Abnormal thermal quenching behavior and optical properties of a novel apatite-type NaCa3Bi(PO4)3F:Sm3+ orange-red-emitting phosphor for w-LED applications

Novel apatite-type NaCa₃Bi(PO₄)₃F:xSm³⁺ (0.01 ≤ x ≤ 0.30) orange-red-light phosphors were synthesized through the solid-state method at high temperature. The crystal structure, energy band structure, density of state, phase purity, particle morphology, photoluminescence properties, thermostability, and luminescence decay of the phosphors were comprehensively characterized. When λ_ex = 404 nm, the optimal NaCa₃Bi(PO₄)₃F:0.05 S m³⁺ phosphor showed the orange-red emission (597 nm). The NaCa₃Bi(PO₄)₃F:Sm³⁺ phosphors exhibited abnormal thermal quenching properties as their emission intensity increased by about 2.57% from 300 to 380 K. Their intensity at 440 K was still 1.01-fold stronger than that at room temperature. The abnormal thermal quenching mechanisms were well explained via the coordinate configuration scheme. The thermal activation energy (E_a) was calculated to be 0.79 eV. The color purity of all the phosphors reached 99.9%. Ultimately, a white light-emitting diode (w-LED) was fabricated based on the tri-color RGB method. The color rendering index and the chromaticity coordinates of the fabricated w-LED were 89 and (0.310, 0.319), respectively. Thus, these high thermostability NaCa₃Bi(PO₄)₃F:Sm³⁺ orange-red phosphors can be potentially used in w-LED applications.     

Optical transition and luminescence properties of Sm3+-doped YNbO4 powder phosphors

A series of YNbO₄: Sm³⁺ powder phosphors with different doping concentrations were synthesized by a traditional high-temperature solid-state reaction method. The crystal structure of the obtained samples was characterized by means of X-ray diffraction. Concentration quenching, energy-transfer mechanism, and luminescence thermal stability of YNbO₄: Sm³⁺ samples were studied through the fluorescence spectra and decays. It was concluded that electric dipole-dipole interaction was the dominant energy-transfer mechanism between Sm³⁺ ions according to both Van Uitert's model and Dexter's model. Using the Arrhenius model, crossover process was proven to be responsible for the luminescence thermal quenching of Sm³⁺. Moreover, a novel approach for evaluating the optical transition properties of Sm³⁺ ion in YNbO₄ powders using the diffuse-diffraction spectrum and fluorescence decay was examined in the framework of Judd-Ofelt (J-O) theory. It was confirmed that the J-O parameters Ω_λ (λ = 2, 4, 6) of Sm³⁺ in YNbO₄ powder were reliable by comparing the radiation transition rate with the measured emission results.     

Polyaminocarboxylate promoted synthesis of Hafnium/ Zirconium substituted anion excess In2O3: Structure,optical and electrical conductivity properties

The current study aimed to generate Hf/Zr substituted In₂O₃ with the ultimate aim of realizing a potential transparent conducting oxide. We applied a co-complexation method to bring the reactively dissimilar In and Hf/Zr together in one oxide network. We prepared an EDTA complex containing an equimolar concentration of In and Hf/Zr and examined their characteristics with FTIR and TG-DSC traces. Rietveld refinement results of calcined complexes and their Raman spectra confirmed the formation of anion excess bixbyite structure for (In_1-xM_x)₂O_3+δ (M = Hf, Zr, and x = 0.50). The lattice expanded after substituting with Hf/Zr, and the optical bandgap increased from 2.87 eV (In₂O₃) to 3.20–3.60 eV. The high percentage reflectance in the visible region and absorbance in the UV region fulfilled some of the prerequisites of transparent conducting oxide. Electrical resistivity reduced up to two orders in magnitude with increasing temperature for Hf and Zr incorporated In₂O₃.     

White light emitting from YVO4/Y2O3:Eu3+,Bi3+ composite phosphors for UV light-emitting diodes

A series of (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 (0≤x≤0.54) composite phosphors was synthesized in one step by high temperature solid state reaction and the photoluminescence properties were investigated. By means of co-doping Eu³⁺ and Bi³⁺ ions into the composite matrices composed of YVO₄ and Y₂O₃ crystals, the YVO₄/Y₂O₃:Eu³⁺,Bi³⁺ phosphor exhibits simultaneously the blue (418 nm), green (540 nm) and orange-red (595, 620 nm) emissions. The broad blue and green emissions are attributed to the ³P₁–¹S₀ transitions of Bi³⁺ ion both in Y₂O₃ and in YVO₄ matrices. Moreover, the sharp orange-red emissions are attributed to the ⁵D₀–⁷F_1,2 transitions of Eu³⁺ ion in YVO₄ matrix. By tuning the mole ratio of YVO₄/Y₂O₃ matrices the white light-emitting could be obtained. The results indicated that when the mole ratio of Y₂O₃ (x) is at 0.11–0.54 mol, the (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 phosphors emit white light by combining the blue, green and orange-red emissions under the excitation of 360–370 nm wavelength which matches the emission of the commercial UV-LED diode. This implies that the phosphors may be the promising white light materials with broad absorption band for white light-emitting diodes.     

Luminescence properties of Sm3+ ions doped heavy metal oxide tellurite-tungstate-antimonate glasses

The trivalent Sm³⁺ ion doped tellurium-antimony-tungsten oxides based glasses were prepared by conventional melt quenching and pressing method. Spectroscopic characterizations such as optical absorption, photoluminescence and decay profile measurements were performed on the glasses. Judd-Ofelt theory is used to evaluate the oscillator strengths and the three phenomenological intensity parameters (Ω_λ, λ = 2, 4, 6) of the glasses. The photoluminescence spectra recorded under 479 nm excitation exhibited the emission bands at 562, 598, 645 and 708 nm corresponding to the transitions ⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2, 11/2) respectively. Using J-O parameters (Ω_λ) various important radiative parameters viz., transition probabilities, emission cross-sections, branching ratios of various emission bands were evaluated. Decay profiles were recorded to find the lifetime of the ⁴G_5/2 excited level and the obtained life time values are observed to decrease with an increase of Sm³⁺ ion concentration; such decrease is attributed due to clustering of Sm³⁺ ions which may cause luminescence quenching.     

Effect of Sm3+ doping on ferroelectric,energy storage and photoluminescence properties of BaTiO3 ceramics

Rare earth doped ferroelectric ceramics have attracted much attention due to their great potential application for novel multifunctional optical-electro devices. Herein, the x% mol Sm³⁺ doped BaTiO₃ (BTO:xSm³⁺) ceramics were fabricated by the conventional solid-state reaction method. The Sm³⁺ ions composition dependent phase structure, ferroelectric, energy storage and photoluminescence properties were systematically investigated. With the increase of Sm³⁺ ions composition, the remanent polarization decreases dramatically from 15.705 μC/cm² (BTO) to 7.132 μC/cm² (BTO:3.0%Sm³⁺), but the energy storage density and efficiency increase greatly with a relative change of 79.76% and 31.13%, respectively. Furthermore, Sm³⁺ doping causes the transformation from the tetragonal to pseudo-cubic phase for BTO ceramics at room temperature, resulting in a broader temperature transition range from the ferroelectric to paraelectric phase and a lower Curie temperature. Particularly, the pure BTO and BTO:xSm³⁺ ceramics show great thermal stability for energy storage properties. In addition, under the excitation of 408 nm near-ultraviolet light, the BTO:xSm³⁺ ceramics exhibit the strongest orange-red emission peak around 596 nm with a large relative tunability of intensity by 88.97%. The results suggest that the BTO:xSm³⁺ ceramics are suitable for the design of optoelectronic devices.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Y(PO4)3 red phosphors

A series of red-emitting phosphors Eu³⁺-doped Sr₃Y(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Y(PO₄)₃:Eu³⁺ phosphors exhibit peaks associated with the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The integral intensity of the emission spectra of Sr₃Y_0.94(PO₄)₃:0.06Eu³⁺ phosphors excited at 392 nm is about 3.4 times higher than that of Y₂O₃:Eu³⁺ commercial red phosphor. The Commission Internationale de l’Eclairage chromaticity coordinates, the quantum efficiencies and decay times of the phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Y(PO₄)₃ phosphors are promising red-emitting phosphors pumped by near-UV light.     

Sr2SiO4:Sm3+红色荧光粉的发光特性

用高温固相法合成了Sr2SiO4:Sm3 红色荧光粉,并研究粉体的发光性质.发射光谱由位于红橙区的3个主要荧光发射峰组成,峰值分别位于570,606nm和653nm,对应了Sm3 的4G5/2→6H5/2,4G5/2→6H7/2和4G5/2→6H9/2特征跃迁发射,606nm的发射最强.激发光谱表现从350 nm到420nm的宽带,可以被近紫外光辐射二极管(near-ultraviolet light-emitting diodes,UVLED)管芯产生的350～410 nm辐射有效激发.研究了Sm3 掺杂和不同电荷补偿剂对样品发光亮度的影响,Sm3 掺杂摩尔分数为6%、电荷补偿剂为Cl-时的效果最好.Sr2SiO4:Sm3 是一种适用于白光LED的红色荧光粉.     

Formation and photoluminescence of pure hexagonal and monoclinic Sm2+/Sm3+ codoped BaAl2Si2O8 phase using a simple sol–gel technique

The synthesis of pure hexagonal and monoclinic BaAl₂Si₂O₈:Sm crystals using a simple sol–gel technique is discussed in detail. The pure hexagonal BaAl₂Si₂O₈:Sm phase (H-BASO:Sm) can be obtained by adjusting the amount of the citric acid. The pure monoclinic BaAl₂Si₂O₈:Sm phase (M-BASO:Sm) can be easily obtained by a three-step-calcinations process. Possibly it is the carbon existing in the crystal that can stabilize the hexagonal BaAl₂Si₂O₈:Sm phase (H-BASO:Sm) and retard the conversion from the hexagonal to monoclinic phase. Photoluminescence, UV–vis absorption spectra and X-ray photoelectron spectra (XPS) demonstrate the existence of Sm²⁺ and Sm³⁺ ions in Sm doped H-BASO and M-BASO calcined under a reducing atmosphere. Photoluminescence properties of Sm³⁺ and Sm²⁺ ions in M-BASO and Sm²⁺ ions in H-BASO are reported.     

Sm3+掺杂GdVO4荧光材料的制备及其上转换发光性能

以水热法制备GdVO4:Sm3+上转换发光材料,表征了其形貌,考察了Sm3+掺杂量、焙烧温度及乙二胺四乙酸二钠(EDTA)掺杂量对材料上转换发光性能的影响. 结果表明,所制材料为四方晶系,在816 nm近红外光激发下,Sm3+掺杂量1.5%(mol)、焙烧温度800℃、EDTA:Sm3+(摩尔比)为1:1时,其上转换发光性能最好,发射峰位于565, 604, 647和706 nm处,分别归属于Sm3+的4G5/2→6HJ (量子数J=5/2, 7/2, 9/2, 11/2)电子跃迁,材料有可能用作LED灯荧光粉.     

Hydrothermal synthesis and luminescence properties of YF3:Ln (Ln=Sm,Dy, Tb and Pr) nano-/microcrystals

YF₃:Ln (Ln=Sm, Dy, Tb and Pr) nano-/microcrystals with uniform morphology and size have been successfully prepared by a facile, and environmentally friendly hydrothermal method. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) have been used to study the morphologies and crystal structure of the products. The effects of the molar ratio of EDTA to Y³⁺, and chelator on the crystal growth have been investigated in detail. The time-dependent experiments have been conducted to investigate the morphology evolution process. Based on the results, a possible growth mechanism is proposed. The photoluminescence spectra at room temperature show that the as-prepared YF₃:Ln (Ln=Sm, Pr, Tb and Dy) nano-/microcrystals show strong light emissions with different colors coming from different activator ions. It is noticed that morphology and size of the products have great influence on their emission intensity. Interestingly, in the YF₃:Sm system, we observed the Sm²⁺ emission peaks when excited at 323 nm. The results reveal that some of the Sm³⁺ ions should have been reduced to the divalent state during the hydrothermal process.     

Greenish-yellow emitting CdS: Sm3+ nanoparticles: Structural and optical analysis

Different concentrations of trivalent samarium (Sm³⁺) ions doped cadmium sulphide (CdS) nanoparticles were fabricated by one-step solid-state method at low temperature using C₁₀H₆(SO₃Na)₂ as surfactant for optoelectronic and solar cell applications. They were characterized through powder X-ray diffraction, Fourier transform infrared, Raman, scanning electron microscopy, transmission electron microscopy, UV–Vis absorption and photoluminescence studies. These nanoparticles establish cubic structure without any foreign phase and it was confirmed by Raman studies. The Raman spectrum of CdS nanoparticles shows first three longitudinal optical phonon orders. The adjacent lattice fringes were spaced about 0.30 nm. The direct band gap energy was found slightly higher than the bulk crystallites. The photoluminescence spectra of CdS: Sm³⁺ exhibits a broad peak at 563 nm with a shoulder at around 607 nm corresponding to Sm³⁺: ⁴G_5/2 → ⁶H_7/2 transition at 402 nm excitation. A luminescence quenching was noticed at higher Sm³⁺ ions concentration due to transfer of energy among the excited Sm³⁺ ions. The CdS: Sm³⁺ particles were fabricated with a size of the order of nanoscale and they can be used for efficient energy conversion. The studied CdS: Sm³⁺ nanoparticles are suitable for optoelectronic and solar cell applications.     

Charge transfer band excitation of La3NbO7:Sm3+ phosphors induced abnormal thermal quenching toward high-sensitivity thermometers

Different luminescent behaviors of La₃NbO₇:Sm³⁺ phosphors under the excitations of charge transfer band (CTB, 250 nm) and featured absorption peak (⁶H_5/2 → ⁴H_7/2, 405 nm) of Sm³⁺ ions were demonstrated. Under the excitation wavelength of 405 nm, the optimal La₃NbO₇:0.1Sm³⁺ phosphor exhibited an orange-red emission while the chromatic coordinate was found to be (0.609, 0.387), which also showed the excellent thermal performance, exhibiting its emission intensity of about 90.67% at 423 K with respect to 303 K. In the case of CTB excitation, the La₃NbO₇:0.1Sm³⁺ phosphor emitted an orange-yellow region with the chromaticity coordinate of (0.540, 0.443), and the emission intensity was stronger than the above one (λ_ex =405 nm) even though the optimized sample would be changed to the La₃NbO₇:0.05Sm³⁺ phosphor. With the increase of temperature, the obtained sample revealed an abnormal thermal quenching phenomenon between the emission peak of the host material and the emission transition of ⁴G_5/2 → ⁶H_9/2 under the excitation wavelength of 250 nm, which could be suggested to turn into a pair of thermal-couple levels. Therefore, the sensing sensitivity of the obtained sample was further investigated based on the fluorescence intensity ratio theory. Eventually, the absolute and relative sensing sensitivities of the La₃NbO₇:0.01Sm³⁺ phosphor were estimated to be as high as 5.379 × 10⁻² K⁻¹ and 1.60% K⁻¹, respectively.     

Dielectric properties with high dielectric permittivity and low loss tangent and nonlinear electrical response of sol-gel synthesized Na1/2Sm1/2Cu3Ti4O12 perovskite ceramic

Giant dielectric ceramic, Na_1/2Sm_1/2Cu₃Ti₄O₁₂, was successfully prepared by a modified sol-gel method. X-ray diffraction experiments indicated that a body-centered cubic structure with a space group of Im3 was obtained. Our density functional theory calculations revealed that codoping Na and Sm in the CaCu₃Ti₄O₁₂ structure resulted in charge compensation between Na and Sm ions in this structure, whereas the oxidation states of Cu and Ti were unaltered. Giant dielectric permittivity ～7.21 × 10³ - 8.04 × 10³ and low dielectric loss tangent ～0.045–0.049 were accomplished at a sintering temperature of 1050 °C for 12–18 h. Nonlinear J - E property with breakdown electric field ～5.13 – 5.78 × 10³ V/cm and nonlinear coefficient ～6.08–6.82 were also achieved. The n-type semiconducting grain originated from short-range migrations of mixed Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ charges. Finally, our charge analysis showed that the occurrence of Cu⁺ and Ti³⁺ was related to the existence of oxygen vacancy in these ceramics.     

Colossal dielectric properties of Na1/3Ca1/3Sm1/3Cu3Ti4O12 ceramics: Computational and experimental investigations

A modified sol?gel technique was used to synthesize a high dielectric ceramic, Na_1/3Ca_1/3Sm_1/3Cu₃Ti₄O₁₂. The crystal structure of this sintered ceramic matches the standard pattern of a body?centered cubic (bcc) system within the Im3 space group (JCPDS No. 75–2188). No impurity phases were observed. Interestingly, a high dielectric permittivity of ～1.14–1.35 × 10⁴ and a low loss tangent of ～0.027–0.039 were achieved in this sintered Na_1/3Ca_1/3Sm_1/3Cu₃Ti₄O₁₂ ceramic. Our DFT calculations disclosed that substitution of Na⁺ ions at Cu²⁺ sites causes an observed excess Cu concentration. As a result, metastable insulating phases were formed at a relatively high sintering temperature. Additionally, our electron density calculations revealed that Na ions lose their electrons to Sm ions, whereas the oxidation states of Cu and Ti are unaltered. Our results show that Cu⁺ and Ti³⁺ were observed after introducing an oxygen vacancy into this lattice. Significantly different values of R_g, R_gb, and E_g, E_gb support an internal barrier layer capacitor as the most likely origin of the giant dielectric properties of this ceramic. XPS results show mixed Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ in all ceramics, suggesting that electron hopping between Cu⁺?Cu²⁺ and Ti³⁺?Ti⁴⁺ is the probable origin of the n?type semiconducting state inside the grains.     

Synthesis and photoluminescence properties of Sr3(PO4)2:Re3+, Li+ (Re = Eu,Sm) red phosphors for white light-emitting diodes

Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) red phosphors were prepared via a high temperature solid state reaction, and their structure and luminescence properties were investigated. X-ray diffraction patterns indicate that the phase of as-prepared samples is in good agreement with standard Sr₃(PO₄)₂ structure. Under 395 nm excitation, the emission of Sr₃(PO₄)₂:Eu³⁺ consists of a strong peak centered at 622 nm and two weak peaks centered at 598 nm and 660 nm, which correspond to ⁵D₀→⁷F₂, ⁵D₀→⁷F₁ and ⁵D₀→⁷F₃ transitions, respectively. Also, the emission spectrum of Sr₃(PO₄)₂:Sm³⁺ shows three main peaks at 568 nm, 603 nm and 651 nm, which are attributed to ⁴G_5/2→⁶H_I/2 (I = 5, 7, 9) transitions of Sm³⁺. Furthermore, luminescence properties of Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) samples are enhanced significantly by Li⁺ ions doping as charge compensator. Results indicate that as-prepared Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) could be the potential red phosphors used in white light-emitting diodes.     

The optical properties and the natural lifetime calculation of a Sm(III) complex

The photophysical properties of the complex Sm(PM)₃(TP)₂ [PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone, TP = triphenyl phosphine oxide] are determined in crystal state, and energy transfer process is modeled for ligands to center Sm(III) ion. The characteristic luminescence of Sm(III) is sensitized by PM and TP, and most of transitions from excited state ⁴G_5/2 of Sm³⁺ are detected. According to the Judd–Ofelt theory, values of three oscillator strength parameters were obtained. The radiative transition rates for the emission from ⁴G_5/2 to the lower manifolds were obtained, and calculated radiative lifetime of the ⁴G_5/2 manifold is 3.1 ms. The corresponding fluorescence quantum efficiency is 2.7%.     

Investigation of Eu2+ luminescence in barium tetraphosphate Ba3P4O13 polycrystalline ceramics

In this paper, Ba₃P₄O₁₃:Eu²⁺ phosphor was synthesized by a solid-state reaction. The photoluminescence (PL) emission spectrum and luminescence decay kinetics confirm that the doped Eu²⁺ ions can occupy two different Ba²⁺ sites. The PL excitation spectrum shows a broad band matching well with the emission of near-UV chip. Ba₃P₄O₁₃:Eu²⁺ is a promising phosphor for near-UV chip excited white LEDs. The doped Eu³⁺ ions can also be reduced to Eu²⁺ ions in air atmosphere at high temperature. Charge compensation mechanism is applied to explain this kind of abnormal reduction.     

Structural and spectral properties of red light emitting Eu3+ activated TiO2 nanophosphor for white LED application

The structural and luminescent properties of Eu³⁺ doped TiO₂ nanophosphors synthesized by low cost combustion method were investigated. The X-ray diffraction analysis revealed that crystallite size decreases with doping concentration. Lattice volume expansion occurred due to the substitution of Ti⁴⁺ ions by larger ionic radii ions Eu³⁺. FESEM images showed prepared phosphors to be nano size spherical shaped particles. Energy band gap of 3 mol% Eu³⁺ doped samples decreased to 3.15 eV due to doping effect. The Eu³⁺ doped TiO₂ nanophosphors exhibited main red emission peak centered at 616 nm under 395 nm UV light excitation. Concentration quenching was observed at 3 mol% doping, that has been ascribed to dipole-dipole interaction. The covalent nature of Eu-O bond and environment around Eu³⁺ ions were discussed using Judd-Ofelt (J-O) intensity parameters. Internal quantum efficiency was calculated using excited state lifetime ⁵D₀ state of Eu³⁺ ion and J-O theory. The CIE colour coordinates and colour purity were calculated using the spectral energy distribution function. Low excited state life time indicated that Eu³⁺ doped TiO₂ can be used as red emitting phosphor for white light emitting diode applications.     

Elimination of pyrochlore phase in high-concentration Sm3+-doped PMN-PT piezoelectric ceramics by excessive MgO

Undesirable pyrochlore phase often appears in Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT)-based ceramics with high rare-earth ion (RE³⁺) doping concentration, which greatly limits their development. In this study, 0–5 mol% Sm³⁺-doped Pb(Mg_1/3Nb_2/3)O₃-29PbTiO₃ (PMN-29PT:0-5Sm) ceramics were first synthesized using traditional precursor method. In the X-ray diffraction spectra and scanning electron microscope images of PMN-29PT:3-5Sm ceramics, the diffraction peaks of pyrochlore phase and pyrochlore grains with octahedral morphology were observed, respectively. The reason for the appearance of the pyrochlore phase is that Sm³⁺ doping causes the Nb-rich regions. To eliminate the pyrochlore phase, PMN-29PT:3-5Sm ceramics were resynthesized by an improved precursor method in which an excess of 4 mol% MgO was added to the reactants before pre-sintering. After adding an excess of 4 mol% MgO, the concentration ratio of Nb⁵⁺ and Mg²⁺ in the pyrochlore grains returned to the value in the perovskite grains, and the pyrochlore phase was transformed into the perovskite phase PMN. The dielectric, ferroelectric, and electromechanical properties were compared before and after eliminating the pyrochlore phase. The results show that the comprehensive performance of the ceramics is improved after eliminating the pyrochlore phase.