-Doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> Powder Phosphors

Yb³⁺-Tm³⁺ co-doped up-conversion powder phosphors using Zn(Al_xGa_1-x)₂O₄ (ZAGO) as the host materials were synthesized via solid-state reaction successfully. In addition, the morphology, structural characterization and up-conversion luminescent properties were all investigated by scanning electron microscope (SEM), x-ray diffraction (XRD) and fluorescence spectrophotometer (F-7000), respectively. Under the excitation of a 980 nm laser, all as-prepared powders can carry out blue emission at about 477 nm (corresponding to ¹G₄ → ³H₆ transition of Tm³⁺ ions), and red emission at about 691 nm (attributed to ³F₃ → ³H₆ transition of Tm³⁺ ions). Also, the influence of doping Al³⁺ ions were investigated. In brief, the doping of Al³⁺ ions has no effect on the position of emission peak. Howbeit the up-conversion efficiency and intensity of ZAGO:Yb,Tm phosphors are stronger than ZGO:Yb,Tm and ZAO:Yb,Tm phosphors, while the crystallinity is the opposite. More particularly, all as-prepared powder phosphors emit strong luminescence, which is observable by the naked eye, demonstrating the potential applications in luminous paint, luminescent dye, etc.     

Spectral luminescence properties of Ca1 ? x Sr x F2:Ce3+ (0 < x <1) crystals

The luminescence, reflection, and luminescence excitation spectra of two-component Ca_{1 ? x} Sr _x F₂:Ce³⁺ (0.05 mol %) (x = 0.14, 0.25, 0.4, 0.6, and 0.75) have been studied at room temperature and T = 8 K. It is shown that the luminescence bands (upon 130-eV photon excitation) in the range of 200 to 400 nm are attributed to singlet and triplet self-trapped exciton luminescence and to 5d-4f transitions in Ce³⁺.     

Cool white light emission on Ca3−(l+n)MgSi2O8:\mathrm{Ce}_{\mathrm{l}}^{3+}, \mathrm{Eu}_{n}^{2+} phosphors and analysis of energy transfer mechanism

Rare earth ions (Ce³⁺, Eu²⁺) activated Ca₃MgSi₂O₈ (CMSO) phosphors have been synthesized using solid-state reaction method in 95%N₂+5%H₂ reduction atmosphere at elevated temperatures by varying Eu²⁺ concentration from 0.0075 to 0.0300 at the fixed Ce_0.03 concentration to study their photoluminescence (PL) properties. An energy transfer occurs from Ce³⁺ to Eu²⁺ through a significant overlap of Eu²⁺ excitation spectrum with Ce³⁺ emission spectrum in CMSO, together with the systematic relative decrease and increase in emission bands of Ce³⁺ and Eu²⁺, respectively, have been observed. To support the phenomenon, diffuse reflectance spectra show various absorption levels corresponding to Ce³⁺, Eu²⁺, and/or mixture of both rare earth ions. An optimum emission was realized at 0.0150 of Eu²⁺ via. energy transfer from Ce³⁺ ion. By utilizing the principle of energy transfer, the critical distance (R _c ) between activator ions was found to be 18.64 Å. The CIE chromaticity coordinates measured on the Ca₃MgSi₂O₈:Ce³⁺, Eu²⁺ phosphors excited under ultraviolet (365 nm) source shows the values lie in cool white light region could be applied to solid state lighting.     

Luminescence properties of novel NaBa4(BO3)3:Ce, Eu phosphors

Novel Eu³⁺, Ce³⁺ activated NaBa₄(BO₃)₃ phosphors were synthesized by solid-state reactions. The excitation spectrum of NaBa₄(BO₃)₃:Ce³⁺ consists of an intense band peaking at 350 nm and a weak band in the higher energy side, and the emission spectrum exhibits a blue band with a maximum at about 420 nm. The Eu³⁺ emission in NaBa₄(BO₃)₃ consists of the transitions from ⁵D₀ to ⁷F_J, and the excitation spectrum consists of broad excitation band peaking at 270 nm and some intense narrow lines. The optimum doped concentration, the critical distance of the concentration quenching, and the fluorescence lifetime have also been investigated.     

VUV spectroscopic properties of Ce and Pr-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

Spectroscopic properties of Ce³⁺ and Pr³⁺-doped AREP₂O₇-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu) have been investigated using VUV spectroscopy technique. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 325-450 nm. The strong host absorption band starting at around 160 nm indicates that the optical band gap of AREP₂O₇ hosts is at least 7.7 eV, and the host→Ce³⁺ energy transfer process is rather efficient. However, AREP₂O₇:Pr³⁺ samples show less efficient host→Pr³⁺ energy transfer. The direct Pr³⁺ 4f²→4f¹5d¹ excitation, which are 12160±640 cm⁻¹ higher respect to that of Ce³⁺, leads to strong 4f¹5d¹→4f² emission bands in the range of 230-325 nm but no obvious 4f²→4f² emission lines.     

Violet-blue-shift of emission and enhanced luminescent properties of Ca3(PO4)2:Ce3+ phosphor induced by substitution of Gd3+ ions

Ca₃(PO₄)₂:1mol%Ce³⁺/xGd³⁺ (where x = 0.5, 1.0, 3.0 and 5.0 mol%) phosphors were synthesized by the conventional combustion synthesis method. The X-ray diffraction patterns showed their rhombohedral structure with space group of R3c. The optical properties including reflectance, excitation and emission were investigated. The band gaps of the phosphors were calculated from diffuse reflectance spectra data using the Kubelka–Munk function. The photoluminescence (PL) excitation spectra exhibited the broadband 4f–5d transition of Ce³⁺ ions centered at ~265 nm. The PL emission properties of the Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphors were studied as a function of the Gd³⁺ ion concentration. The Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphor had a wide emission band ranging from 320 to 400 nm, and peaking at 365 nm. This emission is ascribed to the transition from the higher 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. The 365 nm peak shifted to longer wavelengths with increasing concentration of the Gd³⁺ ion. The CIE chromaticity diagram of Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphor showed tunable emission colour from violet to violet-blue, suggesting that this phosphor can act as a source of violet-blue colour for application in information displays, phototherapy and photoluminescent liquid crystal displays.